JP2006110476A - Organic thin film forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for stably forming a fine organic thin film with reduced impurities which can rapidly form the film, and to provide a solution for forming the organic thin film used for the method. <P>SOLUTION: The organic thin film forming method has a process of making the solution for forming the organic thin film into contact with the surface of a substrate. The organic thin film forming method is characterized in that the solution for forming the organic thin film is prepared by treating a metal based surfactant having a hydroxy group or a hydrolyzable group in a solvent with at least one kind selected from a metal, a metal oxide, a metal hydroxide, a metal carried on a carrier, a metal salt carried on a carrier, a metal oxide carried on a carrier, a chelated or coordinated metal compound and a metal nano particle, and water. The solution for forming the organic thin film is also disclosed. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming an organic thin film formed on a surface of a substrate via a metal-oxygen bond or the like, and an organic thin film forming solution used in this method.

  As a method of forming a coating film for modifying the substrate surface, there are several known methods for producing a chemisorbed film that has excellent peeling resistance, high transparency, and does not impair the gloss of the substrate surface or the transparency of the substrate. It has been. (See Patent Documents 1 to 3)

  As a method of forming a chemical adsorption film on the surface of a substrate containing active hydrogen, at least an alkoxysilane surfactant, a non-aqueous solvent not containing active hydrogen, a carboxylic acid metal salt, a carboxylic acid ester metal salt, a carboxylic acid metal A mixed solution containing at least one silanol condensation catalyst selected from a salt polymer, a carboxylic acid metal salt chelate, a titanate ester and a titanate ester chelate is brought into contact with the substrate surface, and a siloxane bond is formed on the substrate surface. A method of manufacturing a chemisorbed film that forms a covalently bonded chemisorbed film is known. (See Patent Document 4)

As a method of forming a crystalline chemisorbed film on the surface of a substrate, a method of forming a crystalline monomolecular film by developing an organic solvent solution of a silane-based surfactant on the surface of a silicon wafer to which purified water is dropped is known. It has been. (See Non-Patent Document 1)
As a method of forming a water repellent film, a water repellent film composed of a monomolecular layer using a hydrolyzed monomer or polymer of a fluoroalkyl group-containing silane compound hydrolyzed under an acid catalyst, A method for fixing to the surface of a substrate via a silanol group is known. (See Patent Documents 5 and 6)

  As a method for forming a monomolecular film on the surface of a substrate containing active hydrogen, a chemical adsorption solution prepared using a non-aqueous organic solvent and a silane surfactant in a dry atmosphere is applied to the substrate surface, While evaporating and concentrating the organic solvent, the surfactant molecules in the adsorbent are chemically reacted with the substrate surface to bond and fix the surfactant molecules to the substrate surface at one end, and after evaporating the organic solvent, the organic solvent is removed. There is known a method for producing a chemisorbed monomolecular film comprising a step of washing and removing unreacted surfactant remaining on the surface of a substrate used. (See Patent Document 7)

  In addition, as a method for producing a self-assembled monolayer, a metal surfactant having at least one hydrolyzable group is added with an organic solvent, a metal oxide, or a metal alkoxide partial hydrolysis product and water. A method for producing a dense self-assembled monolayer with few impurities in a short time by using a treated solution is known. (See Patent Document 8)

  However, the methods described in Patent Documents 1 to 7 and Non-Patent Document 1 have a problem that it takes time to form a film, a silanol condensation catalyst remains in the film, and the catalyst inhibits chemical adsorption, so that a dense monomolecular film cannot be produced. There is a problem that the base material is limited because an acidic substance is generated, and a problem that a film must be formed in a non-aqueous system. Further, in the method described in Patent Document 8, a dense self-assembled monolayer with few impurities can be produced in a short time. Particularly, in fine patterning in the design of an electric device or the like, there are few impurities in a shorter time. There is a demand for dense self-assembled monolayers.

JP-A-4-132737 JP-A-4-221630 JP-A-4-367721 JP-A-8-337654 Japanese Patent Laid-Open No. 11-228942 JP-A-11-322368 JP-A-11-147074 WO 037664 Bull.Chem.Soc.Jpn., 74, 1397-1401 (2001)

  An object of the present invention is to provide a method for stably forming a dense organic thin film that can form a film quickly and has few impurities, and an organic thin film forming solution used for the forming method.

  As a result of intensive studies to solve the above problems, the present inventors have supported a metal-based surfactant having a hydroxyl group or a hydrolyzable group in a metal; a metal salt; a metal oxide; Metal; metal salt supported on carrier; metal oxide supported on carrier; metal compound chelated or coordinated; and at least one selected from metal nanoparticles, and organic thin film by treatment with water A forming solution was prepared. And when this solution was processed on the surface of a base material, it discovered that the precise | minute monomolecular film (organic thin film) with few impurities could be formed rapidly, and came to complete this invention.

That is, the present invention
(1) An organic thin film forming method comprising a step of bringing an organic thin film forming solution into contact with the surface of a substrate, wherein the organic thin film forming solution comprises a metal-based surfactant having a hydroxyl group or a hydrolyzable group. Metal in organic solvent; metal salt; metal oxide; metal hydroxide; metal supported on support; metal salt supported on support; metal oxide supported on support; chelated or coordinated A method of forming an organic thin film characterized by being obtained by treating with water, at least one selected from metal compounds; and metal nanoparticles;
(2) The method for forming an organic thin film according to (1), wherein the amount of water in the organic thin film forming solution is set within or maintained within a predetermined range.
(3) The amount of water in the organic thin film forming solution is set within a predetermined amount range or maintained by providing an aqueous layer in contact with the organic thin film forming solution. Regarding organic thin film formation method,
(4) The water content in the organic thin film forming solution is allowed to coexist in a state where water is contained in the organic thin film forming solution so that the water content in the organic thin film forming solution is within a predetermined range. (2) or (3) characterized in that
(5) The method for forming an organic thin film according to (4), wherein the water-retaining substance is a glass fiber filter or a cellulose fiber material.
(6) The water content in the organic solvent solution is set within a predetermined amount range or maintained by blowing a gas containing water into the organic thin film forming solution (2) to (5) Regarding the organic thin film forming method according to any one of
(7) The method for forming an organic thin film according to any one of (2) to (6), wherein the amount of water in the organic thin film forming solution is in the range of 50 to 1000 ppm or maintained.
(8) The water content in the predetermined amount range is a value obtained by measuring the solution obtained by collecting a part of the solution for forming an organic thin film by a Karl Fischer method, any of (2) to (7) Regarding the organic thin film forming method according to
(9) Said metal; metal salt; metal oxide; metal hydroxide; metal supported on support; metal salt supported on support; metal oxide supported on support; chelated or coordinated The metal compound; and at least one selected from metal nanoparticles are used in an amount of 0.001 to 1 mol with respect to 1 mol of the metal-based surfactant having a hydroxyl group or a hydrolyzable group (1) To the organic thin film formation method according to any one of to (8),
(10) The metal surfactant having the hydroxyl group or hydrolyzable group is represented by the formula (I)

[Wherein, R ¹ represents a hydrocarbon group which may have a substituent, a halogenated hydrocarbon group which may have a substituent, a hydrocarbon group containing a linking group, or a halogen containing a linking group. Represents a hydrogenated hydrocarbon group, M represents at least one metal atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom, and X represents a hydroxyl group or a hydrolyzable group. N represents an integer of 1 to (m-1), m represents a valence of M, and when n is 2 or more, R ¹ may be the same or different. In addition, when (mn) is 2 or more, Xs may be the same or different. In the method for forming an organic thin film according to any one of claims 1 to 9,
(11) A metal-based surfactant having a hydroxyl group or a hydrolyzable group is represented by the formula (II)

