JP2001329018A - Organic-inorganic composite material with component gradient structure and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic-inorganic composite material with a component gradient structure in which the content of a metal component changes continuously in the thickness-wise direction of the material, having excellent adhesion, durability and flexibility. SOLUTION: This organic-inorganic composite material with a component- gradient structure has a compound obtained by chemically bonding an organic polymer with a metal oxide compound. It has a component-gradient structure in which the content of the metal component changes continuously in the depth- wise direction from the surface of the material. As an organic polymer, a copolymer of an ethylenically unsaturated monomer having a hydrolyzable metal- containing group is used. The metal oxide compound is formed from a mixture and/or a reaction product of a silicon alkoxide compound and/or a hydrolysis- polycondensation polymer thereof, and alkoxide components of different metals other than silicon and/or hydrolysis-polycondensation polymers thereof. The different metal components are mixed with each other substantially in a homogeneous manner.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organic-inorganic composite gradient material and its use. More specifically, the present invention has a component gradient structure in which the content of two or more kinds of substantially homogeneous mixed metal components continuously changes in the thickness direction of the material, and also has an improved adhesion and durability to the substrate. An organic-inorganic composite gradient material that is excellent, has good flexibility, hardly causes cracks and cracks, and is useful for various applications as a functional material, a coating agent for forming a film made of the gradient material, particularly an organic material The present invention relates to a coating agent used for an intermediate film interposed between a base material and a photocatalytically active material layer, and a structure having on its surface a coating made of the gradient material.

[0002]

2. Description of the Related Art In recent years, with the diversification of requirements concerning the performance and functions of organic polymer materials, it has become difficult to satisfy with a single polymer compound, and different materials having different properties are added to the polymer compound. Compounding is being done.

[0003] For example, the modification of physical properties by dispersing a reinforcing material in an organic polymer material is widely performed, and specifically, organic fibers such as carbon fiber, glass fiber, metal fiber, ceramic fiber, and aramid fiber are used. And inorganic fibrous substances, or powdered inorganic fillers such as calcium carbonate, silica, and alumina are added and uniformly dispersed. In addition, studies are being actively conducted to mix new polymer compounds, optionally compatibilize them via a compatibilizer, and form a polymer alloy, thereby expressing new functions.

On the other hand, recently, a functionally graded material, which is a composite material in which the composition of the material is changed little by little and whose properties are completely different between the front and the back, attracts attention. For example, a metal-ceramic having both the heat resistance of ceramic and the strength of metal Composite functionally graded materials have been developed as airframe materials for supersonic aircraft.

[0005] Such functionally graded materials are classified into inorganic gradient materials, organic gradient materials and organic-inorganic composite gradient materials, and are classified into a plurality of materials, for example, a plurality of different inorganic materials, and a plurality of different organic materials. By mixing each other or one or more organic materials and one or more inorganic materials, and controlling the distribution density, orientation, etc., depending on the location, the physical properties of a plurality of component materials can be expressed.
It is expected to be used in the aviation, automotive, electronics, medical, energy, and radiation and electromagnetic shielding fields.

[0006] The present inventors have previously proposed various uses as a novel functional material, for example, a coating film, an adhesive between an organic material and an inorganic or metal material, and a coating material between an organic substrate and a photocatalytic coating film. The composition is continuous in the thickness direction, which is useful for applications such as an intermediate film that prevents deterioration of the organic base material and an intermediate film that improves the adhesion between the organic base material and the inorganic or metal material layer. -Graded organic-inorganic composite gradient material (Japanese Patent Application No.
-264592).

This organic-inorganic composite gradient material is an organic-inorganic composite material containing a chemical bond of an organic polymer compound and a metal compound, and the content of the metal compound is increased in the thickness direction of the material. It has a component gradient structure that changes continuously,
It is a novel material that is extremely useful for the various applications described above.

However, this organic-inorganic composite gradient material is formed depending on the type of the inorganic component or organic polymer compound used in the gradient material in order to form the polymer portion by utilizing the ability of the polymer portion to adsorb to the substrate. Adhesion to certain organic substrates may not always be fully satisfactory.

For example, as the organic-inorganic composite gradient material, one containing a chemical bond of an acrylic organic polymer compound and an inorganic component composed of silica is preferably used. Is generally poor in affinity with an organic base material such as polyethylene terephthalate, so that sufficient adhesion cannot be obtained. Therefore,
By applying an easily-adhesive primer to the base material or performing a pretreatment such as a corona discharge treatment, a measure for improving the adhesion is usually taken, but in this case, the operation becomes complicated and the cost increases. There is a problem that it is unavoidable.

As another method for improving the adhesion, as described above, since the composite gradient material is formed by adsorption of the polymer compound to the organic substrate, the organic gradient material is directly in contact with the substrate. It is conceivable to improve the organic component itself by, for example, introducing a polymer compound having excellent adhesion to the substrate into the component. On the other hand, it is considered that not only the affinity of the organic component for the substrate but also the mechanical strength (cohesion) of the gradient material itself is greatly affected on the adhesion to the substrate.
For example, in general, a thin film has a smaller thickness than a thick film.
It is said that the adhesiveness is excellent due to the relatively high cohesion. That is, an improvement in the adhesiveness can be expected by improving the strength of the film.

Here, the organic-inorganic composite gradient material comprises:
Since most are composed of inorganic components, it is considered that the effect of the inorganic components on the film strength is naturally large. In the gradient material, silica is mainly used as an inorganic component, and exists as a so-called dry gel after film formation. Although the strength of the inorganic layer can be increased by performing high-temperature sintering or the like, it is not a method that is practically impossible because the base material is organic. In addition, low temperature processing is possible in excimer laser processing or the like, but disadvantages such as long processing time are required. Therefore, even in the dry gel state, forming an inorganic layer having better mechanical strength than conventional silica is considered to be an advantageous method for improving the adhesion. In this case, it is important to consider the flexibility and not to cause cracks, cracks, and the like.

In addition, silica, which has been mainly used as an inorganic component, has a relatively low reaction rate of silicon alkoxide, which is a raw material thereof, so that a large amount of unreacted alkoxide and hydroxyl groups are likely to remain in a coating film after film formation. . Therefore, when using an organic-inorganic composite gradient material using silicon alkoxide as a raw material, for example, as a photocatalyst intermediate layer,
In addition to being inferior in blocking property to active species generated from the photocatalyst layer, it has poor durability because of a large change with time.

[0013]

SUMMARY OF THE INVENTION Under such circumstances, the present invention has a component gradient structure in which the content of a metal component changes continuously in the thickness direction of a material, and has a close contact with a substrate. Organic-inorganic composite graded material having excellent properties and durability, and having good flexibility, hardly causing cracks and cracks, and useful for various uses as a functional material, and its use,
In particular, it is an object of the present invention to provide a material that achieves high blocking characteristics for active species from a photocatalyst layer.

