WO2016063463A1

WO2016063463A1 - Process for producing thin organic film

Info

Publication number: WO2016063463A1
Application number: PCT/JP2015/005023
Authority: WO
Inventors: 大幹芝田
Original assignee: 日本曹達株式会社
Priority date: 2014-10-21
Filing date: 2015-10-02
Publication date: 2016-04-28
Also published as: TW201615375A; JPWO2016063463A1

Abstract

The present invention addresses the problem of providing a process for thin-organic-film production whereby a thin organic film that is dense can be formed on substrates constituted of various materials, in cases when the substrates are brought into contact with a solution for thin-organic-film formation which contains a metal-based surfactant as a main raw material, after an ultraviolet/ozone treatment as the only treatment. The following steps (A) and (B) are conducted: step (A) in which the surface of a substrate is treated with light from an excimer lamp containing Xe gas enclosed therein and with ozone generated by the light from an excimer lamp containing Xe gas enclosed therein; and step (B) in which the substrate is subsequently brought into contact with an organic-solvent solution containing both a metal-based surfactant having at least one hydrolyzable group and a compound capable of interacting with the metal-based surfactant.

Description

Organic thin film manufacturing method

The present invention relates to a method for producing an organic thin film, and more particularly to a method for efficiently producing an organic thin film such as a monomolecular film on a substrate made of various materials.
This application claims priority to Japanese Patent Application No. 2014-214111 filed on Oct. 21, 2014, the contents of which are incorporated herein by reference.

As a method for forming a monomolecular film on various base materials, for example, a base material such as a molding die or an electroforming mother board is applied to the formula [1].
R _n —Si—X _4-n ...... [1]
(In the formula [1], R represents a C1-20 hydrocarbon group which may have a substituent, a C1-20 halogenated hydrocarbon group which may have a substituent, and a C1 containing a linking group. Represents a hydrocarbon group of 1 to 20 or a C1 to 20 halogenated hydrocarbon group containing a linking group, X represents a hydroxyl group, a halogen atom, a C1 to C6 alkoxy group or an acyloxy group, and n represents an integer of 1 to 3 And an organic solvent solution containing a catalyst capable of interacting with the silane surfactant is known (see Patent Document 1). Although it is described that it is preferable to perform ultraviolet treatment and ozone treatment before contacting the silane-based surfactant with a base material such as a mold for molding or a matrix substrate for electroforming, ultraviolet rays of any wavelength are described. However, it is not described what kind of wavelength the ultraviolet ray / ozone treatment apparatus actually used uses.

International Publication No. 06/070857 Pamphlet

A low pressure mercury lamp is generally used as the light source of the ultraviolet / ozone treatment apparatus. However, depending on the substrate, a dense thin film cannot be formed even if the organic solvent solution is brought into contact with the treatment using only the low pressure mercury lamp. In some cases, performance such as contact angle cannot be obtained.
An object of the present invention is to provide an organic thin film manufacturing method capable of forming a dense organic thin film when the organic solvent solution is brought into contact with a substrate made of various materials only by ultraviolet / ozone treatment. To do.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by treating the substrate surface with an ultraviolet / ozone treatment apparatus using an excimer lamp as a light source, and the present invention has been completed. It came to do.

That is, the present invention
(1) An organic thin film manufacturing method for forming an organic thin film on a surface of a substrate, wherein the substrate surface is produced by light of an excimer lamp enclosing Xe gas and ozone generated by light of an excimer lamp enclosing Xe gas. Step (A) of using the surface treatment, and then adding the metal surfactant having at least one hydrolyzable group and an organic solvent solution containing a compound capable of interacting with the metal surfactant to the group. An organic thin film manufacturing method for performing the step (B) of contacting the material;
(2) The metal surfactant having at least one hydrolyzable group is represented by the formula (I)
R ¹ _n1 MX ¹ _m-n1 (I)
[In the formula, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and includes a linking group. M represents a metal atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom, X ¹ represents a hydroxyl group or a hydrolyzable group, and m represents an atom of M. Represents the value. n1 represents any positive integer from 1 to (m−1), and when n1 is 2 or more, R ¹ may be the same or different. When (mn-1) is 2 or more, X ¹ may be the same or different, but at least one of X ¹ is a hydrolyzable group. ] The organic thin-film manufacturing method as described in (1) which is a compound represented by these,
(3) The compound capable of interacting with the metal surfactant is a metal oxide, metal hydroxide, metal alkoxide, metal alkoxide partial hydrolysis product, metal alkoxide hydrolysis product, chelation or coordination. The method for producing an organic thin film according to (1) or (2), which is at least one selected from the group consisting of a coordinated metal compound and a silanol condensation catalyst,
(4) Metal oxide, metal hydroxide, metal alkoxide, metal alkoxide partial hydrolysis product, metal alkoxide hydrolysis product, chelated or coordinated metal compound, and metal in silanol condensation catalyst Is at least one selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead, the method for producing an organic thin film according to (3),
(5) The organic thin film manufacturing method according to (1), wherein the organic solvent solution is an organic solvent solution adjusted and maintained at a moisture content within a predetermined range.
(6) The method for producing an organic thin film according to (5), wherein the predetermined range of the moisture content within the predetermined range is a range of 30 to 1000 ppm,
(7) The organic thin film manufacturing method according to any one of (1) to (6), wherein the organic thin film is a monomolecular film,
About.