[Wherein, M, X and m represent the same meaning as described above. R ^{2 to} R ⁶ each independently represents a hydrogen atom or a fluorine atom, and R ⁷ represents an alkylene group, a vinylene group, an ethynylene group, an arylene group, or a divalent linkage containing a silicon atom and / or an oxygen atom. Represents a group. Y represents a hydrogen atom, an alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group. p represents 0 or a natural number, and q represents 0 or 1. When p is 2 or more, R ⁵ and / or R ⁶ may be the same or different. r represents a positive integer from 0 or 1 to (m−2), and when r is 2 or more, Y may be the same or different, and (m−r−1) is 2 or more. Sometimes X may be the same or different. In the method for forming an organic thin film according to any one of (1) to (10),
(12) The hydrolyzable group of X is a hydrocarbonoxy group that may have a substituent, an acyloxy group that may have a substituent, or a halogen atom (10 ) Or the organic thin film forming method according to (11),
(13) The organic solvent according to any one of (1) to (12), wherein the organic solvent is at least one selected from a hydrocarbon solvent, a fluorocarbon solvent, and a silicone solvent. Regarding the thin film formation method,
(14) The organic thin film is a crystalline organic thin film, wherein the organic thin film forming method according to any one of (1) to (13),
(15) The organic thin film according to any one of (1) to (14), wherein the organic thin film is a chemical adsorption film,
(16) The organic thin film is a self-assembled film, wherein the organic thin film forming method according to any one of (1) to (15),
(17) The organic thin film is a monomolecular film, wherein the organic thin film forming method according to any one of (1) to (16),
(18) The organic thin film forming method according to any one of (1) to (17), wherein the base material is a base material having active hydrogen on a surface thereof.
(19) The base material is a base material made of at least one material selected from glass, silicon wafer, ceramics, metal, plastic, paper, fiber, and leather (1) to (18) The organic thin film forming method according to any one of the above.

The present invention also provides:
(20) A metal surfactant having a hydroxyl group or a hydrolyzable group in an organic solvent, metal; metal salt; metal oxide; metal hydroxide; metal supported on the carrier; metal salt supported on the carrier A metal oxide supported on a carrier; a metal compound chelated or coordinated; and at least one selected from metal nanoparticles; and an organic material prepared by treatment with water Regarding thin film forming solution,
(21) The organic thin film forming solution according to (20), wherein the amount of water in the organic thin film forming solution is set within or maintained within a predetermined range.
(22) The amount of water in the organic thin film forming solution is set within a predetermined amount range or maintained by providing an aqueous layer in contact with the organic thin film forming solution. (21) Regarding the organic thin film forming solution,
(23) The water content in the organic thin film forming solution is allowed to coexist in a state where water is contained in the organic thin film forming solution so that the water content in the organic thin film forming solution is within a predetermined amount range or maintained. (21) or (22), wherein the organic thin film forming solution is characterized by
(24) The water-holding substance is a glass fiber filter or a cellulose fiber material, and the organic thin film forming solution according to (23),
(25) The water content in the organic solvent solution is set within a predetermined amount range or maintained by blowing a gas containing water into the organic thin film forming solution (21) to (24). Regarding the organic thin film forming solution according to any one of
(26) The organic thin film forming solution according to any one of (21) to (25), wherein the amount of water in the organic thin film forming solution is in the range of 50 to 1000 ppm or is maintained.
(27) The water content in the predetermined amount range is a value obtained by measuring the solution obtained by collecting a part of the solution for forming an organic thin film by a Karl Fischer method, any of (21) to (26) Regarding the organic thin film forming solution according to
(28) The metal; metal salt; metal oxide; metal hydroxide; metal supported on the support; metal salt supported on the support; metal oxide supported on the support; chelated or coordinated The metal compound; and at least one selected from metal nanoparticles are used in an amount of 0.001 to 1 mol with respect to 1 mol of the metal-based surfactant having a hydroxyl group or a hydrolyzable group (20). To the organic thin film forming solution according to any one of to (27),
(29) The metal surfactant having a hydroxyl group or a hydrolyzable group has the formula (I)

[Wherein, R ¹ represents a hydrocarbon group which may have a substituent, a halogenated hydrocarbon group which may have a substituent, a hydrocarbon group containing a linking group, or a halogen containing a linking group. Represents a hydrogenated hydrocarbon group, M represents at least one metal atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom, and X represents a hydroxyl group or a hydrolyzable group. N represents an integer of 1 to (m-1), m represents a valence of M, and when n is 2 or more, R ¹ may be the same or different. In addition, when (mn) is 2 or more, Xs may be the same or different. A solution for forming an organic thin film according to any one of (20) to (28),
(30) A metal surfactant having a hydroxyl group or a hydrolyzable group is represented by the formula (II)

[Wherein, M, X and m represent the same meaning as described above. R ^{2 to} R ⁶ each independently represents a hydrogen atom or a fluorine atom, and R ⁷ represents an alkylene group, a vinylene group, an ethynylene group, an arylene group, or a divalent linkage containing a silicon atom and / or an oxygen atom. Represents a group. Y represents a hydrogen atom, an alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group. p represents 0 or a natural number, and q represents 0 or 1. When p is 2 or more, R ⁵ and / or R ⁶ may be the same or different. r represents a positive integer from 0 or 1 to (m−2), and when r is 2 or more, Y may be the same or different, and (m−r−1) is 2 or more. Sometimes X may be the same or different. A solution for forming an organic thin film as described in any one of (20) to (29),
(31) The hydrolyzable group of X is a hydrocarbon oxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom (29 ) Or the solution for forming an organic thin film according to (30),
(32) The organic solvent according to any one of (20) to (31), wherein the organic solvent is at least one selected from a hydrocarbon solvent, a fluorocarbon solvent, and a silicone solvent. The present invention relates to a thin film forming solution.

  According to the solution for forming an organic thin film and the method for forming an organic thin film of the present invention, a dense monomolecular film with low energy and low cost, high productivity and less impurities can be formed. It can be suitably used in fields such as fine patterning in the design of electrical devices and the like.

  Hereinafter, the present invention will be described in detail.

  The present invention is an organic thin film forming method comprising a step of bringing an organic thin film forming solution into contact with the surface of a substrate, wherein the organic thin film forming solution has a hydroxyl group or a hydrolyzable group. (Hereinafter also referred to as “component A”) in an organic solvent, metal; metal salt; metal oxide; metal supported on the carrier; metal salt supported on the carrier; metal oxidation supported on the carrier A metal compound chelated or coordinated; and at least one selected from metal nanoparticles (hereinafter, these may be collectively referred to as “component B”), and obtained by treating with water. What is claimed is: 1. A method for forming an organic thin film, comprising:

1) Organic thin film forming solution (1) Component A A metal surfactant having a hydroxyl group or a hydrolyzable group has a hydroxyl group or a hydrolyzable functional group and a hydrophobic group in the same molecule. If it exists, it is not particularly limited, but those having a hydroxyl group or a hydrolyzable group capable of reacting with active hydrogen on the substrate surface to form a bond are preferred. The hydroxyl group or hydrolyzable group may have one or more. The metal surfactant having a hydroxyl group or a hydrolyzable group can be used alone or in combination of two or more. As such A component, specifically, the compound represented by the formula (I) can be preferably exemplified.