[0014]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, as a polymer having an organic polymer, a metal-containing compound capable of being bonded to a metal oxide by hydrolysis in a molecule. An ethylenically unsaturated monomer having a group,
Using a metal-free copolymer with an ethylenically unsaturated monomer, as a metal oxide compound, an alkoxide compound of silicon and / or an alkoxide compound of a different metal other than silicon, Alternatively, a composite gradient material formed using a mixture and / or a reaction product thereof with a hydrolysis-condensation polymer, wherein the above-mentioned different metal components are substantially uniformly mixed, is suitable for the purpose. The present inventors have found that the present invention has been completed based on this finding.

That is, the present invention provides (1) a composite in which an organic polymer compound and a metal oxide compound are chemically bonded, and the content of the metal component is continuous from the surface of the material in the depth direction. An organic-inorganic composite gradient material having a component gradient structure that changes gradually, as the organic polymer compound,
(A) an ethylenically unsaturated monomer having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule;
A compound obtained by copolymerizing an ethylenically unsaturated monomer containing no metal is used, and (c) a silicon alkoxide compound and / or a hydrolyzed polycondensate thereof (d) is used as the metal oxide-based compound. A) a mixture and / or reaction product of an alkoxide compound of a different metal other than silicon and / or a hydrolyzed polycondensate thereof, and wherein the different metal components are substantially uniformly mixed with each other; An organic-inorganic composite gradient material, (2) a coating agent characterized by forming a coating made of the organic-inorganic composite gradient material on a substrate, and (3) an organic-inorganic composite. A structure having a coating made of a gradient material.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The organic-inorganic composite gradient material of the present invention is an organic-inorganic composite material including a composite obtained by chemically bonding an organic polymer compound and a metal oxide compound, preferably the composite , Having a component gradient structure in which the content of a metal component in the material continuously changes in the depth direction from the material surface. The metal component is composed of a substantially homogeneous mixed metal oxide compound having different metal elements.

Such a composition gradient structure can be confirmed, for example, by sputtering the surface of a coating film of an organic-inorganic composite gradient material provided on a substrate made of an organic material, and shaving the film to form a film over time. The measurement can be performed by measuring the content of carbon atoms and metal atoms on the surface by X-ray photoelectron spectroscopy or the like. Specifically, FIG. 1 shows an organic-inorganic composite material having a thickness of 71 nm provided on a polyethylene terephthalate film (including silicon atoms and titanium atoms as metal atoms in Example 1 described later). Is a graph showing the relationship between the sputtering time and the contents of carbon atoms, silicon atoms and titanium atoms in the coating film consisting of), and as can be seen from this figure, the surface of the coating film before sputtering is almost 100%.
However, as the film is eroded by sputtering, the content of titanium and silica atoms decreases continuously, and the content of carbon atoms decreases. Increase, organic components appear,
From the point in time when the sputtering time exceeds 25 minutes, the film surface contains almost only organic components. That is, it is shown that, in this graded material, the content of the metal component composed of two substantially homogeneous mixed metal oxide-based compounds in the material gradually decreases from the surface toward the substrate.

The content of the mixed metal component in such a gradient material is not particularly limited, but is usually 5 to 98% by weight, preferably 20 to 98% by weight, and particularly preferably 50 to 98% by weight in terms of metal oxide. It is in the range of 90% by weight. The degree of polymerization and the molecular weight of the organic polymer compound are not particularly limited as long as they can form a film, and may be appropriately selected according to the type of the polymer compound, desired coating film properties, and the like.

The mixed metal component contains a silicon atom and one or more other kinds of foreign metal atoms. As the foreign metal atom, titanium, zirconium and aluminum are preferable. The content of atoms is preferably in the range of 5 to 95 mol% based on the total amount of metal atoms. If the content is less than 5 mol%, the effect of improving adhesion and durability due to the introduction of dissimilar metal atoms will not be sufficiently exhibited, and if it exceeds 95 mol%, the film will be hardened, the flexibility will be reduced, and cracks will occur. May occur. In consideration of adhesion, flexibility, and the like, the more preferable content of the dissimilar metal atom is in the range of 20 to 80 mol%.

Further, the gradient material of the present invention preferably has a thickness of 5 μm or less, particularly in the range of 0.01 to 1.0 μm, from the viewpoint of the gradient and the coating film performance. Such an organic-inorganic composite gradient material can be efficiently produced by the following method.

First, (A) (a) an ethylenically unsaturated unit having a metal-containing group capable of bonding to a metal oxide by hydrolysis (hereinafter sometimes referred to as a hydrolyzable metal-containing group) in a molecule. Obtained by copolymerizing a monomer and (b) an ethylenically unsaturated monomer containing no metal, and (B)
A coating liquid containing a mixture and / or a reaction product of (c) an alkoxide compound of silicon and / or a hydrolyzed condensation polymer thereof and (d) an alkoxide compound of a different metal other than silicon and / or a hydrolysis and condensation polymer thereof. Is prepared.

The ethylenically unsaturated monomer having a hydrolyzable metal-containing group (A) or (a) is a compound represented by the following general formula (I):

[0023]

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(Wherein 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, and R ² is a hydrolyzable group or a non-hydrolyzable group, at least one of which is hydrolyzed to form (B)
Must be a component chemically bonded may hydrolyzable group, and when R ² is plural, each R ² may be mutually identical or different, M ¹ is silicon, titanium, zirconium, a metal atom such as aluminum, m is the valence of the metal atom M ^1. )).

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

Examples of the metal-containing group represented by -M ¹ R ² _m-1 in the general formula (I) include, for example, trimethoxysilyl, triethoxysilyl, tri-n-propoxysilyl, and triisopropoxy. Silyl group, tri-n-butoxysilyl group, triisobutoxysilyl group, tri-se
c-butoxysilyl group, tri-tert-butoxysilyl group, trichlorosilyl group, dimethylmethoxysilyl group,
Methyldimethoxysilyl group, dimethylchlorosilyl group,
Methyldichlorosilyl group, triisocyanatosilyl group,
Methyldiisocyanatosilyl group, etc., trimethoxy titanium group, triethoxy titanium group, tri-n-propoxy titanium group, triisopropoxy titanium group, tri-n-butoxy titanium group, triisobutoxy titanium group, tri-sec- Butoxy titanium group,
Tri-tert-butoxytitanium group, trichlorotitanium group, further, trimethoxyzirconium group, triethoxyzirconium group, tri-n-propoxyzirconium group, triisopropoxyzirconium group, tri-
n-butoxyzirconium group, triisobutoxyzirconium group, tri-sec-butoxyzirconium group, tri-tert-butoxyzirconium group, trichlorozirconium group, and further, dimethoxyaluminum group, diethoxyaluminum group, di-n-propoxy Examples include an aluminum group, a diisopropoxyaluminum group, a di-n-butoxyaluminum group, a diisobutoxyaluminum group, a di-sec-butoxyaluminum group, a di-tert-butoxyaluminum group, and a trichloroaluminum group. One type of the ethylenically unsaturated monomer as the component (a) may be used alone, or two or more types may be used in combination.

