JPH0987526A - Production of organic polymer/metal oxide composite material having structure of gradient component concentration - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composite material excellent in heat resistance properties, mechanical properties such as breaking strength and bondability and capable of having an optionally changed transparency by impregnating an organic polymer solid with a metal alkoxide so as to form a concentration gradient and polycondensing the metal alkoxide to fix it in the form of a metal oxide. SOLUTION: A solid organic polymer (e.g. polyamide) is immersed in a metal alkoxide (e.g. tetramethoxysilane) or a solution thereof, and the impregnation operation is stopped before the polymer is uniformly impregnated with the alkoxide to form a structure of a gradient metal alkoxide concentration inside the polymer. The impregnated polymer is then immersed in water and/or an aqueous solution containing an acid catalyst (e.g. formic acid) or a basic catalyst (e.g. ammonia) to polycondense the alkoxide and to thereby fix it in the form of a metal oxide. The ratio of the maximum local concentration of the metal oxide distributed in the composite material to the minimum one should be 1.5 or above.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, which is useful in various fields such as various materials, molding materials, films and fibers.
Organic polymers and metal oxides having a so-called component concentration gradient structure, in which metal oxide particles having a continuous concentration gradient structure are dispersed in an organic polymer solid having improved mechanical properties and chemical resistance. The present invention relates to a method for producing a composite with.

[0002]

2. Description of the Related Art Various studies have been made so far for the purpose of improving the performance of organic polymers. As one of the attempts, it is widely practiced to mix powdery inorganic materials such as calcium carbonate, silica, titania, and alumina, which have excellent heat resistance, mechanical properties, chemical resistance, etc., into organic polymers. ing.

When a composite is prepared by mixing it with an inorganic material, the inorganic material has properties such as heat insolubility, chemical insolubility, high specific gravity, and surface characteristics which are greatly different from those of the organic polymer material, so that it is in a dispersed state. Is not easy to control microscopically, and it is generally compounded for the purpose of obtaining a homogeneous bulk composite material.

That is, in order to improve the modifying effect, it is necessary to select an inorganic material having excellent wettability with the organic polymer of the matrix and having a smaller shape and to disperse them as homogeneously as possible. Is becoming an important factor in However, the finer the particles of the inorganic material, the more difficult it becomes to uniformly disperse in the organic polymer, and the manufacturing cost becomes high.

Therefore, in order to obtain a high-performance composite material in which the organic material and the particulate inorganic material are microscopically homogeneous and have a controlled dispersion structure, the above-mentioned simply particulate inorganic material is mixed and dispersed. It is difficult to obtain by the method, and the development of new technology is necessary.

[0006]

The problem to be solved by the present invention is that the heat resistance property is useful as various materials such as molding materials, electric / electronic parts, mechanical parts, automobile parts, sports equipment, films and fibers. , Mechanical properties such as breaking strength,
And excellent adhesion, excellent production of a composite of an organic polymer and a metal oxide having a so-called component concentration gradient structure, in which a metal oxide is dispersed with a continuous concentration gradient structure inside the organic polymer. To provide a method.

[0007]

As a result of intensive studies, the inventors of the present invention have impregnated a solid organic polymer with a metal alkoxide and / or a solution of a metal alkoxide so as to generate a concentration gradient, or By a simple method of impregnating a solution of water and / or an acidic or basic catalyst in a concentration gradient, and then polycondensing the metal alkoxide to immobilize the metal oxide, a continuous concentration gradient of the metal oxide is obtained. It has been found that a composite of an organic polymer having a structure having a component concentration gradient structure and a metal oxide having a structure can be produced, and the present invention has been completed.

That is, the present invention is characterized in that a metal alkoxide is impregnated into an organic polymer solid so as to have a concentration gradient, and then the metal alkoxide is subjected to a polycondensation reaction to be immobilized as a metal oxide. Which is a method for producing a composite of an organic polymer having a component concentration gradient structure and a metal oxide in which a metal oxide is dispersed with a concentration gradient.

Further, according to the present invention, a solid organic polymer is immersed in a metal alkoxide or a solution containing a metal alkoxide, and the immersion operation is completed before the metal alkoxide is uniformly impregnated in the organic polymer. A method for producing a composite of an organic polymer having a component concentration gradient structure and a metal oxide, characterized in that a concentration gradient structure of a metal alkoxide is formed inside the polymer.

By immersing a solid organic polymer in a solution containing a metal alkoxide and water and impregnating the solid organic polymer with the metal alkoxide, a concentration gradient structure of the metal alkoxide is formed inside the organic polymer. And a method for producing a composite of an organic polymer having a gradient structure of component concentration and a metal oxide.

Further, in the present invention, the solid organic polymer is dipped in a metal alkoxide or a solution containing the metal alkoxide to impregnate the solid organic polymer with the metal alkoxide, and then the metal organic alkoxide is removed from the organic polymer. Part is removed to form a concentration gradient structure of metal alkoxide inside the organic polymer, and then polycondensation reaction of the metal alkoxide is carried out, and the organic polymer and the metal oxide having the component concentration gradient structure are characterized. A method for producing a complex with

A solid organic polymer is uniformly impregnated with a metal alkoxide, and the organic polymer is impregnated with water and / or an acidic catalyst or a basic catalyst in a concentration gradient,
It includes a method for producing a complex of an organic polymer having a component concentration gradient structure and a metal oxide, which is characterized by carrying out a polycondensation reaction of a metal alkoxide. The present invention also includes a manufacturing method using a solid organic polymer swollen with a swelling liquid as the solid organic polymer.

More specifically, in the production method of the present invention, a solid organic polymer impregnated with a metal alkoxide is immersed in water and / or an aqueous solution containing an acidic catalyst or a basic catalyst to obtain water and / or an acidic solution. Impregnating a catalyst or a basic catalyst into the organic polymer, polycondensing the metal alkoxide in the organic polymer to immobilize it as a metal oxide,

Alternatively, by holding the solid organic polymer impregnated with the metal alkoxide in a steam atmosphere containing an acidic catalyst or a basic catalyst, the metal alkoxide inside the organic polymer is reacted to form a metal oxide. It is characterized in that it is fixed.

Further, in the present invention, the solid organic polymer is immersed in a mixed solvent consisting of an organic solvent for swelling the organic polymer and water and / or a solution of an acidic catalyst or a basic catalyst, Water, and / or an organic polymer is impregnated with water and / or an acidic catalyst or a basic catalyst, and then the organic polymer is immersed in a metal alkoxide or a solution containing a metal alkoxide to carry out a polycondensation reaction of the metal alkoxide. And a method for producing a composite of an organic polymer having a component concentration gradient structure and a metal oxide.

In the production method of the present invention, as a solid organic polymer used as a raw material, in particular, polyamide, polyolefin, polyester, polyvinyl chloride, acrylic resin,
Use of at least one selected from polystyrene copolymers, thermoplastic elastomers, polyacetals, and fluororesins, and the resulting composite of organic polymer and metal oxide is a metal oxide distributed in the composite. The ratio of the maximum value to the minimum value of the local concentration is 1.5 or more, and the obtained composite of the organic polymer and the metal oxide has a component gradient structure of the metal oxide in the thickness direction of the composite. And a manufacturing method.

