JP2003192329A - Production method for silica-based thin film and organic- inorganic composite functionally gradient material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a dense silica-based thin film by the low temperature thermal treatment of a sol obtained by hydrolyzing and condensing a tetraalkoxysilane, and also provide an organic-inorganic composite functionally gradient material comprising a metal oxide thin film with a dense surface obtained by using the above sol. <P>SOLUTION: This method for producing the dense silica-based thin film comprises forming, on a substrate, the film of a sol obtained by hydrolyzing and condensing a tetraalkoxysilane while controlling the condensation degree by an IR measurement, or controlling the hydrolysis degree and the condensation degree by a<SP>29</SP>Si-NM R measurement. The organic-inorganic composite functionally gradient material is produced by hydrolyzing an organic macromolecular compound having a hydrolysable metal-containing group in the presence of the above controlled silica-based sol and forming the objective material using the obtained coating liquid. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a silica-based thin film and an organic-inorganic composite gradient material. More specifically, the present invention relates to a method for efficiently producing a dense silica-based thin film by a sol-gel method, and a metal oxide-based thin film having a substantially substantially dense surface, and having a metal component content of a material. The present invention relates to an organic-inorganic composite gradient material having a component gradient structure that continuously changes from the surface to the thickness direction.

[0002]

2. Description of the Related Art Conventionally, silica-based coatings are excellent in heat resistance, abrasion resistance, corrosion resistance, etc., and therefore, for example, an insulating film between a semiconductor substrate and a metal wiring layer in a semiconductor element or between metal wiring layers, a semiconductor A film for flattening irregularities caused by a metal wiring layer provided on a substrate, a film between a glass substrate and an ITO (indium tin oxide) film in a liquid crystal display cell, a film between a transparent electrode and an alignment film, etc. Widely used as an insulating film to be provided.

Various methods are known as methods for forming such a silica-based coating film, but in general, the sol-gel method which can produce a silica film of high purity is widely used. This sol-gel method is a method in which an alkoxysilane is dissolved in an organic solvent mainly containing alcohol, and a coating solution is prepared by hydrolysis and condensation, which is then coated and heat-treated to form a silica film. is there. In such a sol-gel method, heat treatment of at least 600 ° C. or higher is required to obtain a dense glassy silica film.

On the other hand, a hard coat film having good surface hardness and excellent scratch resistance and abrasion resistance is, for example,
It is widely used as a surface sticker for window glass and window plastic boards for vehicles and buildings, and for protecting CRT displays and flat panel displays.

In addition, since plastic lenses are lighter in weight and superior in safety, workability, fashionability, etc., as compared with glass lenses, they have been rapidly spread in recent years. However, this plastic lens has a drawback in that it is more likely to be scratched than a glass lens, and therefore its surface is covered with a hard coat layer.

As a material for the hard coat layer provided on such a hard coat film or a plastic lens, a silica coating agent by a sol-gel method is generally used. However, in this case, since the coating film is applied to the organic substrate, the high temperature heat treatment of the coating film is impossible, and the heat treatment is usually performed at a temperature of 200 ° C. or lower. As a result, it is difficult to form a dense and strong silica film, and the alkoxyl groups of the raw material alkoxysilane are often left in the film, and the elimination reaction progresses over time, causing cracking. Often causes.

As a technique for forming a silica film by low temperature firing, for example, an alcoholic silica sol prepared by hydrolyzing a lower alkyl silicate in methanol or ethanol is coated and heat treated at a low temperature of room temperature to 100 ° C. By doing so, it is disclosed that a strong film can be formed (JP-A-6-52796). However, in the examples described in this publication, the concentration of the alkyl silicate is low and the reaction time is as short as 5 hours, so that the growth of the sol is insufficient and the film shrinkage after film formation is large. Therefore, there is a possibility that unevenness may occur during film formation.

Under these circumstances, the present inventors have
Repeated research on a method for producing a dense silica-based thin film prepared by the sol-gel method and having a low temperature heat treatment of 200 ° C. or less, which hardly causes cracks and has a small film thickness shrinkage ratio during drying and heat treatment, First, by forming a film of a silica sol having a weight average molecular weight of 85,000 to 500,000, which is a hydrolysis or condensation product of tetraalkoxysilane, it is possible to obtain a silica-based thin film having the above-mentioned preferable properties. Found (Japanese Patent Application No. 2000-27851)
No. 9).

In this case, the weight average molecular weight of the silica sol needs to be 85,000 or more. With a sol of less than 85,000, it is difficult to obtain a dense silica-based thin film having a small film thickness shrinkage rate by low temperature heat treatment, Weight average molecular weight of 85,
If a silica-based thin film having the above-mentioned properties can be formed by low-temperature heat treatment using a silica sol of less than 000, it will be more advantageous in terms of operability and the like.

On the other hand, the present inventors have previously proposed various applications as novel functional materials such as coating films, adhesives between organic materials and inorganic or metallic materials, organic substrates and photocatalytic coating films. A continuous composition that is useful in applications such as an intermediate film that is provided between layers to prevent deterioration of the organic base material and an intermediate film that improves the adhesion between the organic material and the inorganic or metal-based material layer. We have found an organic-inorganic composite gradient material that changes to (Japanese Patent Application No. 11-264592).

This organic-inorganic composite gradient material is an organic-inorganic composite material containing a chemical combination of an organic polymer compound and a metal-based compound, and the material surface is substantially composed of a metal-based compound thin film, and It is a novel material which has a component gradient structure in which the content of the metal-based compound continuously changes in the thickness direction of the material, and is useful for the above various uses. Such an organic-
When a thin film made of an inorganic composite gradient material is provided on a substrate,
A low temperature heat treatment is required, and the metal compound film on the surface of the thin film is preferably as dense as possible.

[0012]

Under the circumstances, the present invention provides a method for efficiently producing a dense silica thin film by a low temperature heat treatment by a sol-gel method, and a metal having a substantially dense surface. An object of the present invention is to provide an organic-inorganic composite gradient material which is composed of an oxide thin film and has a gradient component structure in which the content of metal components continuously changes from the surface of the material in the thickness direction.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the degree of hydrolysis and condensation of silica sol obtained by hydrolysis and condensation of tetraalkoxysilane. By controlling the degree by using a specific analysis method, even in the case of a sol having a weight average molecular weight of less than 85,000, a dense silica having a small film thickness shrinkage rate and suppressed crack generation by low temperature heat treatment. It was found that a system thin film can be provided.

In addition, an organic polymer compound having a metal-containing group capable of binding to a metal oxide by hydrolysis in the molecule,
It has been found that a desired organic-inorganic composite gradient material can be obtained by using a coating liquid obtained by hydrolyzing in the presence of the silica sol.