On the other hand, the metal-free ethylenically unsaturated monomer as the component (b) includes, for example, a compound represented by the following general formula (I)
I)

[0028]

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(Wherein R ³ is a hydrogen atom or a methyl group,
X is a monovalent organic group. ), Preferably an ethylenically unsaturated monomer represented by the general formula (II-a)

[0030]

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(Wherein, R ³ is the same as described above, and R ⁴ represents a hydrocarbon group) or an ethylenically unsaturated monomer represented by the general formula (II) General formula (III) as a water-soluble unsaturated monomer and an adhesion improver optionally added

[0032]

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(Wherein R ⁵ is a hydrogen atom or a methyl group,
R ⁶ represents an epoxy group, a mercapto group, a halogen atom or a hydrocarbon group having an ether bond. )) And a mixture with the ethylenically unsaturated monomer represented by the formula (1).

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

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

In the ethylenically unsaturated monomer represented by the general formula (III), the epoxy group, hydroxyl group, mercapto group, amino group, halogen atom or hydrocarbon group having an ether bond represented by R ⁶ may be: , Having 1 to 1 carbon atoms
10 linear or branched alkyl groups, having 3 to 3 carbon atoms
Preferred are a cycloalkyl group having 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. The halogen atom of the above substituent is preferably a chlorine atom or a bromine atom, and the amino group may be any of a free amino group, a monoalkyl-substituted amino group, and a dialkyl-substituted amino group. Specific examples of the hydrocarbon group include the same thing as the groups exemplified in the description of R ⁴ in the above general formula (II).

Examples of the ethylenically unsaturated monomer represented by the general formula (III) include a monomer represented by the general formula (II-a), specifically, glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate,
2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Mercaptoethyl (meth) acrylate, 3-mercaptopropyl (meth) acrylate, 2-mercaptopropyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-aminopropyl (meth) ) Acrylate, 2
-Dimethylaminoethyl (meth) acrylate, 4-dimethylaminobenzyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-bromoethyl (meth) acrylate and the like can be preferably mentioned, but in addition to these, styrene, α -Methylstyrene, α
-Acetoxystyrene, m-, o- or p-bromostyrene, m-, o- or p-chlorostyrene, m-,
o- or p-vinylphenol, 1- or 2-vinylnaphthalene, or the like 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 (II) and the ethylenically unsaturated monomer represented by the general formula (III) are used in combination, the former ethylenically unsaturated monomer is used. For the saturated monomer, the latter ethylenically unsaturated monomer is 1 to
It is preferable to use 100 mol%. (A)
Radical copolymerization of an ethylenically unsaturated monomer having a hydrolyzable metal-containing group as a component and a metal-free ethylenically unsaturated monomer as a component (b) in the presence of a radical polymerization initiator As a result, a desired copolymer is obtained.

On the other hand, examples of the silicon alkoxide compound in the component (c) of the component (B) include, for example, a silicon compound having at least two alkoxyl groups having 1 to 6 carbon atoms. Silanes are preferred. Specific examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n
-Butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane and the like, which may be used alone or 2
A combination of more than one species may be used.

The alkoxide compound of a different metal other than silicon in the component (d) of the component (B) includes, for example, at least 2 alkoxyl groups having 1 to 6 carbon atoms.
Titanium compounds, zirconium compounds, and aluminum compounds having two or more carbon atoms can be exemplified, and tetraalkoxytitanium, tetraalkoxyzirconium, and trialkoxyaluminum are particularly preferable. Here, examples of tetraalkoxy titanium include tetramethoxy titanium,
Tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra-sec-
Butoxytitanium, tetra-tert-butoxytitanium and the like, as examples of tetraalkoxyzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetraisobutoxy Zirconium, tetra-se
Examples of c-butoxyzirconium, tetra-tert-butoxyzirconium and the like are trialkoxyaluminums such as trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum and tri-n-butoxyaluminum. -Isobutoxyaluminum, tri-sec
-Butoxyaluminum, tri-tert-butoxyaluminum and the like. These different metal alkoxide compounds may be used alone or in combination of two or more.

The component (B) in the present invention comprises the above-mentioned hydrolyzed condensation polymer of the silicon alkoxide compound as the component (c) and the hydrolysis and condensation of the alkoxide compound of a different metal other than silicon as the component (d). A mixture and / or a reaction product with a polymer, and the method for preparing the component (B) includes: (1) at least one selected from the group consisting of an alkoxide compound of silicon, a partial hydrolyzate of the compound, and a condensate thereof. One type (hereinafter referred to as silicon alkoxide or partial hydrolyzate / condensate thereof) and at least one selected from alkoxide compounds of different metals other than silicon, partial hydrolyzate of the compound and condensate thereof ( Hereinafter, referred to as a heterometallic alkoxide or a partial hydrolysis / condensate thereof)).
Or (2) silicon alkoxide or its partial hydrolysis
Condensate, different metal alkoxide and its partial hydrolysis
After condensates are separately hydrolyzed and condensed,
A preferred method is to mix both.

In the above method (1), first, silicon alkoxide or its partial hydrolysis / condensate and heterometal alkoxide or its partial hydrolysis / condensation are dissolved in an appropriate polar solvent such as alcohol, ketone or ether. And the like, so that the content of the dissimilar metal is in the range of preferably 5 to 95 mol%, more preferably 20 to 80 mol%, based on the total amount of the metal, and then acid such as hydrochloric acid, sulfuric acid, nitric acid, etc. Alternatively, using a cation exchange resin as a solid acid, co-hydrolytic polycondensation is carried out usually at a temperature of -10 to 70 ° C, preferably 10 to 40 ° C, preferably for 5 minutes or more. And the component (B) is prepared. At this time, if the cohydrolysis-condensation polymerization reaction time is too short, the metal components in the gradient material are not uniformly mixed with each other, which may cause phase separation or extreme component unevenness. It is desirable to carry out decomposition polycondensation.