By using the organic thin film manufacturing method of the present invention, a dense organic thin film can be formed only by surface treatment with ultraviolet rays / ozone, regardless of the type of substrate.

In the organic thin film production method of the present invention, the substrate surface is treated with light using an excimer lamp enclosing Xe gas as a light source and ozone generated by the light, and at least one hydrolyzable group is further removed. A step of bringing the surface-treated substrate into contact with an organic solvent solution containing a metal surfactant having a compound and a compound capable of interacting with the metal surfactant.
The formed organic thin film is a monomolecular film that spontaneously organizes due to the interaction between molecules. A film having a monomolecular thickness is simply referred to as a “monomolecular film”.

<1> Substrate The substrate used in the method for producing an organic thin film of the present invention is a substrate having a functional group on the surface capable of interacting with molecules forming an organic thin film in a solution for forming an organic thin film described later. A substrate having a functional group having active hydrogen on the surface is particularly preferable. When a substrate having a functional group 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 described later easily chemistry on the substrate surface through chemical interaction. An adsorption film can be formed.

Here, the active hydrogen means one that is easily dissociated as a proton from a functional group. The functional group containing active hydrogen includes a hydroxyl group (—OH), a carboxyl group (—COOH), an imino group (═NH), an amino group. (—NH ₂ ), thiol group (—SH) and the like can be mentioned, and among them, a hydroxyl group is preferable.

Specific examples of base materials having hydroxyl groups on the surface of the base material include metals such as aluminum, copper, and stainless steel; glass; silicon wafers; ceramics; plastics; paper; fibers such as natural fibers and synthetic fibers; And a substrate made of a substance such as: Especially, the base material which consists of a metal, glass, a silicon wafer, ceramics, paper, a fiber, and a plastic is preferable.

<2> Excimer lamp An excimer lamp enclosing Xe gas used in the present invention applies high energy electrons from the outside to a space enclosing Xe gas to generate discharge plasma (dielectric barrier discharge). An Xe gas atom is excited by the discharge plasma, instantaneously enters an excimer state, and refers to a lamp that emits a spectrum unique to the excimer when returning from this excimer state. For example, the structure is not particularly limited. When Xe gas is used, particularly ultraviolet light having a wavelength of 172 nm can be efficiently emitted.
By irradiating light using the excimer lamp in the presence of oxygen, active oxygen can be generated at a high concentration, and the substrate surface can be purified at high speed.

<3> Solution for forming an organic thin film For the production of the organic thin film of the present invention, (1) a metal-based surfactant having at least one hydrolyzable group, (2) interacting with the metal-based surfactant. An organic solvent solution containing the compound to be obtained (sometimes referred to as “organic thin film forming solution”) is used.
(1) Metal-based surfactant As the “metal-based surfactant having at least one hydrolyzable group” used in the present invention, at least one hydrolyzable functional group and the hydrophobic group are the same. Although it will not restrict | limit especially if it has in a molecule | numerator, What has a hydrolysable group which can react with the active hydrogen on the base-material surface and can form a bond is preferable. A hydroxyl group, particularly a hydroxyl group directly bonded to a metal atom can react with active hydrogen to form a bond.
As the metal-based surfactant having at least one hydrolyzable group, specifically, the formula (I)

R ¹ _n1 MX ¹ _m-n1 (I)

The metal-type surfactant represented by these can be illustrated preferably.
In the formula, R ¹ is an optionally substituted hydrocarbon group having 1 to 30 carbon atoms, or an optionally substituted hydrocarbon group having 1 to 30 carbon atoms including a linking group. To express.
Examples of the hydrocarbon group of “optionally substituted hydrocarbon group having 1 to 30 carbon atoms” include 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-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-decyl group And alkyl groups having 1 to 30 carbon atoms such as octadecyl group; alkenyl groups having 2 to 30 carbon atoms such as vinyl group, allyl group and propenyl group; aryl groups such as phenyl group and naphthyl group.

Examples of the substituent of the “optionally substituted hydrocarbon group having 1 to 30 carbon atoms” include a halogeno group such as a fluoro group and a chloro group; a carboxyl group; a carbamoyl group; an imide group; an alkoxycarbonyl group; Examples thereof include alkoxy groups such as methoxy group and ethoxy group; hydroxyl groups and the like. The number of these substituents is preferably 0-3.