The present invention has been completed based on these findings.
It is a thing. That is, the present invention is (1) General formula (I) Si (OR)_Four                … (I) (In the formula, R represents an alkyl group having 1 to 3 carbon atoms,
The ORs may be the same or different. )
Obtained by hydrolyzing and condensing tetraalkoxysilane
The silica-based thin film is manufactured by forming a film of the sol on the substrate.
In the method of
Wave number 966 cm^-1(SiOH) and wave number 1
082 cm ^-1(SiO₂) Absorption intensity ratio (SiOH / S
iO₂) Is controlled to be 0.3 or more.
, The wave number in infrared absorption spectrum measurement 1130c
m^-1(SiOx) and wave number 1068 cm^-1(SiO₂)of
Absorption intensity ratio (SiOx / SiO₂) And wave number 946c
m^-1(SiOH) and wave number 1068 cm^-1(SiO₂)of
Absorption intensity ratio (SiOH / SiO₂) Is 0.3
5 or less and 0.14 or less, and X-ray total reflection measurement
To form a silica-based thin film with a density of 1.88 or more
A method for producing a silica-based thin film,

(2) A method for producing a silica thin film by forming a sol obtained by hydrolyzing and condensing a tetraalkoxysilane represented by the general formula (I) on a substrate to produce a silica-based thin film. The sol had a degree of hydrolysis of tetraalkoxysilane of 95% or more within 10 minutes after the start of the reaction, and was ²⁹ Si.
-Q ₁ / (Q ₁ + Q ₂ + Q ₃ ) in nuclear magnetic resonance spectroscopy
Ratio (where Q ₁ is the peak area of Si atom having one SiOSi bond, Q ₂ is S having two SiOSi bonds)
The peak area of i atom, Q ₃ is the peak area of Si atom having three SiOSi bonds. ) Is controlled to be 0.1 or less, thereby forming a silica-based thin film having a density of 1.88 or more by X-ray total reflection measurement.

(3) A method for producing a silica thin film by forming a sol obtained by hydrolyzing and condensing the tetraalkoxysilane represented by the general formula (I) on a substrate to produce a silica-based thin film. The sol has a wave number of 966 cm ^-1 (SiOH) and a wave number of 1082 cm in its infrared absorption spectrum measurement.
^-1 (SiO ₂ ) absorption intensity ratio (SiOH / SiO ₂ ) is 0.3 or more, the degree of hydrolysis of tetraalkoxysilane is 95% or more 10 minutes after the start of the reaction, and ²⁹ S
Q ₁ / (Q ₁ + Q ₂ + in i-Nuclear Magnetic Resonance Spectroscopy
Q ₃ ) ratio (where Q ₁ is S having one SiOSi bond)
The peak area of the i atom, Q ₂ is the peak area of the Si atom having two SiOSi bonds, and Q ₃ is the peak area of the Si atom having three SiOSi bonds. ) Is controlled to be 0.1 or less, the wave number is 1130 cm ^-1 (SiOx) and the wave number is 1 in the infrared absorption spectrum measurement.
Absorption intensity ratio of 068 cm ^-1 (SiO ₂ ) (SiOx / S
iO ₂ ) and wave number 946 cm ^-1 (SiOH) and wave number 1
Absorption intensity ratio of 068 cm ^-1 (SiO ₂ ) (SiOH / S
iO ₂₎ is, is 0.35 or less and 0.14 or less, and the manufacture of silica-based film density by X-ray total reflection is characterized by forming a silica-based thin film is 1.88 or more Method,

(4) A component gradient containing a complex in which an organic polymer compound and a metal oxide compound are chemically bound, and the content of the metal component continuously changes from the surface of the material to the depth direction. An organic-inorganic composite gradient material having a structure, wherein the composite comprises (B) a silica-based organic polymer compound having (A) a metal-containing group capable of binding to a metal oxide by hydrolysis in a molecule. It is formed by using a coating solution obtained by hydrolyzing in the presence of a sol, and as the silica-based sol of the component (B), a tetra-siloxane represented by the general formula (I). Hydrolyzes alkoxysilane,
A sol obtained by condensation,

(A) Wave number 966 cm ^-1 (SiOH) and wave number 1082c in the infrared absorption spectrum measurement of sol
The absorption intensity ratio (SiOH / SiO ₂ ) of m ⁻¹ (SiO ₂ ) is 0.3 or more, and the formed silica-based thin film has a wave number of 1130 cm ⁻¹ (SiO 2 in the infrared absorption spectrum measurement.
x) a wavenumber 1068cm ^-1 absorption intensity ratio of _{(SiO 2) (SiOx / SiO} 2) and a wavenumber of 946cm ^-1 (Si
OH) and the wave number 1068 cm ⁻¹ (SiO ₂ ) absorption intensity ratio (SiOH / SiO ₂ ) is 0.35 or less and 0.14 or less, respectively, and the density by X-ray total reflection measurement is 1.88 or more. Something, or

(B) The degree of hydrolysis of the tetraalkoxysilane in the sol is 95% or more 10 minutes after the start of the reaction, and
²⁹ Q ₁ / (Q ₁ + Q ₂ in Si-Nuclear Magnetic Resonance Spectroscopy
+ Q ₃ ) ratio (where Q ₁ is the peak area of Si atoms having one SiOSi bond, Q ₂ is the peak area of Si atoms having two SiOSi bonds, and Q ₃ is ₃ SiOSi bonds).
It is the peak area of the Si atom which it has. ) Is 0.1 or less, and the deposited silica-based thin film has a density of 1.88 or more as measured by X-ray total reflection, or one satisfying both conditions (a) and (b) above. An organic-inorganic composite gradient material,

(5) An organic polymer compound having a metal-containing group capable of binding to a metal oxide by hydrolysis in the molecule which is the component (A) is represented by the general formula (I) by hydrolysis in the molecule (a). Hydrolysis of tetraalkoxysilane represented by
The organic compound according to item (4), which is a copolymer of an ethylenically unsaturated monomer having a metal-containing group capable of binding to a condensation compound and (b) an ethylenically unsaturated monomer not containing a metal. -Inorganic composite gradient material,

(6) The surface of the film-like material formed on the organic base material, which is substantially in contact with the organic base material is the organic polymer compound component. The organic-inorganic composite gradient material according to the above (4) or (5), wherein the open system surface is a metal oxide compound component containing silica.

(7) The above (4) used as an intermediate film interposed between the organic base material and the photocatalytically active material layer,
An organic-inorganic composite gradient material according to item (5) or (6) is provided.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for producing a silica-based thin film of the present invention, a silica-based sol obtained by hydrolyzing and condensing a raw material tetraalkoxysilane is used to form a film on a substrate to obtain a silica-based sol. Produce a thin film. As the tetraalkoxysilane as the raw material, a compound represented by the general formula (I) Si (OR) ₄ ... (I) is used.

In the above general formula (I), R has 1 carbon atom.
~ 3 alkyl groups, specifically methyl group, ethyl group, n
A propyl group and an isopropyl group. Four ORs
They may be the same or different. R has 4 carbon atoms
In the case of the above, the hydrolyzability is poor and it is difficult to obtain a silica-based sol having the desired properties described below.