In the present invention, a solid organic polymer impregnated with a metal alkoxide is impregnated with water and / or an acidic catalyst or a basic catalyst so as to have a concentration gradient, and a polycondensation reaction of the metal alkoxide is carried out. A composite of an organic polymer having a gradient structure of metal oxide and a metal oxide, characterized in that the particle size of the metal oxide dispersed in the organic polymer is continuously changed. It includes a method of manufacturing the body.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As the solid organic polymer used in the present invention, various commercially available solid thermoplastic resins and thermosetting resins can be used. Among them, an organic polymer impregnated with an organic solvent or a swelling liquid specified below in an amount of 1% by weight or more, preferably 5% by weight or more is preferable.

Specifically, for example, polyolefins such as polyethylene, polypropylene and poly-4-methylpentene-1; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyamides such as nylon-6 and nylon-66; polyacetals and polychlorinated materials. Vinyl, polyester-based or polyamide-based thermoplastic elastomers, styrene and butadiene, styrene copolymers such as methacrylic acid,

Acrylic resin such as polymethylmethacrylate, fluorine resin such as polyvinylidene fluoride, polycarbonate, phenoxy resin, polyphenylene oxide, polysulfone, polyethersulfone, etc. are used, and sheets, films, fibers, lots, pellets, It is used in the form of powder and various molded articles.

The metal alkoxide or the solution containing the metal alkoxide of the present invention can be used as a metal alkoxide represented by the general formula: R4-nM (OR) n (M is Si, R is an alkyl group,
When CmH2m + 1, m = 1 to 6, n is 3 or 4), a silicone alkoxide-based monomer or a polymerization degree of 2
About 10 to about those partially hydrolyzed polycondensates or mixtures thereof and / or a solution containing the same and an organic solvent are used.

As metal atoms, in addition to Si, Ti,
It is also possible to use Sn, Al, or Zr alone or in combination of two or more. As the swelling liquid used for swelling the organic polymer in the present invention, an organic solvent which is compatible with a metal alkoxide or a solution containing a metal alkoxide, and which can swell an organic polymer solid to be used or a mixed liquid of those organic solvents. Is used.

A specific organic solvent used for a solution containing a metal alkoxide or a swelling liquid is different depending on the type of organic polymer or metal alkoxide used, and therefore cannot be specified unconditionally. For example, diethyl ether, Dioxane, ether such as tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (NM
Amide type such as P),

Ester type such as ethyl acetate and methyl acetate,
Ketone-based compounds such as acetone and 2-butanone (MEK), alcohol-based compounds such as methanol, ethanol, 2-propanol and butanol, hydrocarbon-based compounds such as hexane and cyclohexane, fragrances such as toluene, xylene, m-cresol, benzene and nitrobenzene. Group-based, carbon tetrachloride, chloroform, halogenated hydrocarbons such as dichloromethane and dichloroethane,

Silicone type such as dimethyl polysiloxane and cyclomethicone, amine type such as triethylamine, diethylamine, pyridine, etc., dimethylsulfoxide (DMSO), acetonitrile, carbon disulfide,
Organic solvents such as methyl ethyl cellosolve, or diketone-based compounds such as acetylacetone and 2,4-heptadione,

Ketoesters such as methyl acetoacetate and ethyl acetoacetate, hydroxycarboxylic acid compounds such as lactic acid and methyl lactate, keto alcohols such as 4-hydroxy-4-methyl-2-pentanone, amino alcohols such as monoethanolamine and diethanolamine. It is possible to use an organic solvent such as a single kind or a mixture of plural kinds.

The solution containing the swelling liquid or the metal alkoxide can be used in combination with the solution containing water and / or an acidic catalyst or a basic catalyst. In this case, water and / or
Alternatively, it is preferable to use a solvent miscible with a solution containing an acidic catalyst or a basic catalyst. In particular, when water is used, specifically, water-miscible alcohols such as methanol and ethanol, ketone solvents such as acetone and 2-butanone, or hydrophilic organic solvents such as tetrahydrofuran, dimethylformamide, and pyridine. Is mentioned. When water is not used, the same organic solvent as the swelling liquid can be used.

As the acidic catalyst for the polycondensation reaction of the metal alkoxide of the present invention, organic acids such as formic acid and acetic acid, and inorganic acids such as hydrochloric acid are used, and as the basic catalyst, ammonia, triethylamine, dimethylamine, It is a basic substance such as ethylenediamine and butylamine.

The composite having a gradient structure of a metal oxide component in the present invention is a composite in which a concentration gradient structure of a metal oxide is formed in the thickness direction of an organic polymer. The morphology of a complex of an organic polymer in which the metal oxide of the present invention has a component concentration gradient structure and the metal oxide is schematically shown in FIG.

Here, FIG. 1 is a diagram schematically showing the morphology of a composite of an organic polymer in which a metal oxide has a component concentration gradient structure and a metal oxide produced by the production method of the present invention. . Each of a to h in FIG. 1 shows one form of a composite of an organic polymer having a component concentration gradient structure of the present invention and a metal oxide. The vertical axis of each represents the concentration of metal oxide, and the horizontal axis represents the distance (thickness) of the cross section of the organic polymer.

A composite of an organic polymer having a gradient structure of a metal oxide and a metal oxide, which is produced by the production method of the present invention, is formed from the surface of one organic polymer to the other such as a. The metal oxide concentration monotonically increases or decreases up to the surface of, the one having a continuous inclined structure in only a part of the inside as in b, and the metal oxide concentration layer having a large metal oxide concentration layer in the surface as in c. Having an inclined structure,

Examples thereof include those having a maximum concentration of metal oxide inside such as d and those having a plurality of maximum values of metal oxide concentration inside such as e. In addition, in the composite of the organic polymer and the metal oxide in which the metal oxide of the present invention has the gradient structure of component concentration, the gradient composite of the metal oxide and the organic polymer is partially formed in the thickness direction of the organic polymer. The present invention also includes a complex in a form including a region which is not complexed with the metal oxide at least in part.

Examples of this case are those in which metal oxides are not present in the composite such as f and g, and h
As described above, the metal oxide compounded on the surface portion and not present is exemplified. Further, the present invention also includes a complex having a form in which discontinuous faults are partially formed in the inclined structure of the form described above. As an example in this case,
For example, one having a form such as i or j can be cited.

The composite of an organic polymer in which the metal oxide has a component concentration gradient structure and the metal oxide obtained by the production method of the present invention usually has the maximum concentration of the metal oxide contained in the composite. The value is 5 to 100% by weight, the minimum value is 0 to 20% by weight, and the ratio of the maximum value and the minimum value (maximum value / minimum value) is 1.5 or more, especially the ratio of the maximum value and the minimum value. Is preferably 5 or more.

If the maximum value of the metal oxide concentration is less than 5% by weight, the effect of complexing is insufficient, and the minimum value is 2%.
When it exceeds 0% by weight, the composite becomes brittle and causes cracks, which is not preferable.

Specific methods for obtaining a composite of an organic polymer in which the metal oxide of the present invention has a component concentration gradient structure and the metal oxide are the following methods A, B and C. Is mentioned.

(Method A) If necessary, the solid organic polymer is swollen with an organic solvent, and then the metal alkoxide or a solution containing the metal alkoxide is impregnated into the solid organic polymer to give the inside of the organic polymer. After the metal alkoxide is impregnated so that it has a concentration gradient, the polycondensation reaction of the metal alkoxide is carried out to immobilize it as a metal oxide. More specifically, the concentration gradient of the metal alkoxide in a solid organic polymer is increased. As a specific method for forming the metal, a method of terminating the impregnation operation before the metal alkoxide is homogeneously impregnated in the organic polymer solid can be mentioned.