Specific examples of the hydrocarbon group of the “hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and include a linking group” include the above-mentioned “optionally substituted 1 carbon atom”. Examples of the hydrocarbon group of “˜30 hydrocarbon groups” are the same as those described above.
The “linking group” is preferably present between the carbon-carbon bond of the hydrocarbon group or between the carbon of the hydrocarbon group and the metal atom M. Specific examples of the linking group include imino group, oxo group, sulfanyl group, sulfonyl group, and carbonyl group.
Examples of the substituent of the “optionally substituted hydrocarbon group having 1 to 30 carbon atoms including a linking group” include “an optionally substituted hydrocarbon group having 1 to 30 carbon atoms”. And the same substituents as

Among these, as R ¹ , from the viewpoint of liquid repellency and durability, an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, or a C ¹ to 30 carbon atom containing a linking group. A fluorinated alkyl group is preferred. Specific examples of R ¹ include an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, or a fluorinated alkyl group having 1 to 30 carbon atoms including a linking group described in WO2008 / 016029 pamphlet. Etc. Of these, an alkyl group having 10 to 18 carbon atoms is more preferable.

M represents one kind of 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.
That is, the “metal surfactant having at least one or more hydrolyzable groups” used in the present invention is preferably “a silane surfactant having at least one or more hydrolyzable groups”.

X ¹ 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, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, a hydrocarbon oxy group which may have a substituent (excluding an alkoxy group), a substituent. Examples thereof may include an acyloxy group, a halogeno group, an isocyanate group, a cyano group, an amino group, or a carbamoyl group.

Examples of the “C 1-6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n -Hexyloxy group and the like.

“Hydrocarbonoxy groups” other than alkoxy groups include cycloaliphatic hydrocarbonoxy groups such as cyclopropyloxy groups, cyclopropylmethyloxy groups, and cyclohexyloxy groups; alkenyl groups such as vinyloxy groups, allyloxy groups, and norbornyloxy groups. Oxy group; alkynyloxy group such as propargyloxy group; aryloxy group such as phenoxy group and naphthyloxy group; aralkyloxy group such as benzyloxy group and phenethyloxy group;
Examples of the “acyloxy group” include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group; an alkenylcarbonyloxy group such as a (meth) acryloyloxy group; an arylcarbonyloxy group such as a benzoyloxy group.

Examples of the substituent “may have a substituent” in X ¹ include a carboxyl group, an amide group, an imide group, an alkoxycarbonyl group, and a hydroxyl group.
X ¹ is particularly preferably a hydroxyl group, a halogeno group, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group, or an isocyanate group, and more preferably an alkoxy group having 1 to 4 carbon atoms or an acyloxy group.

m represents the valence of M. n1 represents any positive integer from 1 to (m−1), and when n1 is 2 or more, R ¹ may be the same or different. When (mn-1) is 2 or more, X ¹ may be the same or different, but at least one of X ¹ is a hydrolyzable group.

Among the compounds represented by formula (I), as one of preferred embodiments, formula (II)

(R ²³ ) (R ²² ) (R ²¹ ) C [C (R ³¹ ) (R ³² )] _p (R ⁴ ) _q MY _r X ¹ _mr-1 (II)
The compound represented by these can be illustrated.
In the formula, M, X ¹ and m represent the same meaning as described above. R ²¹ to R ²³ , R ³¹ and R ³² each independently represent a hydrogen atom or a fluoro group, and R ⁴ represents an alkylene group, a vinylene group, an ethynylene group, an arylene group, or a silicon atom and / or an oxygen atom. Represents a divalent linking group. Y represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group. p represents 0 or a positive integer, and q represents 0 or 1. When p is 2 or more, the groups represented by the formula: C (R ³¹ ) (R ³² ) may be the same or different. r represents a positive integer of 0 or 1 to (m−2), and in order to produce a high-density organic thin film, r is preferably 0, and when r is 2 or more, Y is They may be the same or different, and when (mr-1) is 2 or more, X ¹ may be the same or different. However, at least ^one of Y and X ¹ is a hydrolyzable group. The definition of the hydrolyzable group is as described above.

Specific examples of R ⁴ in formula (II) include functional groups represented by the following formula.

In the above formula, a and b represent an arbitrary positive integer of 1 or more.
Specific examples of Y include 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, and neopentyl group. Alkyl groups such as t-pentyl group, n-hexyl group and isohexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group An alkoxy group such as n-pentyloxy group or n-hexyloxy group; a fluorinated alkyl group in which a part or all of the alkyl groups are substituted with a fluoro group; or a part or all of the atoms of the alkoxy group Represents a fluorine-containing alkoxy group substituted with a fluoro group.

Specific examples of the compound represented by the formula (I) include compounds in which the metal atom described in WO2008 / 016029 pamphlet is a silicon atom.
Specific examples include decyltrimethoxysilane, dodecyltrimethoxysilane, and octadecyltrimethoxysilane.
These compounds can be used alone or in combination of two or more.

(2) Compound capable of interacting with metal-based surfactant The “compound capable of interacting with metal-based surfactant” used in the present invention includes a metal atom part or a hydrolyzable group part of a metal-based surfactant. If it is a compound which has the effect | action which activates a hydrolysable group or a hydroxyl group by interacting through a coordination bond, a hydrogen bond, etc., and accelerates | stimulates condensation, it will not be restrict | limited.
Specifically, metal oxides, metal hydroxides, metal alkoxides, metal alkoxides partial hydrolysis products, metal alkoxide hydrolysis products, chelated or coordinated metal compounds, silanol condensation catalysts, etc. Is mentioned.

