JP2001316635A - Coating material for forming organic-inorganic composite gradated film and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating material capable of forming an organic-inorganic composite gradated film having a component gradation structure which continuously varies the content of an inorganic component in the direction of thickness of the film simply and with high reliability even in hand coating or hand spray coating. SOLUTION: This coating material for forming an organic-inorganic composite gradated film comprises a composite obtained by chemically binding an organic polymeric compound with a metal oxide based compound and uses, as the solvent, a mixed solvent of (a) a good solvent to the above organic polymeric compound and (b) a poor solvent to the organic polymeric compound, the solvent of component (b) being more difficult to dry than the solvent of component (a) and having a lower vapor pressure at 20 deg.C than water.

Description

DETAILED DESCRIPTION OF THE INVENTION

TECHNICAL FIELD The present invention relates to a coating agent for forming an organic-inorganic composite gradient film and a method for producing the same. More specifically, the present invention relates to an organic-inorganic composite film containing a chemical bond of an organic polymer compound and a metal oxide compound, wherein the content of the metal oxide compound is in the thickness direction of the film. An organic-inorganic composite gradient film that has a continuously changing component gradient structure, high transparency, and is useful for various applications as a functional material can be easily and reliably formed by hand coating or manual spray coating. The present invention relates to a coating agent capable of forming a film and a method for producing the same.

2. Description of the Related Art Conventionally, layers composed of various inorganic or metallic materials, for example, photocatalytically active materials, conductive materials, hard coat agents, optical recording materials, magnetic powders, infrared absorbing materials, etc., have been provided on organic substrates. Production of functional materials is widely performed. When such an inorganic or metal material layer is provided on an organic base material, the adhesion to the base material is generally insufficient.For example, an inorganic primer layer is provided on an organic base material. A method of forming an inorganic or metal material layer on the substrate is often used. However, in this method, although the adhesion between the inorganic primer layer and the inorganic or metal material layer is good, the adhesion between the organic base material and the inorganic primer layer is not always sufficient, Inferior or poor adhesion over time. In addition, WO97 / 00
No. 134 discloses a method of improving the adhesiveness to an inorganic substance stepwise through a plurality of adhesive layers on an organic substrate. However, in this method, the operation is complicated and the transparency may be impaired. Therefore, development of a technique for forming an inorganic or metal material layer on an organic substrate with good adhesion has been desired. Under such circumstances, the present inventors have previously described various uses as a novel functional material, for example, a coating film, an adhesive between an organic material and an inorganic or metal material, an organic substrate and a photocatalyst. Thickness useful for applications such as an intermediate film that is provided between the coating film and 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. An organic-inorganic composite gradient material whose composition continuously changes in the direction has been found (Japanese Patent Application No. 11-264592). 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 continuously increases in the thickness direction of the material. It is a novel material that has a variable component gradient structure and is extremely useful for the various applications described above. However, in such graded materials, the concentration of the organic polymer compound contained in the coating solution and the amount of coating on the substrate are precisely controlled in order to form the polymer using the ability of the polymer to adsorb to the substrate. It is important to optimize it. By the way, the manual spray coating method and the method of forming a thin film by hand coating using a brush or the like do not require a large-scale film forming machine, are extremely simple, and have advantages such as being not limited to the shape of the base material. have. When the organic-inorganic composite gradient film is formed by such a manual spray coating method or manual coating, it is difficult to precisely optimize the amount of application on the base material, so that coating unevenness occurs. There have been cases where problems such as insufficient inclination have occurred.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and is directed to an organic-inorganic composite film containing a chemical bond of an organic polymer compound and a metal oxide compound.
An organic-inorganic composite gradient film having a component gradient structure in which the content of the metal oxide compound continuously changes in the thickness direction of the film, having high transparency, and being useful as a functional material for various applications,
Even in hand coating and manual spray coating,
An object of the present invention is to provide a coating agent that can easily and reliably form a film.

Means for Solving the Problems The present inventors have intensively studied to develop a coating agent having the above-mentioned excellent functions, and as a result, as a solvent, two kinds of solvents having specific properties were combined. It has been found that the purpose can be achieved by using a mixed solvent, and the present invention has been completed based on this finding. That is, the present invention
(1). On an organic substrate, a complex in which an organic polymer compound and a metal oxide compound are chemically bonded is contained, and the content of the metal oxide compound continuously changes from the film surface in the depth direction. A coating agent for forming an organic-inorganic composite gradient film having a component gradient structure,
(A) A mixed solvent comprising a good solvent for the organic polymer compound used for the coating agent and (b) a poor solvent for the organic polymer compound is used, and the solvent of the component (b) is a solvent of the component (a). Less dry than 20 ℃
In, a coating agent for forming an organic-inorganic composite gradient film, the vapor pressure of which is lower than the vapor pressure of water,
And (2). A mixture of (A) an organic polymer compound having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule and (B) a metal compound capable of forming a metal oxide by hydrolysis is subjected to hydrolysis treatment. A method for producing a coating agent for forming an organic-inorganic composite gradient film on an organic substrate, wherein: (a) a good solvent for the organic polymer compound; and (b) a good solvent for the organic polymer compound. A mixed solvent comprising a poor solvent is used, and the solvent of the component (b) is harder to dry than the solvent of the component (a), and at a temperature of 20 ° C., its vapor pressure is lower than that of water. And a method for producing a coating agent for forming an organic-inorganic composite gradient film.

BEST MODE FOR CARRYING OUT THE INVENTION An organic-inorganic composite gradient film formed on an organic substrate by the coating agent of the present invention comprises:
An organic-inorganic composite film containing a composite formed by chemically bonding an organic polymer compound and a metal oxide compound, preferably an organic-inorganic composite film comprising the composite, wherein the metal oxide in the film It has a component gradient structure in which the content of the system compound changes continuously from the film surface in the depth direction. To confirm such a component gradient structure, for example, the surface of an organic-inorganic composite gradient film provided on an organic substrate is sputtered to scrape the film, and the carbon atoms and metal atoms on the film surface with time. Can be carried out by measuring the content of the compound by X-ray photoelectron spectroscopy or the like. The gradient film having a thickness of 5 μm or less, particularly in the range of 0.01 to 1.0 μm, is suitable from the viewpoint of the gradient and the coating film performance. The content of the metal oxide compound in the gradient film is not particularly limited, but is usually 5 to 98% by weight, preferably 20 to 98% by weight, particularly preferably 50 to 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 coating agent of the present invention that forms such an organic-inorganic composite gradient film can be efficiently produced by the method of the present invention described below. In the method of the present invention, (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 a molecule; (B) A coating agent is produced by subjecting a mixture with a metal compound capable of forming a metal oxide by hydrolysis (hereinafter sometimes referred to as a hydrolyzable metal compound) to hydrolysis treatment. As the metal in the metal-containing group capable of bonding to the metal oxide by hydrolysis in the organic polymer compound as the component (A) and the metal in the metal compound capable of forming the metal oxide by hydrolysis as the component (B), For example, at least one selected from silicon, titanium, zirconium and aluminum can be preferably mentioned. Examples of the organic polymer compound of the component (A) include (a) an ethylenically unsaturated monomer having a hydrolyzable metal-containing group in the molecule and (b) an ethylenically unsaturated monomer containing no metal. Those obtained by copolymerization with a body can be preferably used. As the ethylenically unsaturated monomer having a hydrolyzable metal-containing group as the component (A) or (A), a compound represented by the general formula (I)

Embedded image (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, and R ² is a hydrolyzable group or a non-hydrolyzable group. One needs to be a hydrolyzable group capable of chemically bonding to the component (B) by hydrolysis.
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 a metal atom M ¹ Is the valence of )). In the general 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 oxyhalogen 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 a trimethoxysilyl group, a triethoxysilyl group, a tri-n-propoxysilyl group, a triisopropoxysilyl group, Tri-n-butoxysilyl group, triisobutoxysilyl group, tri-sec-butoxysilyl group, tri-tert-butoxysilyl group, trichlorosilyl group, dimethylmethoxysilyl group, methyldimethoxysilyl group, dimethylchlorosilyl group, methyl Dichlorosilyl group, triisocyanatosilyl group, methyldiisocyanatosilyl group, etc., trimethoxytitanium group, triethoxytitanium group, tri-n-propoxytitanium group, triisopropoxytitanium group, tri-n-butoxytitanium group, Triisobutoxy titanium group, tri-s ec-butoxytitanium 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 furthermore, dimethoxyaluminum group, diethoxyaluminum group, di-n-propoxyaluminum Group, diisopropoxy aluminum group, di-
n-butoxyaluminum group, diisobutoxyaluminum group, di-sec-butoxyaluminum group, di-t
tert-butoxyaluminum group, trichloroaluminum group and the like. One of the ethylenically unsaturated monomers of component (A) may be used alone, or two or more of them 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 general formula (II):

Embedded image (Wherein, R ³ is a hydrogen atom or a methyl group, and X is a monovalent organic group.)