Further, the fact that the amount and rate of the metal alkoxide impregnated in the organic polymer varies depending on the degree of polymerization of the metal alkoxide, the length of the alkoxy group, the solution composition containing the metal alkoxide, the solution temperature, etc. Impregnation of metal alkoxide by using a plurality of metal alkoxides having different degrees of polymerization or different lengths of alkoxy groups as a mixed solution, or by adding a poor solvent or good solvent of an organic polymer used in a solution containing a metal alkoxide. A method of controlling the speed may be used.

When water is added to a solution containing a metal alkoxide, the impregnation rate into the organic polymer is changed by changing the solvent composition in the solution, and the presence of water causes the metal alkoxide to be changed. Since the polymerization reaction of (1) proceeds and the impregnation rate decreases as the molecular weight increases, impregnation of the metal alkoxide in the organic polymer spontaneously stops, and a graded structure is formed. The form of the gradient depends on the impregnation rate and the polymerization rate of the metal alkoxide, and both the impregnation rate and the polymerization rate are controlled by the solution temperature, the catalyst species, the catalyst concentration, and the water amount.

(Method B) If necessary, a solid organic polymer is swollen with an organic solvent, and then a metal alkoxide or a solution containing the metal alkoxide is (uniformly) impregnated into the solid organic polymer. The organic polymer is impregnated with water and / or an aqueous solution containing an acidic catalyst or a basic catalyst so that the water and / or the acidic catalyst or the basic catalyst forms a concentration gradient inside the polymer, and the reaction of the metal alkoxide is performed. A method of carrying out a polycondensation reaction of a metal alkoxide by giving a gradient to the property,

More specifically, as a specific method for forming a concentration gradient of water and / or acidic catalyst or basic catalyst in a solid organic polymer, water and / or acidic catalyst or basic catalyst There is a method of terminating the impregnation operation before homogeneously impregnating the molecular solid.

(Method C) If necessary, the solid organic polymer is swollen with an organic solvent, and then the solid organic polymer is dipped in a metal alkoxide or a solution containing the metal alkoxide to be added to the solid organic polymer. After impregnating the metal alkoxide, a part of the metal alkoxide is removed from the organic polymer to form a concentration gradient structure of the metal alkoxide inside the organic polymer, and then a polycondensation reaction of the metal alkoxide is performed.

More specifically, a solid organic polymer is immersed in a metal alkoxide or a solution containing a metal alkoxide and then kept at room temperature or high temperature under normal pressure or reduced pressure for a specific time, or The metal alkoxide impregnated in the organic polymer is mainly removed from the surface portion by a method such as extraction with an organic solvent, and then immersed in water and / or an aqueous solution containing an acidic catalyst or a basic catalyst,
Then, the metal alkoxide is polycondensed.

Similarly, after the solid organic polymer is swollen with an organic solvent, if necessary, the solid organic polymer is immersed in water and / or an aqueous solution containing an acidic catalyst or a basic catalyst. , Water impregnated into the organic polymer mainly from the surface portion by a method such as removing or extracting water and / or an acidic catalyst or a basic catalyst with an organic solvent miscible with water under normal pressure or reduced pressure. And / or the method of removing the acidic catalyst or the basic catalyst and then immersing in a solution containing a metal alkoxide or a metal alkoxide to cause a polycondensation reaction of the metal alkoxide may be used.

(Method D) A solid organic polymer is immersed in a mixed solvent consisting of an organic solvent for swelling the organic polymer and water and / or a solution of an acidic catalyst or a basic catalyst,
The organic polymer is swollen, and the organic polymer is impregnated with water and / or an acidic catalyst or a basic catalyst, and then the organic polymer is immersed in a metal alkoxide or a solution containing the metal alkoxide, and the metal alkoxide is added thereto. Method of condensation reaction.

Similarly, a solid organic polymer is mixed with a metal alkoxide or a solution containing the metal alkoxide and an organic solvent which is compatible with the metal alkoxide or the solution containing the metal alkoxide and can swell the organic polymer. The metal alkoxide is dipped in a solvent to swell the organic polymer, and the organic polymer is impregnated with the metal alkoxide. Then, the organic polymer is dipped in a solution containing water and / or an acidic catalyst or a basic catalyst to form a metal alkoxide. A method of polycondensation reaction with

In these methods, permeation of the impregnating liquid into the organic polymer and diffusion of the swelling liquid in the organic polymer to the outside occur at the same time, so that the content of the metal oxide in the organic polymer is inclined. It is thought that the structure is generated. The swelling liquid for swelling the organic polymer of the present invention is preferably one capable of swelling the solid organic polymer used by 1% by weight or more, particularly 5% by weight or more.

In the production method of the present invention, it is not always necessary to swell the organic polymer in advance, and an untreated organic polymer may be used as it is. That is, depending on the organic polymer to be used and the desired form of the complex of the organic polymer having the target component concentration gradient structure and the metal oxide, whether or not the pre-swollen organic polymer is used is determined as necessary. Then, it may be appropriately selected.

Here, in the present invention, a metal alkoxide or a solution containing a metal alkoxide, and in some cases, a solution further containing water and / or an acidic catalyst or a basic catalyst may be referred to as an impregnating liquid.

In the present invention, it is possible to obtain composites having various forms of the graded component structure by these methods. For example, by contacting only one surface of the organic polymer solid with the impregnating liquid, performing the impregnating operation, and stopping the impregnating operation before the impregnating liquid has sufficiently permeated the other surface, as shown in a or b of FIG. It is possible to obtain a graded composite.

Further, after impregnation with the impregnating liquid, by the method of removing the constituent components of the impregnating liquid containing the metal alkoxide, water and / or catalyst from the surface portion, such as d, e, g, or j in FIG. It is possible to obtain a complex.

The component gradient structure formed by the metal alkoxide, water and / or catalyst, etc. inside the organic polymer is the composition of the impregnating liquid or swelling liquid, the dipping conditions such as dipping time and dipping temperature, and the pretreatment. It is possible to control it by combining the swelling degree of the organic polymer.

In the method of removing the components in the impregnating liquid after the organic polymer is impregnated with the impregnating liquid, the temperature at which the components are removed depends on the type of the organic polymer used. Although not specified, it is usually in the range of normal temperature to 150 ° C. under normal pressure or reduced pressure. The metal alkoxide that can be effectively removed by this method has a boiling point of 250.
It is below ° C.

These include, for example, tetramethoxysilane and tetraethoxysilane. Further, in the method of evaporating and removing the metal alkoxides after impregnating with the metal alkoxide, at the same time as the evaporation depending on the temperature conditions used, the condensation reaction of the metal alkoxides proceeds to some extent, and the degree of polymerization of the metal alkoxides increases. Due to the increased evaporation, it can no longer be removed.

As a result, a graded composite having a maximum metal oxide concentration inside the organic polymer solid can be obtained without evaporating all the impregnated metal alkoxides. Therefore, it becomes possible to control the gradient form by adding the catalyst to the holding temperature or the impregnating liquid.

As a method of forming a concentration gradient of water and / or an acidic catalyst or a basic catalyst inside an organic polymer impregnated with a metal alkoxide by an impregnation operation, the organic polymer may be added, if necessary. Examples thereof include a method of maintaining an aqueous solution containing an acidic catalyst or a basic catalyst in a steam atmosphere, and a method of immersing the solution in the aqueous solution.

By these methods, it is possible to obtain a complex having a form such as c, f, i, or h in FIG. Further, it is possible to add a hydrophilic organic solvent to the aqueous solution for the purpose of smoothly diffusing / infiltrating the water vapor and the components of the aqueous solution into the organic polymer. Depending on the amount, the impregnated metal alkoxides may diffuse to the outside before they react, and the amount of metal oxide immobilized may become small, or the slope of the complex may become gentle, so the amount used is small. It is preferable.