The metal in the metal oxide or the like is not particularly limited, but is preferably at least one selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead. Zirconium, aluminum or silicon is more preferred, and titanium or silicon is particularly preferred.

(A) Metal oxide The metal oxide can be used in any state such as sol, gel, and solid. The method for producing the gel or sol is not particularly limited. For example, when silica sol is taken as an example, a method of cation exchange of a sodium silicate solution, a method of hydrolyzing silicon alkoxide, and the like can be exemplified. In particular, a sol that is stably dispersed in an organic solvent is preferable, and the particle size of the sol is more preferably in the range of 10 to 100 nm, and still more preferably in the range of 10 to 20 nm. The shape of the sol is not particularly limited, and any shape such as a spherical shape or an elongated shape can be used.

Specific examples of metal oxides include methanol silica sol, IPA-ST, IPA-ST-UP, IPA-ST-ZL, NPC-ST-30, DMAC-ST, MEK-ST, MIBK-ST, and XBA-ST. And PMA-ST (all of which represent the trade names of organosilica sol manufactured by Nissan Chemical Industries, Ltd.).

(B) Metal hydroxide The metal hydroxide may be obtained by any production method as long as it is a metal hydroxide. As a manufacturing method of a metal hydroxide, the method of hydrolyzing the below-mentioned metal alkoxide, the method of making a metal salt react with a metal hydroxide, etc. are mentioned. Moreover, what is marketed as a metal hydroxide can also be refine | purified and used if desired.

(C) Metal alkoxides The number of carbon atoms of the alkoxy group of the metal alkoxides is not particularly limited. However, the number of carbon atoms should be 1 to 4 because of the concentration of the oxide contained, the ease of detachment of organic substances, and the availability. Is more preferable. Specific examples of metal alkoxides used in the present invention include silicon alkoxides such as tetramethoxysilane, tetraethoxysilane, tetra-i-propoxysilane, and tetra-t-butoxysilane; tetramethoxytitanium, tetraethoxytitanium, tetra-i -Titanium alkoxides such as propoxy titanium and tetra-n-butoxy titanium; tetrakistrialkylsiloxy titaniums such as tetrakis (trimethylsiloxy) titanium (IV); zirconium (IV) ethoxide, zirconium (IV) isopropoxide, zirconium (IV) Zirconium alkoxides such as tert-butoxide; aluminum alkoxides such as trimethoxyaluminum, triethoxyaluminum, tri-i-propoxyaluminum and tri-n-butoxyaluminum De; Germanium (IV) methoxide and the like of germanium alkoxide; tantalum (V) methoxide, tantalum (V) ethoxide, tantalum alkoxides such as tantalum (V) butoxide; and the like. These metal alkoxides can be used alone or in combination of two or more.

In the present invention, as a metal alkoxide, a reaction of a composite alkoxide obtained by reaction of two or more metal alkoxides, one or more metal alkoxides, and one or two or more metal salts. It is also possible to use a composite alkoxide obtained by the above and a combination thereof.

The composite alkoxide obtained by the reaction of two or more kinds of metal alkoxides includes a complex alkoxide obtained by the reaction of an alkali metal or alkaline earth metal alkoxide and a transition metal alkoxide, or a complex salt by a combination of Group 3B elements. The compound alkoxide obtained by the form of this can be illustrated.

(D) Metal alkoxide partial hydrolysis product The metal alkoxide partial hydrolysis product is obtained before the metal alkoxide is completely hydrolyzed.

The metal alkoxide partial hydrolysis product has a property of being stably dispersed without aggregation in an organic solvent in the absence of an acid, a base and a dispersion stabilizer. That is, if it defines from the presence state in an organic solvent, it corresponds to a dispersoid.
In this case, the dispersoid refers to fine particles dispersed in the dispersion system, and specific examples include colloidal particles. Here, the dispersed state refers to a state where the dispersoids are not condensed in an organic solvent and are not separated inhomogeneously, preferably a transparent and homogeneous state. Transparent means a state in which the transmittance in visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, and the control sample is organic. This is a state in which the transmittance is preferably 80 to 100%, expressed as a spectral transmittance measured under the condition of using a solvent and a light wavelength of 550 nm. The particle size of the metal alkoxide partial hydrolysis product is not particularly limited, but is preferably in the range of 1 to 100 nm and more preferably in the range of 1 to 50 nm in order to obtain high transmittance in visible light. Preferably, it is in the range of 1 to 10 nm.

Examples of the method for producing the partial hydrolysis product of metal alkoxides include the production methods described in WO2008 / 016029 pamphlet.

(E) Metal alkoxide hydrolysis product The metal alkoxide hydrolysis product used in the present invention is a product obtained by hydrolysis with two or more equivalents of water of the metal alkoxide. Even if the hydrolysis product is obtained by hydrolyzing a metal alkoxide with water at least twice as much as the metal alkoxide, the metal alkoxide is less than twice the equivalent of the metal alkoxide. The partial hydrolysis product of the metal alkoxides was obtained by partial hydrolysis with water, and the partial hydrolysis product was further mixed with a predetermined amount of water (the amount of water used in the previous partial hydrolysis and In a total amount of 2 times the equivalent of metal alkoxides).