Embedded image (Wherein, R ³ is the same as described above, and R ⁴ represents a hydrocarbon group.) Or an ethylenically unsaturated monomer represented by the above general formula (II) A monomer represented by the general formula (III):

Embedded image (Wherein, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an epoxy group, a hydroxyl group, a mercapto group, an amino group, a halogen atom, or a hydrocarbon group having an ether bond.) And a mixture with a monomer. 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, Preferable 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 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 a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cyclooctyl group.
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 (II) include the general formula (II-
monomer represented by a), specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth)
Acrylates and the like can be preferably mentioned. In addition to these, styrene, α-methylstyrene, α-acetoxystyrene, m-, o- or p-bromostyrene, m-, o- or p-chlorostyrene, m- , O-
Alternatively, p-vinylphenol, 1- or 2-vinylnaphthalene, or the like can be used. These may be used alone or in combination of two or more.
In the ethylenically unsaturated monomer represented by the general formula (III), an epoxy group, a hydroxyl group, a mercapto group, an amino group, a halogen atom or a hydrocarbon group having an ether bond represented by R ⁶ has a carbon number of A linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms,
And preferably 10 to 10 aralkyl groups.
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 as those groups exemplified in the description of R ⁴ in the above general formula (II-a). Examples of the ethylenically unsaturated monomer represented by the general formula (III) include 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-
Examples include aminopropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 4-dimethylaminobenzyl (meth) acrylate, 2-chloroethyl (meth) acrylate, and 2-bromoethyl (meth) acrylate, which are used alone. May be used,
Two or more kinds may be used in combination. Further, the ethylenically unsaturated monomer represented by the general formula (II) and the general formula (I
When the ethylenically unsaturated monomer represented by II) is used in combination, the latter ethylenically unsaturated monomer is used in a proportion of 1 to 100 mol% with respect to the former ethylenically unsaturated monomer. It is preferably used. The ethylenically unsaturated monomer having a hydrolyzable metal-containing group of the component (A) and the metal-free ethylenically unsaturated monomer of the component (B) are subjected to radical polymerization in the presence of a radical polymerization initiator. By copolymerizing,
The desired copolymer is obtained. The component (B) a metal compound capable of forming a metal oxide by hydrolysis is as the (hydrolyzable metal compound), for example, the general formula _{^{(IV) M 2 R 7 n}} ... (IV) ( wherein, ^{R 7} Is a hydrolyzable group or a non-hydrolyzable group, at least two are hydrolyzable groups, and at least one is a hydrolyzable group capable of chemically bonding to the component (A) by hydrolysis. A plurality of R ⁷ may be the same or different, M ² is a metal atom such as silicon, titanium, zirconium, and aluminum, and n is a valence of the metal atom M ² . )). Examples of the hydrolyzable group in R ⁷ in the general formula (IV) include an alkoxyl group, a halogen atom such as a chlorine atom, an oxyhalogen group, an acetylacetonate group, and an isocyanate group. Preferred examples of the functional group include a lower alkyl group, an aryl group, and an alkenyl group. As the hydrolyzable metal compound, an oligomer derived from the metal compound represented by the general formula (IV) or a mixture of a plurality of metal compounds represented by the general formula (IV) can be used. . As the metal compound represented by the general formula (IV), a metal alkoxide is particularly preferable. Examples of this metal alkoxide include tetramethoxysilane, tetraethoxysilane,
Tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraisocyanate silane, methyltrimethoxysilane, methyltriethoxy Silane, dimethyldimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltriisocyanatesilane, phenyltriisocyanatesilane, etc. And their corresponding tetraalkoxytitanium, trialkoxytitanium, dialkoxytitanium and tetraalkoxyzirconium, trialco Shi zirconium, dialkoxy zirconium, more trimethoxy aluminum, triethoxy aluminum, tri -n- propoxy aluminum, tri-isopropoxy aluminum, tri -n- butoxy aluminum, tri iso-butoxy aluminum,
Tri-sec-butoxyaluminum, tri-tert
Metal alkoxides such as butoxyaluminum, or metal alkoxide oligomers, for example, commercially available alkoxysilane oligomers such as “methyl silicate 5
1 "and" Ethylsilicate 40 "(both are trade names manufactured by Colcoat). These may be used alone or in combination of two or more. In the present invention, a mixture of the organic polymer compound having a hydrolyzable metal-containing group of the component (A) and the hydrolyzable metal compound of the component (B) is mixed in a polar solvent such as alcohol, ketone, or ether. In the above, a coating agent is produced by a hydrolysis treatment, and the following solvent is used as the solvent. That is, the solvent used in the present invention,
A mixed solvent of (a) a good solvent for the organic polymer compound and (b) a poor solvent for the organic polymer compound, wherein the solvent of the component (b) is dried more than the solvent of the component (a). And at a temperature of 20 ° C., its vapor pressure must be lower than that of water. In addition, temperature 2
The vapor pressure of water at 0 ° C. is 172 Pa. As the good solvent for the organic polymer compound as the component (a), those having a solubility of the organic polymer compound at a temperature of 20 ° C. of 5.0 g / liter or more are preferable.
As the poor solvent for the organic polymer compound as the component (b), those having a solubility of less than 5.0 g / liter at a temperature of 20 ° C. are preferable. The good solvent is at least twice the polymer concentration in the solution actually adjusted with respect to the saturation concentration of the polymer component, while the poor solvent has the saturation concentration of the polymer component actually increased. It is preferable that the concentration is not higher than the polymer concentration in the adjusted solution. The polymer concentration to be actually adjusted is obtained from the adsorption isotherm of the solution, and varies depending on the combination of the solvents. Therefore, it is difficult to strictly define the numerical value, but it is approximately 3 g / liter or less. It is operationally preferable that the poor solvent has a saturated concentration of the polymer component of 3 g.
/ Liter or less, and the good solvent preferably has a saturated concentration of the polymer component of 6 g / liter or less. Further, at a temperature of 20 ° C., the vapor pressure of the solvent of the component (a) is preferably at least twice the vapor pressure of the solvent of the component (b). The use ratio of the component solvent (a) and the component solvent (b) is not particularly limited, but is usually 90: 1 by volume ratio.
0 to 10:90, preferably 70:30 to 3
0:70, more preferably 60:40 to 40:60
Range. By using such a mixed solvent, it is possible to form a coating film having high reliability and good gradient even without manual coating or manual spray coating. The reason will be described in detail in the “action” described later.
Examples of the solvent of the component (a) include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as ethylene glycol monoethyl ether, esters such as ethyl acetate and butyl acetate, and aromatics such as xylene and toluene. Among the hydrocarbons, chlorinated hydrocarbons such as 1,2-dichloroethane, and the like, those that satisfy the above requirements can be appropriately selected and used. The solvent of the component (a) may be used alone or in combination of two or more. On the other hand, as the solvent of the component (b), for example, 1-propanol, 1-butanol, 1-butanol,
Among the medium or higher alcohols such as hexanol and ethers such as ethylene glycol monobutyl ether, those satisfying the above requirements can be appropriately selected and used. As the solvent of the component (b), one kind may be used, or two or more kinds may be used in combination. When producing the coating agent of the present invention, for example, first, the above (a)
The organic polymer compound of the component (A) is dissolved at an arbitrary concentration in the solvent of the component to prepare a polymer compound solution.
On the other hand, in the solvent of the component (b), the hydrolyzable metal compound of the component (B) is dissolved at an optional concentration, and an acid such as hydrochloric acid, sulfuric acid, nitric acid, or a cation exchange resin as a solid acid is used. Usually 0-100 ° C, preferably 20-6
Hydrolysis at a temperature of 0 ° C., and when a solid acid is used, after removing it, mixing it with the polymer compound solution, further hydrolyzing, and then subjecting the solvent to The coating agent of the present invention can be obtained by adjusting the viscosity to a level suitable for coating by distilling off or adding.
If the hydrolysis treatment temperature is too low, the hydrolysis reaction does not proceed, and if it is too high, the hydrolysis and polycondensation reaction proceeds too quickly, making it difficult to control, and as a result, the gradient of the obtained gradient film decreases. There is a possibility that. Further, the organic polymer compound (A) and the hydrolyzable metal compound (B) are dissolved in a mixed solvent of the solvent (a) and the solvent (b). May be added to carry out hydrolysis treatment to prepare the coating agent of the present invention. Depending on the type of the inorganic component, even after the preparation of the coating agent, hydrolysis and polycondensation may gradually progress and the application conditions may fluctuate. Therefore, a solid dehydrating agent insoluble in the coating agent, such as anhydrous magnesium sulfate, etc. By adding, a reduction in pot life can be prevented. In this case, the coating agent is used for application after removing the dehydrating agent. Next, using the coating agent thus obtained, on an organic substrate, the thickness of a dried coating film, usually 5 μm or less, particularly as an intermediate film, preferably 0.01 to 1.0 μm, more preferably Is 0.02
Hand coating with a brush or the like, or a manual spray coating method, or a dip coating method, a spin coating method, a spray coating method, so as to be in a range of about 0.7 μm.
A coating film is formed by a known means such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, and a known drying treatment, for example, heating and drying at a temperature of about 40 to 150 ° C. By performing the treatment, a desired organic-inorganic composite gradient film can be obtained simply and with high reliability. In the thus formed organic-inorganic composite gradient film, the content of the metal oxide compound in the film is almost 100% on the surface, but gradually decreases in the direction of the substrate, and in the vicinity of the substrate, It has a structure of almost 0%, and has a uniform surface state and a gradient without reflection of coating spots at the time of application. The organic substrate is not particularly limited, for example, acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and ABS 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, polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins,