A metal alkoxide is contained in the swelling liquid to swell the solid organic polymer in advance, and the organic polymer is dipped in the impregnating liquid to allow the impregnating liquid to permeate the polymer and Utilizing that the ability of the impregnating liquid to penetrate into the polymer decreases over time due to the simultaneous progress of diffusion of the components in the swelling liquid contained in the polymer to the outside (in the impregnating liquid). Then, the method of forming the component concentration gradient structure of the metal oxide inside the organic polymer is a particularly effective method for the organic polymer which is difficult to be impregnated with the impregnating liquid such as polyolefin, polyamide, polyacetal and polyester. .

When an impregnating solution having a composition which can be impregnated in a swollen organic polymer but hardly impregnated in a non-swollen organic polymer itself is used, c, f in FIG.
It is possible to obtain gradient composites such as i or h.

When water and / or an acidic catalyst or a basic catalyst is used in combination with the swelling liquid, water impregnated in the organic polymer solid during the impregnation operation of the impregnation liquid containing the metal alkoxide, The catalyst diffuses to the outside. Therefore, the concentrations of water and catalyst that control the reactivity of these metal alkoxides decrease near the surface of the organic polymer and are distributed with a maximum value inside. As a result, the obtained composite has a component gradient structure such as e, g, or j in FIG. 1 having the maximum value of the metal oxide concentration inside the organic polymer.

In the present invention, the swelling operation of the swelling liquid and the impregnation operation of the impregnating liquid are usually carried out by immersing the organic polymer solid in these liquids. It is also possible to use a method of contacting with and impregnating.

In the present invention, the production and immobilization of the metal oxide by the polycondensation reaction of the metal alkoxide are carried out by treating the organic polymer impregnated with the metal alkoxide with water (including water in the air) and / or an acidic catalyst or a base. By maintaining in the presence of an organic catalyst, that is, usually by holding and heating at room temperature to a temperature below the melting point of the organic polymer, more specifically at 20 to 230 ° C, preferably at 50 to 200 ° C. To be done.

A metal oxide having a composition in which the particle size of the metal oxide dispersed in the organic polymer of the present invention is continuously changed, The complex with the metal oxide is a complex having a form in which the particle diameter of the metal oxide particles continuously changes in the thickness direction and / or the longitudinal direction of the organic polymer.

The particle size of the metal oxide varies depending on the type of the metal oxide or the organic polymer, the purpose of use, etc., and therefore cannot be specified unconditionally, but is usually 10 μm or less, preferably 2
It is in the range of μm or less. When it exceeds 10 μm, properties such as mechanical strength of the composite are deteriorated, which is not preferable. Also,
The minimum value of particle size is not particularly specified. This can be confirmed up to a particle size of about 5 nm by scanning electron microscope observation, but in the composite of the present invention, particles having a particle size smaller than this, that is,
This is because particles below the detection limit may be present, and even if they are present, the characteristics targeted by the present invention are not impaired.

Further, the transparency of the composite is changed due to the difference in particle size of the metal oxide dispersed in the organic polymer. Normally, a milky-turbid or turbid complex is obtained with a particle size of about 0.2 μm or more, and a transparent complex is obtained with a particle size of about 0.2 μm or less. By changing the particle size of the metal oxide in the organic polymer, it is possible to obtain a composite with changed transparency. Such properties are particularly useful when using a transparent resin such as a styrene copolymer, an acrylic resin, or a polycarbonate.

Specific examples of the method for obtaining a composite of an organic polymer in which the metal oxide particles of the present invention have a component concentration gradient structure and a metal oxide include the following methods.

For example, the solid organic polymer is pre-swelled with a swelling liquid according to the form of the organic polymer used and the desired composite, and then the solid organic polymer is impregnated with a metal alkoxide and water. Since the particle size of the metal oxide depends on the pH of the reaction field of the metal alkoxide, the concentration of water, the temperature, etc., the organic polymer is impregnated with water and / or an acidic catalyst or a basic catalyst in a concentration gradient. By carrying out the polycondensation reaction of the metal alkoxide, it is possible to obtain a composite in which the particle size of the metal oxide dispersed in the organic polymer is continuously changed.

By advancing the polycondensation reaction of the metal alkoxide with the temperature gradient inside the organic polymer, the particle size of the metal oxide dispersed in the organic polymer was changed. It is also possible to obtain morphological complexes.

Particularly, since the particle size of the metal oxide strongly depends on the pH of the reaction field of the metal alkoxide, the method in which the acidic catalyst or the basic catalyst has a concentration gradient is the most effective. Further, by using an acidic catalyst or a basic catalyst in the swelling liquid for preliminarily swelling the organic polymer, it becomes possible to adjust the pH in the organic polymer to a desired gradient form, and the metal in the organic polymer is changed. A composite is obtained in which the size of the oxide particles is continuously changed.

In the present invention, as a further pretreatment for the swelling operation and the impregnation operation, an acidic aqueous solution of sulfuric acid, nitric acid, phosphoric acid, etc., a basic aqueous solution of sodium hydroxide, etc., or ozone, plasma, etc. It is also possible to increase the fixing rate of the metal oxide on the surface portion by subjecting the organic polymer described above to surface treatment in advance.

It is also possible to improve the affinity between the organic polymer and the metal oxide by using an organic silane compound such as aminoalkoxysilane, epoxyalkoxysilane, vinylalkoxysilane and mercaptoalkoxysilane together.

[0072]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the examples shown below.

(Example 1) Nylon-6 in the form of a film
(Ube Industries, Ltd .: UBE Nylon 1022B)
Was immersed in a swelling liquid consisting of methanol and distilled water (weight ratio = 2: 1) and stirred at 80 ° C. for 3 hours. About 25% by weight
An increase in weight was observed. Next, tetramethoxysilane at 30 ° C. (hereinafter referred to as TMOS: manufactured by Tokyo Chemical Industry Co., Ltd.)
After being immersed in the liquid for special grade reagent for 5 hours, the test piece was taken out from the solution, the surface solution was wiped off well, and dried at room temperature for 5 hours. Further, heat treatment was carried out in vacuum at 80 ° C. for 24 hours to obtain a composite of nylon-6 and silica.

Electron beam microanalyzer (EPMA)
Was used to measure the distribution of Si in the cross section of the composite. FIG.
The results are shown in. In the figure, the vertical axis represents silica (Si) concentration, and the horizontal axis represents the distance in the depth direction of the composite. In the figures showing the EPMA measurement results showing the distribution of silica obtained in the following examples, the vertical axis and the horizontal axis in the figure have the same meaning. A dense Si distribution was observed near the surface, and a compositionally graded composite having a form in which the Si concentration sharply decreased between 70 and 80 microns from the surface was obtained.

The maximum silica concentration is found within about 20 microns from the surface, with a maximum concentration of about 13% by weight and a minimum concentration of zero. When baked at 800 ° C for 2 hours, about 2.
6% by weight of bag-like ash was found. When the silica particles of the composite layer were observed by a scanning electron microscope (SEM), it was observed that extremely small particles of 10 to 30 nm were uniformly dispersed.

For EPMA measurement, an EPM-810 manufactured by Shimadzu Corporation was used, and output was 15 kV-50n.
A, resolution 1 micron, scan speed 100 micron / min, and detection was performed with Si Kα ray (7.126 ohm strong). Also, SEM is FE- manufactured by Hitachi, Ltd.
SEM S-800 was used.