In the formula (I), R ¹ is a hydrocarbon group which may have a substituent, a halogenated hydrocarbon group which may have a substituent, a hydrocarbon group containing a linking group, or a linking group. Represents a halogenated hydrocarbon group containing

  Examples of the hydrocarbon group that may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-decyl group and the like. An alkenyl group having 2 to 30 carbon atoms such as a vinyl group, a propenyl group, a butenyl group or a pentenyl group; an aryl group such as a phenyl group or a naphthyl group;

  Examples of the halogenated hydrocarbon group of the halogenated hydrocarbon group which may have a substituent include a halogenated alkyl group having 1 to 30 carbon atoms, a halogenated alkenyl group having 2 to 30 carbon atoms, and a halogenated aryl group. Etc. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, A fluorine atom is preferable. Specific examples include groups in which one or more of the hydrogen atoms in the hydrocarbon groups exemplified above are substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

  Among these, the halogenated hydrocarbon group is preferably a group in which two or more of the hydrogen atoms in the alkyl group having 1 to 30 carbon atoms are substituted with halogen atoms, and in the alkyl group having 1 to 30 carbon atoms, More preferred is a fluorinated alkyl group in which two or more of the hydrogen atoms are substituted with fluorine atoms. In addition, when the fluorinated alkyl group has a branched structure, the branched portion is preferably a short chain having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.

The fluorinated alkyl group is preferably a group in which one or more fluorine atoms are bonded to the terminal carbon atom, more preferably a group having a CF ₃ group part in which _three fluorine atoms are bonded to the terminal carbon atom, and the terminal is a fluorine atom. May be a carbon chain in which a fluorine atom is substituted for an internal carbon chain with a hydrocarbon group that is not substituted. The terminal portion has a perfluoroalkyl portion in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and-(CH ₂ ) _h- (wherein h is 1) with the metal atom M described later. Represents an integer of ˜6, preferably an integer of 2 to 4.), and particularly preferred is a group having an alkylene group.
The number of fluorine atoms in the fluorinated alkyl group is [(number of fluorine atoms in the fluorinated alkyl group) / (number of hydrogen atoms present in the alkyl group having the same carbon number corresponding to the fluorinated alkyl group) × 100]%. Is preferably 60% or more, and more preferably 80% or more.

  Examples of the substituent of the hydrocarbon group that may have a substituent or the halogenated hydrocarbon group that may have a substituent include a carboxyl group; an amide group; an imide group; an ester group; a methoxy group, and an ethoxy group. An alkoxy group such as a group; or a hydroxyl group. The number of these substituents is preferably 0-3.

Specific examples of the hydrocarbon group including a linking group include the same hydrocarbon groups as those described above as the hydrocarbon group of the hydrocarbon group which may have a substituent.
In addition, as the halogenated hydrocarbon group of the halogenated hydrocarbon group containing a linking group, specifically, those listed as the halogenated hydrocarbon group of the halogenated hydrocarbon group which may have the above substituent The same thing is mentioned.

The linking group is preferably present between carbon-carbon bonds of a hydrocarbon group or a halogenated hydrocarbon group, or between carbon of the hydrocarbon group and a metal atom M described later.
Specific examples of the linking group include —O—, —S—, —SO ₂ —, —CO—, —C (═O) O—, or —C (═O) NR ⁸ — (wherein R ⁸ Represents a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, an n-propyl group, or an isopropyl group).
Among these, R ¹ is an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, or a fluorinated alkyl group containing a linking group from the viewpoint of water repellency and durability. Is preferred.

More preferable specific examples of R ¹ include CH ₃ —, CH ₃ CH ₂ —, (CH ₃ ) ₂ CH—, (CH ₃ ) ₃ C—, CH ₃ (CH ₂ ) ₂ —, CH ₃ (CH ₂ ) ₃ −, CH ₃ (CH ₂ ) ₄ —, CH ₃ (CH ₂ ) ₅ —, CH ₃ (CH ₂ ) ₆ —, CH ₃ (CH ₂ ) ₇ —, CH ₃ (CH ₂ ) ₈ —, CH _{3 (CH 2) 9 -,} CH 3 (CH 2) 10 -, CH 3 (CH 2) 11 -, CH 3 (CH 2) 12 -, CH 3 (CH 2) 13 -, CH 3 (CH 2) _{14 -, CH 3 (CH 2} ) 15 -, CH 3 (CH 2) 16 -, CH 3 (CH 2) 17 -, CH 3 (CH 2) 18 -, CH 3 (CH 2) 19 -, CH 3 _{(CH 2) 20 -, CH} 3 (CH 2) 21 -, CH 3 (CH 2) 22 -, CH 3 (CH 2) 23 -, CH 3 (CH 2) 24 -, CH 3 (CH 2) 25 −,

CF _3- , CF ₃ CF _2- , (CF ₃ ) ₂ CF-, (CF ₃ ) ₃ C-, CF ₃ (CH ₂ ) _2- , CF ₃ (CF ₂ ) ₃ (CH ₂ ) _2- , CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ —, CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃₋ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ —, CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ —, CF ₃ (CF ₂ ) ₇ O (CF ₂ ) ₂ (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ —, CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ —, CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ —,

CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₁₀ ( _{CH 2) 2 -, CH 3} (CF 2) 11 (CH 2) 2 -, CH 3 (CF 2) 12 (CH 2) 2 -, CH 3 (CF 2) 7 (CH 2) 3 -, CH 3 (CF ₂ ) ₉ (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₁₁ (CH ₂ ) ₃ —, CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ —, CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ —, CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ —, CH ₃ (CF ₂ ) _{7 (CH 2) 2 O (} CH 2) 3 -, CH 3 (CF 2) 8 (CH 2) 2 O (CH 2) 3 -, CH 3 (CF 2) 9 (CH 2) 2 O (CH 2 ) ₃₋ , CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ O (CH ₂ ) ₃ −, CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ —, CH ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF ( CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ — and the like, but are not limited thereto.

  M represents at least one atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom. Among these, a silicon atom is particularly preferable from the viewpoints of availability of raw materials and reactivity.

  X represents a hydroxyl group or a hydrolyzable group, and the hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes. Specifically, a hydrocarbon oxy group which may have a substituent; an acyloxy group which may have a substituent; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an isocyanate group; A cyano group; an amino group; or an amide group can be exemplified.

  Examples of the hydrocarbon oxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, and an n-hexyloxy group. An alkoxy group having 1 to 6 carbon atoms; an alicyclic hydrocarbonoxy group such as a cyclopropyloxy group, cyclopropylmethyloxy, cyclohexyl group, norbornyloxy group; an alkenyloxy group such as a vinyloxy group, an allyloxy group; a propargyloxy group And alkynyloxy groups such as phenoxy group and naphthyloxy group; aralkyloxy groups such as benzyloxy group and phenethyloxy group; and the like.

  Examples of the acyloxy group include an acetoxy group, a propionyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, and a benzoyloxy group.

  Examples of these substituents include a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group. Among these, X is preferably a hydroxyl group; a hydrocarbonoxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom, and an alkoxy group having 1 to 6 carbon atoms. Is more preferable.

m represents the valence of the metal atom M.
n represents any integer of 1 to (m−1). In producing a high-density organic thin film, n is preferably 1.
When n is 2 or more, R ¹ may be the same or different.
When (mn) is 2 or more, Xs may be the same or different.