Examples of the tetraalkoxysilane represented by the general formula (I) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, ethoxytrimethoxysilane, propoxytrimethoxysilane and isopropoxy. Examples thereof include trimethoxysilane, methoxytriethoxysilane, propoxytriethoxysilane, isopropoxytriethoxysilane, methoxytripropoxysilane, ethoxytripropoxysilane, diethoxydimethoxysilane and dimethoxydipropoxysilane. In addition, these oligomers, for example, commercially available "methyl silicate 51", "ethyl silicate 40" (all are trade names manufactured by Colcoat Co., Ltd.), "MS-51", "MS-56" (all manufactured by Mitsubishi Chemical Corporation. Product name) etc. can also be used. These may be used alone or in combination of two or more, but in the present invention,
Of these, tetramethoxysilane and tetraethoxysilane are preferable in terms of hydrolyzability and availability.

In the hydrolysis and condensation reaction, an acid such as hydrochloric acid, sulfuric acid or nitric acid or a cation exchange resin as a solid acid is usually used in a suitable polar solvent such as alcohol, ketone or ether, and usually 0 to 60. C., preferably at 20-40.degree. C., to form a silica-based sol. When a solid acid is used, after the hydrolysis and condensation reactions are completed, the solid acid is removed, and then the SiO ₂ concentration is preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight. Alcohol, to be in range
A coating liquid containing a silica-based sol is prepared by diluting it with an appropriate polar solvent such as ketone or ether.

In the present invention, by defining the properties of the silica-based sol thus obtained, a silica-based thin film having a specific property of excellent compactness is formed by a low temperature heat treatment. In this case, there are the following three modes for defining the properties of the silica-based sol.

In the first embodiment, infrared absorption of the sol is carried out.
Wave in absorption spectrum (abbreviated as IR hereinafter) measurement
Number 966 cm^-1(SiOH) and wave number 1082 cm^-1(S
iO ₂) Absorption intensity ratio (SiOH / SiO₂) Is less than 0.3
By controlling as above, in the IR measurement
Wave number 1130 cm^-1(SiOx) and wave number 1068 cm ^-1
(SiO₂) Absorption intensity ratio (SiOx / SiO₂)and
Wave number 946 cm^-1(SiOH) and wave number 1068 cm
^-1(SiO₂) Absorption intensity ratio (SiOH / SiO₂)But,
0.35 or less and 0.14 or less, respectively, and
Film thickness with a density of 1.88 or more measured by X-ray total reflection measurement
Dense with low shrinkage and suppressed cracking
Heat treatment of highly functional silica thin film at low temperature below 200 ℃
Can be formed by.

Here, in the IR measurement of the sol, the absorption intensity ratio SiOH / SiO ₂ of 0.3 or more means that the condensation reaction in the sol has not proceeded too much. If the condensation reaction proceeds too much in the sol state, the sol becomes less likely to undergo molecular movement during and after film formation, and the condensation reaction inside the sol and between the sol becomes difficult to proceed.
Therefore, by forming a film by using a sol having SiOH / SiO ₂ of 0.3 or more, the condensation reaction is likely to proceed during or after the film formation, and as a result, the absorption intensity ratio SiOx / SiO ₂ in IR measurement becomes A silica-based thin film having a ratio of 0.35 or less and SiOH / SiO ₂ of 0.14 or less can be obtained.

In the second embodiment, the silica-based sol
The degree of hydrolysis of traalkoxysilane is 10 minutes after the start of the reaction.
95% or more, and²⁹Si-nuclear magnetic resonance spectroscopy (hereinafter
under, ²⁹It is abbreviated as Si-NMR. ) Q in measurement₁/
(Q₁+ Q₂+ Q₃) Ratio (where Q₁Is a SiOSi bond
Peak area of one Si atom, Q₂Is SiOSi
Peak area of Si atom having two atoms, Q₃Is SiOS
It is the peak area of Si atoms having three i-bonds. )But
By controlling it to be 0.1 or less, the total X-ray
If the density is 1.88 or more, the film thickness shrinkage is
Small and highly dense with suppressed cracking
Form a silica thin film by low-temperature heat treatment at 200 ℃ or lower
Can be made.

Here, the fact that the Q ₁ / (Q ₁ + Q ₂ + Q ₃ ) ratio in the ²⁹ Si-NMR measurement of the sol is 0.1 or less means that the number of Si atoms located at the ends is small, which means that Since it disappears at the initial stage of the reaction, it is expected that a tri- or tetrameric cyclic cluster structure is formed at the initial stage of hydrolysis and condensation. Therefore, the degree of initial hydrolysis of tetraalkoxysilane is extremely important,
When the degree of hydrolysis does not reach 95% within 10 minutes after the start of the reaction, the remaining tetraalkoxysilane causes steric hindrance,
A cluster having a ring structure is less likely to be formed and may be incorporated into the condensate as it is as a terminal (Q1). As a result, an organic group is likely to remain and a dense film is difficult to obtain. The degree of hydrolysis of tetraalkoxysilane can be determined by gas chromatography analysis or ¹ H-NMR.
Can be measured by

By controlling the degree of condensation and the degree of hydrolysis as in the case of the first and second aspects, even if the heat treatment is performed at a low temperature of, for example, 80 ° C. for 1 hour after film formation, X
It is possible to obtain a dense silica-based thin film having a density of 1.88 or more as measured by line total reflection measurement.

A third mode is the first mode and the second mode.
It is an embodiment in which That is, the IR of the sol
Wave number 966cm in measurement^-1(SiOH) and wave number 10
82 cm^-1(SiO₂) Absorption intensity ratio (SiOH / Si
O₂) Is 0.3 or more, and tetraalkoxysilane
The degree of hydrolysis of is 95% or more 10 minutes after the start of the reaction,
And²⁹Q in Si-NMR measurement₁/ (Q₁+ Q₂+
Q₃) Ratio (where Q₁Is Q₂And Q₃Is the same as above
Is. ) Is controlled to be 0.1 or less.
, The wave number in IR measurement is 1130 cm^-1(SiOx)
And wave number 1068cm ^-1(SiO₂) Absorption intensity ratio (Si
Ox / SiO₂) And wave number 946 cm^-1(SiOH)
And wave number 1068cm^-1(SiO₂) Absorption intensity ratio (Si
OH / SiO₂) Are less than 0.35 and 0.
It is 14 or less, and the density by X-ray total reflection measurement is 1.
88 or more, the film thickness shrinkage rate is small, and cracks
A highly dense silica-based thin film whose generation is suppressed
It can be formed by low-temperature heat treatment at a temperature of not higher than 0 ° C.

In the method of the present invention, the first and second
And, as in the third aspect, by controlling the degree of condensation and the degree of hydrolysis of the silica-based sol obtained by the hydrolysis and condensation of the tetraalkoxysilane, even if the sol has a weight average molecular weight of less than 85,000, By the low-temperature heat treatment at a temperature of not higher than 0 ° C., it is possible to obtain a highly dense silica-based thin film having a small film thickness shrinkage and suppressing generation of cracks.