(Example 2 and Comparative Example 1) Nylon-6 having a thickness of 2 mm was used in the same manner as in Example 1.
A composite of 6 and silica was prepared. As a result of EPMA measurement, silica was observed only in the vicinity of the surface.
A graded composite of the same morphology was obtained.

When the composite was heat treated at 150 ° C. for 2 hours, no change was observed in the appearance of the composite. on the other hand,
When nylon-6 alone was heat-treated at 150 ° C. for 2 hours, it turned yellow (Comparative Example 1). Furthermore, when the IZOD impact characteristics of the composite heat-treated at 150 ° C. were measured,
It was about 55 kg cm. The nylon-6 heat-treated at 150 ° C. has an IZOD strength of 12 kg cm, and it can be seen that the heat resistance characteristics are remarkably improved in the examples. Incidentally, IZ
The OD test was performed without a notch using a sample having a thickness of 2 mm and a width of 4 mm.

Example 3 The composition of the impregnating liquid during the TMOS impregnation operation was TMOS and methanol (weight ratio = 20: 1).
The case was examined. The conditions other than the composition of the impregnating liquid were the same as in Example 1. The Si distribution in the cross section of the composite obtained by EPMA measurement is shown in FIG. A graded composite of nylon-6 and silica having a maximum silica concentration (two) at a depth of about 90 μm from the surface was obtained. The maximum / minimum silica concentration was about 26.
When calcined at 800 ° C. for 2 hours, about 4.3% by weight of ash was found.

(Example 4) A case was examined in which the composition of the impregnating liquid during the TMOS impregnation operation was TMOS and methanol (weight ratio = 5: 1). The conditions other than the composition of the impregnating liquid were the same as in Example 1. The Si distribution in the cross section of the composite obtained by the EPMA measurement is shown in FIG. A graded composite of nylon-6 and silica in the form of having a maximum silica concentration in the center of the composite was obtained. The maximum / minimum silica concentration was about 2.8. When baked at 800 ° C. for 2 hours, about 3.8% by weight of ash was found.

Example 5 The composition of the impregnating liquid during the TMOS impregnation operation was TMOS and methanol (weight ratio = 25: 2).
And the impregnation temperature was 50 ° C. The conditions other than the composition of the impregnation liquid and the impregnation temperature were the same as in Example 1. EPM
The Si distribution in the cross section of the composite obtained from the A measurement is shown in FIG. It has an extremely high silica concentration on the surface,
The concentration was rapidly decreased to 1/2 in the range of μm, and the concentration was gradually decreased inside the gradient composite. The maximum / minimum silica concentration was about 25.
When baked at 800 ° C. for 2 hours, about 8.0% by weight of ash was found.

Example 6 Film-like nylon-6 was immersed in a swelling solution consisting of methanol and a 0.8 mol / l aqueous ammonia solution (weight ratio = 2: 1), and stirred at 80 ° C. for 3 hours. A weight gain of about 24.5% by weight was observed.
Then, after immersing in an impregnating solution consisting of TMOS and methanol (weight ratio = 5: 1) and holding at 30 ° C for 5 hours, the sample is taken out from the solution, the surface solution is wiped off well, and dried at room temperature for 5 hours. Let Further, heat treatment was performed in a vacuum at 80 ° C. for 24 hours to obtain a composite of nylon-6 and silica.

Using EPMA, the distribution of Si in the cross section of the composite was measured. FIG. 6 shows the results. 100μ from the surface
There is obtained a tilted composite body in which the maximum value is formed inside m and the central portion is depressed with a gentle tilt. The maximum / minimum value of the silica concentration is about 3.5, and the ratio of the maximum value to the center saddle (maximum value / saddle) is about 1.5. 2 at 800 ° C
After firing for an hour, an ash content of about 11.2% by weight was found. The amount of silica fixed in the composite was increased by using the ammonia catalyst during the swelling operation.

(Example 7) Nylon film 6 having a thickness of 0.5 mm was dipped in a swelling solution composed of methanol and a 0.23 mol / l hydrochloric acid aqueous solution (weight ratio = 2: 1),
The mixture was stirred at 80 ° C for 3 hours. A weight gain of about 26% by weight was observed. Next, TMOS and methanol (weight ratio = 2
0: 1) and soaking in the impregnating solution of 5: 1 and holding at 30 ° C for 5 hours, take out the sample from the solution, wipe off the solution on the surface well, and in a saturated steam atmosphere of 0.4 mol / l ammonia water. The temperature was maintained at 20 ° C for 10 hours. 1 at room temperature
After drying for 5 hours, vacuum drying was performed at 80 ° C. for 24 hours to obtain a composite of nylon-6 and silica.

The distribution of Si in the cross section of the composite was measured using EPMA. The results are shown in FIG. 7. A morphologically graded composite with a very high silica concentration on the surface was obtained. 80
When baked at 0 ° C. for 2 hours, about 6.4% by weight of ash was found.

Example 8 The composition of the impregnating liquid during the TMOS impregnation treatment was TMOS and methanol (weight ratio = 10: 1).
The case was examined. The conditions other than the composition of the impregnating liquid were the same as in Example 7. The Si distribution in the cross section of the composite obtained by the EPMA measurement is shown in FIG. Morphologically graded composites with extremely complex silica distribution were obtained. The maximum / minimum silica concentration is about 6. When baked at 800 ° C. for 2 hours, about 5.1% by weight of ash was found. It can be seen that the distribution of silica changes significantly only by slightly changing the amount of methanol in the impregnation liquid.

(Embodiment 9) Instead of TMOS, TMO
The case of using a partial polymer of S (MS-51; manufactured by Mitsubishi Chemical Corporation, molecular weight about 500) was examined. MS-51 is used as the silicone alkoxide, and MS-
The conditions were the same as in Example 1 except that the temperature of immersion in 51 was 50 ° C. FIG. 9 shows the Si distribution in the cross section of the composite obtained by the EPMA measurement. A graded composite having a very high silica concentration on the surface and having a silica concentration rapidly decreasing to zero within 60 μm from the surface was obtained. 800
When baked at 0 ° C. for 2 hours, a bag-shaped ash content of about 1.2% by weight was found.

(Example 10) An examination was carried out in the case where the composition of the impregnating liquid of MS-51 was MS-51 / methanol (weight ratio = 4: 1). The conditions other than the composition of the impregnating liquid were the same as in Example 9. FIG. 10 shows the Si distribution in the cross section of the composite obtained by the EPMA measurement. A gradient composite having a maximum silica concentration near the surface and gradually decreasing inward was obtained. Maximum silica concentration /
The minimum value is about 2.8. When baked at 800 ° C. for 2 hours, an ash content of about 4.8% by weight was found.

Example 11 A sheet of vinyl chloride (manufactured by Mitsubishi Chemical Co., Ltd.) was replaced with acetone and distilled water (weight ratio = 2:
1) Immersed in a mixed solvent at 30 ° C. for 3 hours. A weight gain of about 21% by weight was observed. Then, after immersing in an impregnating solution of TMOS and acetone (weight ratio = 20: 1) for 5 hours at 30 ° C., a sample piece was taken out from the solution, and the surface solution was wiped off thoroughly to a concentration of 0.5 mol / l. It was kept in a steam atmosphere of an aqueous ammonia solution for 8 hours.