Among the compounds represented by the formula (I), as one of preferred embodiments, a compound represented by the formula (II) can be exemplified.
In formula (II), M, X, and m represent the same meaning as described above, and R ^{2 to} R ⁶ each independently represent a hydrogen atom or a fluorine atom.
R ⁷ represents an alkylene group, a vinylene group, an ethynylene group, an arylene group, or a divalent linking group containing a silicon atom and / or an oxygen atom. Specific examples of R ⁷ are shown below.

In the above formula, a and b represent an arbitrary natural number of 1 or more.
Y is a hydrogen atom; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t -Alkyl groups such as pentyl group, n-hexyl group, isohexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n An alkoxy group such as a pentyloxy group or an n-hexyloxy group; a fluorinated alkyl group in which part or all of the hydrogen atoms are substituted with fluorine atoms; or a part or all of the alkoxy groups in which fluorine atoms are fluorine A fluorine-containing alkoxy group substituted with an atom;

r represents 0 or an integer of 1 to (m−2). In order to produce a high-density adsorption film, it is preferable that r is 0. When r is 2 or more, Y may be the same or different from each other, and when (m−r−1) is 2 or more, X may be the same or different from each other. May be. p represents 0 or a natural number, and q represents 0 or 1. When p is 2 or more, R ⁵ and / or R ⁶ may be the same or different.

As the compound represented by the formula (I), in addition to the compound represented by the formula (II), (1) CH ₃ — (CH ₂ ) _g —MY _r X _{mr −1
(2) CH 3 - (CH} 2) s -O- (CH 2) t -MY r X mr-1
_{(3) CH 3 - (CH} 2) u -Si (CH 3) 2 - (CH 2) v -MY r X mr-1
_{(4) CF 3 COO- (CH} 2) w -MY r X mr-1
Etc. can be illustrated as one of the preferable embodiments.

In the formula, g, s, t, u, v, and w represent arbitrary integers, but as a particularly preferable range, g is 1 to 25, s is 0 to 12, t is 1 to 20, and u is 0. -12, v is 1-20, and w is 1-25.
M, Y, X, r, and m represent the same meaning as in formula (II).

  Specific examples of the compound represented by the formula (I) include those shown below.

  In the following, compounds in which the metal atom M is a silicon atom are shown as representative examples, but the present invention is not limited to these. Also, the hydrolyzable group is not limited to the exemplified functional groups, and may be one in which another hydrolyzable group is bonded.

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃ ,
CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₃
CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ — (CH═CH) ₃ —Si (OCH ₃ ) ₃
CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃
CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OC ₂ H ₅ )
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OCH ₃ )

CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) −
CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃

CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) −
CONH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂

CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₃
CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) 4 _O (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ Si (OCH ₃ ) _{3
CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) -
CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) (OH) ₂
CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₁ (OH) ₂
CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) (OH) _{2
CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OCH 3) (OH) 2
CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OCH ₃ ) (OH) ₂
CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) (OH) _{2
CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) (OH) 2
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) (OH) 2
CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) (OH) ₂
CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) (OH) ₂
CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) (OH) ₂
CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OC ₂ H ₅ ) (OH) ₂
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH)
CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OCH ₃ ) ₂ (OH)
CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₂ (OH)
CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₂ (OH)
CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OC ₂ H ₅ ) ₂ (OH)
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OC ₂ H ₅ ) (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) (OH)

CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂

CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)

CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) (OH) ₂
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) (OH) ₂
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (NCO) (OH) ₂
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (NCO) (OH) ₂
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) (OH) ₂
CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) (OH) _{2
CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ Si (OCH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ Si (OCH ₃ ) (OH) _{2
CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) (OH) 2

CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) (OH)
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) (OH)
CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) (OH)
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) ₂ (OH)
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₂ (OH)
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (NCO) ₂ (OH)
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (NCO) ₂ (OH)
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (NCO) ₂ (OH)
CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) 4 _O (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
_{CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) 2 (OH)

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OH) ₃
CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OH) ₃
CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OH) ₃
CH ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OH) ₃
CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OH) ₃
CH ₃ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (CH ₂ ) ₁₅ Si (OH) ₃
CH ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OH) ₃
CF ₃ (CH ₂ ) ₆ Si (CH ₃ ) ₂ (CH ₂ ) ₉ Si (OH) ₃
CH ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH═CH) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃

CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) ₂ (OH)
CF ₃ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (OH) ₃

CH ₃ (CH ₂ ) ₇ Si (OH) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ CH ₂ (CF ₂ ) ₈ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ (CF ₂ ) ₄₀ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (OH) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OH) ₃
CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OH) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OH) ₃
CH ₃ CH ₂ (CF ₂ ) ₆ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OH) ₃
CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ Si (OH) ₃
CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ Si (OH) ₃
CH ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (OH) ₃

CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₄ (CF ₂ ) ₂ (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₄ (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₃ O [CF (CF ₃ ) CF (CF ₃ ) O] ₂ CF (CF ₃ ) CONH (CH ₂ ) ₃ Si (CH ₃ ) (OH) ₂
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
These compounds can be used alone or in combination of two or more.

(2) Component B In the present invention, the component A is a metal; a metal salt; a metal oxide; a metal hydroxide; a metal supported on a carrier; a metal salt supported on a carrier; a metal supported on a carrier. The treatment is performed using at least one selected from an oxide; a chelated or coordinated metal compound; and metal nanoparticles. Metal: Metal salt; Metal oxide; Metal hydroxide; Metal supported on support; Metal salt supported on support; Metal oxide supported on support; Chelated or coordinated metal compound; The metal of the metal nanoparticle is preferably palladium or platinum.

  The metal of the B component is not particularly limited, but palladium, platinum, nickel, rhodium, iridium, ruthenium, molybdenum, rhenium, tungsten, vanadium, osmium, chromium, cobalt, iron, titanium, zirconium, aluminum, silicon, germanium. Indium, tin, tantalum and zinc are preferable, and palladium and platinum are particularly preferable.

  Although it does not restrict | limit especially as a metal salt of the said B component, A chloride, nitrate, a sulfate, acetate, formate, an oxalate etc. are mentioned. More specifically, nickel (II) chloride, nickel (II) bromide, palladium (II) chloride, palladium (II) bromide, platinum (II) chloride, nickel (II) nitrate, palladium (II) nitrate, Examples thereof include nickel (II) sulfate, palladium (II) sulfate, platinum (II) bromide, nickel (II) acetate, palladium (II) acetate, platinum (II) acetate, and palladium (II) oxalate.

  Although it does not restrict | limit especially as a metal oxide of the said B component, Palladium oxide (IV), platinum oxide (II), etc. are mentioned.

  Although it does not restrict | limit especially as a metal hydroxide of the said B component, Palladium hydroxide (II), platinum hydroxide (II), etc. are mentioned.

  The metal supported on the carrier of component B, the metal salt supported on the carrier, and the metal oxide carrier supported on the carrier are not particularly limited, but carbon materials such as activated carbon and graphite; silica, alumina, Metal oxides such as titania, zirconia and magnesia; composite metal oxides such as silica / alumina, titania / silica and silica / magnesia; inorganic oxides such as zeolite (ZSM-5 etc.) and mesoporous silicate (MCM-41 etc.) And natural minerals such as clay, diatomaceous earth, and pumice. Examples of the metal supported on the support, the metal salt supported on the support, and the metal, metal salt, and metal oxide of the metal oxide supported on the support are the same as described above. These metals, metal salts, metal oxides, metals supported on carriers, metal salts supported on carriers, and metal oxides supported on carriers can be used alone or in combination of two or more. Can be used.