On the other hand, in the method (2), the silicon alkoxide and its partial hydrolysis / condensate and the heterometallic alkoxide and its partial hydrolysis / condensate are separately separated from each other by alcohol, ketone, ether, etc. In an appropriate polar solvent, an acid such as hydrochloric acid, sulfuric acid, nitric acid, or a cation exchange resin as a solid acid is used.
Hydrolysis-condensation polymerization is carried out at a temperature of 0 to 70 ° C, preferably 10 to 40 ° C, and when a solid acid is used, it is removed and used for preparing the component (B). Then, both
The content of the dissimilar metal is preferably 5 based on the total amount of the metal.
~ 95 mol%, more preferably 20-80 mol%, preferably mixed and stirred for 5 minutes or more,
(B) Prepare the component. At this time, if the mixing and stirring time is too short, the respective metal components in the gradient material are not uniformly mixed with each other, and there is a possibility of forming a gradient structure.
It is desirable to mix and stir for 5 minutes or more.

The coating liquid is prepared by mixing the component (B) and the copolymer of the component (A). The timing of mixing the component (A) with the component (B) is as follows. There is no particular limitation, and when the component (B) is prepared by the method (1), the component (A) may be added to the mixed solution before the hydrolysis-condensation polymerization reaction is performed, or the hydrolysis-condensation may be performed. The component (A) may be added to the polymerization reaction solution. In the case of preparing the component (B) by the method (2), the component (A) may be added to any of the components before the hydrolysis-condensation polymerization reaction is performed, or the respective hydrolysis-condensation polymerization may be performed. Before mixing the polymerization reaction solution,
During the process, the component (A) may be added later. The copolymer of the component (A) may be added in a solid form or a solution form. The solid content concentration in the coating liquid thus prepared is not particularly limited as long as the coating liquid has a viscosity at which the coating liquid can be applied.

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

As the organic substrate, for example, an acrylic resin such as polymethyl methacrylate, polystyrene or A
Styrene resins such as BS resin, olefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as 6-nylon and 6,6-nylon, polyvinyl chloride resins, Examples of the base material include polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins, polyimide resins, and cellulose resins such as cellulose acetate.

These organic base materials can be subjected to a surface treatment by an oxidation method or a concavo-convex method, if desired, in order to further improve the adhesion to the gradient material of the present invention.
Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet method), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and examples of the unevenness method include a sand blast method and a solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of the base material.

In the present invention, the organic base material is applied to the surface of a base material made of a material other than an organic material, for example, a metal material, a glass or ceramic material, or other various inorganic or metal materials. Those having a membrane are also included.

In the organic-inorganic composite gradient material of the present invention thus obtained, the surface layer contains almost 100% of the metal component in the material, but gradually decreases in the direction of the base material. It becomes almost 0% near the base material. The metal component is composed of a substantially homogeneous mixed metal oxide compound having different metal elements.

That is, the organic-inorganic composite gradient material of the present invention generally comprises a film-like material formed on a substrate, and the surface of the film-like material in contact with the substrate is substantially organic. The other open system surface is a polymer compound component and is a metal oxide compound component.

As an inorganic component, titanium, which generally has higher reactivity than an alkoxide compound of silicon,
Since zirconium and an alkoxide compound of a different metal such as aluminum are used in combination with the alkoxide compound of silicon, even in a dry gel state, it has excellent mechanical strength,
In addition, since an inorganic layer in which the metals are uniformly mixed with each other and the film is densified is formed, a composite gradient material having excellent adhesion to a substrate and durability can be obtained, and the composite gradient material is acceptable. It has good flexibility and is less likely to crack.

The present invention also provides a coating agent for forming a coating comprising the organic-inorganic composite gradient material on a substrate. Examples of the coating agent include a copolymer having a hydrolyzable metal-containing group as the component (A) and a hydrolysis-condensation polymer of a silicon alkoxide compound and a heterometallic alkoxide compound as the component (B). What consists of a coating liquid containing a mixture and / or a reactant is used.

This coating agent can be used for the following purposes. First, it is used for application as a coating film.
Since the organic-inorganic composite gradient material has excellent adhesiveness to an organic substrate and the surface of a coating film has the property of a metal oxide, for example, a coating layer made of the material is provided on various plastic films. Thereby, it is possible to obtain a hard coat film having excellent scratch resistance and heat resistance, as well as good adhesion.

Next, it is used for application as an adhesive.
As described above, the graded material of the present invention has excellent adhesion to an organic base material and has excellent adhesion to an inorganic or metal material because its surface is a metal oxide compound. Therefore, it is suitable as an adhesive between an organic material and an inorganic or metal material.

Further, it is used as an intermediate film interposed between an organic base material and a coat layer containing at least an inorganic or metallic material. When forming a coating layer containing an inorganic or metal-based material on an organic substrate, generally the adhesion between the organic substrate and the coating layer is insufficient, poor in durability, peeled over time, Alternatively, there is a problem that the film is easily peeled off by heat or moisture.

By using the gradient material of the present invention as an intermediate film and interposing it between the organic substrate and the coat layer containing an inorganic or metallic material, the intermediate film has the gradient as described above. From the excellent adhesion to the organic substrate, and also excellent adhesion to the coating layer containing an inorganic or metal-based material provided thereon, as a result, the inorganic or metal-based material on the organic substrate Can be formed with extremely good adhesion. In the present invention,
The thickness of the interlayer is usually 5 μm or less, preferably 0.0 μm.
1 to 1.0 μm, more preferably 0.02 to 0.7 μm
Range.

The coat layer containing the inorganic or metal material is not particularly limited, and various coat layers can be formed. For example, (1) a photocatalytic active material layer,
(2) an inorganic or metallic conductive material layer, (3) a hard coat layer containing an inorganic or metallic material, (4) an inorganic or metallic optical recording material layer or an inorganic or metallic dielectric layer, etc. Are preferred.

Next, the coat layer containing each inorganic or metal material will be described. (1) Photocatalytic active material layer: When a coat layer of a photocatalytic active material such as titanium dioxide is provided on the surface of an organic base material, the photocatalytic action causes a problem that the organic base material is deteriorated 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 via an inorganic binder which is hardly deteriorated by photocatalysis. However, there is a problem that the inorganic binder has insufficient adhesion to an organic base material and is inferior in durability.

When the gradient material of the present invention is used as an intermediate film and is interposed between the organic base material and the coat 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 coat layer of the photocatalytically active material, and the intermediate film is not easily degraded by the photocatalytic action, so that the organic substrate can be sufficiently protected. Examples of the organic substrate include building materials such as sound insulation walls and windows, signboards, films and the like.

Further, the gradient material of the present invention can be interposed as an intermediate film between a metal base having an organic coating film on the surface and the photocatalytic active material layer. This intermediate film has excellent adhesion with an organic coating film, and has good adhesion with a coating layer of a photocatalytically active material, as well as the organic base material, and is hardly deteriorated by a photocatalytic action. The coating film can be sufficiently protected. Such a use is particularly useful when a photocatalytically active material layer is provided on a steel sheet for automobiles having an organic coating film on the surface.