Further, after drying in a room (temperature 23 ° C., humidity 35%) for 17 hours, heat treatment was carried out at 80 ° C. for 24 hours to obtain a composite of vinyl chloride and silica. The Si distribution in the cross section of the composite obtained by the EPMA measurement is shown in FIG. The silica layer gradually decreases from the surface to the inside, and a composite layer is formed over about 190 microns from the surface. A fault occurs within about 190 microns and the inside is not complexed. A gradient composite of was obtained. The maximum / minimum silica concentration in the composite layer is about 1.8.
When baked at 800 ° C. for about 2 hours, about 8.9% by weight of ash was found.

Example 12 Vinyl chloride in acetone 1
Immersion was performed at 30 ° C. for 0 minutes. A weight gain of about 50% by weight was observed. Next, TMOS and toluene (weight ratio =
After immersing in the impregnating solution of 1: 1) for 8 hours at 30 ° C., the specimen is taken out of the solution and the surface solution is wiped off thoroughly.
8 in a vapor atmosphere of 0.5 mol / l aqueous ammonia solution
Hold for hours. Furthermore, indoors (temperature 23 ° C, humidity 35%)
After drying for 3 hours at 80 ° C., heat treatment was performed at 80 ° C. for 24 hours to obtain a composite of vinyl chloride and silica.

FIG. 12 shows the Si distribution of the composite obtained by the EPMA measurement. Has the maximum value of silica concentration on the surface,
The concentration is rapidly reduced up to a certain thickness, and a graded composite is formed in which the silica concentration is uniform inside. The graded layer is between about 80 μm from the surface and the maximum / minimum silica concentration is about 1.9. When baked at 800 ° C. for about 2 hours, about 8.9% by weight of ash was found.

Example 13 In Example 12, TM
After impregnating with OS, do not keep it in the vapor atmosphere of aqueous ammonia solution, and keep it at room temperature (23 ° C, humidity 35%)
The case of drying for 5 hours was examined. FIG. 13 shows the result of EPMA measurement. At the center of the composite, a graded composite having a morphology having the maximum silica concentration is formed.
After impregnating TMOS, TMOS evaporates from the surface,
It is considered that such a form is formed. The maximum / minimum value of the silica concentration was about 2.3. When baked at 800 ° C. for about 2 hours, about 10% by weight of ash was recognized.

(Example 14) An acrylic resin (Acrylite-L; manufactured by Mitsubishi Rayon Co., Ltd.) film was used for TMOS.
And dipped in methanol (weight ratio = 1: 1) at 30 ° C. for about 7 days. A weight gain of about 98% by weight was observed. Then, the test piece was taken out of the liquid, the surface solution was wiped off well, and the sample was immersed in an aqueous 0.5 mol / l ammonia solution for about 3 hours (25 ° C.), and then indoors (temperature 20 ° C., humidity 35 ° C.).
%) For about 17 hours and further heat-treated at 80 ° C. for 24 hours to obtain a composite of acrylic resin and silica.

S of the cross section of the composite obtained from the EPMA measurement
The i distribution is shown in FIG. A graded composite is obtained in which the silica concentration gradually decreases from the surface to the inside, and the central about 45 μm portion is not composited. The thickness of the composite layer is 330 μm from the surface, and the maximum / minimum value of the silica concentration in the composite layer is about 3. 800
When baked for 2 hours at ℃, about 17% by weight of ash was found.

(Example 15) An acrylic resin film was used as 5
It was immersed in a TMOS and methanol (weight ratio = 1: 1) impregnating solution at 0 ° C. for about 1 hour. A weight gain of about 105% was seen. Then, the test piece was taken out of the liquid, the surface solution was wiped off well, and immersed in an aqueous 1.2 mol / l ammonia solution for 5 hours (30 ° C.), and then indoors (temperature 20 ° C., humidity 35%) It was dried for about 17 hours and further heat-treated at 80 ° C. for 24 hours to obtain a composite of acrylic resin and silica.

S of the cross section of the composite obtained by EPMA measurement
The i distribution is shown in FIG. A composite having a form in which the silica concentration gradually decreases from the surface portion to the inside was obtained. The maximum / minimum silica concentration in the composite layer is about 2.5.
The inclination is gentler than that of Example 14, but the entire region is combined. When baked at 800 ℃ for 2 hours,
About 19 wt% ash was found.

Example 16 An acrylic resin film was treated with methanol and MS-51 (weight ratio = 1: 1) for about 2 days,
It was immersed at 30 ° C. A weight gain of about 12% by weight was observed. Then, the test piece was taken out of the liquid, the surface solution was thoroughly wiped off, and the piece was immersed in 0.5 mol / l ammonia water for about 5 hours, and then left in a room (temperature 20 ° C, humidity 35%) for about 17 hours. It was dried and further heat-treated at 80 ° C. for 24 hours to obtain a composite of acrylic resin and silica.

Si of composite cross section obtained by EPMA measurement
The distribution is shown in FIG. There was a maximum value of silica concentration on the surface, and a gradient composite having a form in which the concentration was rapidly decreased to zero within 25 μm from the surface was obtained. The silica concentration is almost zero inside the surface of 25 μm or more and is not composited. When baked at 800 ° C for 2 hours, it was about 0.0
8% by weight of bag-like ash was found.

Example 17 A nylon-66 film was immersed in a swelling solution of tetrahydrofuran (THF), distilled water and triethylamine (weight ratio = 40: 10: 1) to 80%.
It was soaked at ℃ for 5 hours. A weight gain of about 15% by weight was seen. Then, after immersing in TMOS solution at 30 ° C for about 12 hours, the sample is taken out from the solution, the surface solution is wiped well, dried at room temperature for about 4 hours, and further heat treated at 80 ° C in vacuum for 24 hours. Then, a composite of nylon-66 and silica was obtained.

S of the cross section of the composite obtained from the EPMA measurement
The i distribution is shown in FIG. A graded composite with a maximum surface silica concentration and a decreasing inward morphology was obtained. When baked at 800 ° C for 2 hours, it is about 2.1% by weight.
Ash content was found.

Example 18 and Comparative Example 2 A film of polypropylene (Mitsubishi Polypro PY-240B, manufactured by Mitsubishi Chemical Co., Ltd.) was immersed in toluene at 105 ° C. for about 2 hours. A weight gain of about 100% by weight was observed. Then, after immersing in TMOS at 30 ° C. for 20 hours, the sample is taken out of the solution, and the surface solution is wiped off well,
It was kept for 17 hours under an atmosphere of 0.6 mol / l of ammonia. After drying at room temperature for 5 hours, at 80 ° C for 3 hours, 1
Heat treatment was carried out at 50 ° C. for 2 hours to obtain a composite of polypropylene and silica.

No change in the appearance of polypropylene was observed. FIG. 18 shows the Si distribution in the cross section of the composite obtained by the EPMA measurement. A morphologically graded composite with a maximum silica concentration on the surface was obtained. When calcined at 800 ° C. for 2 hours, about 18% by weight of ash was obtained.

Dynamic viscoelasticity measurement showed that the Young's modulus of the composite at 30 ° C. and 100 ° C. was 1.5 GPa respectively.
And 530 MPa, and the peak temperature of tan δ was 143 ° C. In addition, Young's modulus of polypropylene alone (Comparative Example 2) at 30 ° C. and 100 ° C. is 0.8 GPa and 250 M, respectively.
Pa and tan δ peak was 81 ° C. It can be seen that the elastic properties are remarkably improved.

The adhesiveness to an epoxy adhesive (Cemedine High Super 30, manufactured by Cemedine Co., Ltd., Araldite) was examined. An adhesive was applied to each of the composite and the polypropylene resin alone, and the surfaces coated with the adhesive were overlapped with each other to cure the adhesive. When the bonded portion was peeled off, peeling occurred on the bonding surface between the polypropylene and the adhesive, and it can be seen that the adhesiveness to the epoxy adhesive is improved.