  When a chelated or coordinated metal compound is used as the component B, a metal hydroxide, a metal salt, or the like can be used as the metal compound. As the metal, palladium and platinum are preferable.

  A chelated or coordinated metal compound can be prepared by adding a chelating agent or a coordination compound capable of forming a complex with a metal of the metal compound to a solution of these metal compounds.

  The chelating agent or coordination compound is not particularly limited as long as it can be chelated or coordinated to a metal such as a metal hydroxide or a metal salt to form a complex.

  Specific examples of chelating agents or coordination compounds include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid; oxalic acid, malonic acid, succinic acid Saturated aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, array acid, and maleic acid; benzoic acid, Aromatic carboxylic acids such as toluic acid and phthalic acid; halogenocarboxylic acids such as chloroacetic acid and trifluoroacetic acid; acetylacetone, 2,6-dimethyl-3,5-heptanedione, dipivaloylmethane, benzoylacetone, hexafluoro Β-diketones such as acetylacetone; methyl acetoacetate, ethyl acetoacetate Roh β- ketoesters; tetrahydrofuran, furan, furancarboxylic acid, thiophene, thiophenecarboxylic acid, pyridine, nicotinic acid, heterocyclic compounds such as isonicotinic acid; and the like. These can be used alone or in combination of two or more.

  The addition amount of the chelating agent or the coordination compound is 0.1 to 10 times mol, preferably 0.3 to 2 times mol, more preferably 0 to 1 mol of metal such as metal hydroxide or metal salt. 0.5 to 1.2 moles.

  After adding the chelating agent or coordination compound, the solution of the metal complex can be obtained by thoroughly stirring the whole volume. The stirring temperature is usually in the temperature range from 0 ° C. to the boiling point of the solvent used. The stirring time is usually several minutes to several hours.

  As the chelated or coordinated metal compound, an isolated one can be used, or chelation or coordination obtained by adding a chelating agent or a coordination compound to the solution of the metal compound. It can also be used as a solution of the prepared metal compound.

  Specific examples of the chelated or coordinated metal compound include palladium-2,4-pentadionate, platinum-2,4-pentadionate, and the like.

  The size of the metal nanoparticles of the component B is usually 100 nm or less, preferably in the range of 1 to 10 nm. Moreover, the same thing as the above can be illustrated as a metal of a metal nanoparticle.

  The method for preparing the metal nanoparticles is not particularly limited. For example, a vapor phase method in which metal vapor evaporated at a high temperature in the gas phase is supplied and rapidly cooled by collision with gas molecules to form fine particles, metal ions It can be synthesized by a solution method (liquid phase method) in which a metal ion is reduced by adding a reducing agent to a solution in which is dissolved.

  The metal nanoparticles are preferably used in a state where they are dispersed in a solvent. Examples of such a solvent include water; esters such as butyl acetate and cellosolve acetate; ketones such as methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; Chlorinated hydrocarbons such as 2-dichloroethane and chloroform; Amides such as dimethylformamide; Hydrocarbons such as cyclohexane, heptane, octane and isooctane; Ethers such as tetrahydrofuran, ethyl ether and dioxane; Ethanol, n-propanol, isopropanol, n-butanol, n -Alcohols such as octanol and diacetone alcohol; fluorinated solvents such as 2,2,3,3-tetrafluoropropanol; ethylene glycol monomethyl ether, ethylene glycol mono Chirueteru, glycol ethers such as propylene glycol monomethyl ether; and the like. These solvents can be used alone or in combination of two or more.

The metal nanoparticle dispersion solution preferably contains an adsorbing compound (dispersant) that adsorbs to the surface of the metal nanoparticles. The particle surface can be dispersed in a solvent with the surface of the particles modified with an adsorbent compound, and a stable nanoparticle-containing dispersion (colloid dispersion) can be obtained. In this case, the amount of the adsorptive compound used is not particularly limited as long as the dispersibility is sufficiently increased. As the adsorptive compound, —SH, —CN, —NH ₂ , —SO ₂ OH, —SOOH, —OPO (OH) ₂ , —COOH, or —COH-containing compounds are effective, and among these, —SH , —NH ₂ —COOH, or —COH-containing compounds are preferred. Also, anionic surfactants such as sodium dodecylbenzenesulfonate, sodium n-tetradecyl sulfate, sodium dodecyl sulfate, sodium decyl sulfate, sodium n-nonyl sulfate, sodium n-octyl sulfate, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl Hydrophilic polymers such as pyrrolidone, polyvinyl alcohol, polyethylene glycol, and gelatin can also be used. These adsorptive compounds can be used alone or in combination of two or more.

(3) Organic thin film forming solution The organic thin film forming solution of the present invention can be prepared by treating the component A with water in the presence of a component B in an organic solvent.

The method for preparing the organic thin film forming solution of the present invention is not particularly limited. Specifically,
(I) A method of adding water to an organic solvent solution containing the A component and the B component,
(Ii) A method of adding the B component to the organic solvent solution of the A component and water can be exemplified.

  In order to suppress a rapid reaction, it is preferable to dilute the water added in the method (i) and the component B added in the method (ii) with an organic solvent or the like.

  As an organic solvent used for the preparation of the organic thin film forming solution of the present invention, a hydrocarbon solvent, a fluorocarbon solvent, and a silicone solvent are preferable, and a hydrocarbon solvent is more preferable. Especially, a thing with a boiling point of 100-250 degreeC is especially preferable.

Specifically, hydrocarbon solvents such as n-hexane, cyclohexane, benzene, toluene, xylene, petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, ligroin; CBr; _{2 ClCF 3, CClF 2 CF 2} CCl 3, CClF 2 CF 2 CHFCl, CF 3 CF 2 CHCl 2, CF 3 CBrFCBrF 2, CClF 2 CClFCF 2 CCl 3, Cl (CF 2 CFCl) 2 Cl, Cl (CF 2 CFCl ) Fluorocarbon solvents such as ₂ CF ₂ CCl ₃ , Cl (CF ₂ CFCl) ₃ Cl and other chlorofluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass); dimethyl silicone, phenyl silicone, alkyl modified Silicone, polyether silicone, etc. Recone solvents; and the like. These solvents can be used alone or in combination of two or more.

  The content of the component A in the solution for forming an organic thin film of the present invention is not particularly limited, but is preferably in the range of 0.1 to 30% by weight in order to produce a dense monomolecular film.

  The amount of component B used for preparing the organic thin film forming solution of the present invention is not particularly limited as long as it does not affect the physical properties of the monomolecular organic thin film to be formed. Usually, it is 0.001-1 mol, preferably 0.001-0.2 mol.

  The amount of water used for the preparation of the organic thin film forming solution of the present invention is not particularly limited, but in the solution, it can quickly form a dense organic thin film corresponding to substrates of any material. It is preferable to keep or keep the water content within a predetermined range.

  The amount of water in the organic thin film forming solution of the present invention is determined by the type of substrate used, component A, component B, organic solvent, and the like. Specifically, chemical adsorption on the substrate surface is inhibited, a dense monomolecular film cannot be produced, the loss amount of the A component used is large, the amount that does not cause problems such as deactivation of the B component, etc. And more than the amount sufficient to promote and activate the formation of the film.