Examples of the metal base material having an organic coating film on its surface include metal base materials such as cold-rolled steel sheets, galvanized steel sheets, aluminum / zinc alloy-plated steel sheets, stainless steel sheets, aluminum sheets, and aluminum alloy sheets. An organic coating film can be used. When the gradient material of the present invention is used as such an intermediate film, it is particularly effective when the coating layer of the photocatalytically active material provided thereon is titanium dioxide having a high photocatalytic ability.

(2) Inorganic or metallic conductive material layer:
Organic substrates having a conductive material layer on the surface, particularly plastic films, are used for electroluminescence devices (EL devices), liquid crystal display devices (LCD devices), solar cells, etc., and further include electromagnetic wave shielding films and antistatic films. It is used as Examples of the conductive material used in such applications include metal oxides such as indium oxide, tin oxide, zinc oxide, cadmium oxide, and ITO (indium tin oxide); gold, platinum, silver, nickel, aluminum, and copper. Inorganic or metallic conductive materials such as metals as described above are used. And these inorganic or metallic conductive materials are usually formed on an organic substrate such as a plastic film by a known means such as a vacuum deposition method, a sputtering method, and an ion plating method.
It is formed as a thin film having a thickness of about 50 to 2000 angstroms.

Since the inorganic or metallic conductive material layer thus formed has insufficient adhesion to the organic base material, the gradient material of the present invention is used as an intermediate film to form the organic base material and the organic base material. By interposing between the inorganic or metal-based conductive material layer, the adhesion between the organic base and the inorganic or metal-based conductive material layer can be improved. Further, even when a transparent conductive film is required, transparency is hardly impaired by interposing the intermediate film made of the gradient material of the present invention.

(3) Hard coat layer containing inorganic or metallic material: A hard coat film having a good surface hardness and excellent scratch resistance and abrasion resistance is, for example, a vehicle,
It is widely used for attaching surfaces such as window glass of buildings and plastic boards for windows, and for protecting CRT displays and flat panel displays.

On the other hand, plastic lenses have been rapidly spread in recent years because they are lighter in weight and more excellent in safety, processability, fashionability and the like than glass lenses. However, this plastic lens has a drawback that it is easily damaged as compared with a glass lens, and therefore, its surface is coated with a hard coat layer.

Examples of the material of the hard coat layer provided on such a hard coat film or a plastic lens include a mixture of alkyltrihydroxysilane and its partial condensate, colloidal silica and a silicon-modified acrylic resin, and organotrialkoxysilane. Inorganic or metallic materials such as a mixture of a hydrolysis condensate, a mixture of an alkoxysilane hydrolysis condensate and colloidal silica, a zirconium, a metal selected from aluminum and titanium and a chelate compound and a silicon-modified acrylic resin. Hard coating agents are frequently used.

To form a hard coat layer on an organic substrate such as a plastic film or a plastic lens,
The hard coat agent containing the inorganic or metal-based material, using a known method such as a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, a gravure coat method, a spray coat method, or the like. A method of applying the composition on an organic substrate so that the dry film thickness is about 1 to 30 μm and performing a drying treatment is usually used.

Since the thus formed hard coat layer containing an inorganic or metallic material has insufficient adhesion to an organic substrate, the hard coat layer containing the gradient material of the present invention is used as an intermediate film to form an organic substrate. By interposing the hard coat layer between the organic base material and the hard coat layer containing an inorganic or metallic material, the adhesion between the organic base material and the hard coat layer containing an inorganic or metallic material can be improved. Further, in the plastic lens, even if an intermediate film made of the inclined material of the present invention is interposed, it hardly causes a decrease in the transparency of the plastic lens or the generation of interference fringes.

(4) Inorganic or metallic optical recording material layer or inorganic or metallic dielectric layer: In recent years, rewritable, high-density, large-capacity storage capacity, non-contact with recording / reproducing head, etc. Uses a phase change from a magneto-optical disk or crystal to amorphous using an optical recording medium that records information using the magnetization reversal of the magnetic film using the heat energy of a semiconductor laser beam or the like and uses the magneto-optical effect to read. Phase change disks have been developed and are now in practical use.

Such an optical recording medium is generally formed by forming an optical recording material layer, a dielectric layer, a metal reflective layer, an organic protective layer on a light-transmitting resin substrate (organic substrate), for example, a substrate such as polycarbonate or polymethyl methacrylate. It has a structure in which layers are sequentially laminated, and a dielectric underlayer may be provided between the substrate and the optical recording material layer in some cases.

The optical recording material layer provided on the substrate includes, for example, Tb-Fe, Tb-Fe-Co, Dy-Fe-C
o, inorganic magneto-optical recording materials such as Tb-Dy-Fe-Co, or TeOx, Te-Ge, Sn-Te-
Ge, Bi-Te-Ge, Sb-Te-Ge, Pb-S
An inorganic phase change recording material such as n-Te or Tl-In-Se is used. If desired, the dielectric underlayer provided between the substrate and the optical recording material layer may include, for example, S
Inorganic materials such as iN, SiO, SiO ₂ and Ta ₂ O ₅ are used. The inorganic optical recording material layer and the dielectric underlayer are usually formed by a known means such as a vacuum evaporation method, a sputtering method, and an ion plating method.

Since the inorganic or metallic optical recording material layer or the inorganic dielectric underlayer formed as described above has insufficient adhesion to the translucent resin substrate, the gradient material of the present invention is not used. As an intermediate film, by interposing between a light-transmitting resin substrate and the optical recording material layer or the dielectric underlayer,
Adhesion between the substrate and the optical recording material layer or the dielectric underlayer can be improved.

Other coating layers containing inorganic or metallic materials include titanium oxide, zinc oxide, indium oxide, tin oxide, zinc sulfide, and antimony-doped tin oxide (AT
O), an inorganic infrared absorbing layer such as tin-doped indium oxide (ITO), and a magnetic layer on which metal is deposited.

The present invention further provides a structure having a coating made of the above-mentioned organic-inorganic composite gradient material. As such a structure, for example, an organic substrate having a coat layer containing at least an inorganic or metal material, with the organic-inorganic composite gradient material of the present invention interposed as an intermediate film,
Alternatively, the organic-inorganic composite gradient material of the present invention is interposed as an intermediate film, and has a photocatalytically active material layer, such as a metal base material provided with an organic coating film on its surface. An article having a coat layer interposed as a film and containing at least an inorganic or metal material can be given.

As a specific example of the article, a coat layer containing at least an inorganic or metal material is composed of (1) a photocatalytic active material layer, (2) an inorganic or metal conductive material layer, and (3)
A hard coat layer containing an inorganic or metal material, and
(4) An inorganic or metallic optical recording material layer or an inorganic or metallic dielectric layer can be preferably exemplified.