The dynamic viscoelasticity was measured at 1 Hz using DMA-200 manufactured by Seiko Denshi Kogyo Co., Ltd. at a temperature of 2 ° C./min.

(Example 19) A polyacetal (Iupital F-10, manufactured by Mitsubishi Gas Chemical Co., Inc.) was immersed in etolachloroethane at 100 ° C for 3 hours. A weight gain of about 18% by weight was observed. Next, after immersing in TMOS liquid at 30 ° C. for 17 hours, the sample is taken out of the liquid,
The surface solution was wiped off well and kept under an atmosphere of 0.6 mol / l of ammonia for 17 hours. After drying at room temperature for 5 hours, heat treatment was performed at 80 ° C. for 3 hours and 150 ° C. for 2 hours to obtain a polyacetal / silica composite. FIG. 19 shows the Si distribution in the cross section of the composite obtained by the EPMA measurement.
A morphologically graded composite with a maximum silica concentration on the surface was obtained. When it was calcined at 800 ° C. for 2 hours, about 11% by weight of ash was obtained.

Example 20 A film of polyvinylidene fluoride (1000 VLD, Showa Denko KK) was immersed in a 2-butanone solution at 50 ° C. for 4 hours. About 9.
A weight gain of 5% by weight was seen. Then TM at 30 ° C
After being immersed in an impregnating solution of OS and triethylamine (weight ratio = 10: 1) for 15 hours, it was dried at room temperature for 15 hours. Further, heat treatment was performed at 80 ° C. for 24 hours and at 150 ° C. for 2 hours to obtain a composite of polyvinylidene fluoride and silica. The Si distribution in the cross section of the composite obtained by the EPMA measurement is shown in FIG. A morphologically graded composite with a maximum silica concentration on the surface was obtained.

(Example 21) A sheet of polybutylene terephthalate (PBT; Planac BT-128 manufactured by Dainippon Ink and Chemicals, Inc.) was used at 80 ° C in tetrahydrofuran (THF), distilled water and triethylamine (weight ratio = 40:10). It was immersed in the mixed solvent of 1) for 8 hours. A weight gain of about 4% by weight was observed. Then TM at 30 ° C
1 for the impregnating solution of OS and chloroform (weight ratio = 10: 1)
After soaking for 5 hours, the sample was taken out of the solution, the surface solution was wiped off well, and dried at room temperature for 24 hours. Further, heat treatment was performed at 80 ° C. for 10 hours and at 150 ° C. for 3 hours to obtain a composite of PBT and silica.

FIG. 21 shows the Si distribution near the surface of the cross section of the composite obtained by EPMA measurement. A gradient composite having a maximum silica concentration on the surface and having a concentration of 70 μm and rapidly decreasing to zero was obtained. The silica concentration is almost zero inside the surface of 70 μm or more, and the composite is not formed. When fired at 800 ° C for 2 hours, about 0.6% by weight
Sack-like ash content was observed.

Example 22 A sheet of PBT was immersed in chloroform at 60 ° C. for 4 hours. A weight gain of about 28% was seen. Next, after immersing in a TMOS solution at 30 ° C. for 5 hours, the sample was taken out from the solution, the surface solution was wiped off well, and dried at room temperature for 24 hours. Furthermore,
Heat treated at 80 ℃ for 10 hours and 150 ℃ for 3 hours to perform PB
A composite of T and silica was obtained. FIG. 22 shows the Si distribution near the surface of the cross section of the composite obtained by the EPMA measurement. A tilted composite having a maximum silica concentration on the surface and gently tilted in the thickness direction was obtained. When baked at 800 ° C. for 2 hours, a bag-shaped ash content of about 1% by weight was found.

(Example 23) Polyethylene terephthalate (PET; J-125 manufactured by Mitsui Pet Co., Ltd.) 2 was added.
After melt pressing at 50 ° C., it was rapidly cooled in water to obtain a transparent PET film having high amorphousness. The transparent PET film was immersed in a chloroform solution at 60 ° C. for 4 hours. A weight gain of about 45% by weight was observed. Then, after immersing in an impregnating solution of TMOS and chloroform (weight ratio = 10: 1) at 30 ° C. for 15 hours, the test piece was taken out from the solution, and the surface solution was wiped off thoroughly to obtain 0.15 mol / l. It was immersed in an aqueous ammonia solution for about 5 hours. Further, it is dried at room temperature for 5 hours, and then 8
Heat treatment was performed at 0 ° C. for 4 hours and at 150 ° C. for 3 hours to obtain a composite of PET and silica.

FIG. 23 shows the Si distribution near the surface of the cross section of the composite obtained by the EPMA measurement. A graded composite having a maximum silica concentration on the surface and a concentration decreasing in the thickness direction was obtained. When baked at 800 ° C. for 2 hours, a bag-shaped ash content of about 5.3% by weight was found.

Example 24 An oriented film of PET was immersed in a solution of chloroform and triethylamine (weight ratio = 50: 2) at 60 ° C. for 5 hours. A weight gain of about 18% by weight was observed. Then add 15 to 30 ℃ TMOS solution.
After soaking for a period of time, the test piece was taken out of the liquid, the surface solution was wiped off well, and the sample was kept in a vapor atmosphere of a 0.5 mol / l ammonia aqueous solution for about 5 hours. Further, it was dried at room temperature for 5 hours, heat-treated at 80 ° C. for 4 hours, and heat-treated at 150 ° C. for 3 hours to obtain a composite of PET and silica.

FIG. 24 shows the Si distribution in the cross section of the composite obtained by the EPMA measurement. A gradient composite having a high silica concentration on the surface and having a gradient in the thickness direction was obtained. The composite is formed within 15 μm from the surface, and the silica concentration is almost zero inside the composite, and the composite is not formed. When it was baked at 800 ° C. for 2 hours, about 1% by weight of ash was found.

Example 25 A PET film was immersed in tetrachloroethane at 110 ° C. for 5 hours. A weight gain of about 32% was seen. Then, it was immersed in an impregnating solution of TMOS and tetrachloroethane (weight ratio = 1: 1) at 30 ° C. for 1 hour.
After soaking for 0 hour, the test piece was taken out of the solution, the surface solution was wiped off well, and the sample was kept under a vapor atmosphere of 0.5 mol / l ammonia aqueous solution for about 5 hours. Further, it was dried at room temperature for 5 hours, heat-treated at 80 ° C. for 4 hours, and heat-treated at 150 ° C. for 3 hours to obtain a composite of PET and silica. E in Figure 25
The Si distribution of the cross section of the composite obtained by PMA measurement is shown.
When baked at 800 ° C. for 2 hours, about 3.5% by weight of ash was found.

Example 26 A sheet of polyester-based thermoplastic elastomer (Grelax E-500 manufactured by Dainippon Ink and Chemicals, Inc.) was impregnated with chloroform and tetraethoxytin (weight ratio = 10: 1). It was immersed for 5 days. A weight gain of about 100% by weight was observed. Then, the sample was taken out from the liquid, the surface solution was wiped off well, dried at room temperature for 24 hours, and then heat-treated at 100 ° C. for 24 hours to obtain a composite of a thermoplastic elastomer and tin oxide.