Substrates made of a polyimide resin, a cellulose resin such as cellulose acetate, and the like can be given. These base materials can be subjected to a surface treatment by an oxidation method, a roughening method, or the like, if desired, in order to further improve the adhesion to the inclined film. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet method), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of the base material. In addition, the organic substrate in the present invention has a material other than the organic material, for example, a metal-based material, a glass or ceramic-based material, and a surface of a substrate made of other various inorganic or metal-based materials, having an organic-based coating film. Also encompasses The organic-inorganic composite gradient film thus obtained has the excellent gradient as described above,
(1) a property of relieving stress caused by thermal shrinkage or physical expansion and contraction of a base material and an inorganic film, (2) a refractive index changes continuously, and (3) a mixing ratio of an inorganic component and an organic component is arbitrary and simple. It is useful for various uses as a new functional material because it has properties such as the ability to control its gradient and the ability to control the surface structure during film formation by the form of inorganic components. . The coating agent of the present invention can be used, for example, for the following applications. First, it is used for application as a coating film. The organic-inorganic composite gradient film is excellent in adhesiveness to an organic substrate, and since the coating film surface has the properties of a metal oxide or a metal nitride, the film is formed of the gradient film on various plastic films, for example. By providing the coat layer, a hard coat film having excellent abrasion resistance, heat resistance, and the like and good adhesion can be obtained. Next, it is used for use as an adhesive. As described above, the gradient film according to the present invention has excellent adhesion to the organic base material, and also has excellent adhesion to inorganic or metal materials because the surface is a metal-based compound. Therefore, it is suitable as an adhesive between an organic material and an inorganic or metal material. Further, it is used for an intermediate film interposed between an organic base material and a coat layer containing at least an inorganic or metal material. When forming a coat layer containing an inorganic or metal material on an organic base material, there is generally insufficient adhesion between the organic base material and the coat layer,
There is a problem that the durability is poor and the film is peeled off with time or easily peeled off due to heat or moisture. By providing the gradient film according to the present invention as an intermediate film, by interposing between the organic base material and the coat layer containing an inorganic or metal material, the intermediate film has a gradient as described above, It has excellent adhesion to the organic base material and also has excellent adhesion to the coating layer containing an inorganic or metal material provided thereon, and as a result, contains the inorganic or metal material on the organic substrate The coat layer can be formed with extremely good adhesion. The coating layer containing the inorganic or metal material is not particularly limited, and various coating layers can be formed. For example, (1) a photocatalytic active material layer, and (2) an inorganic or metal conductive material. Preferred examples include a layer, (3) a hard coat layer containing an inorganic or metallic material, and (4) an inorganic or metallic optical recording material layer or an inorganic or metallic dielectric layer. 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 film according to the present invention is used as an intermediate film and is interposed between the organic base material and the coat layer of the photocatalytic active material,
It has excellent adhesion to organic substrates and its surface is almost a metal compound, so it has good adhesion to the photocatalytically active material coat layer, and the intermediate film is not easily degraded by the photocatalytic action. Can be protected. Further, the gradient film according to the present invention can be interposed between the metal-based substrate having an organic coating film on the surface and the photocatalytic active material layer as an intermediate film. 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 organic 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. One having a film formed thereon can be given. When the gradient film according to the present invention is used as such an intermediate film, it is particularly effective when the coat layer of the photocatalytically active material provided thereon is titanium dioxide having high photocatalytic ability. (2) Inorganic or metallic conductive material layer: An organic substrate having a conductive material layer on its surface, particularly a plastic film, can be used for electroluminescent devices (EL devices), liquid crystal display devices (LCD devices), solar cells, etc. It is used as an electromagnetic wave shielding film and an antistatic film. 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. These inorganic or metallic conductive materials are usually formed on an organic substrate such as a plastic film by a known method such as a vacuum evaporation method, a sputtering method, or an ion plating method to a thickness of 5 μm.
It is formed as a thin film of about 0 to 2000 angstroms. Since the inorganic or metallic conductive material layer formed in this way has insufficient adhesion to the organic substrate, the gradient film according to the present invention is used as an intermediate film, and the organic substrate and the inorganic material are used. Alternatively, the interposition between the organic base material and the inorganic or metal-based conductive material layer can be improved by intervening between the organic base material and the inorganic or metal-based conductive material layer. Further, even when a transparent conductive film is required, transparency is hardly impaired by interposing the intermediate film composed of the gradient film according to the present invention. (3) Hard coat layer containing inorganic or metallic material:
Hard coat films having good surface hardness and excellent scratch resistance and abrasion resistance are used, for example, for adhering to the surface of window glasses and plastic boards for windows of vehicles and buildings, or for CRT displays and flat panel displays. Widely used for protection and the like.
On the other hand, plastic lenses, compared to glass lenses,
In recent years, it has been rapidly spreading because of its light weight and excellent safety, workability, fashionability and the like. 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. As a material of the hard coat layer provided on such a hard coat film or a plastic lens,
For example, a mixture composed of alkyltrihydroxysilane and its partial condensate, colloidal silica, and a silicon-modified acrylic resin, an organotrialkoxysilane hydrolyzed condensate, a mixture of an alkoxysilane hydrolyzed condensate and colloidal silica, zirconium, aluminum, and titanium Hard coating agents containing an inorganic or metal material such as a mixture of a metal selected from the group consisting of a metal, a chelate compound and a silicon-modified acrylic resin are frequently used. In order to form a hard coat layer on an organic substrate such as a plastic film or a plastic lens, a hard coat agent containing the above-mentioned inorganic or metallic material can be formed by a known method, for example, a bar coat method, a knife coat method, or a roll. A coating method, a blade coating method, a die coating method, a gravure coating method, a spray coating method, or the like, is applied to an organic substrate so that a dry film thickness is about 1 to 30 μm, and a method of drying is usually used. Can be The thus formed hard coat layer containing an inorganic or metal material has insufficient adhesion to an organic substrate, and therefore, the gradient film according to the present invention is used as an intermediate film, and the organic substrate and By interposing between the hard coat layer and the hard coat layer, the adhesion between the organic base material and the hard coat layer containing an inorganic or metal material can be improved. Further, in the plastic lens, even if the intermediate film composed of the inclined film according to the present invention is interposed, the transparency of the plastic lens and the occurrence of interference fringes hardly occur. (4) Inorganic or metal-based optical recording material layer or inorganic or metal-based dielectric layer: an optical recording medium having characteristics such as rewritable, high-density, large-capacity storage capacity, and non-contact with a recording / reproducing head in recent years. A phase change using a phase change from a magneto-optical disk or crystal to an amorphous phase by recording information using the magnetization reversal of the magnetic film using the heat energy of a semiconductor laser beam and reading it using the magneto-optical effect Discs have been developed and are now in practical use. Such an optical recording medium generally has an optical recording material layer, a dielectric layer, a metal reflective layer, an organic protective layer, and the like on a translucent resin substrate (organic base material), for example, a substrate such as polycarbonate or polymethyl methacrylate. It has a structure that is sequentially laminated,
In some cases, a dielectric underlayer is provided between the substrate and the optical recording material layer. The optical recording material layer provided on the substrate includes, for example, Tb-Fe, Tb-Fe-Co, Dy-Fe-Co,
Inorganic magneto-optical recording materials such as Tb-Dy-Fe-Co, or TeOx, Te-Ge, Sn-Te-G
e, Bi-Te-Ge, Sb-Te-Ge, Pb-Sn
An inorganic phase change type recording material such as -Te or Tl-In-Se is used. If desired, a dielectric underlayer provided between the substrate and the optical recording material layer may be made of, for example, Si.
Inorganic materials such as N, 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 in this manner has insufficient adhesion to the translucent resin substrate, the gradient film according to the present invention is used as an intermediate film. By interposing between the light-transmitting resin substrate and the optical recording material layer or the dielectric underlayer, the 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, antimony-doped tin oxide (ATO),
Examples include an inorganic infrared absorbing layer such as tin-doped indium oxide (ITO) and a magnetic layer on which metal is deposited.