[0076]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The properties of the films formed in each example were determined according to the following methods. (1) Gradient Argon sputtering (4 kV) using an XPS apparatus “PHI-5600” (manufactured by ULVAC-PHI, Inc.)
Was performed at intervals of 3 minutes to scrape the film, the content of carbon atoms and metal atoms on the film surface was measured by X-ray photoelectron spectroscopy, and the inclination was examined.

(2) Flexibility Using a stainless steel rod having a diameter of 6 mm, bending the coated surface to the outside and holding it for 10 seconds, observe the bent portion with an optical microscope to check for cracks or peeling. Flexibility was evaluated according to the following criteria. ：: No cracking or peeling occurred. ×: Cracking is observed.

(3) Adhesion According to JIS K5400, 100 square grids of 1 mm square were attached with a rotary cutter, and a cellotape (manufactured by Nichiban, registered trademark) was pressed and then 30,000 m
A 90 degree peel test was performed at a speed of m / min. 10
The adhesion was evaluated by counting the number of remaining films in 0 cells.

(4) Photocatalyst Durability On the organic-inorganic composite gradient material, as a photocatalyst layer, a 10-weight-fold diluted solution of isopropanol of "Vistrator L NSC-200C" manufactured by Nippon Soda Co., Ltd. at 1500 rpm,
A test sample was obtained by spin coating for 0 second and aging at 80 ° C. for 1 hour. After that, JIS B
A durability test of the coating film was performed by an accelerated weathering test using a carbon arc lamp type sunshine weather meter (Sunshine Weather Meter S300, manufactured by Suga Test Instruments Co., Ltd.) according to 7753, surface state observation after the acceleration test, haze value of the test piece. (Haze) measurement and water contact angle measurement were used to evaluate the durability of the photocatalyst.

The haze value was measured according to JIS K7361 by a haze meter “NDH2000” manufactured by Nippon Denshoku Co., Ltd.
And 5% at which transparency was impaired was used as a guide for evaluation. In addition, water contact angle measurement was performed using ultraviolet light of 2 mW / cm ² for ² hours.
It was performed after irradiation for an hour, and whether or not superhydrophilicity (5 ° or less) was developed was used as a guideline for evaluation.

In the photocatalytic durability test, when the substrate was polyethylene terephthalate (hereinafter abbreviated as PET) or polycarbonate (hereinafter abbreviated as PC), the acrylic resin was subjected to an accelerated weathering test for 600 hours. In this case, the evaluation was performed after 1500 hours of the same test.

Examples 1 to 3 (1) Preparation of Inorganic Component Liquid 12 g of titanium tetraisopropoxide and 10 g of ethanol
A mixed solution of 5 g of ethanol, 2.5 g of concentrated hydrochloric acid, and 0.5 g of water was added dropwise to the mixed solution of 5 g in a water bath, stirred, and reacted at room temperature for 5 hours to prepare an inorganic component liquid. Separately, to a mixed solution of 12 g of tetraethoxysilane and 10 g of ethanol, a mixed solution of 5 g of ethanol, 0.1 ml of a 1 mol / liter nitric acid aqueous solution and 12.5 g of water was dropped and stirred in a water bath, and then stirred at room temperature. The reaction was carried out for a time to prepare an inorganic component liquid.

(2) Preparation of Organic Component Solution 0.1 g of 2,2'-azobisisobutyronitrile was dissolved in a mixed solution of 10.9 g of methyl methacrylate and 1.36 g of 3-methacryloxypropyltrimethoxysilane. After that, the mixture was reacted at 75 ° C. for 3 hours with stirring, and gel permeation chromatography (GP
The weight average molecular weight in terms of polystyrene by the method C) is about 6
Ten thousand copolymers were obtained. 0.1 g of this copolymer was dissolved in 10 ml of acetone to prepare an organic component solution having a concentration of 10 g / liter.

(3) Preparation of Coating Liquid and Evaluation of Film Using acetone and ethanol as diluents, each component was mixed at a ratio shown in Table 1, and stirred at 25 ° C. for 10 minutes to prepare a coating liquid. . Next, a 50 μm thick PET film “Tetron HB3” [Teijin DuPont Film Co., Ltd.
The above coating solution was spin-coated at 1500 rpm for 20 seconds and dried at 80 ° C. overnight to obtain a coating solution as shown in Table 2.
Films having different titania contents with respect to silica having the film thickness shown in Table 2 were formed.

Table 2 shows the evaluations of the adhesion, flexibility and photocatalytic durability of each film.
FIG. 3 is a graph showing the relationship between the sputtering time and the contents of carbon atoms, titanium atoms, and silicon atoms.

From FIGS. 1 to 3, it was confirmed that titania and silica were present in a uniformly dispersed state and had a gradient. In addition, each of them showed good adhesion, good flexibility, no cracks were observed, and in the photocatalytic durability test, the surface condition was good even after 600 hours of the accelerated weathering test, and the haze value was 5%. Keeps transparency below, and water contact angle is 5 °
The super hydrophilicity was shown below.

Example 4 (1) Preparation of Inorganic Component Liquid A mixed solution of 6 g of titanium tetra-n-butoxide, 4 g of tetraethoxysilane and 10 g of ethanol, and 5 g of ethanol, 2.5 g of concentrated hydrochloric acid and 0.5 g of water Was dropped in a water bath and stirred, and reacted at room temperature for 5 hours to prepare an inorganic component liquid having a titania content of about 50% by mole relative to silica.

(2) Preparation of Coating Solution and Evaluation of Film Using the organic component solution prepared in (2) of Examples 1 to 3 and the inorganic component solution prepared in (1) above, the ratio shown in Table 1 was used. After mixing each component and preparing a coating liquid in the same manner as in (3) of Examples 1 to 3, a film having a thickness shown in Table 2 was formed on a PET film.

Table 2 shows the evaluation of the adhesion, flexibility and photocatalytic durability of the film.
2 is a graph showing the relationship between the sputtering time and the contents of carbon atoms, titanium atoms and silicon atoms. From FIG. 4, it was confirmed that titania and silica were present in a uniformly dispersed state and had a gradient. In addition, this film showed good adhesion, good flexibility, no cracks were observed, and in the photocatalytic durability test, the surface condition was good even after 600 hours of the accelerated durability test, and the haze value was 5 % Or less, and showed superhydrophilicity at a water contact angle of 5 ° or less.

Example 5 (1) Preparation of Inorganic Component Solution A mixed solution of 2 g of zirconium tetra-n-propoxide, 5 g of tetraethoxysilane and 6 g of ethanol was mixed with 2.5 g of ethanol, 1.5 g of concentrated hydrochloric acid and 0.1 g of water. The mixture was dropped and stirred in a water bath, and reacted at room temperature for 5 hours. The zirconia content relative to silica was about 5% by mole.
A 0% inorganic component liquid was prepared.