(F) Chelated or coordinated metal compound A chelated or coordinated metal compound is prepared by adding a chelating agent or coordination compound capable of forming a complex with a metal of the metal compound to a solution of the metal compound. It can be prepared by adding. As a chelating agent or coordination compound, a metal hydroxide, metal alkoxide, or metal alkoxide is chelated or coordinated to the metal of the hydrolysis product obtained by treating with water to form a complex. If it can do, it will not specifically limit.

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; β-diketones such as acetylacetone, benzoylacetone and hexafluoroacetylacetone; β-diketones such as methyl acetoacetate and ethyl acetoacetate Ketoesters: tetrahydrofuran, furan, francal And heterocyclic compounds such as boronic acid, thiophene, thiophenecarboxylic acid, pyridine, nicotinic acid, and isonicotinic acid. These can be used alone or in combination of two or more.

(G) Silanol condensation catalyst Examples of the silanol condensation catalyst include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates.

(H) Organic solvent The organic solvent used in the organic thin film forming solution is not particularly limited as long as it is an organic solvent that dissolves these compounds. Specifically, hydrocarbon solvents, fluorocarbon solvents , And silicone solvents are preferred. Of these, hydrocarbon solvents are preferred, and those having a boiling point of 100 to 250 ° C. are particularly preferred.

Specific examples of organic solvents include hydrocarbons such as n-hexane, cyclohexane, benzene, toluene, xylene, petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene and ligroin. system _{_{_{_{solvent; 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 Fluorocarbon solvents such as (CF ₂ CFCl) ₂ CF ₂ CCl ₃ , Cl (CF ₂ CFCl) ₃ Cl and other fluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass); dimethyl silicone, phenyl Silicone, al And silicone-based solvents such as kill-modified silicone and polyether silicone. These solvents can be used alone or in combination of two or more.

(3) Preparation Method The content of the metal surfactant in the organic thin film forming solution is not particularly limited, but from the viewpoint of producing a denser organic thin film, it is 0.1 to 30 with respect to the organic thin film forming solution. It is preferably in the range of% by weight.

The amount of the compound that can interact with the metal surfactant is not particularly limited as long as it does not adversely affect the physical properties of the organic thin film to be formed. The converted mole number is preferably 0.001 to 1 mole, and more preferably 0.001 to 0.2 mole.

The method for preparing the organic thin film forming solution used in the present invention is not particularly limited. For example, a metal surfactant having at least one hydrolyzable group, a compound capable of interacting with the metal surfactant, And a mixture containing the organic solvent can be prepared by stirring.

The stirring temperature is not particularly limited, but may be, for example, −100 ° C. to + 100 ° C., preferably −20 ° C. to + 50 ° C. Further, the stirring time is not particularly limited, but it can be performed for several minutes to several hours.

In the prepared solution for forming an organic thin film, a precipitate containing a metal oxide or the like may be generated. In order to obtain a dense organic thin film with less impurities, the substrate is a base material. It is preferable to remove or reduce these impurities before contacting them. Precipitates can be easily removed or reduced by operations such as filtration and decanting.

The organic thin film forming solution may not be a solution adjusted to or retained in a predetermined moisture content, but a denser and more homogeneous organic thin film corresponding to a substrate of any material. Since it can be formed more rapidly, it is preferable that the solution is adjusted and held so as to have a moisture content within a predetermined range.

The “moisture content within a predetermined range” can be determined depending on the type of substrate, metal surfactant, compound capable of interacting with the metal surfactant, organic solvent, and the like. Specifically, as the “water content within a predetermined range”, for example, chemisorption on the substrate surface occurs more actively, a denser organic thin film is produced, and film formation is accelerated and activated. The amount of water content is more than a certain amount, or the amount of loss of the metal surfactant used is less, and the amount of water content is more than the amount that the compound capable of interacting with the metal surfactant can exhibit more sufficient activity. Preferably mentioned.

For example, when the solution is brought into contact with the substrate by the dip method, the amount that is activated and activated is a dense and homogeneous in one contact (dip) within 10 minutes, preferably within 5 minutes. An amount that can form a simple organic thin film on the entire surface of the substrate.
Specifically, the water content of the solution for forming an organic thin film is preferably 10 ppm or more, and is in the range of the saturated water content from 10 ppm to the organic solvent, more specifically in the range of 10 to 2000 ppm. Is more preferable, and is more preferably within the range of 30 to 1000 ppm and 50 to 800 ppm. When the water content is 10 ppm or more, the organic thin film can be formed more rapidly. When the water content is 2000 ppm or less, the metal surfactant and the like can exhibit more sufficient activity. .
The moisture content shown here is a value obtained by collecting a part of the solution for forming an organic thin film 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 collected and measured. When the organic solvent layer and the water layer are two layers, a part of the organic solvent layer is partly measured. Collect and measure. When the water layer is dispersed in an organic solvent and cannot be separated, the value obtained by collecting the dispersion as it is is shown.