The composite film formed on the organic substrate using the coating agent of the present invention has a gradient structure because the organic polymer compound in the coating agent is organized through the process of adsorption to the substrate. Because it is done. Therefore, under the condition that the adsorbed polymer compound is not formed with a sufficient thickness, that is, when the concentration of the polymer compound in the solution is low and saturation adsorption has not been reached, a favorable gradient structure is not organized.
FIGS. 1 and 2 are graphs showing one example of the adsorption isotherm of the polymer compound and one example of the concentration dependence of the film thickness of the polymer adsorption layer, respectively. It can be seen that the structure is not organized. On the other hand, in the formation of the adsorptive polymer layer from the dense polymer solution, the gel is formed by the cross-linking reaction with the metal alkoxide due to the rich polymer solution, and the desired gradient structure is not organized. Also, even if the gelation of the components is suppressed in the semi-concentrated solution, a large amount of the remaining polymer compound that did not lead to the formation of the adsorption layer may cause spots through the aggregation process, forming an apparently thick adsorption layer. Although (FIG. 2), it has been found to disrupt the component gradient structure. For these reasons, there is a limit on the amount of the active ingredient, particularly the high molecular weight component, applied per unit area. On the other hand, in manual coating using manual spray coating or brushing, it is undeniable that unevenness in the amount of application to the base material occurs. Although it depends greatly on the skill of the worker, it is generally said that the density ratio of the applied amount is 6 times. As described above, in the film formation, the amount of application (in this case, it is considered to be synonymous with the concentration in consideration of the concentration in the drying process) is severely restricted. Cannot be tolerated. The present invention actively promotes the formation of a polymer adsorption layer during solvent drying,
It is a solution to the above problem. That is, by using a mixed solvent of a solvent (a) that is a good solvent for the polymer compound and is relatively easy to dry and a solvent (b) that is a poor solvent for the polymer compound and is relatively hard to dry, In, the composition ratio of both solvents changes continuously, and the ratio of the solvent (b), which is a poor solvent, to the polymer compound gradually increases. FIG. 3 is a graph showing an example of a change in the solvent composition with drying. From this figure, it can be understood that the ratio of the solvent (b) increases with drying. As shown in FIG. 4, it is clear that the adsorption of the polymer compound is likely to occur even at the lower concentration side due to the poor solvent in the solvent, as shown in FIG. It has the effect of promoting the adsorption of the compound.
FIG. 4 is a graph showing an example of the composition dependence of the adsorption isotherm of a polymer compound. However, the moving speed of the polymer compound in the solvent is never high, and the drying speed of the solvent is preferably low. Although the reason is not clear, it has been empirically shown that a poor solvent having a lower vapor pressure than water is preferable.

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 gradient of the composite film was examined according to the following method. The XPS device “PHI-5” is attached to the composite membrane.
Using "600" [manufactured by ULVAC-FY Inc.], the film was shaved by argon sputtering (2 kV), and the ratio of inorganic components on the film surface was measured by X-ray photoelectron spectroscopy to examine the slope. . Reference Example 1 (1) Preparation of polymer solution Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 11.5
g, and 1.4 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and after stirring well, 2,2'-azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) 0.2 g) was added and dissolved, and reacted at 70 ° C. for 2.5 hours with stirring. After the completion of the reaction, the mixture is cooled to room temperature, and then methyl ethyl ketone (hereinafter sometimes referred to as MEK) as a solvent (a).
And the above polymer 6.
0 g was dissolved to prepare a solution having a concentration of 6.0 g / liter (hereinafter, referred to as a polymer solution). (2) Preparation of inorganic component solution Tetramethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.) 150
g and 100 g of 1-butanol (hereinafter sometimes referred to as 1-BtOH) in a mixed solution of 25 g of concentrated hydrochloric acid and 1-butanol.
A mixed solution with 50 g of BtOH was added dropwise with stirring, and stirring was continued at room temperature for 5 hours. Next, 1-BtOH 68.5
g was added and diluted so that the solid component concentration became 4%, to prepare an inorganic component solution. The solvent used here is referred to as a solvent (b). (3) Formation of Organic-Inorganic Composite Film The polymer solution obtained in the above (1) and the inorganic component solution obtained in the above (2) were mixed in an amount of 40 ml each, and the liquid film amount was reduced to 6 by a bar coating method. The film was adjusted to 0.86 μm. This was designated as Sample 1-1. Next, after mixing the polymer solution obtained in the above (1) and the inorganic component solution obtained in the above (2) by 40 ml each,
K / 1-BtOH mixed solvent (mixing volume ratio 50/50) 1
The solution was diluted 2.7 times by adding 36 ml, and the film was formed by a bar coating method by adjusting the liquid film amount to 18.3 μm. This was designated as Sample 1-2. By heating both samples at 70 ° C. for 12 hours, an organic-inorganic composite film was obtained. The thickness of each of the composite films was about 100 nm. FIG. 5 is a graph showing the relationship between the sputtering time and the inorganic component ratio of these composite films. Reference Example 2 An organic-inorganic composite film was obtained in the same manner as in Reference Example 1, except that ethyl cellosolve was used instead of 1-BtOH. Note that the sample names were Sample 2-1 and Sample 2-2, respectively. The thickness of each of the obtained composite films was about 100 nm. FIG. 6 is a graph showing the relationship between the sputtering time and the inorganic component ratio of these composite films. As shown in FIG. 5 and FIG. 6, it is obvious at a glance that depending on the combination of solvents, there is a case where a sufficiently graded structure is organized even when the concentration is low and a case where it is not. It has been found that both of the solvents used in Reference Example 2 show good solubility in the polymer compound. On the other hand, in Reference Example 1, the solvent (a) having a relatively high volatility was used.
Has a good solubility in high molecular compounds, whereas the solvent (b) having relatively low volatility is difficult to dissolve the high molecular compound. In Reference Example 1, it is considered that the mixing ratio of the solvent (b) continuously increased during the drying of the solvent, and the formation of the adsorption layer was promoted by the synergistic effect with the concentration effect accompanying the volatilization of the solvent. Therefore, in selecting a combination of solvents, a solvent having good solubility and high volatility for the polymer compound, and a poor solvent for the polymer compound and a solvent having low volatility are mixed to form a gradient structure. It is expected to be promoted. Example 1 In the same manner as in Preparation of Sample 1-2 in Reference Example 1, the obtained coating liquid was diluted 2.7-fold, and the spray amount was reduced to 24 ml / min using a spray nozzle. , And manually applied on the polymethacrylate substrate once at a speed of about 12 m / min to form a film.
Heat drying treatment was performed at 12 ° C. for 12 hours to form an organic-inorganic composite film. The thickness of the obtained composite film was about 70 nm.
Table 1 shows the evaluation results of the performance of the composite membrane. Example 2 An organic-inorganic composite film was formed in the same manner as in Example 1, except that methyl isobutyl ketone was used as the solvent (a). The thickness of the obtained composite film was about 70 nm. Table 1 shows the evaluation results of the performance of the composite membrane. Comparative Example 1 An organic-inorganic composite film was formed in the same manner as in Example 1, except that methanol was used as the solvent (b). The thickness of the obtained composite film was about 70 nm. Table 1 shows the evaluation results of the performance of the composite membrane. Comparative Example 2 An organic-inorganic composite film was formed in the same manner as in Example 1, except that acetone was used as the solvent (a) and ethanol was used as the solvent (b). The thickness of the obtained composite film was about 70 nm. Table 1 shows the evaluation results of the performance of the composite membrane. Comparative Example 3 An organic-inorganic composite film was formed in the same manner as in Example 1, except that ethyl cellosolve was used as the solvent (b). The thickness of the obtained composite film was about 70 nm. Table 1 shows the evaluation results of the performance of the composite membrane.

[Table 1] 1) MEK: methyl ethyl ketone, MIBK: methyl isobutyl ketone, MeOH: methanol, EtOH: ethanol, 1-BtOH: 1-butanol, EC: ethyl cellosolve 2) Vapor pressure of water at 20 ° C .: 172 Pa 3) Spot: composite membrane The spots were visually observed. 4) Slope: Ten arbitrary points on the composite membrane were selected, the slope was examined according to the above-described method, and evaluated according to the following criteria. ；: All exhibit the same gradient. Δ: Slope is not recognized in part, or the slope is poor overall. X: No inclination was observed at all. 5) Cloudiness: The presence or absence of cloudiness in the composite film was visually observed. From Table 1, it can be seen that the vapor pressure of the solvent (a) is at least twice the vapor pressure of the solvent (b), the solubility of the polymer compound in the solvent (b) is less than 5.0 g / liter, and the solvent ( It can be seen that when the vapor pressure of b) is lower than the vapor pressure of water, a composite film having excellent gradient can be obtained with high reliability even by a manual spray coating method.