In the method for producing a silica-based thin film of the present invention, a silica-based thin film is formed by applying a coating solution containing the above-mentioned silica-based sol to the surface of a substrate and then drying and heat-treating the coating liquid. At this time, as the base material, either an inorganic base material or an organic base material can be used, but in the present invention, since the organic base material is dried and heat-treated at a temperature of 200 ° C. or lower, the organic base material has low heat resistance. Is particularly useful against. Even if it is dried and heat-treated at a temperature of 200 ° C. or lower, a dense silica-based thin film without cracks can be obtained.

At this time, known coating methods include, for example, dip coating method, spin coating method, spray coating method, bar coating method, knife coating method, roll coating method, blade coating method, die coating method, gravure coating method, and the like. Means can be used. The thickness of the formed silica-based thin film is usually 1 μm or less, preferably 0.01 μm or less.
To 0.7 μm, more preferably 0.03 to 0.5 μm.

When an organic base material is used, in order to improve the adhesion to the silica-based thin film, a surface treatment can be carried out, if desired, by an oxidation method or a textured method. Examples of the oxidization method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like, and as the roughening method, for example, sandblast method, solvent treatment method, etc. Is mentioned. These surface treatment methods are appropriately selected depending on the type of substrate.

The organic base material in the present invention is an organic coating on the surface of a material other than organic materials such as metal materials, glass or ceramic materials, and other inorganic or metal materials. Those having a membrane are also included.

Next, the organic-inorganic composite gradient material of the present invention will be described. The organic-inorganic composite gradient material of the present invention,
An organic-inorganic material that includes a complex in which an organic polymer compound and a metal oxide compound are chemically bound, and has a component gradient structure in which the content of the metal component continuously changes from the surface of the material to the depth direction. A composite gradient material, wherein the composite is
(A) an organic polymer compound having a metal-containing group capable of binding to a metal oxide by hydrolysis (hereinafter sometimes referred to as a hydrolyzable metal-containing group) in the molecule, It is formed by using a coating liquid obtained by hydrolyzing in the presence, and as the silica-based sol of the component (B), the above-mentioned first aspect, second aspect or The sol satisfying the conditions of the third aspect (the properties of the sol itself and the properties of the silica-based thin film formed by depositing the sol are defined) are used.

The organic polymer compound having a hydrolyzable metal-containing group as the component (A) is, for example, hydrolyzed in the molecule (a) to hydrolyze the tetraalkoxysilane represented by the general formula (I). By copolymerizing an ethylenically unsaturated monomer having a metal-containing group (hydrolyzable metal-containing group) capable of binding with a condensation compound and (b) a metal-free ethylenically unsaturated monomer, Obtainable.

The ethylenically unsaturated monomer having a hydrolyzable metal-containing group, which is the component (A) or (a), has the general formula (II)

[0043]

[Chemical 1]

(In the formula, R ¹ is a hydrogen atom or a methyl group,
A is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, R ² is a hydrolyzable group or a non-hydrolyzable group, at least one of which is (B)
It is necessary that it is a hydrolyzable group capable of chemically bonding to the component, and when R ² is plural, each R ² may be the same or different, and M Is a metal atom such as silicon, titanium, zirconium, indium, tin, and aluminum, and k is the valence of the metal atom M. And a group represented by).

In the above general formula (II), the hydrolyzable group of R ² which can be chemically bonded to the component (B) by hydrolysis is, for example, an alkoxyl group, an isocyanate group, a halogen atom such as a chlorine atom or an oxy group. Halogen group,
Examples thereof include an acetylacetonate group and a hydroxyl group. On the other hand, examples of the non-hydrolyzable group that does not chemically bond with the component (B) include a lower alkyl group.

Examples of the metal-containing group represented by -MR ² _k-1 in the general formula (II) include trimethoxysilyl group, triethoxysilyl group, tri-n-propoxysilyl group and triisopropoxysilyl group. , Tri-n-butoxysilyl group, triisobutoxysilyl group, tri-sec-
Butoxysilyl group, tri-tert-butoxysilyl group, trichlorosilyl group, dimethylmethoxysilyl group, methyldimethoxysilyl group, dimethylchlorosilyl group, methyldichlorosilyl group, triisocyanatosilyl group, methyldiisocyanatosilyl group, etc., Trimethoxytitanium group, triethoxytitanium group, tri-n-propoxytitanium group, triisopropoxytitanium group, tri-n-butoxytitanium group, triisobutoxytitanium group, tri-sec-butoxytitanium group, tri-ter
t-butoxytitanium group, trichlorotitanium group,
Furthermore, trimethoxy zirconium group, triethoxy zirconium group, tri-n-propoxy zirconium group, triisopropoxy zirconium group, tri-n-butoxy zirconium group, triisobutoxy zirconium group, tri-sec-butoxy zirconium group, tri −tert
-Butoxyzirconium group, trichlorozirconium group, and further, dimethoxyaluminum group, diethoxyaluminum group, di-n-propoxyaluminum group, diisopropoxyaluminum group, di-n-butoxyaluminum group, diisobutoxyaluminum group, diisobutoxyaluminum group, -Sec-butoxyaluminum group, di-tert-butoxyaluminum group, trichloroaluminum group and the like can be mentioned. Among these, the silicon-containing group is preferable because the component (B) is a silica sol. The ethylenically unsaturated monomer as the component (a) may be used alone or in combination of two or more kinds.

On the other hand, examples of the metal-free ethylenically unsaturated monomer which is the component (b) include compounds represented by the general formula (II
I)

[0048]

[Chemical 2]

(In the formula, R ³ is a hydrogen atom or a methyl group,
X is a monovalent organic group. ) An ethylenically unsaturated monomer represented by formula (III-a), preferably

[0050]

[Chemical 3]

(In the formula, R ³ is the same as the above, and R ⁴ represents a hydrocarbon group.) An ethylenically unsaturated monomer represented by the above or the above general formula (III-a). General formula (III-b) as an adhesion improver that is added as necessary with an ethylenically unsaturated monomer

[0052]

[Chemical 4]

(In the formula, R ⁵ is a hydrogen atom or a methyl group,
R ⁶ represents an epoxy group, a halogen atom or a hydrocarbon group having an ether bond. ) And a mixture with an ethylenically unsaturated monomer.

In the ethylenically unsaturated monomer represented by the general formula (III-a), the hydrocarbon group represented by R ⁴ is a linear or branched alkyl group having 1 to 10 carbon atoms. Preferred examples include a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, and various butyl group, pentyl group, hexyl group, octyl group, decyl group and the like. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cyclooctyl group and the like, and 6 to 1 carbon atoms.
Examples of the aryl group of 0 include a phenyl group, a tolyl group,
Examples of the aralkyl group having 7 to 10 carbon atoms such as a xylyl group, a naphthyl group and a methylnaphthyl group include a benzyl group, a methylbenzyl group, a phenethyl group and a naphthylmethyl group.

Examples of the ethylenically unsaturated monomer represented by the general formula (III-a) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate and butyl (meth) acrylate. , Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth)
Examples thereof include acrylate. These may be used alone or in combination of two or more.