  For example, when the solution is brought into contact with the substrate by a dip method, the amount sufficient to accelerate and activate the film formation is a dense and homogeneous organic thin film with a contact time of 10 minutes or less, preferably 5 minutes or less. Is the degree that can be formed on the entire surface of the substrate at once. Specifically, 50 ppm or more is preferable, the range of the saturated water content from 50 ppm to the organic solvent, more specifically, the range of 50 to 1000 ppm is more preferable, and the range of 200 to 800 ppm is particularly preferable. When the water content is 50 ppm or more, the organic thin film can be formed quickly, and when the water content is 1000 ppm or less, there is no problem that the metal surfactant and the like are deactivated.

  The water content shown here is a value obtained by collecting a part of the organic thin film forming solution and measured by the Karl Fischer method, and if it is a value measured by a device using the method principle, There is no particular limitation. In addition, when the organic thin film forming solution is uniform, a part of the uniform solution is sampled and measured. When the organic solvent layer and the moisture layer are two layers, a part of the organic solvent layer is part of the organic solvent layer. When the water layer is dispersed in an organic solvent and cannot be separated, the value obtained by directly collecting the dispersion is shown.

  The organic thin film forming solution of the present invention can be obtained by stirring the mixture of the component A, the organic solvent, the component B, and water. The stirring temperature is usually −100 ° C. to + 100 ° C., preferably −20 ° C. to + 50 ° C. The stirring time is usually several minutes to several hours. In this case, it is also preferable to perform ultrasonic treatment in order to obtain a uniform solution for forming an organic thin film.

  In the prepared organic thin film forming solution, precipitates containing metal oxides and the like may be generated. Impurities such as these precipitates are used to obtain a dense monomolecular organic thin film without impurities. And may be removed by performing operations such as filtration and decanting, or may be removed by washing after forming an organic thin film as described later.

Specifically, as a method of keeping or keeping the moisture amount within a predetermined amount range,
(1) A method of providing an aqueous layer in contact with a solution for forming an organic thin film,
(2) A method of allowing a water-retaining substance to coexist in a state in which water is contained in a solution for forming an organic thin film,
(3) A method of bringing the organic thin film forming solution into contact with a gas containing moisture,
(4) The method of adding water suitably etc. can be illustrated.
These methods may be used alone or in combination of two or more.
The water used is not particularly limited as long as it is neutral, but it is preferable to use pure water or distilled water. The organic solvent to be used may be anhydrous or may contain a certain amount of moisture in advance.

In the above method (1), when an organic solvent that separates from the aqueous layer, such as a hydrocarbon solvent, is used, the aqueous layer may coexist in a form separated from the organic solvent layer, or an organic thin film An organic solvent layer separated by circulating or passing the forming solution through the aqueous layer may be used.
When using an organic solvent with high water solubility that does not separate from the aqueous layer, such as a lower alcohol, the organic thin film forming solution and the aqueous layer are brought into contact with each other through a membrane that does not penetrate the organic solvent but penetrates the water. The method of making it etc. can be illustrated.

In the above method (2), the water-retaining substance is preferably a substance that does not float in the organic thin film forming solution without separating water in the organic thin film forming solution.
Specifically, organic water-retaining materials such as water-absorbing polymers; inorganic water-retaining materials such as zeolite, silicate clay, vermiculite, porous ceramics; A compound that can be formed; among them, a glass fiber filter or a cellulose fiber material is particularly preferable because of avoiding contamination of dust and the like.

Further, examples of water-retaining substances include compounds capable of forming micelle molecules with water as a nucleus in the solution, specifically, surfactants and the like. It is preferable to make it coexist.
A method using a hydrophilic solvent to increase the solubility of water in an organic solvent is also conceivable. The hydrophilic solvent in this case is also included as a substance that can be retained for convenience.

  The amount of water contained in the water-retaining substance is not particularly limited, but is preferably the amount of water until the water is separated from the water-retaining substance and not released in the organic thin film forming solution. Moreover, it can also be contained in the substance which can add and hold | maintain a water | moisture content timely. In addition, by providing a water-retaining substance in the solution continuously from the interface between the solution and the outside air or outside air, moisture can be supplied to the solution by absorbing moisture of the outside air.

In the method (3), the gas used is not particularly limited as long as it does not affect each component in the solution. Specifically, air, nitrogen gas, argon gas, etc. are exemplified. Can do.
Examples of a method for obtaining a gas containing moisture include a method of adding moisture to the gas; a method of humidifying the gas; and the like.
Examples of the method of adding moisture to the gas include a method of bringing water into contact with water such as submerging the gas in water, bringing the gas into contact with water or hot water surface, and the like using a gas containing water vapor as it is. it can.

  As a method for humidifying the gas, a steam humidification method, a water spray humidification method, a vaporization heating method, or the like can be exemplified.

  As a method of bringing the gas containing water into contact with the organic thin film forming solution, a method of blowing a gas containing water into the organic thin film forming solution or spraying the organic thin film forming solution surface; Examples include a method in which the organic thin film forming solution is allowed to stand in a humidified atmosphere with stirring if necessary; and the like; it can. In the method of blowing a gas containing moisture, it is preferable to attach a blowing device, a cleaning device, a filtering device, or the like as necessary.

  In the method (4), specifically, a decrease in the amount of water in the organic thin film forming solution is observed, and water, a compatible organic solvent or the same organic solvent is used according to the amount of decrease. Examples thereof include a method of appropriately adding diluted water; a method of supplying a solution for forming an organic thin film having the same composition containing a certain amount of water; and the like.

2) Organic thin film forming method The organic thin film forming method of the present invention includes a step of bringing the organic thin film forming solution obtained as described above into contact with the surface of the substrate.

  Although there is no restriction | limiting in particular as a base material to be used, The base material which has the functional group which can interact with the molecule | numerator which forms the organic thin film in the solution for organic thin film formation on a surface is preferable, and especially the base material which has an active hydrogen on the surface Is preferred. When a substrate having active hydrogen on the surface is used, the active hydrogen on the substrate surface and the molecules in the organic thin film forming solution can easily form an organic thin film on the substrate surface by chemical interaction. .

Active hydrogen refers to those that are easily dissociated as protons, and functional groups containing active hydrogen include hydroxyl group (—OH), carboxyl group (—COOH), formyl group (—CHO), imino group (═NH), amino group (-NH _2), such as a thiol group (-SH). Among them, a hydroxyl group are preferred.

  Specific examples of the base material having a hydroxyl group on the surface of the base material include metals such as aluminum, copper, and stainless steel; glass; silicon wafer; ceramics; plastic; paper; natural fiber or synthetic fiber; Examples of the base material are as follows. Especially, the base material which consists of a metal, glass, a silicon wafer, ceramics, or a plastic is preferable.

  For a base material made of a material having no hydroxyl group on its surface such as plastic or synthetic fiber, the surface of the base material is previously treated in a plasma atmosphere containing oxygen (for example, at 100 W for 20 minutes), or is corona-treated for hydrophilicity. Groups can be introduced. A substrate made of a polyamide resin or a polyurethane resin has an imino group on the surface, and the active hydrogen of the imino group and the alkoxysilyl group of the metal-based surfactant undergo a dealcoholization reaction to form a siloxane bond (- Since SiO-) is formed, no surface treatment is required.

Further, when using a base material having no active hydrogen on the surface, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , Cl— (SiCl ₂ O) _c —SiCl ₃ (wherein c It is also possible to form a silica underlayer having active hydrogen on the surface thereof by contacting with at least one compound selected from (natural number) and then dehydrochlorinating.