The coating agent for forming an organic-inorganic composite gradient film of the present invention is an organic-inorganic composite film containing a chemical bond of an organic polymer compound and a metal oxide compound, wherein the metal oxide Organic-inorganic composite gradient film, which has a component gradient structure in which the content of a compound-based compound changes continuously in the thickness direction of the film, has high transparency, and is useful for various applications as a functional material, can be manually or manually coated. Can be easily and reliably formed by spray coating.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of an adsorption isotherm of a polymer compound.

FIG. 2 is a graph showing an example of the concentration dependence of the thickness of a polymer adsorption layer.

FIG. 3 is a graph showing an example of a change in solvent composition due to drying.

FIG. 4 is a graph showing an example of the composition dependence of a solvent in an adsorption isotherm of a polymer compound.

FIG. 5 is a graph showing the relationship between the sputtering time and the inorganic component ratio in the composite film obtained in Reference Example 1.

FIG. 6 is a graph showing the relationship between the sputtering time and the inorganic component ratio in the composite film obtained in Reference Example 2.

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[Procedure amendment]

[Submission date] July 18, 2000 (2007.1.
8)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

Patent application title: Coating agent for forming organic-inorganic composite gradient film and method for producing the same

[Claims]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a coating agent for forming an organic-inorganic composite gradient film and a method for producing the same. More specifically, the present invention relates to an organic-inorganic composite film containing a chemical bond of an organic polymer compound and a metal oxide compound, wherein the content of the metal oxide compound is in the thickness direction of the film. An organic-inorganic composite gradient film that has a continuously changing component gradient structure, high transparency, and is useful for various applications as a functional material can be easily and reliably formed by hand coating or manual spray coating. The present invention relates to a coating agent capable of forming a film and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, layers composed of various inorganic or metallic materials, for example, photocatalytically active materials, conductive materials, hard coat agents, optical recording materials, magnetic powders, infrared absorbing materials, etc., have been provided on organic substrates. Production of functional materials is widely performed. When such an inorganic or metal material layer is provided on an organic base material, the adhesion to the base material is generally insufficient.For example, an inorganic primer layer is provided on an organic base material. A method of forming an inorganic or metal material layer on the substrate is often used. However, in this method, although the adhesion between the inorganic primer layer and the inorganic or metal material layer is good, the adhesion between the organic base material and the inorganic primer layer is not always sufficient, Inferior or poor adhesion over time.

[0003] In addition, WO97 / 00134 discloses a method of improving the adhesiveness to an inorganic substance in a stepwise manner via a plurality of adhesive layers on an organic substrate. However, in this method, the operation is complicated and the transparency may be impaired. Therefore, development of a technique for forming an inorganic or metal material layer on an organic substrate with good adhesion has been desired.

[0004] Under these circumstances, the present inventors have:
Previously, various applications as a new functional material, such as coatings, adhesives between organic materials and inorganic or metal materials, provided between the organic substrate and the photocatalytic coating, the deterioration of the organic substrate An organic-inorganic composite gradient material whose composition continuously changes in the thickness direction, which is useful for applications such as an intermediate film for preventing or an intermediate film for improving the adhesion between an organic base material and an inorganic or metallic material layer. (Japanese Patent Application No. 11-264592).

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, in such graded materials, the concentration of the organic polymer compound contained in the coating solution and the amount of coating on the substrate are precisely controlled in order to form the polymer using the ability of the polymer to adsorb to the substrate. It is important to optimize it.

The manual spray coating method and the method of forming a thin film by hand coating using a brush or the like do not require a large-scale film-forming machine, are extremely simple, and are not limited to the shape of the base material. It has such advantages. When the organic-inorganic composite gradient film is formed by such a manual spray coating method or manual coating, it is difficult to precisely optimize the amount of application on the base material, so that coating unevenness occurs. There have been cases where problems such as insufficient inclination have occurred.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and is directed to an organic-inorganic composite film containing a chemical bond of an organic polymer compound and a metal oxide compound.
An organic-inorganic composite gradient film having a component gradient structure in which the content of the metal oxide compound continuously changes in the thickness direction of the film, having high transparency, and being useful as a functional material for various applications,
Even in hand coating and manual spray coating,
An object of the present invention is to provide a coating agent that can easily and reliably form a film.

[0008]

Means for Solving the Problems The present inventors have intensively studied to develop a coating agent having the above-mentioned excellent functions, and as a result, as a solvent, two kinds of solvents having specific properties were combined. It has been found that the purpose can be achieved by using a mixed solvent, and the present invention has been completed based on this finding.

That is, the present invention provides (1). On an organic substrate, a complex in which an organic polymer compound and a metal oxide compound are chemically bonded is contained, and the content of the metal oxide compound continuously changes from the film surface in the depth direction. A coating agent for forming an organic-inorganic composite gradient film having a component gradient structure, wherein: (a) a good solvent for the organic polymer compound used in the coating agent; and (b) a poor solvent for the organic polymer compound. A mixed solvent comprising a solvent and a solvent of the component (b), which is more difficult to dry than the solvent of the component (a), and that at a temperature of 20 ° C., its vapor pressure is lower than that of water. Organic-inorganic composite gradient film forming coating agent, and

(2). A mixture of (A) an organic polymer compound having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule and (B) a metal compound capable of forming a metal oxide by hydrolysis is subjected to hydrolysis treatment. A method for producing a coating agent for forming an organic-inorganic composite gradient film on an organic substrate, wherein: (a) a good solvent for the organic polymer compound; and (b) a good solvent for the organic polymer compound. A mixed solvent comprising a poor solvent is used, and the solvent of the component (b) is harder to dry than the solvent of the component (a), and at a temperature of 20 ° C., its vapor pressure is lower than that of water. And a method for producing a coating agent for forming an organic-inorganic composite gradient film.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION An organic-inorganic composite gradient film formed on an organic substrate by the coating agent of the present invention comprises:
An organic-inorganic composite film containing a composite formed by chemically bonding an organic polymer compound and a metal oxide compound, preferably an organic-inorganic composite film comprising the composite, wherein the metal oxide in the film It has a component gradient structure in which the content of the system compound changes continuously from the film surface in the depth direction.

[0012] Such a composition gradient structure can be confirmed by, for example, cutting the film by sputtering the surface of an organic-inorganic composite gradient film provided on an organic substrate, and gradually removing carbon atoms on the film surface. And the content of metal atoms can be measured by X-ray photoelectron spectroscopy or the like. This gradient film has a thickness of 5 μm or less, particularly 0.01 to
Those having a range of 1.0 μm are preferred from the viewpoints of gradient and coating film performance.

The content of the metal oxide compound in the gradient film is not particularly limited, but is usually 5 to 9%.
It is in the range of 8% by weight, preferably 20-98% by weight, particularly preferably 50-90% 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. Such organic-
The coating agent of the present invention for forming an inorganic composite gradient film,
Efficient production can be achieved by the method of the present invention described below.

In the method of the present invention, (A) an organic polymer having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule (hereinafter sometimes referred to as a hydrolyzable metal-containing group). A coating agent is produced by subjecting a mixture of the compound and (B) a metal compound capable of forming a metal oxide by hydrolysis (hereinafter sometimes referred to as a hydrolyzable metal compound) to hydrolysis treatment. As the metal in the metal-containing group capable of bonding to the metal oxide by hydrolysis in the organic polymer compound as the component (A) and the metal in the metal compound capable of forming the metal oxide by hydrolysis as the component (B), For example, at least one selected from silicon, titanium, zirconium and aluminum can be preferably mentioned.

Examples of the organic high molecular compound of the component (A) include (a) an ethylenically unsaturated monomer having a hydrolyzable metal-containing group in the molecule and (b) an ethylenically unsaturated monomer containing no metal. Those obtained by copolymerizing with a saturated monomer can be preferably used. As the ethylenically unsaturated monomer having a hydrolyzable metal-containing group as the component (A) or (A), a compound represented by the general formula (I)

[0016]

Embedded image

(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 a metal atom such as silicon, titanium, zirconium, and aluminum, and m is the valence of the metal atom M ¹ . )).

In the above formula (I), examples of the hydrolyzable group of R ² that 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, triisopropoxy Silyl 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-butoxy titanium group, trichloro titanium group,
Further, 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, or even dimethoxyaluminum group, diethoxyaluminum group, di-n-propoxyaluminum group, diisopropoxyaluminum group, di-n-butoxyaluminum group, diisobutoxyaluminum group, -Sec-butoxyaluminum group, di-tert-butoxyaluminum group, trichloroaluminum group and the like. The ethylenically unsaturated monomer of the component (a) is 1
Species may be used, or two or more 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 general formula (I)
I)

[0021]

Embedded image

(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)

[0023]

Embedded image

(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

[0025]

Embedded image

(Wherein R ⁵ is a hydrogen atom or a methyl group,
R ⁶ is an epoxy group, a hydroxyl group, a mercapto group, an amino group,
It represents 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 a monomer represented by the general formula (II-a), specifically, methyl (meth) acrylate, Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. And styrene, α-methylstyrene, α-acetoxystyrene, m-, o- or p-bromostyrene, and m-, o-.
Alternatively, p-chlorostyrene, m-, o- or p-vinylphenol, 1- or 2-vinylnaphthalene, or the like can be used. These may be used alone,
Two or more kinds may be used in combination.