(2) Preparation of Coating Solution and Evaluation of Film Using the organic component solution prepared in (2) of Examples 1 to 3 and the inorganic component solution prepared in (1) above, the ratio shown in Table 1 was used. After mixing each component and preparing a coating liquid in the same manner as in (3) of Examples 1 to 3, a film having a thickness shown in Table 2 was formed on a PET film.

Table 2 shows the evaluation of the adhesion, flexibility and photocatalytic durability of the film.
2 is a graph showing the relationship between the sputtering time and the contents of carbon atoms, zirconium atoms, and silicon atoms.
From FIG. 5, it was confirmed that zirconia and silica were present in a uniformly dispersed state and had a gradient. In addition, this film shows good adhesion, good flexibility, and no cracks.
Even after the elapse of time, the surface condition was good, transparency was maintained at a haze value of 5% or less, and super hydrophilicity was exhibited at a water contact angle of 5 ° or less.

Example 6 (1) Preparation of Inorganic Component Solution A mixed solution of 1.5 g of aluminum tri-sec-butoxide, 5 g of tetraethoxysilane and 6 g of ethanol was mixed with 2.5 g of ethanol, 1.5 g of concentrated hydrochloric acid and 0.1 g of water. After dropping and stirring 1 g of the mixed solution in a water bath, the mixture was allowed to react at room temperature for 5 hours.
A 0% inorganic component liquid was prepared.

(2) Preparation of Coating Liquid and Evaluation of Film Using the organic component solution prepared in (2) of Examples 1 to 3 and the inorganic component liquid prepared in (1) above, the ratio shown in Table 1 was used. After mixing each component and preparing a coating liquid in the same manner as in (3) of Examples 1 to 3, a film having a thickness shown in Table 2 was formed on a PET film.

Table 2 shows the evaluation of the adhesion, flexibility and photocatalytic durability of the film.
2 is a graph showing the relationship between the sputtering time and the contents of carbon atoms, aluminum atoms, and silicon atoms.
From FIG. 6, alumina and silica are present in a uniformly dispersed state,
And it was confirmed that it had a gradient. In addition, this film showed good adhesion, good flexibility, no cracks were observed, and in the photocatalytic durability test, the surface condition was good even after 600 hours of the accelerated durability test, and the haze value was 5 % Or less, and showed superhydrophilicity at a water contact angle of 5 ° or less.

Example 7 Example 1 was repeated except that a 2 mm thick acrylic resin sheet (Acrylite L, manufactured by Mitsubishi Rayon Co., Ltd.) was used as the base material.
A film having the thickness shown in Table 2 was formed on the acrylic resin sheet in the same manner as in Example 1. Table 2 shows the evaluation of the adhesion and photocatalytic durability of the film, and FIG. 7 shows the relationship between the sputtering time and the contents of carbon atoms, titanium atoms and silicon atoms in a graph. From FIG. 7, it was confirmed that titanium and silica were present in a uniformly dispersed state and had a gradient. Further, this film shows good adhesion to the acrylic resin sheet, and in the photocatalytic durability test, the surface condition is good even after the lapse of 1500 hours of the accelerated weathering test, and the transparency is maintained at a haze value of 5% or less. And a water contact angle of 5 ° or less, indicating super hydrophilicity.

Example 8 A film having a thickness shown in Table 2 was formed on a PC sheet in the same manner as in Example 1 except that a PC sheet having a thickness of 5 mm (Polycaace, manufactured by Tsutsunaka Plastics Industry Co., Ltd.) was used as the base material. Formed. Table 2 shows the evaluation of the adhesion and photocatalytic durability of the film, and FIG. 8 shows the relationship between the sputtering time and the contents of carbon atoms, titanium atoms, and silicon atoms with respect to the gradient. From FIG. 8, it was confirmed that titanium and silica were present in a uniformly dispersed state and had a gradient. Further, this film shows good adhesion to the PC sheet, and in the photocatalytic durability test, the surface condition is good even after 600 hours of the accelerated weathering test, and the transparency is maintained at a haze value of 5% or less. And water contact angle showed super hydrophilicity at 5 ° or less.

Comparative Example 1 The procedure of Examples 1 to 3 (3) was repeated except that only the inorganic component liquid was used as the inorganic component liquid and the components were mixed at the ratios shown in Table 1. After preparing a coating liquid in the same manner as in 3), a film having a thickness shown in Table 2 was formed on the PET film. Table 2 shows the evaluation of the adhesion, flexibility and photocatalytic durability of the film. FIG. 9 is a graph showing the relationship between the sputtering time and the contents of carbon atoms and titanium atoms for the gradient. . This film had good adhesion and photocatalytic durability, but cracking was observed in the flexibility test.

Comparative Example 2 The procedure of Examples 1 to 3 (3) was repeated except that only the inorganic component liquid was used as the inorganic component liquid and the components were mixed at the ratios shown in Table 1. After preparing a coating liquid in the same manner as in 3), a film having a thickness shown in Table 2 was formed on the PET film. Table 2 shows the evaluation of adhesion, flexibility and photocatalytic durability of the film, and FIG. 10 shows the relationship between the sputtering time and the contents of carbon atoms and silicon atoms in a graph for the gradient. . Although this film did not show any cracks in the flexibility test, it had poor adhesion and peeling of the coating film was observed in the photocatalytic durability.

Comparative Example 3 Coating was performed in the same manner as in (3) of Examples 1 to 3, except that the components were mixed in the proportions shown in Table 1 and stirred for 30 seconds. After preparing the working solution, a film having a thickness shown in Table 2 was formed on the PET film. The evaluation of the adhesion, flexibility and photocatalytic durability of this film is shown in Table 2, and regarding the gradient, FIG. 11 shows the relationship between the sputtering time and the content of carbon, titanium and silicon atoms. Shown in a graph. It was found from FIG. 11 that this film had a three-component two-gradient structure of silica / titania / carbon in order from the film surface side. In addition, no crack was observed in the flexibility test, but the adhesion and photocatalytic durability were poor.

Comparative Example 4 Comparative Example 2 was repeated except that a 2 mm thick acrylic resin sheet (Acrylite L, manufactured by Mitsubishi Rayon Co., Ltd.) was used as the base material.
A film having the thickness shown in Table 2 was formed on the acrylic resin sheet in the same manner as in Example 1. Table 2 shows the evaluation of the adhesion and photocatalytic durability of the film, and FIG.
The graph shows the relationship between the sputtering time and the content of carbon atoms and silicon atoms. This film had poor adhesion to the acrylic resin and poor photocatalytic durability.