In the ethylenically unsaturated monomer represented by the general formula (III-b), the epoxy group represented by R ⁶ , the halogen atom or the hydrocarbon group having an ether bond has 1 to 10 carbon atoms. Preferred examples thereof include a linear or branched alkyl group, a C3-10 cycloalkyl group, a C6-10 aryl group, and a C7-10 aralkyl group. The halogen atom for the above substituent is preferably a chlorine atom or a bromine atom. Specific examples of the hydrocarbon group include the above-mentioned general formula (III-
The same groups as those exemplified in the description of R ⁴ in a) can be mentioned.

Examples of the ethylenically unsaturated monomer represented by the general formula (III-b) include glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate and 2- (3,4). -Epoxycyclohexyl) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate and the like can be preferably mentioned.

As the ethylenically unsaturated monomer represented by the general formula (III), styrene, α-methylstyrene, α-acetoxystyrene, m
-, O- or p-bromostyrene, m-, o- or p-chlorostyrene, m-, o- or p-vinylphenol, 1- or 2-vinylnaphthalene and the like, and further having an ethylenically unsaturated group Stabilizer for polymerizable polymer,
For example, an antioxidant, an ultraviolet absorber and a light stabilizer having an ethylenically unsaturated group can also be used. These may be used alone or in combination of two or more.

When the ethylenically unsaturated monomer represented by the general formula (III-a) and the ethylenically unsaturated monomer represented by the general formula (III-b) are used in combination, the former It is preferable to use the latter ethylenically unsaturated monomer in an amount of 1 to 100 mol% relative to the ethylenically unsaturated monomer.

In the presence of a radical polymerization initiator, the ethylenically unsaturated monomer having a hydrolyzable metal-containing group as the component (a) and the ethylenically unsaturated monomer containing no metal as the component (b) are present. Below, by radical copolymerization, (A)
An organic polymer compound having a hydrolyzable metal-containing group as a component is obtained.

In the present invention, the thus obtained component (A), an organic polymer compound having a hydrolyzable metal-containing group, is dissolved in a suitable polar solvent such as alcohol, ketone or ether. The solution and the solution of the above-mentioned silica-based sol which is the component (B) are mixed to prepare a coating liquid having a viscosity suitable for coating. At this time, if necessary, water and / or an acidic catalyst can be added to the coating solution.

Next, using the coating liquid thus obtained, the thickness of the dry coating film on the organic substrate is usually 5 μm or less, and particularly 0.01 to 1 for use as an interlayer film. ．
0 μm, more preferably in the range of 0.02 to 0.7 μm, dip coating method, spin coating method, spray coating method, bar coating method, knife coating method, roll coating method, blade coating method, die coating method, The organic-inorganic composite gradient material of the present invention is obtained by forming a coating film by a known means such as a gravure coating method and performing a known drying treatment, for example, a heat drying treatment at a temperature of about 40 to 150 ° C.

Examples of the organic base material include acrylic resins such as polymethylmethacrylate, polystyrene and A.
Styrene resin such as BS resin, olefin resin such as polyethylene and polypropylene, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyamide resin such as 6-nylon and 6,6-nylon, polyvinyl chloride resin, Examples of the base material include a polycarbonate resin, a polyphenylene sulfide resin, a polyphenylene ether resin, a polyimide resin, and a cellulose resin such as cellulose acetate.

These organic base materials can be subjected to a surface treatment, if desired, by an oxidation method or a textured method in order to further improve the adhesion to the gradient material of the present invention.
Examples of the oxidization method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like, and as the roughening method, for example, sandblast method, solvent treatment method, etc. Is mentioned. These surface treatment methods are appropriately selected depending on the type of substrate.

The organic base material in the present invention is an organic coating material on the surface of a material other than the organic material, for example, a metal material, glass or ceramic material, or other inorganic or metal material. Those having a membrane are also included.

In the thus obtained organic-inorganic composite gradient material of the present invention, the surface layer has a high density and the content of the metal component in the material is almost 100%. It gradually decreases in the direction, and becomes almost 0% in the vicinity of the base material.

That is, the organic-inorganic composite gradient material of the present invention is generally composed of a film-like material formed on a substrate, and substantially the surface of the film-like material contacting the substrate is organic. The polymer compound component is the metal oxide compound component having silica on the other open side.

The organic-inorganic composite gradient material of the present invention can be used for various purposes as a functional material. Among them, between the organic base material and the coating layer containing at least an inorganic or metallic material. It is preferably used as an intermediate film to be interposed.

When a coating layer containing an inorganic or metallic material is formed on an organic substrate, the adhesion between the organic substrate and the coating layer is generally insufficient, resulting in poor durability and peeling over time. There is a problem in that it easily peels off due to heat or moisture.

By interposing the gradient material of the present invention as an intermediate film between the organic base material and the coating layer containing an inorganic or metallic material, the intermediate film has a gradient as described above. Therefore, the adhesiveness with the organic base material is excellent, and the adhesiveness with the coating layer containing the inorganic or metal-based material provided thereon is also excellent, and as a result, the inorganic or metal-based material is provided on the organic base material. It is possible to form a coat layer containing P with excellent adhesion.

The coat layer containing the inorganic or metallic material is not particularly limited, and various coat layers can be formed. For example, (1) a photocatalytically active material layer,
(2) Inorganic or metallic conductive material layer, (3) Hard coat layer containing inorganic or metallic material, (4) Inorganic or metallic optical recording material layer or inorganic or metallic dielectric layer, etc. Can be preferably mentioned. Among these, it is particularly preferable to use the gradient material of the present invention as an intermediate film interposed between the photocatalytically active material layer and the organic base material.

When a coating layer of a photocatalytically active material such as titanium dioxide is provided on the surface of the organic base material, the photocatalytic action causes a problem that the organic base material deteriorates in a short time. Therefore, it has been attempted to provide a coating layer of a photocatalytically active material such as titanium dioxide on an organic substrate through an inorganic binder that is less likely to deteriorate due to a photocatalytic action. However, the inorganic binder has a problem that the adhesive strength to the organic base material is insufficient and the durability is poor.

When the graded material of the present invention is used as an intermediate film and interposed between the organic base material and the coating layer of the photocatalytically active material, the adhesion to the organic base material is excellent, and the surface is almost metal oxide-based. Since it is a compound, it has good adhesion to the coating layer of the photocatalytically active material, and the intermediate film is unlikely to deteriorate due to the photocatalytic action, so that the organic base material can be sufficiently protected.

Further, the gradient material of the present invention can be interposed as an intermediate film between the metal-based base material having the organic coating film on the surface and the photocatalytically active material layer. Similar to the case of the above-mentioned organic base material, this intermediate film has excellent adhesiveness to the organic coating film, good adhesion to the coating layer of the photocatalytically active material, and is not easily deteriorated by the photocatalytic action. The coating film can be sufficiently protected. As such an application, when the material and a photocatalytically active material layer are provided on the surface of an organic substrate film and used by adhering to various materials, or on a steel sheet for automobiles having an organic coating film on the surface. This is useful when a photocatalytically active material layer is provided on the.