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 as those groups exemplified in the description of R ⁴ in the above general formula (II-a).

Examples of the ethylenically unsaturated monomer represented by the general formula (III) include glycidyl (meth) acrylate, 3-glycidoxypropyl (meth) acrylate, and 2- (3,4-epoxy). Cyclohexyl) 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. 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%.

The presence of a radical polymerization initiator between the ethylenically unsaturated monomer having a hydrolyzable metal-containing group of component (A) and the metal-free ethylenically unsaturated monomer of component (B) The desired copolymer is obtained by radical copolymerization below. The component (B) a metal compound capable of forming a metal oxide by hydrolysis is as the (hydrolyzable metal compound), for example, the general formula _{^{(IV) M 2 R 7 n}} ... (IV) ( wherein, R ⁷ Is a hydrolyzable group or a non-hydrolyzable group, at least two are hydrolyzable groups, and at least one is a hydrolyzable group capable of chemically bonding to the component (A) by hydrolysis. A plurality of R ⁷ may be the same or different, M ² is a metal atom such as silicon, titanium, zirconium and aluminum, and n is a valence of the metal atom M ² . )).

Examples of the hydrolyzable group of R ⁷ in the general formula (IV) include an alkoxyl group, a halogen atom such as a chlorine atom, an oxyhalogen group, an acetylacetonate group and an isocyanate group. Preferred examples of the non-hydrolysable group include a lower alkyl group, an aryl group, and an alkenyl group. As the hydrolyzable metal compound, an oligomer derived from the metal compound represented by the general formula (IV) or a mixture of plural kinds of the metal compounds represented by the general formula (IV) can be used. .

As the metal compound represented by the general formula (IV), a metal alkoxide is particularly preferable. Examples of the metal alkoxide include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane,
Tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetraisocyanatesilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyl Diethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltriisocyanatesilane, phenyltriisocyanatesilane, etc.
And corresponding tetraalkoxytitanium, trialkoxytitanium, dialkoxytitanium and tetraalkoxyzirconium, trialkoxyzirconium,
Dialkoxyzirconium, further trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum,
Metal alkoxides such as tri-tert-butoxyaluminum, or metal alkoxide oligomers, for example, commercially available alkoxysilane oligomers “methyl silicate 51” and “ethyl silicate 40” (both are trade names manufactured by Colcoat Co., Ltd.) and the like. These may be used alone or in combination of two or more.

In the present invention, the organic polymer compound having a hydrolyzable metal-containing group of the component (A) and the organic polymer compound (B)
A mixture of the component and the hydrolyzable metal compound is hydrolyzed in a polar solvent such as alcohol, ketone, or ether to produce a coating agent. The following solvent is used as the solvent.

That is, the solvent used in the present invention is (a)
A mixed solvent comprising a good solvent for the organic polymer compound and (b) a poor solvent for the organic polymer compound, wherein the solvent of the component (b) is less likely to dry than the solvent of the component (a), and At a temperature of 20 ° C., its vapor pressure needs to be lower than the vapor pressure of water. In addition, temperature 20 ° C
Is 172 Pa.

As a good solvent for the organic polymer compound as the component (a), those having a solubility of the organic polymer compound at a temperature of 20 ° C. of 5.0 g / liter or more are preferable. As a poor solvent for an organic polymer compound, a solvent having a solubility of less than 5.0 g / liter at a temperature of 20 ° C. is preferable.

The above-mentioned good solvent has a saturation concentration of the polymer component which is twice or more the saturation concentration of the polymer component in the solution actually adjusted, while the poor solvent has a saturation concentration of the polymer component. It is preferable that the concentration is not more than the polymer concentration in the solution actually adjusted. The polymer concentration to be actually adjusted is determined from the adsorption isotherm of the solution, and varies depending on the combination of the solvents. Therefore, it is difficult to strictly define the numerical value, but it is approximately 3 g / liter or less. Therefore, it is more preferable that the poor solvent has a saturated concentration of the polymer component of 3 g / liter or less and the good solvent has a saturated concentration of the polymer component of 6 g / liter or less.

At a temperature of 20 ° C., the vapor pressure of the solvent of the component (a) is preferably at least twice the vapor pressure of the solvent of the component (b). The use ratio of the component solvent (a) and the component solvent (b) is not particularly limited.
Usually 90:10 to 10:90, preferably 70: 3
The range is from 0 to 30:70, more preferably from 60:40 to 40:60. By using such a mixed solvent, it is possible to form a coating film having high reliability and good gradient even without manual coating or manual spray coating.
The reason will be described in detail in the “action” described later.

Examples of the solvent of the component (a) include ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as ethylene glycol monoethyl ether, esters such as ethyl acetate and butyl acetate, xylene and toluene. Aromatic hydrocarbons, 1,
Among chlorinated hydrocarbons such as 2-dichloroethane,
Those satisfying the above requirements can be appropriately selected and used. The solvent of the component (a) may be used alone or in combination of two or more.

On the other hand, as the solvent of the component (b), for example, the above-mentioned requirements can be selected from medium and higher alcohols such as 1-propanol, 1-butanol and 1-hexanol and ethers such as ethylene glycol monobutyl ether. Those that satisfy the conditions can be appropriately selected and used. As the solvent of the component (b), one kind may be used, or two or more kinds may be used in combination.

When producing the coating agent of the present invention,
For example, first, the organic polymer compound of the component (A) is dissolved in the solvent of the component (a) at an arbitrary concentration to prepare a polymer compound solution. On the other hand, in the solvent of the component (b), the hydrolyzable metal compound of the component (B) is dissolved at an optional concentration, and an acid such as hydrochloric acid, sulfuric acid, nitric acid, or a cation exchange resin as a solid acid is used. Usually 0-100
C., preferably at a temperature of 20 to 60 ° C., and when a solid acid was used, after removing it, this was mixed with the polymer compound solution, and further subjected to hydrolysis treatment. Then, the coating agent of the present invention can be obtained by adjusting the viscosity to a level suitable for coating by distilling or adding a solvent as necessary. If the hydrolysis treatment temperature is too low, the hydrolysis reaction does not proceed, and if it is too high, the hydrolysis and polycondensation reaction proceeds too quickly, making it difficult to control, and as a result, the gradient of the obtained gradient film decreases. There is a possibility that.

Further, in a mixed solvent of the solvent of the component (a) and the solvent of the component (b), the organic polymer compound of the component (A) and the hydrolyzable metal compound of the component (B) are dissolved. The coating agent of the present invention may be prepared by adding an acid thereto and subjecting it to a hydrolysis treatment. The inorganic components are
Depending on the type of the coating agent, even after the preparation of the coating agent, the hydrolysis and polycondensation may gradually progress and the application conditions may fluctuate. Therefore, a solid dehydrating agent insoluble in the coating agent, such as anhydrous magnesium sulfate, should be added. Thereby, a decrease in pot life can be prevented. in this case,
The coating agent is used for application after removing the dehydrating agent.

Next, using the coating agent thus obtained, a dry coating film having a thickness of usually 5 μm was formed on an organic substrate.
m or less, particularly as an intermediate film, preferably from 0.01 to
1.0 μm, more preferably in the range of 0.02 to 0.7 μm, hand coating with a brush or the like, a manual spray coating method, or a dip coating method,
A coating film is formed by a known means such as a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, and a known drying treatment, for example, 40 to 40 150 ° C
The desired organic-inorganic composite gradient film can be obtained simply and with high reliability by performing the heat drying treatment at about the same temperature.

In the organic-inorganic composite gradient film thus formed, the content of the metal oxide compound in the film is almost 100% on the surface, but gradually decreases in the direction of the base material. In the vicinity of the material, it has a structure of almost 0%, and the coating has no uniform reflection at the time of application, and has a uniform surface state and gradient. The organic substrate is not particularly limited, for example, acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene and ABS 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, polycarbonate resins, polyphenylene sulfide resins, polyphenylene ether resins,
Substrates made of a polyimide resin, a cellulose resin such as cellulose acetate, and the like can be given.

These substrates 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 inclined film. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet),
A flame treatment, a hot air treatment, an ozone / ultraviolet irradiation treatment and the like can be mentioned, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatment methods are appropriately selected according to the type of the base material.