  The method for bringing the organic thin film forming solution into contact with the substrate is not particularly limited, and a known method can be used. Specific examples include a dipping method, a spin coating method, a spray method, a roller coating method, a Meyer bar method, a screen printing method, a brush coating method, and the like, and among them, the dipping method is preferable.

  The step of bringing the organic thin film forming solution into contact with the substrate may be performed for a long time at a time or may be performed in a short time by dividing it into several times. Ultrasound can also be used to promote film formation.

  The temperature to be contacted is not particularly limited as long as the solution can maintain stability, but is usually in the range from room temperature to the reflux temperature of the solvent used for preparing the solution. In order to obtain a temperature suitable for contact, the solution may be heated or the substrate itself may be heated.

The step of bringing the substrate into contact with the organic thin film forming solution is preferably a step of dipping the substrate in the organic thin film forming solution. As a method of immersing the substrate while maintaining the amount of water in the organic thin film forming solution, specifically,
(1) A method of providing a moisture adjustment tank and a base material immersion tank, and circulating the liquid adjusted in the moisture adjustment tank to the base material immersion tank,
(2) A method in which a plurality of base material immersion tanks are provided, and moisture adjustment is performed in another immersion tank while the base material is immersed in one base material immersion tank,
(3) A method of directly providing the substrate dipping tank with means for keeping the above-described moisture content within a predetermined range and appropriately supplying moisture is exemplified.

  In the method for forming an organic thin film of the present invention, the step of bringing the substrate into contact with the organic thin film forming solution can be repeated a plurality of times. At this time, it is preferable to keep the water content within a predetermined range. The predetermined amount range means the same as the predetermined range of the moisture amount described above, and by holding the moisture amount in such a range, the step of contacting the substrate without changing the liquid is repeated a plurality of times. In addition, a dense and homogeneous organic thin film can be formed.

  In this case, the same solution means a case in which all or a part of the solution is discarded and replaced with a new solution after a single contact step operation. The solution in which the moisture content is maintained within the predetermined amount range shall be included as the same solution.

  After the step of bringing the substrate into contact with the organic thin film forming solution, a step of washing the surface of the substrate can be provided in order to remove excess reagents and impurities attached to the film surface. By providing the cleaning step, the film thickness can be controlled.

  The cleaning method is not particularly limited as long as it can remove surface deposits. Specifically, the substrate is immersed in a solvent capable of dissolving the component A; in a vacuum or under normal pressure. Examples thereof include a method of evaporating by leaving in the atmosphere; a method of blowing an inert gas such as dry nitrogen gas and blowing away; and the like.

  Moreover, in order to stabilize the film | membrane formed on the base-material surface after the process which makes a base material contact the organic thin film formation solution, the process of heating a base material can also be provided. The step of heating the substrate is preferably provided after the cleaning step. The heating temperature can be appropriately selected depending on the stability of the substrate and the film.

  The step of bringing the substrate into contact with the organic thin film forming solution is preferably performed in a space where the humidity is maintained at 40% RH or higher, and is performed in a space where the humidity is maintained at 60% RH or higher. More preferred. In such a space, the amount of water in the organic thin film forming solution is more preferably maintained, and a dense monomolecular film can be formed with good reproducibility even if the substrate is continuously contacted.

  The organic thin film forming method of the present invention can be used for the production of a monomolecular film or a multilayer film of two or more layers, and can be particularly suitably used for the production of a monomolecular film. It can also be used as a method of forming a film on the surface by physical adsorption.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, the scope of the present invention is not limited to an Example.

(Example 1)
(1) Preparation of a solution for forming an organic thin film Octadecyltrimethoxysilane (0.5 g) was diluted with toluene (99.5 g) to which ion-exchanged water (30 mg) was added, so that the solid content concentration was 0.5% by weight. A solution was obtained. This solution was mixed with 24.7 mg of platinum-activated carbon (containing 2.47 mg of platinum), stirred for 1 day, and allowed to stand for 1 day to prepare an organic thin film forming solution (SO-1). The water content at this time was 390 ppm.

  The moisture content was measured by a coulometric titration Karl Fischer moisture meter (CA-07, manufactured by Dia Instruments Co., Ltd.).

(2) Formation of organic thin film For the above organic thin film forming solution, a soda lime glass substrate washed with ultrasonic detergent, ion-exchanged water and ethanol sequentially with a detergent, dried at 60 ° C., and washed in an ozone generator, Alternatively, after immersing the silicon wafer substrate in the organic thin film forming solution at 25 ° C., the substrate is pulled out and ultrasonically washed in toluene for 30 seconds to remove the multilayer adsorbed components. An organic thin film of a compound [soda lime glass substrate (SAM-1), silicon wafer substrate (SAM-2)] was formed by drying for a minute.

(3) Contact angle change measurement by light irradiation of organic thin film 2 μl of water or tetradecane is dropped from a micro syringe onto the organic thin film surface of SAM-1 and SAM-2 formed on the soda lime glass and silicon wafer. After 5 seconds, the contact angle was measured using a contact angle measuring instrument (Kyowa Interface Chemical Co., Ltd., DropMaster 700). The results are shown in Table 1.

(Comparative Example 1)
(1) Preparation of a solution for forming an organic thin film Octadecyltrimethoxysilane (0.5 g) was diluted with toluene (99.5 g) to which ion-exchanged water (30 mg) was added, so that the solid content concentration was 0.5% by weight. A solution was obtained. This solution was stirred for 1 day and then allowed to stand for 1 day to prepare an organic thin film forming solution (SO-2). The water content at this time was 367 ppm.

(2) Formation of organic thin film For the above organic thin film forming solution, a soda lime glass substrate washed with ultrasonic detergent, ion-exchanged water and ethanol sequentially with a detergent, dried at 60 ° C., and washed in an ozone generator, Alternatively, after immersing the silicon wafer substrate in the organic thin film forming solution at 25 ° C., the substrate is pulled out and ultrasonically washed in toluene for 30 seconds to remove the multilayer adsorbed components. An organic thin film of a compound [soda lime glass substrate (SAM-3), silicon wafer substrate (SAM-4)] was formed by drying for a minute.

(3) Contact angle change measurement by light irradiation of organic thin film 2 μl of water or tetradecane was dropped from the microsyringe onto the organic thin film surface of SAM-3 and SAM-4 formed on the soda lime glass and silicon wafer. After 5 seconds, the contact angle was measured using a contact angle measuring instrument (Kyowa Interface Chemical Co., Ltd., DropMaster 700). The results are shown in Tables 1 and 2.

  From Table 1 and Table 2, the organic thin film forming solution obtained in Example 1 can form an organic thin film on the substrate surface at high speed only by immersing the substrate for a short time.