Examples of the metal-based substrate having an organic coating film on its surface include cold-rolled steel plates, zinc-plated steel plates, aluminum / zinc alloy-plated steel plates, stainless steel plates, aluminum plates and aluminum alloy plates. The thing which formed the organic type coating film can be mentioned.

When the gradient material of the present invention is used as such an intermediate film, when the coating layer of the photocatalytically active material provided thereon is titanium dioxide having high photocatalytic activity,
Especially effective.

[0077]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 2-methoxyethanol in tetramethoxysilane (5 wt% in terms of SiO _{2 with} respect to the entire reaction solution) and 1
An aqueous solution of nitric acid having a concentration of mol / liter was added so that the amount of water would be 8 times the molar amount of tetramethoxysilane, and the mixture was heated at 30 ° C.
A time hydrolysis-condensation reaction was performed. The obtained silica sol solution was diluted with 2-methoxyethanol so as to be 3 wt% in terms of SiO ₂ , and 1500r was deposited on a silicon wafer.
The film was formed at pm / 20 seconds. This was heat-treated at 80 ° C. for 1 hour to obtain a silica thin film.

<IR Measurement of Solution> After the hydrolysis-condensation reaction for 48 hours, the IR of the reaction solution was measured.
Using a Magna 760 manufactured by Nicollet as an apparatus, the reaction solution was dropped on an ATR crystal, and measurement was carried out by a single reflection ATR method (crystal Ga). From the obtained IR chart, the solvent was subtracted from the difference spectrum to obtain SiOH (966 cm ⁻¹ ) and SiO ₂ (10
The absorption intensity ratio of 82 cm ^-1 ) was calculated to be SiOH.
/ SiO ₂ = 0.35.

<IR Measurement of Thin Film> A silica thin film formed on a silicon wafer was measured by a transmission IR method. As a device, Magna 760 manufactured by Nicollet was used. From the obtained chart, the absorption of the silicon wafer was subtracted by the difference spectrum to obtain SiOx (1130 cm
⁻¹ ), SiO ₂ (1068 cm ⁻¹ ), and SiOH (94
The ratio of the absorption intensity at 6 cm ^-1 ) was determined. As a result, SiO
x / SiO ₂ = 0.33 and SiOH / SiO ₂ = 0.
It was 13.

<Measurement of Density of Thin Film> Measuring device: ATX-G manufactured by Rigaku Denki Measuring conditions: voltage / current: 50 kV / 300 mA, incident optical system: Ge (220) channel monochromator, measuring range: 2 Theta = 0.1 to 1.2 deg, scan speed: 0.1 deg / min, sampling width: 0.002 deg The film density of the silica thin film obtained by X-ray total reflection measurement was calculated. As a result, the density was 1.90. Figure 1
The IR spectrum of silica sol is shown in FIG.

Example 2 Tetramethoxysilane (16 wt% in terms of SiO ₂ with respect to the entire reaction solution) was added to isopropyl alcohol, and
An aqueous solution of nitric acid having a concentration of 1 mol / liter was added so that the amount of water was 6 times that of tetramethoxysilane, and the mixture was heated at 30 ° C. for 2 hours.
A time hydrolysis-condensation reaction was performed. The obtained silica sol solution was diluted with 2-methoxyethanol so as to be 3 wt% in terms of SiO ₂ , and 1500r was deposited on a silicon wafer.
The film was formed at pm / 20 seconds. This was heat-treated at 80 ° C. for 1 hour to obtain a silica thin film.

<Measurement of Degree of Hydrolysis> Ten minutes after the start of the reaction, the amount of methanol hydrolyzed and desorbed from tetramethoxysilane was quantified by gas chromatography. As a result, it was found that 97% of the methoxy groups were eliminated and methanol was produced.

<Measurement of ²⁹ Si-NMR> The obtained silica sol was subjected to ²⁹ Si-NM by "GSX270" manufactured by JEOL Ltd.
R measurement was performed. Q ₁ (-8 in the obtained chart
5 to −80 ppm peak), Q ₂ (−95 to −88 p)
pm peak) and Q ₃ (minus the baseline obtained from the peak) in the -105~-97ppm,
When the area ratio of Q ₁ / (Q ₁ + Q ₂ + Q ₃ ) was calculated,
It was 0.06.

<Measurement of Density of Thin Film> In the same manner as in Example 1, the film density of the silica thin film was calculated by X-ray total reflection measurement. As a result, the density was 1.89. FIG. 2 shows the ²⁹ Si-NMR spectrum of silica sol.

Example 3 2-methoxyethanol, tetramethoxysilane (16 wt% in terms of SiO ₂ with respect to the entire reaction solution), and
An aqueous solution of nitric acid having a concentration of 1 mol / liter was added so that the amount of water was 6 times that of tetramethoxysilane, and the mixture was heated at 30 ° C. for 2 hours.
A time hydrolysis-condensation reaction was performed. The obtained silica sol solution was diluted with 2-methoxyethanol so as to be 3 wt% in terms of SiO ₂ , and 1500r was deposited on a silicon wafer.
The film was formed at pm / 20 seconds. This was heat-treated at 80 ° C. for 1 hour to obtain a silica thin film.

<Measurement of Hydrolysis Degree> Ten minutes after the start of the reaction, the amount of methanol hydrolyzed and desorbed from tetramethoxysilane was quantified by gas chromatography. As a result, it was found that 97% of the methoxy groups were eliminated and methanol was produced.

<IR Measurement of Solution> After performing the hydrolysis-condensation reaction for 2 hours, the IR of the reaction solution was measured. Using a Magna 760 manufactured by Nicollet as an apparatus, the reaction solution was dropped on an ATR crystal, and measurement was carried out by a single reflection ATR method (crystal Ga). From the obtained IR chart, the solvent was subtracted from the difference spectrum to obtain SiOH (966 cm ⁻¹ ) and SiO ₂ (108
The ratio of absorption intensity at 2 cm ^-1 ) was calculated to be SiOH /
SiO ₂ = 0.5.

<IR Measurement of Thin Film> The silica thin film formed on the silicon wafer was measured by the transmission IR method. As a device, Magna 760 manufactured by Nicollet was used. From the obtained chart, the absorption of the silicon wafer was subtracted by the difference spectrum to obtain SiOx (1130 cm
⁻¹ ), SiO ₂ (1068 cm ⁻¹ ), and SiOH (94
The ratio of the absorption intensity at 6 cm ^-1 ) was determined. As a result, SiO
x / SiO ₂ = 0.30 and SiOH / SiO ₂ = 0.
It was 12.