In the present invention, the organic substrate is coated on the surface of a substrate made of a material other than the organic material, for example, a metal material, a glass or ceramic material, or any other inorganic or metal material. Those having a membrane are also included.
The organic-inorganic composite gradient film obtained in this manner has the above-described excellent gradient, and (1) a property of relieving stress due to thermal contraction or physical contraction of the substrate and the inorganic film, 2) The refractive index changes continuously. (3) The gradient can be arbitrarily and easily controlled by the mixing ratio of the inorganic component and the organic component. (4) The surface structure at the time of film formation in the form of the inorganic component. It is useful for various uses as a new functional material because it has properties such as the ability to be controlled.

The coating agent of the present invention can be used, for example, for the following applications. First, it is used for application as a coating film. The organic-inorganic composite gradient film is excellent in adhesiveness to an organic substrate, and since the coating film surface has the properties of a metal oxide or a metal nitride, the film is formed of the gradient film on various plastic films, for example. By providing the coat layer, a hard coat film having excellent abrasion resistance, heat resistance, and the like and good adhesion can be obtained.

Next, it is used for use as an adhesive.
As described above, the gradient film according to the present invention has excellent adhesion to the organic base material, and also has excellent adhesion to inorganic or metal materials because the surface is a metal-based compound. Therefore, it is suitable as an adhesive between an organic material and an inorganic or metal material. Further, it is used for an intermediate film interposed between an organic base material and a coat layer containing at least an inorganic or metal material.

When a coat layer containing an inorganic or metallic material is formed on an organic substrate, the adhesion between the organic substrate and the coat layer is generally insufficient, and the durability is poor. Or peeling is easily caused by heat or moisture. By providing the gradient film according to the present invention as an intermediate film, by interposing between the organic base material and the coat layer containing an inorganic or metal material, the intermediate film has a gradient as described above, It has excellent adhesion to the organic base material and also has excellent adhesion to the coating layer containing an inorganic or metal material provided thereon, and as a result, contains the inorganic or metal material on the organic substrate The coat layer can be formed with extremely good adhesion.

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 film according to the present invention is used as an intermediate film and is interposed between the organic base material and the coat layer of the photocatalytic active material,
It has excellent adhesion to organic substrates and its surface is almost a metal compound, so it has good adhesion to the photocatalytically active material coat layer, and the intermediate film is not easily degraded by the photocatalytic action. Can be protected.

Further, the gradient film according to the present invention can be interposed as an intermediate film between the metal base material having an organic coating film on the surface and the photocatalytic active material layer. This interlayer is
As in the case of the above-mentioned organic base material, the adhesiveness with the organic coating film is excellent, and the adhesiveness with the coating layer of the photocatalytically active material is good. Can be protected. Such applications include:
It is particularly useful when a photocatalytically active material layer is provided on an automotive steel sheet 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 film according to the present invention is used as such an intermediate film, it is particularly effective when the coat layer of the photocatalytically active material provided thereon is titanium dioxide having 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 substrate, the gradient film according to the present invention is used as an intermediate film and By interposing between the inorganic or metallic conductive material layer, the adhesion between the organic base and the inorganic or metallic conductive material layer can be improved. Further, even when a transparent conductive film is required, transparency is hardly impaired by interposing the intermediate film composed of the gradient film according to 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, workability, 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 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 coat 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 base material, the gradient film according to the present invention is used as an intermediate film to form an organic base material. By interposing between the material and the hard coat layer, the adhesion between the organic substrate and the hard coat layer containing an inorganic or metal material can be improved. Further, in the plastic lens, even if the intermediate film composed of the inclined film according to the present invention is interposed, the transparency of the plastic lens and the occurrence of interference fringes hardly occur.

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

Such an optical recording medium is generally provided on a light-transmitting resin substrate (organic substrate), for example, a substrate such as polycarbonate or polymethyl methacrylate, an optical recording material layer, a dielectric layer, a metal reflection layer, an organic protective layer, or the like. 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-Co, Tb-Dy-Fe-Co and other inorganic magneto-optical recording materials, or TeOx, T
e-Ge, Sn-Te-Ge, Bi-Te-Ge, Sb
An inorganic phase change recording material such as -Te-Ge, Pb-Sn-Te, Tl-In-Se, or the like is used. If desired, the dielectric underlayer provided between the substrate and the optical recording material layer may include, for example, SiN, SiO, SiO ₂ , Ta ₂
An inorganic material such as O ₅ is used.

The inorganic optical recording material layer and the dielectric underlayer are usually formed by 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 in this manner has insufficient adhesion to the translucent resin substrate, the gradient film according to the present invention is used as an intermediate film. By interposing between the light-transmitting resin substrate and the optical recording material layer or the dielectric underlayer, the 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, antimony-doped tin oxide (ATO),
Examples include an inorganic infrared absorbing layer such as tin-doped indium oxide (ITO) and a magnetic layer on which metal is deposited.

[0065]

The composite film formed on the organic substrate using the coating agent of the present invention has a gradient structure because the organic polymer compound in the coating agent is organized through the process of adsorption to the substrate. Because it is done. Therefore, under the condition that the adsorbed polymer compound is not formed with a sufficient thickness, that is, when the concentration of the polymer compound in the solution is low and saturation adsorption has not been reached, a favorable gradient structure is not organized.
FIGS. 1 and 2 are graphs showing one example of the adsorption isotherm of the polymer compound and one example of the concentration dependence of the film thickness of the polymer adsorption layer, respectively. It can be seen that the structure is not organized.

On the other hand, in the formation of the adsorbed polymer layer from the concentrated polymer solution, the gel is formed by the cross-linking reaction with the metal alkoxide due to the concentration, so that the desired inclined structure is not organized. . Also, even if the gelation of the components is suppressed in the semi-concentrated solution, a large amount of the remaining polymer compound that did not lead to the formation of the adsorption layer may cause spots through the aggregation process, forming an apparently thick adsorption layer. Although (FIG. 2), it has been found to disrupt the component gradient structure. For these reasons, there is a limit on the amount of the active ingredient, particularly the high molecular weight component, applied per unit area.

On the other hand, in hand coating using manual spray coating or brushing, it is undeniable that unevenness in the amount of application to the substrate occurs. Although it depends greatly on the skill of the worker, it is generally said that the density ratio of the applied amount is 6 times. As described above, in the film formation, the amount of application (in this case, it is considered to be synonymous with the concentration in consideration of the concentration in the drying process) is severely restricted. Cannot be tolerated.

The present invention solves the above problem by positively promoting the formation of a polymer adsorption layer during solvent drying. That is, by using a mixed solvent of a solvent (a) that is a good solvent for the polymer compound and is relatively easy to dry and a solvent (b) that is a poor solvent for the polymer compound and is relatively hard to dry, In, the composition ratio of both solvents changes continuously, and the ratio of the solvent (b), which is a poor solvent, to the polymer compound gradually increases. FIG.
Is a graph showing an example of a change in solvent composition with drying. From this figure, it can be understood that the proportion of the solvent (b) increases with drying.

It is apparent from FIG. 4 that the poor solvent content of the solvent makes it easier for the polymer compound to be adsorbed even at the lower concentration side, as shown in FIG. This has the effect of promoting the adsorption of the polymer compound. FIG. 4 is a graph showing an example of the composition dependence of the adsorption isotherm of a polymer compound. However,
The moving speed of the polymer compound in the solvent is not fast,
It is preferable that the drying speed of the solvent is low. Although the reason is not clear, it has been empirically shown that a poor solvent having a lower vapor pressure than water is preferable.

[0070]

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 gradient of the composite film was examined according to the following method. The XPS device “PHI-5” is attached to the composite membrane.
Using "600" (manufactured by ULVAC-PHI, Inc.), the film was shaved by argon sputtering (2 kV), the ratio of inorganic components on the film surface was measured by X-ray photoelectron spectroscopy, and the slope was examined. .

Reference Example 1 (1) Preparation of Polymer Solution Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 11.5
g, and 1.4 g of 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.), and after stirring well, 2,2'-azobisisobutyronitrile (Wako Pure Chemical Industries, Ltd.) 0.2 g) was added and dissolved, and reacted at 70 ° C. for 2.5 hours with stirring. After the completion of the reaction, the mixture is cooled to room temperature, and then methyl ethyl ketone (hereinafter sometimes referred to as MEK) as a solvent (a).
And the above polymer 6.
0 g was dissolved to prepare a solution having a concentration of 6.0 g / liter (hereinafter, referred to as a polymer solution).

(2) Preparation of Inorganic Component Solution Tetramethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.) 150
g and 100 g of 1-butanol (hereinafter sometimes referred to as 1-BtOH) in a mixed solution of 25 g of concentrated hydrochloric acid and 1-butanol.
A mixed solution with 50 g of BtOH was added dropwise with stirring, and stirring was continued at room temperature for 5 hours. Next, 1-BtOH 68.5
g was added and diluted so that the solid component concentration became 4%, to prepare an inorganic component solution. The solvent used here is referred to as a solvent (b).