When preparing a solution for forming an organic thin film that can be stored for a long period of time, it is necessary to sufficiently perform hydrolysis with a smaller amount of water. In such a case, a part of the metal surfactant is hydrolyzed in advance with a compound capable of interacting with the metal surfactant, and this is added as an auxiliary agent to the remaining amount of the metal surfactant. It is preferable to prepare it.
The auxiliary agent can be prepared by mixing a metal surfactant and a compound capable of interacting with the metal surfactant in an organic solvent without adding or adding water.

In the present invention, the metallic surfactant is contained in the auxiliary agent in an amount of 0.5 to 80% by weight, preferably 5 to 50% by weight.
The compound capable of interacting with the metal surfactant is contained in an amount of 0.1 ppm to 5% by weight, preferably 10 ppm to 2% by weight in terms of metal.
The metal surfactant is preferably from 0.1 to 20 mol, more preferably from 0.5 to 5.0 mol, based on 1 mol of the compound capable of interacting with the metal surfactant. .
The water to be used is 0.01 to 5.0 mol, preferably 0.1 to 2.0 mol, per 1 mol of the metal surfactant. However, it is not always necessary to add water, and it is possible to use only moisture absorbed from the air and moisture contained in the raw material.

The reaction temperature is 0 to 100 ° C., and the reaction time is 1 hour to 10 days.
As a method of adding water when mixing a metal surfactant with a compound capable of interacting with the metal surfactant in an organic solvent, specifically, (A) Metal surfactant A method of adding water to an organic solvent solution containing an agent and a compound capable of interacting with a metal surfactant, (B) a metal surfactant and an organic solvent solution containing water and a metal surfactant Examples thereof include a method of adding a compound capable of interacting. A compound that can interact with a metal surfactant is generally used in a state of being dissolved or dispersed in an organic solvent containing water.
As the organic solvent used for the preparation of the adjuvant, hydrocarbon solvents, fluorocarbon solvents and silicone solvents are preferable, and those having a boiling point of 100 to 250 ° C. are more preferable.

As the organic thin film forming solution, a commercially available product, for example, a monomolecular surface modifier “SAMLAY (registered trademark)” manufactured by Nippon Soda Co., Ltd. can be used.

<4> Organic Thin Film Manufacturing Method The organic thin film manufacturing method of the present invention can be used for manufacturing a monomolecular film or a multilayer film having two or more layers, but is particularly suitable for manufacturing a monomolecular film. Can be used. Moreover, it can be used not only as a method of forming an organic thin film on the surface of the substrate by chemical adsorption, but also as a method of forming an organic thin film on the surface of the substrate by physical adsorption.

The method for bringing the organic thin film forming solution into contact with the substrate is not particularly limited. Specifically, the dip coating method, spin coating method, spray coating method, roller coating method, Mayer bar method, screen printing, A method such as a brush coating method can be exemplified, and among these, a dip coating method can be preferably exemplified.

In the case of the dip coating method, the time for immersing the base material in the organic thin film forming solution depends on the kind of the base material and the like, and cannot be generally specified, but can be 5 minutes to 24 hours. ~ 10 hours is preferred.

The step of bringing the substrate into contact with the solution for forming an organic thin film may be performed for a long time at once, or may be performed in a short time by dividing it into a plurality of times. In addition, ultrasonic waves can be used to promote the formation of the organic thin film.

The temperature of the organic thin film forming solution when the substrate is brought into contact with the organic thin film forming solution is not particularly limited as long as the solution can maintain stability, but usually the temperature of the solvent used for preparing the solution from room temperature is not limited. The range is up to the reflux temperature. In order to bring the organic thin film forming solution to a temperature suitable for contact, the organic thin film forming solution may be heated, the substrate itself may be heated, or both of them may be heated.

The organic thin film manufacturing method of the present invention may further include a step (C) of washing the substrate with distilled water and a step (D) of washing the substrate with alcohol before the step (A). preferable. Thereby, impurities such as dust, dust and organic matter on the surface of the substrate can be removed to a higher degree, and the organic thin film can be formed more densely and firmly.

Here, the distilled water used in the step (C) is not particularly limited, but from the viewpoint of obtaining a more excellent cleaning effect, distilled water having a resistance value of 10 megaohms or more is preferable, and distillation having a resistance value of 15 megaohms or more. More preferably, it is water.

Moreover, as alcohols used in the step (D), ethanol and isopropanol are preferable.

Moreover, the washing | cleaning method in process (C) and (D) is not restrict | limited in particular, For example, the distilled water of process (C) and the alcohol of process (D) are sprayed on a base material, or it showers. The substrate may be hung, or the substrate may be immersed in distilled water in step (C) or alcohol in step (D). Since a more excellent cleaning effect can be obtained, it is preferable to perform ultrasonic treatment in a state where the substrate is immersed in distilled water in the step (C) or alcohols in the step (D).