<Measurement of ²⁹ Si-NMR> The obtained silica sol was subjected to ²⁹ Si-NM by "GSX270" manufactured by JEOL Ltd.
R measurement was performed. Q ₁ (-8 in the obtained chart
5 to −80 ppm peak), Q ₂ (−95 to −88 p)
pm peak) and Q ₃ (minus the baseline obtained from the peak) in the -105~-97ppm,
When the area ratio of Q ₁ / (Q ₁ + Q ₂ + Q ₃ ) was calculated,
It was 0.07.

<Measurement of Density of Thin Film> In the same manner as in Example 1, the film density of the silica thin film was calculated by X-ray total reflection measurement. As a result, the density was 1.92. Fig. 3 shows the IR spectrum of silica sol, and Fig. 4 shows the ²⁹ Si of silica sol.
-Shows an NMR spectrum.

Comparative Example 1 Tetramethoxysilane (5 wt% in terms of SiO _{2 with} respect to the entire reaction solution) was added to isopropyl alcohol, and
An aqueous solution of nitric acid having a concentration of 0.1 mol / liter was added so that the amount of water was 4 times that of tetramethoxysilane, and the temperature was 30 °
The hydrolysis-condensation reaction was performed for 2 hours. The obtained silica sol solution was diluted with 2-methoxyethanol so as to be 3 wt% in terms of SiO ₂ and then diluted on a silicon wafer to give 150
The film was formed at 0 rpm / 20 seconds. This was heat-treated at 80 ° C. for 1 hour to obtain a silica thin film.

<Measurement of Degree of Hydrolysis> Ten minutes after the start of the reaction, the amount of methanol hydrolyzed and desorbed from tetramethoxysilane was quantified by gas chromatography. As a result, it was found that 90% of the methoxy groups were eliminated and methanol was produced.

<IR Measurement of Solution> After performing the hydrolysis-condensation reaction for 2 hours, the IR of the reaction solution was measured. Using a Magna 760 manufactured by Nicollet as an apparatus, the reaction solution was dropped on an ATR crystal, and measurement was carried out by a single reflection ATR method (crystal Ga). From the obtained IR chart, the solvent was subtracted from the difference spectrum to obtain SiOH (966 cm ⁻¹ ) and SiO ₂ (108
The ratio of absorption intensity at 2 cm ^-1 ) was calculated to be SiOH /
SiO ₂ = 0.25.

<IR Measurement of Thin Film> A silica thin film formed on a silicon wafer was measured by a transmission IR method. As a device, Magna 760 manufactured by Nicollet was used. From the obtained chart, the absorption of the silicon wafer was subtracted by the difference spectrum to obtain SiOx (1130 cm
⁻¹ ), SiO ₂ (1068 cm ⁻¹ ), and SiOH (94
The ratio of the absorption intensity at 6 cm ^-1 ) was determined. As a result, SiO
x / SiO ₂ = 0.40 and SiOH / SiO ₂ = 0.
It was 25.

<Measurement of ²⁹ Si-NMR> The obtained silica sol was subjected to ²⁹ Si-NM by "GSX270" manufactured by JEOL Ltd.
R measurement was performed. From the chart obtained, Q ₁ / (Q ₁ +
The area ratio of (Q ₂ + Q ₃ ) was calculated to be 0.6.

<Measurement of Density of Thin Film> In the same manner as in Example 1, the film density of the silica thin film was calculated by X-ray total reflection measurement. As a result, the density was 1.78. Fig. 5 shows the IR spectrum of silica sol, and Fig. 6 shows the ²⁹ Si of silica sol.
-Shows an NMR spectrum.

Example 4 0.12 g of 2,2′-azobisisobutyronitrile was dissolved in a mixed solution of 10.9 g of methyl methacrylate and 1.36 g of γ-methacryloxypropyltrimethoxysilane, and the mixture was stirred. While reacting at 75 ° C for 3 hours, gel permeation chromatography (GP
The polystyrene-equivalent weight average molecular weight by method C) is about 7
10,000 copolymers were obtained. 1.0 g of this copolymer was dissolved in 100 ml of methyl isobutyl ketone to obtain an organic component solution having a concentration of 10 g / L.

After adding 5 ml of this organic component solution to 20 ml of methyl isobutyl ketone, 15 m of ethyl cellosolve was added.
1 and then 5 ml of the silica sol obtained in Example 3 were added to prepare a component gradient film coating liquid. This coating solution was bar-coated on a polyethylene terephthalate film (“Tetron HB-3” manufactured by Teijin DuPont Films Ltd.) having a thickness of 50 μm with a Meyer bar having a wire wire diameter of 0.075 mm, and the solvent was volatilized to make the components A graded film was formed. When this film was subjected to X-ray photoelectron spectroscopy measurement, it was confirmed to be a film having a gradient.

This was heated in an oven at 80 ° C. for 20 hours, and then a photocatalyst solution “ST-K211” manufactured by Ishihara Sangyo Co., Ltd. was applied on the film to a thickness of 50 nm. As a result of conducting an accelerated weathering test on this film with a photocatalyst film using a carbon arc type sunshine weather meter, 900
The haze value after the lapse of time was 3.78%, and the transparency was maintained.

Comparative Example 2 In the same manner as in Example 4 except that the silica sol obtained in Comparative Example 1 was used in place of the silica sol obtained in Example 3, a gradient of components with a photocatalyst film was prepared. A membrane film was obtained. The film with a photocatalyst film was subjected to an accelerated weathering test using a carbon arc type sunshine weather meter, and as a result, the haze value after 900 hours was 20% and whitening occurred. When observing the film surface with an optical microscope,
It was confirmed that the silica portion contracted and a crack was generated.

[0101]

According to the present invention, in the method for producing a silica-based thin film by the sol-gel method, the degree of condensation and the degree of hydrolysis of the sol obtained by the hydrolysis and condensation of tetraalkoxysilane are controlled. By the low temperature heat treatment, it is possible to obtain a dense silica-based thin film having a small film thickness shrinkage and suppressing generation of cracks. An organic-inorganic composite gradient material whose surface layer is composed of a dense metal oxide thin film containing silica and has a component gradient structure in which the content of metal components continuously changes (decreases) in the thickness direction from the surface of the material. Can be provided.

[Brief description of drawings]

1] The silica film obtained in Example 1 was formed into a film at 80 ° C.
It is a figure of IR spectrum change at the time of heating for 1 hour.

FIG. 2 ²⁹ Si—NM of silica sol obtained in Example 2
It is an R spectrum figure.

FIG. 3 is a graph showing the silica film obtained in Example 3 formed at 80 ° C.
It is a figure of IR spectrum change at the time of heating for 1 hour.

FIG. 4 ²⁹ Si—NM of silica sol obtained in Example 3
It is an R spectrum figure.

FIG. 5: Formed the silica film obtained in Comparative Example 1 at 80 ° C.
It is a figure of IR spectrum change at the time of heating for 1 hour.

FIG. 6 ²⁹ Si-NM of silica sol obtained in Comparative Example 1
It is an R spectrum figure.