(3) Formation of Organic-Inorganic Composite Film The polymer solution obtained in the above (1) and the inorganic component solution obtained in the above (2) were mixed in an amount of 40 ml each, and then the liquid film was formed by a bar coating method. The film was adjusted so as to have an amount of 6.86 μm. This was designated as Sample 1-1. Next, after mixing the polymer solution obtained in the above (1) and the inorganic component solution obtained in the above (2) by 40 ml each,
K / 1-BtOH mixed solvent (mixing volume ratio 50/50) 1
The solution was diluted 2.7 times by adding 36 ml, and the film was formed by a bar coating method by adjusting the liquid film amount to 18.3 μm. This was designated as Sample 1-2. By heating both samples at 70 ° C. for 12 hours, an organic-inorganic composite film was obtained. The thickness of each of the composite films was about 100 nm. FIG. 5 is a graph showing the relationship between the sputtering time and the inorganic component ratio of these composite films.

Reference Example 2 An organic-inorganic composite film was obtained in the same manner as in Reference Example 1, except that ethyl cellosolve was used instead of 1-BtOH. Note that the sample names were Sample 2-1 and Sample 2-2, respectively. The thickness of each of the obtained composite films was about 100 nm. FIG. 6 is a graph showing the relationship between the sputtering time and the inorganic component ratio of these composite films.

As shown in FIG. 5 and FIG. 6, it is obvious at a glance that depending on the combination of the solvents, there are cases where the gradient structure is sufficiently organized even when the concentration is low and cases where the structure is not so. It has been found that both of the solvents used in Reference Example 2 show good solubility in the polymer compound.
On the other hand, in Reference Example 1, the solvent (a) having relatively high volatility shows good solubility in the polymer compound, whereas the solvent (b) having relatively low volatility hardly dissolves the polymer compound. I know that. In Reference Example 1, it is considered that the mixing ratio of the solvent (b) continuously increased during the drying of the solvent, and the formation of the adsorption layer was promoted by the synergistic effect with the concentration effect accompanying the volatilization of the solvent. Therefore, in selecting a combination of solvents, a solvent having good solubility and high volatility for the polymer compound, and a poor solvent for the polymer compound and a solvent having low volatility are mixed to form a gradient structure. It is expected to be promoted.

Example 1 In the same manner as in the preparation of Sample 1-2 in Reference Example 1, the obtained coating solution was diluted 2.7-fold, and the spray amount was reduced to 24 using a spray nozzle. It was set to milliliters / minute, manually applied onto the polymethacrylate substrate once at a speed of about 12 m / minute, and formed into a film.
Heat drying treatment was performed at 12 ° C. for 12 hours to form an organic-inorganic composite film. The thickness of the obtained composite film was about 70 nm.
Table 1 shows the evaluation results of the performance of the composite membrane.

Example 2 An organic-inorganic composite film was formed in the same manner as in Example 1, except that methyl isobutyl ketone was used as the solvent (a). The thickness of the obtained composite film was about 70 nm. Table 1 shows the evaluation results of the performance of the composite membrane.

Comparative Example 1 An organic-inorganic composite film was formed in the same manner as in Example 1, except that methanol was used as the solvent (b). The thickness of the obtained composite film was about 70 nm. Table 1 shows the evaluation results of the performance of the composite membrane.

Comparative Example 2 An organic-inorganic composite film was formed in the same manner as in Example 1, except that acetone was used as the solvent (a) and ethanol was used as the solvent (b). The thickness of the obtained composite film was about 70 nm. Table 1 shows the evaluation results of the performance of the composite membrane.

Comparative Example 3 An organic-inorganic composite film was formed in the same manner as in Example 1, except that ethyl cellosolve was used as the solvent (b). The thickness of the obtained composite film was about 70 nm. Table 1 shows the evaluation results of the performance of the composite membrane.

[0081]

[Table 1]

1) MEK: methyl ethyl ketone, MIB
K: methyl isobutyl ketone, MeOH: methanol,
EtOH: ethanol, 1-BtOH: 1-butanol, EC: ethyl cellosolve 2) Vapor pressure of water at 20 ° C: 172 Pa 3) Spots: The coating spots of the composite film were visually observed. 4) Slope: Ten arbitrary points on the composite membrane were selected, the slope was examined according to the above-described method, and evaluated according to the following criteria. ；: All exhibit the same gradient. Δ: Slope is not recognized in part, or the slope is poor overall. X: No inclination was observed at all.

5) Cloudiness: The composite film was visually observed for cloudiness. From Table 1, it can be seen that the vapor pressure of the solvent (a) is at least twice the vapor pressure of the solvent (b), the solubility of the polymer compound in the solvent (b) is less than 5.0 g / liter, and the solvent ( It can be seen that when the vapor pressure of b) is lower than the vapor pressure of water, a composite film having excellent gradient can be obtained with high reliability even by a manual spray coating method.

[0084]

The coating agent for forming an organic-inorganic composite gradient film of the present invention is an organic-inorganic composite film containing a chemical bond of an organic polymer compound and a metal oxide compound, wherein the metal oxide Organic-inorganic composite gradient film, which has a component gradient structure in which the content of a compound-based compound changes continuously in the thickness direction of the film, has high transparency, and is useful for various applications as a functional material, can be manually or manually coated. Can be easily and reliably formed by spray coating.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of an adsorption isotherm of a polymer compound.

FIG. 2 is a graph showing an example of the concentration dependence of the thickness of a polymer adsorption layer.

FIG. 3 is a graph showing an example of a change in solvent composition due to drying.

FIG. 4 is a graph showing an example of the composition dependence of a solvent in an adsorption isotherm of a polymer compound.

FIG. 5 is a graph showing the relationship between the sputtering time and the inorganic component ratio in the composite film obtained in Reference Example 1.

FIG. 6 is a graph showing the relationship between the sputtering time and the inorganic component ratio in the composite film obtained in Reference Example 2.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masuzou Nishikawa 2-1-1, Yabuta Nishi, Gifu City, Gifu Prefecture Within Ube Nitto Kasei Co., Ltd. (72) Norihiro Nakayama 2-1-1, Yabuta Nishi, Gifu City, Gifu Prefecture No. 1 Ube Nitto Kasei Co., Ltd. F term (reference) 4J038 CG111 CG141 CH121 CH141 CH171 CH201 CH231 CH261 CL001 GA02 GA03 GA07 GA09 GA12 GA13 GA15 GA16 JA23 KA06 NA02 NA11 NA12 NA14 NA17 NA20 PB08 PC08

Claims (6)

[Claims] Claims: 1. An organic base material contains a complex in which an organic polymer compound and a metal oxide compound are chemically bonded, and the content of the metal oxide compound is in the depth direction from the film surface. A coating agent for forming an organic-inorganic composite gradient film having a component gradient structure that continuously changes to a solvent, wherein (a) a good solvent for the organic polymer compound used in the coating agent and (b) the organic solvent. A mixed solvent composed of a poor solvent for the polymer compound is used, and the solvent of the component (b) is harder to dry than the solvent of the component (a).
A coating agent for forming an organic-inorganic composite gradient film, wherein the vapor pressure at 0 ° C. is lower than the vapor pressure of water. 2. The solubility of the organic polymer compound in the solvent of the component (a) and the solvent of the component (b) at a temperature of 20 ° C. is 5.0 g / L or more and 5.0 g / L, respectively.
Less than 1 liter and at a temperature of 20 ° C., (a)
The coating agent according to claim 1, wherein the vapor pressure of the component is at least twice the vapor pressure of the component (b). 3. A mixture of (A) an organic polymer compound having a metal-containing group capable of bonding to a metal oxide by hydrolysis in a molecule, and (B) a metal compound capable of forming a metal oxide by hydrolysis. To form a coating agent for forming an organic-inorganic composite gradient film on an organic substrate, wherein (a) a good solvent for the organic polymer compound and (b) a solvent. A mixed solvent composed of a poor solvent for an organic polymer compound is used, and the solvent of the component (b) is harder to dry than the solvent of the component (a). A method for producing a coating agent for forming an organic-inorganic composite gradient film, wherein the coating agent is also low. 4. The solubility of the organic polymer compound in the solvent of the component (a) and the solvent of the component (b) at a temperature of 20 ° C. is 5.0 g / L or more and 5.0 g / L, respectively.
Less than 1 liter and at a temperature of 20 ° C., (a)
The method according to claim 3, wherein the vapor pressure of the component is at least twice the vapor pressure of the component (b). 5. An organic polymer compound having a metal-containing group capable of being bonded to a metal oxide by hydrolysis in the molecule of the component (A) is obtained by combining the above-mentioned ethylenically unsaturated monomer having a metal-containing group with a metal. The method according to claim 3 or 4, which is obtained by copolymerizing an ethylenically unsaturated monomer which does not contain the monomer. 6. The method according to claim 3, wherein the metal compound capable of forming a metal oxide by hydrolysis of the component (B) is a metal alkoxide.