The organic thin film manufacturing method of the present invention may include a step (E) of washing the contacted substrate with an organic solvent after the step (B). If there exists such a washing | cleaning process (E), the excess reagent and impurity adhering to the surface of the organic thin film formed at the process (B) will be removed. Moreover, the film thickness of the organic thin film formed in the base-material surface can be controlled by providing such a washing | cleaning process (E).

The organic solvent in the step (E) is not particularly limited, but hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, benzene, toluene, xylene and the like are preferable.
The cleaning method is not particularly limited as long as it can remove deposits on the substrate surface. For example, a method of immersing the substrate in an organic solvent as described above; in a vacuum or in the atmosphere under normal pressure Examples thereof include a method of allowing the deposit on the surface of the substrate to evaporate; a method of blowing an inert gas such as dry nitrogen gas to blow away the deposit on the surface of the substrate; and the like. Moreover, since the more outstanding cleaning effect is acquired, it is mentioned as a more preferable method to carry out ultrasonic treatment in the state which immersed the base material in the above-mentioned organic solvent.

The organic thin film manufacturing method of the present invention preferably further includes a step (F) of drying the substrate washed in the step (E) after the step (E). The drying method is not particularly limited, and the solution on the surface of the substrate may be an air knife or the like, may be naturally dried, and can be exemplified by a method such as applying hot air, but on the surface of the substrate. A method of applying warm air is preferable because the organic thin film is further stabilized by applying heat to the formed organic thin film.

In addition, when heat is not applied to the base material when drying the base material, the organic thin film production method of the present invention may not further include a step of applying heat to the base material. In order to stabilize, it is preferable to further include the step (G) of applying heat to the substrate. The order of the step (G) is not particularly limited as long as it is after the step (B), but is preferably after the step (E). The heating temperature can be appropriately selected depending on the stability of the base material and the organic thin film, and a preferable range is, for example, 40 to 70 ° C.

The organic thin film obtained by using the production method of the present invention has a property as a film formed with an ordered structure without external force, that is, as a self-assembled film. In the organic thin film forming solution, when the molecules forming the organic thin film, such as metal surfactants having at least one hydrolyzable group, form an aggregate, use the solution. The resulting organic thin film becomes a self-assembled film. The metal-based surfactant molecules in the organic thin film forming solution are not solvated by the solvent alone in the solution, but some are gathered to form an aggregate. The aggregate can be obtained by treating the metal surfactant with a compound capable of interacting with the metal surfactant and water.

The form of the aggregate is a form in which molecules are assembled by hydrophobic forces or hydrophilic parts and intermolecular forces, coordinate bonds, hydrogen bonds, etc .; the molecules forming the membrane are bonded by covalent bonds Aggregated form; form in which other medium such as water forms micelles as a nucleus or mediator; or a form in which these are combined.

The shape of the aggregate is not particularly limited, and may be any shape such as a spherical shape, a chain shape, or a belt shape. The average particle size of the aggregate is not particularly limited, but is preferably in the range of 10 to 1000 nm.

The zeta potential (electrokinetic potential) of the aggregate is preferably larger than the zeta potential of the substrate in the same solvent. It is particularly preferred that the aggregate has a positive zeta potential and the substrate has a negative zeta potential. When a solution for forming an organic thin film that forms an aggregate having such a zeta potential value is used, a denser organic thin film having crystallinity can be produced.

The organic thin film in the present invention is an organic thin film formed on a base material, and the base material does not have crystallinity, and the organic thin film has crystallinity. That is, the organic thin film in the present invention has crystallinity regardless of whether the substrate is crystalline or not. In this case, the crystallinity may be polycrystalline or single crystal.

When the solution for forming an organic thin film of the present invention is brought into contact with a substrate, the metal surfactant in the solution is adsorbed on the surface of the substrate to form an organic thin film. The details of the mechanism by which the metal surfactant is adsorbed on the surface of the substrate are not clear, but in the case of a substrate having active hydrogen on the surface, it can be considered as follows. That is, in the solution for forming an organic thin film, the hydrolyzable group of the metal surfactant is hydrolyzed with water. Then, the metal surfactant in this state reacts with active hydrogen on the surface of the base material to form an organic thin film formed by forming a strong chemical bond with the base material. This organic thin film is formed by reacting with the active hydrogen of the base material and becomes a monomolecular film.

Hereinafter, the present invention will be described more specifically by way of examples. However, the technical scope of the present invention is not limited to these examples.

[Example 1]
On the surface of a 20 mm square surface polished nickel substrate (manufactured by TDC), an excimer surface treatment device (manufactured by Sen Special Light Source, model number: XPL1502-A, lamp: SX150) has a peak wavelength of 172 nm and an illuminance of about 20 mW / Irradiation with ultraviolet rays of cm ² was performed for 60 seconds.
After immersing the above substrate in a monomolecular surface modifier (Nippon Soda Co., Ltd., SAMLAY (registered trademark)) for 10 minutes, this surface was then washed with a hydrocarbon-based detergent (JX Nippon Mining & Energy, NS Clean (registered trademark)) 100). Furthermore, the organic thin film formation board | substrate was obtained by heat-processing for 10 minutes at 100 degreeC after this.