Continued front page    F term (reference) 4G072 AA28 BB09 CC02 GG02 GG03                       HH18 HH30 NN21 PP01 RR05                       TT30 UU01                 4J031 AA20 AA59 AB01 AC15 AD01                       AF02                 4J038 CG141 CG142 CH141 CH142                       CH171 CH172 CH231 CH232                       DL021 DL022 DM021 DM022                       HA216 HA446 MA12 NA11

Claims (7)

[Claims] 1. The general formula (I) Si (OR)_Four                … (I) (In the formula, R represents an alkyl group having 1 to 3 carbon atoms,
The ORs may be the same or different. )
Obtained by hydrolyzing and condensing tetraalkoxysilane
The silica-based thin film is manufactured by forming a film of the sol on the substrate.
In the method of
Wave number 966 cm^-1(SiOH) and wave number 1
082 cm ^-1(SiO₂) Absorption intensity ratio (SiOH / S
iO₂) Is controlled to be 0.3 or more.
, The wave number in infrared absorption spectrum measurement 1130c
m^-1(SiOx) and wave number 1068 cm^-1(SiO₂)of
Absorption intensity ratio (SiOx / SiO₂) And wave number 946c
m^-1(SiOH) and wave number 1068 cm^-1(SiO₂)of
Absorption intensity ratio (SiOH / SiO₂) Is 0.3
5 or less and 0.14 or less, and X-ray total reflection measurement
To form a silica-based thin film with a density of 1.88 or more
A method for producing a silica-based thin film, comprising: 2. General formula (I) Si (OR) ₄ (I) (In the formula, R represents an alkyl group having 1 to 3 carbon atoms, and four ORs may be the same or different from each other. In a method for producing a silica-based thin film by forming a sol obtained by hydrolyzing and condensing a tetraalkoxysilane represented by), the sol having a degree of hydrolysis of tetraalkoxysilane 95% or more 10 minutes after the start of the reaction,
And Q ₁ / (Q ₁ + in ²⁹ Si-nuclear magnetic resonance spectroscopy measurement
Q ₂ + Q ₃ ) ratio (where Q ₁ is the peak area of a Si atom having one SiOSi bond, and Q ₂ is ₂ SiOSi bonds).
Q ₃ is the peak area of Si atom having three SiSi bonds and Q ₃ is the peak area of Si atom having three SiOSi bonds. ) Is 0.1
A method for producing a silica-based thin film, which comprises forming a silica-based thin film having a density of 1.88 or more by X-ray total reflection measurement by controlling as follows. 3. The general formula (I) Si (OR)_Four                … (I) (In the formula, R represents an alkyl group having 1 to 3 carbon atoms,
The ORs may be the same or different. )
Obtained by hydrolyzing and condensing tetraalkoxysilane
The silica-based thin film is manufactured by forming a film of the sol on the substrate.
In the method of
Wave number 966 cm^-1(SiOH) and wave number 1
082 cm ^-1(SiO₂) Absorption intensity ratio (SiOH / S
iO₂) Is 0.3 or more, and tetraalkoxy sila
The degree of hydrolysis of benzene is 95% or more 10 minutes after the start of the reaction.
And ²⁹Q in Si-Nuclear Magnetic Resonance Spectroscopy₁/
(Q₁+ Q₂+ Q₃) Ratio (where Q₁Is a SiOSi bond
Peak area of one Si atom, Q₂Is SiOSi
Peak area of Si atom having two atoms, Q₃Is SiOS
It is the peak area of Si atoms having three i-bonds. )But
Infrared absorption is controlled by controlling the value to be 0.1 or less.
Wave number 1130 cm in the spectrum measurement^-1(SiO
x) and wave number 1068 cm^-1(SiO₂) Absorption intensity ratio
(SiOx / SiO₂) And wave number 946 cm^-1(Si
OH) and wave number 1068 cm^-1(SiO₂) Absorption intensity ratio
(SiOH / SiO₂) Is less than 0.35 and
And 0.14 or less and the density by X-ray total reflection measurement
Special feature is to form a silica-based thin film with a value of 1.88 or more.
A method for producing a silica-based thin film. 4. A gradient component structure containing a complex in which an organic polymer compound and a metal oxide compound are chemically bonded, and in which the content of the metal component continuously changes in the depth direction from the surface of the material. An organic-inorganic composite gradient material having: wherein the composite has an organic polymer compound (A) having a metal-containing group capable of binding to a metal oxide by hydrolysis in a molecule,
(B) a silica-based sol formed by using a coating liquid obtained by hydrolyzing in the presence of a silica-based sol, and having the general formula (I) Si (OR) ₄ (I) (wherein, R represents an alkyl group having 1 to 3 carbon atoms, and the four ORs may be the same or different from each other.) Are hydrolyzed. , A sol obtained by condensation, and having a wave number of 966 cm ⁻¹ (SiOH) and a wave number of 1 in the infrared absorption spectrum measurement of (a) sol.
Absorption intensity ratio (SiOH / S of 082 cm ^-1 (SiO ₂ ).
iO ₂ ) is 0.3 or more, and the formed silica-based thin film has a wave number of 1130c in infrared absorption spectrum measurement.
m ^-1 (SiOx) and wavenumber 1068cm ^-1 absorption intensity ratio of _{(SiO 2) (SiOx / SiO} 2) and a wavenumber 946c
m ^-1 (SiOH) and absorption intensity ratio of wavenumber _{^{1068cm -1 (SiO 2) (SiOH}} / SiO 2) , respectively 0.3
5 or less and 0.14 or less and a density of 1.88 or more by X-ray total reflection measurement, or (b) the degree of hydrolysis of tetraalkoxysilane in the sol is 95% or more within 10 minutes after the start of the reaction. And the Q ₁ / (Q ₁ + Q ₂ + Q ₃ ) ratio in the ²⁹ Si-nuclear magnetic resonance spectroscopy measurement (where Q is
₁ is the peak area of a Si atom having one SiOSi bond, Q ₂ is the peak area of a Si atom having two SiOSi bonds, and Q ₃ is the peak area of a Si atom having three SiOSi bonds. ) Is 0.1 or less, and the deposited silica-based thin film has a density of 1.88 or more as measured by X-ray total reflection, or one satisfying both conditions (a) and (b) above. An organic-inorganic composite gradient material characterized by the above. 5. An organic polymer compound having a metal-containing group capable of binding to a metal oxide by hydrolysis in the molecule which is the component (A) is represented by the general formula (I) by hydrolysis in the molecule (a). Hydrolysis of the tetraalkoxysilane represented,
The organic-inorganic according to claim 4, which is a copolymer of an ethylenically unsaturated monomer having a metal-containing group capable of binding to a condensation compound and (b) an ethylenically unsaturated monomer not containing a metal. Composite graded material. 6. A film-shaped material formed on an organic base material, and substantially the surface of the film-shaped material in contact with the organic base material is an organic polymer compound component. The open system surface is a metal oxide compound component containing silica.
Alternatively, the organic-inorganic composite gradient material according to item 5. 7. The intermediate film used as an intermediate film interposed between an organic base material and a photocatalytically active material layer.
The organic-inorganic composite gradient material according to item 1.