Comparative Example 5 A film having a thickness shown in Table 2 was formed on a PC sheet in the same manner as in Comparative Example 2, except that a PC sheet having a thickness of 5 mm (Polyca Ace, manufactured by Tsutsunaka Plastics Industry Co., Ltd.) was used as the base material. Formed. Table 2 shows the evaluation of the adhesion and the photocatalytic durability of the film, and FIG. 13 shows the relationship between the sputtering time and the contents of carbon atoms and silicon atoms in the graph. This film had poor adhesion to PC and poor photocatalytic durability.

[0104]

[Table 1]

[0105]

[Table 2]

(Note 1) Acrylic resin and PC are not measured because they are on the sheet. (Note 2) PET and PC are 600 hours after accelerated weathering test, and acrylic resin is 1500 hours after the same test.

[0107]

The organic-inorganic composite gradient material of the present invention has the following properties:
It has a component gradient structure in which the content of at least one kind of substantially homogeneous mixed metal component changes continuously in the thickness direction of the material, and has excellent adhesion and durability to the base material and good flexibility. It has no cracks or cracks and is useful for various applications as a functional material.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the sputtering time and the content of carbon, silicon and titanium atoms in an organic-inorganic composite film obtained in Example 1.

FIG. 2 is a graph showing the relationship between the sputtering time and the content of carbon, silicon and titanium atoms in the organic-inorganic composite film obtained in Example 2.

FIG. 3 is a graph showing the relationship between the sputtering time and the content of carbon, silicon and titanium atoms in the organic-inorganic composite film obtained in Example 3.

4 is a graph showing the relationship between the sputtering time and the content of carbon, silicon and titanium atoms in the organic-inorganic composite film obtained in Example 4. FIG.

FIG. 5 is a graph showing the relationship between the sputtering time and the content of carbon, silicon and zirconium atoms in the organic-inorganic composite film obtained in Example 5.

FIG. 6 is a graph showing the relationship between the sputtering time and the content of carbon, silicon and aluminum atoms in the organic-inorganic composite film obtained in Example 6.

7 is a graph showing the relationship between the sputtering time and the content of carbon, silicon and titanium atoms in the organic-inorganic composite film obtained in Example 7. FIG.

FIG. 8 is a graph showing the relationship between the sputtering time and the content of carbon, silicon and titanium atoms in the organic-inorganic composite film obtained in Example 8.

FIG. 9 is a graph showing the relationship between the sputtering time and the content of carbon atoms and titanium atoms in the organic-inorganic composite film obtained in Comparative Example 1.

FIG. 10 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in the organic-inorganic composite film obtained in Comparative Example 2.

11 is a graph showing the relationship between the sputtering time and the content of carbon, silicon, and titanium atoms in the organic-inorganic composite film obtained in Comparative Example 3. FIG.

12 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in the organic-inorganic composite film obtained in Comparative Example 4. FIG.

FIG. 13 is a graph showing the relationship between the sputtering time and the content of carbon atoms and silicon atoms in the organic-inorganic composite film obtained in Comparative Example 5.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 183/04 C09D 183/04 185/00 185/00 // C08F 220/04 C08F 220/04 (72) Inventor Kazuyuki Takami 2-1-1 Yabuta Nishi, Gifu City, Gifu Prefecture Ube Nitto Kasei Co., Ltd. (72) Inventor Norihiro Nakayama 2-1-1 Yabuta Nishi, Gifu City, Gifu Prefecture Ube Nitto Kasei Co., Ltd. F-term (reference) 4F100 AA17A AA21C AH08 AK01A AK04A AK25 AK42 AK52A AL01A AR00C AT00B BA03 BA07 BA10B BA10C BA44A EH46 EJ42 EJ86 JK17 JL08C JL11 YY00A 4G069 AA01 AA03 AA08 AA11 BA04A BA04B BA22A BA22B BA27A BA27B BB04A BB04B BC16A BC50A BC51A BD05A DA06 EA11 ED03 EE06 FA03 FB02 4J038 CL001 CL002 DL031 DL032 DM021 DM022 GA03 GA07 GA09 GA12 GA13 HA066 HA216 KA08 KA12 MA08 MA10 NA11 NA12 PA19 PB01 PB07 PB09 PB10 PC02 PC03 PC08 4J100 AB00Q AB02Q AB03Q AB07Q AB08Q AB09Q AL03Q AL04Q AL08P AL08Q AL09Q AL10Q BA03Q BA04P BA10Q BA29Q BA42P BA52Q BA71P BA77P BA80H BA93P BA95P BA96P BB01P BB01Q BB03 HC04 HC78 BC43

Claims (11)

[Claims] 1. A component gradient structure including a complex in which an organic polymer compound and a metal oxide compound are chemically bonded, and in which the content of a metal component continuously changes in the depth direction from the surface of the material. An organic-inorganic composite gradient material having: (A) an ethylenically unsaturated monomer having a metal-containing group capable of bonding to a metal oxide by hydrolysis in the molecule; b) a compound obtained by copolymerizing a metal-free ethylenically unsaturated monomer with (c) a silicon alkoxide compound and / or a hydrolyzed polycondensate thereof as the metal oxide-based compound; (D) an alkoxide compound of a different metal other than silicon and / or a mixture thereof with a hydrolyzed polycondensate and / or
Alternatively, an organic-inorganic composite gradient material formed by using a reactant, wherein the dissimilar metal components are substantially uniformly mixed with each other. 2. The organic-inorganic composite gradient material according to claim 1, which has a thickness of 5 μm or less. 3. The organic-inorganic composite gradient material according to claim 1, wherein the alkoxide compound of a different metal other than silicon is at least one selected from alkoxide compounds of titanium, zirconium and aluminum. 4. The organic-inorganic composite gradient material according to claim 1, wherein the content of the different metal atom other than the silicon atom is 5 to 95 mol% based on the total amount of the metal atom. 5. A film composed of a film formed on an organic substrate, and the surface of the film in contact with the organic substrate is substantially an organic polymer compound component, and the other The organic-inorganic composite gradient material according to any one of claims 1 to 4, wherein the open system surface is a metal oxide-based compound component. 6. A coating agent, wherein a coating comprising the organic-inorganic composite gradient material according to claim 1 is formed on a substrate. 7. The coating agent according to claim 6, which is used for forming an intermediate film interposed between the organic base material and the photocatalytic active material layer. 8. The coating agent according to claim 7, wherein the photocatalytically active material layer is a coating film containing titanium dioxide. 9. A structure comprising a coating made of the organic-inorganic composite gradient material according to claim 1. Description: 10. The structure according to claim 9, having a coating made of an organic-inorganic composite gradient material on an organic substrate. 11. The structure according to claim 10, wherein a photocatalytically active material layer is provided on the organic base material via a coating made of an organic-inorganic composite gradient material.