[Example 2]
Similar to Example 1 except that an aluminum substrate having a nickel-phosphorus (P) alloy obtained by acidic electroless nickel plating using hypophosphite as a reducing agent was used instead of the surface-polished nickel substrate. And an organic thin film forming substrate was obtained.

[Example 3]
An organic thin film forming substrate was obtained in the same manner as in Example 1 except that a silicon wafer (manufactured by VALQUA FFT) was used instead of the surface polished nickel substrate.

[Example 4]
An organic thin film forming substrate was obtained in the same manner as in Example 1 except that a stainless steel substrate was used instead of the surface polished nickel substrate.

[Example 5]
An organic thin film forming substrate was obtained in the same manner as in Example 1 except that an aluminum plate was used instead of the surface polished nickel substrate.

[Comparative Example 1]
On the surface of a 20 mm square surface-polished nickel substrate (manufactured by TDC), a peak wavelength of 185 nm with a UV ozone surface treatment device (manufactured by Eye Graphic, model number: OC-250615-DA, lamp: QOL25SY), Ultraviolet rays having a wavelength of 254 nm and an illuminance of about 25 mW / cm 2 were irradiated for 20 minutes.
After immersing the substrate in a monomolecular surface modifier (Nippon Soda Co., Ltd., SAMLAY (registered trademark)) for 30 minutes, this surface was subjected to a hydrocarbon-based cleaner (JX Nippon Mining & Energy, NS Clean (registered trademark) 100). ) Was ultrasonically cleaned. Furthermore, the organic thin film formation board | substrate was obtained by heat-processing for 10 minutes at 100 degreeC after this.

[Comparative Example 2]
Comparative Example 1 except that instead of the surface polished nickel substrate, an aluminum substrate having a nickel-phosphorus (P) alloy surface obtained by acidic electroless nickel plating using hypophosphite as a reducing agent was used. It carried out similarly and obtained the organic thin film formation board | substrate.

[Example 1] to [Example 5] and [Comparative Example 1] to [Comparative Example 2] The static contact angle of the obtained organic thin film forming substrate was measured using a contact angle measuring device (Drop Master 700, Kyowa Interface Science Co., Ltd.). ). The results are shown in Table 1.

As is clear from the results shown in Table 1, when the example using the base material irradiated with the light of the excimer lamp filled with Xe gas was compared with the comparative example using the base material irradiated with the light of the low-pressure mercury lamp, In all the examples, the contact angles of water and tetradecane were both increased, but in the comparative examples, it was found that either the contact angle of water or tetradecane was not a satisfactory value.

Claims

An organic thin film manufacturing method for forming an organic thin film on a surface of a substrate, wherein the surface of the substrate is surfaced using ozone generated by light of an excimer lamp encapsulating Xe gas and light of an excimer lamp encapsulating Xe gas Next, the substrate is contacted with an organic solvent solution containing a metal surfactant having at least one hydrolyzable group and a compound capable of interacting with the metal surfactant, and then the step (A) of treating. The organic thin-film manufacturing method which performs the process (B) to make.
The metal surfactant having at least one hydrolyzable group is represented by the formula (I)
R 1 n1 MX 1 m-n1 (I)
[In the formula, R 1 is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent and includes a linking group. M represents a metal atom selected from the group consisting of a silicon atom, a germanium atom, a tin atom, a titanium atom, and a zirconium atom, X 1 represents a hydroxyl group or a hydrolyzable group, and m represents an atom of M. Represents the value. n1 represents any positive integer from 1 to (m−1), and when n1 is 2 or more, R 1 may be the same or different. When (mn-1) is 2 or more, X 1 may be the same or different, but at least one of X 1 is a hydrolyzable group. The method for producing an organic thin film according to claim 1, wherein the compound is represented by the formula:
A compound capable of interacting with a metal surfactant is converted into a metal oxide, metal hydroxide, metal alkoxide, metal alkoxide partial hydrolysis product, metal alkoxide hydrolysis product, chelated or coordinated. The method for producing an organic thin film according to claim 1, which is at least one selected from the group consisting of a metal compound and a silanol condensation catalyst.
Metal oxide, metal hydroxide, metal alkoxide, metal alkoxide partial hydrolysis product, metal alkoxide hydrolysis product, chelated or coordinated metal compound, and metal in silanol condensation catalyst are titanium The method for producing an organic thin film according to claim 3, wherein the organic thin film is at least one selected from the group consisting of zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten and lead.
The method for producing an organic thin film according to claim 1, wherein the organic solvent solution is an organic solvent solution adjusted and maintained at a moisture content within a predetermined range.
6. The method for producing an organic thin film according to claim 5, wherein the predetermined range of the moisture content within the predetermined range is in the range of 30 to 1000 ppm.
The method for producing an organic thin film according to any one of claims 1 to 6, wherein the organic thin film is a monomolecular film.