Claims (32)

An organic thin film forming method comprising a step of bringing an organic thin film forming solution into contact with the surface of a substrate, wherein the organic thin film forming solution contains a metal-based surfactant having a hydroxyl group or a hydrolyzable group as an organic solvent. Metal, metal salt, metal oxide, metal hydroxide, metal supported on support, metal salt supported on support, metal oxide supported on support, metal compound chelated or coordinated And at least one selected from metal nanoparticles, and an organic thin film forming method obtained by treating with water. 2. The organic thin film forming method according to claim 1, wherein the amount of water in the organic thin film forming solution is set within a predetermined range or maintained. 3. The organic thin film formation according to claim 2, wherein the water content in the organic thin film forming solution is set within a predetermined range or maintained by providing an aqueous layer in contact with the organic thin film forming solution. Method. In the organic thin film forming solution, the water content in the organic thin film forming solution is kept within a predetermined amount range or is maintained by allowing a water-retaining substance to coexist in a state of containing water. The organic thin film forming method according to claim 2 or 3. The organic thin film forming method according to claim 4, wherein the water retention substance is a glass fiber filter or a cellulose fiber material. 6. The water content in the organic solvent solution is set within a predetermined amount range or maintained by blowing a gas containing water into the organic thin film forming solution. Organic thin film formation method. The method for forming an organic thin film according to any one of claims 2 to 6, wherein the amount of water in the organic thin film forming solution is set to or maintained in a range of 50 to 1000 ppm. The organic content according to any one of claims 2 to 7, wherein the water content in the predetermined amount range is a value obtained by measuring a part of the organic thin film forming solution by a Karl Fischer method. Thin film forming method. Metal: Metal salt; Metal oxide; Metal hydroxide; Metal supported on support; Metal salt supported on support; Metal oxide supported on support; Chelated or coordinated metal compound; And at least one selected from metal nanoparticles is used in an amount of 0.001 to 1 mol with respect to 1 mol of the metal-based surfactant having a hydroxyl group or a hydrolyzable group. The organic thin film formation method in any one. The metal-based surfactant having the hydroxyl group or hydrolyzable group is represented by the formula (I)

[Wherein, R ¹ represents a hydrocarbon group which may have a substituent, a halogenated hydrocarbon group which may have a substituent, a hydrocarbon group containing a linking group, or a halogen containing a linking group. Represents a hydrogenated hydrocarbon group, M represents at least one metal atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom, and X represents a hydroxyl group or a hydrolyzable group. N represents an integer of 1 to (m-1), m represents a valence of M, and when n is 2 or more, R ¹ may be the same or different. In addition, when (mn) is 2 or more, Xs may be the same or different. ] The organic thin film formation method in any one of Claims 1-9 characterized by the above-mentioned. A metal surfactant having a hydroxyl group or a hydrolyzable group is represented by the formula (II)

[Wherein, M, X and m represent the same meaning as described above. R ^{2 to} R ⁶ each independently represents a hydrogen atom or a fluorine atom, and R ⁷ represents an alkylene group, a vinylene group, an ethynylene group, an arylene group, or a divalent linkage containing a silicon atom and / or an oxygen atom. Represents a group. Y represents a hydrogen atom, an alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group. p represents 0 or a natural number, and q represents 0 or 1. When p is 2 or more, R ⁵ and / or R ⁶ may be the same or different. r represents a positive integer from 0 or 1 to (m−2), and when r is 2 or more, Y may be the same or different, and (m−r−1) is 2 or more. Sometimes X may be the same or different. The method for forming an organic thin film according to any one of claims 1 to 10, wherein the compound is represented by the formula: 12. The hydrolyzable group of X is a hydrocarbon oxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom. The organic thin film formation method as described in any one of. The organic thin film forming method according to claim 1, wherein the organic solvent is at least one selected from a hydrocarbon solvent, a fluorocarbon solvent, and a silicone solvent. The organic thin film forming method according to claim 1, wherein the organic thin film is a crystalline organic thin film. The organic thin film manufacturing method according to claim 1, wherein the organic thin film is a chemical adsorption film. The organic thin film forming method according to claim 1, wherein the organic thin film is a self-assembled film. The organic thin film forming method according to claim 1, wherein the organic thin film is a monomolecular film. The organic thin film forming method according to claim 1, wherein the base material is a base material having active hydrogen on a surface thereof. The said base material is a base material which consists of at least 1 sort (s) of material chosen from glass, a silicon wafer, ceramics, a metal, a plastics, paper, a fiber, and leather, In any one of Claims 1-18 characterized by the above-mentioned. The organic thin film formation method of description. A metal surfactant having a hydroxyl group or a hydrolyzable group is added to an organic solvent in a metal; a metal salt; a metal oxide; a metal hydroxide; a metal supported on a support; a metal salt supported on a support; For forming an organic thin film characterized by being prepared by treating with a supported metal oxide; a chelated or coordinated metal compound; and at least one selected from metal nanoparticles and water. solution. 21. The organic thin film forming solution according to claim 20, wherein the amount of water in the organic thin film forming solution is within a predetermined range or maintained. The organic thin film formation according to claim 21, wherein the water content in the organic thin film forming solution is set within a predetermined range or maintained by providing a water layer in contact with the organic thin film forming solution. Solution. In the organic thin film forming solution, the water content in the organic thin film forming solution is kept within a predetermined amount range or is maintained by allowing a water-retaining substance to coexist in a state of containing water. The solution for forming an organic thin film according to claim 21 or 22. The solution for forming an organic thin film according to claim 23, wherein the water retention substance is a glass fiber filter or a cellulose fiber material. 25. The water content in the organic solvent solution is set within a predetermined range or maintained by blowing a gas containing water into the organic thin film forming solution. Organic thin film forming solution. 26. The organic thin film forming solution according to any one of claims 21 to 25, wherein a water content in the organic thin film forming solution is set to or maintained in a range of 50 to 1000 ppm. 27. The organic substance according to any one of claims 21 to 26, wherein the moisture amount in the predetermined amount range is a value obtained by measuring the solution obtained by collecting a part of the organic thin film forming solution by a Karl Fischer method. Thin film forming solution. Metal: Metal salt; Metal oxide; Metal hydroxide; Metal supported on support; Metal salt supported on support; Metal oxide supported on support; Chelated or coordinated metal compound; And at least one selected from metal nanoparticles is used in an amount of 0.001 to 1 mol per 1 mol of the metal-based surfactant having a hydroxyl group or a hydrolyzable group. The solution for organic thin film formation in any one. The metal-based surfactant having the hydroxyl group or hydrolyzable group is represented by the formula (I)

[Wherein, R ¹ represents a hydrocarbon group which may have a substituent, a halogenated hydrocarbon group which may have a substituent, a hydrocarbon group containing a linking group, or a halogen containing a linking group. Represents a hydrogenated hydrocarbon group, M represents at least one metal atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom, and X represents a hydroxyl group or a hydrolyzable group. N represents an integer of 1 to (m-1), m represents a valence of M, and when n is 2 or more, R ¹ may be the same or different. In addition, when (mn) is 2 or more, Xs may be the same or different. 29. The organic thin film forming solution according to claim 20, wherein the organic thin film forming solution is a compound represented by the formula: A metal surfactant having a hydroxyl group or a hydrolyzable group is represented by the formula (II)

[Wherein, M, X and m represent the same meaning as described above. R ^{2 to} R ⁶ each independently represents a hydrogen atom or a fluorine atom, and R ⁷ represents an alkylene group, a vinylene group, an ethynylene group, an arylene group, or a divalent linkage containing a silicon atom and / or an oxygen atom. Represents a group. Y represents a hydrogen atom, an alkyl group, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group. p represents 0 or a natural number, and q represents 0 or 1. When p is 2 or more, R ⁵ and / or R ⁶ may be the same or different. r represents a positive integer from 0 or 1 to (m−2), and when r is 2 or more, Y may be the same or different, and (m−r−1) is 2 or more. Sometimes X may be the same or different. The solution for organic thin film formation in any one of Claims 20-29 characterized by the above-mentioned. The hydrolyzable group of X is a hydrocarbon oxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom. A solution for forming an organic thin film according to 1. 32. The organic thin film forming solution according to claim 20, wherein the organic solvent is at least one selected from a hydrocarbon solvent, a fluorocarbon solvent, and a silicone solvent.