FIG. 26 shows the distribution of tin in the cross section of the composite obtained by EPMA. A graded composite having a maximum tin oxide concentration on the surface and graded toward the thickness direction was obtained. The inclined region is from the surface to about 140 μm,
The inside of that is a constant density. When calcined at 800 ° C. for 2 hours, about 2.5% by weight of ash was found.

(Example 27) 0.4 g of spherical pellets of polyester-based thermoplastic elastomer was added to a partial polymer of TMOS (MS-56; manufactured by Mitsubishi Chemical Corporation, molecular weight of about 1000), chloroform and ethylenediamine (weight ratio =). 2 g of the impregnation liquid of 10: 100: 1) was impregnated. Then, after keeping for 24 hours in a vapor atmosphere of 0.5 mol / l ammonia aqueous solution, it is kept at room temperature for 24 hours and at 80 ° C. for 24 hours.
Heat treatment was carried out for a time to obtain a composite of thermoplastic elastomer and silica.

FIG. 27 shows the silica distribution from the center to the surface of the cross section of the composite obtained by EPMA measurement. A gradient composite having a maximum silica concentration on the surface and a gradient toward the inside was obtained. The inclined layer extends over 900 μm from the surface, and the silica concentration is constant inside the inclined layer. When baked at 800 ° C. for about 2 hours, a bag-shaped ash content of about 14.5% by weight was recognized.

Example 28 Nylon-6 was immersed in a swelling liquid consisting of methanol and distilled water (weight ratio = 2: 1) and stirred at 80 ° C. for 3 hours. A weight gain of about 25% by weight was observed. Then, it was immersed in an impregnating solution of TMOS and methanol (weight ratio = 10: 1) at 30 ° C. for 4 days. Further, this nylon-6 sheet impregnated with TMOS was treated with methanol, distilled water and triethylamine (weight ratio = 80: 4).
It was immersed in a swelling solution consisting of 0: 1), stirred at 80 ° C. for 3 hours, and then immersed in a TMOS solution at 30 ° C. for 5 hours.
The sample was taken out of the liquid, the surface solution was wiped off well, dried at room temperature for 24 hours, and heat-treated at 80 ° C. in vacuum for 24 hours to obtain a composite of nylon-6 and silica.

Using EPMA, the distribution of Si in the cross section of the composite was measured. The results are shown in FIG. 28. A graded composite having a very high concentration of silica near the surface and a sharp decrease in concentration in the thickness direction was obtained. When baked at 800 ° C. for 2 hours, a bag-shaped ash content of about 15% by weight was found. By performing the gradient composite treatment twice, a component gradient composite having an extremely high silica concentration was obtained.

(Example 29) 30 sheets of vinyl chloride were used.
The impregnating solution was sufficiently impregnated by immersing it in an impregnating solution of TMOS and acetone (weight ratio = 1: 1) at 6 ° C. for 6 hours. About 12
A weight gain of 0% by weight was observed. Then, remove the sample from the liquid, wipe off the surface solution well, and
The vinyl chloride sheet impregnated with was held at 80 ° C. for about 15 hours to obtain a composite of vinyl chloride and silica. The distribution of Si in the cross section of the composite was measured using EPMA. FIG. 29
The results are shown in. Gradient composites with a maximum of two silica concentrations inside and a gradual slope were obtained. 800
After calcination at 2 ° C. for 2 hours, about 13.6% by weight of ash was found.

(Example 30) In Example 29, TM
The vinyl chloride sheet impregnated with OS is immersed in distilled water at 30 ° C. for about 3 hours, and then dried at room temperature for 15 hours to obtain 80
Heat treatment was carried out at 15 ° C. for about 15 hours to obtain a composite of vinyl chloride and silica. The distribution of Si in the cross section of the composite was measured using EPMA. The results are shown in FIG. There is obtained a tilted composite having a maximum peak silica concentration at the surface and having a gentle maximum inside and forming the maximum silica concentration at the center. When baked at 800 ° C. for 2 hours, about 20% by weight of ash was found.

(Example 31) A sheet of vinyl chloride was mixed with toluene and triisopropoxyaluminum (weight ratio = 4:
It was immersed in the impregnating liquid of 1) at 30 ° C. for 15 hours. About 22.
A weight gain of 5% by weight was seen. Then, the sample was taken out of the liquid, the surface solution was wiped off well, and then kept in a vapor atmosphere of 0.5 mol / l ammonia water for about 15 hours to obtain a composite of vinyl chloride and alumina. . EPMA
FIG. 31 shows the measurement result of Si distribution in the cross section of the composite according to. A graded composite having a sharp peak maximum silica concentration on the surface is obtained. When baked at 800 ° C. for 2 hours, about 1.5% by weight of ash was found.

Example 32 Polypropylene modified with carboxylic acid (Dynal GH-110, manufactured by Dainippon Ink and Chemicals, Inc.) was immersed in Toruell at 80 ° C. for about 6 hours. A weight gain of about 24% by weight was observed. Then 3
After soaking in TMOS solution at 0 ℃ for 15 hours, remove the sample from the solution and wipe off the solution on the surface well.
It was kept in a mol / l aqueous ammonia atmosphere for about 5 hours. Further, it is dried at room temperature for 3 hours, and at 80 ° C. for 24 hours, 1
Heat treatment was performed at 50 ° C. for 5 hours to obtain a composite of modified polypropylene and silica. Si of composite cross section by EPMA
The measurement result of the distribution is shown in FIG. A morphologically graded composite with a maximum silica concentration on the surface was obtained. 800 ° C
After calcination for 2 hours, about 6.7% by weight of ash was found.

Example 33 A styrene copolymer (Clearpact TI-300, manufactured by Dainippon Ink and Chemicals, Inc.) was immersed in an impregnating solution of MS-51 and methanol (weight ratio = 1: 1) at 50 ° C. It was immersed for 90 minutes. A weight gain of about 17% by weight was observed. Then, remove the sample from the liquid,
After the surface solution was wiped off well, it was kept in an atmosphere of 0.6 mol / l ammonia aqueous solution for about 5 hours, dried at room temperature for 3 hours, and further heat-treated at 80 ° C. for 24 hours to carry out styrene copolymer and silica. A complex with FIG. 33 shows the measurement result of the Si distribution in the cross section of the composite by EPMA. A graded composite having a morphology having a maximum silica concentration on the surface was obtained. When baked at 800 ° C. for 2 hours, about 3.5% by weight of ash was found.

(Comparative Example 3) A homogeneous transparent sol solution comprising MS-51, methanol and distilled water (weight ratio = 4: 1: 0.8) was prepared. The sol solution was stirred at 25 ° C. for 2 days, then applied onto a sheet of nylon-6 and an acrylic resin and spin-coated (1000 rpm, 20 seconds). Nylon-6 and the acrylic resin were both sol solutions. I flicked and couldn't coat. Furthermore, coating was attempted by the dip coating method, but the sol liquid could not be coated as a droplet on nylon-6 and acrylic resin.

Comparative Examples 4 and 5 MS-51 was directly applied to a nylon-6 sheet and an acrylic resin sheet (0.5 mm).
Thickness) and spin coat (1000 rpm,
20 seconds). MS-51 is not repelled,
It was homogeneously coated. After coating, it was dried at room temperature for 5 hours and further heat-treated at 80 ° C. for 24 hours.

In order to examine the appearance of silica on the surface of the coated organic polymer, the EPMA spectrum of Si on the surface was measured. The results are shown in FIG. 34 (Comparative Example 4, Nylon-6) and FIG. 35 (Comparative Example 5, acrylic resin). Silica is found only on the surface part and is not permeated into the organic polymer. Moreover, the amount of silica applied is extremely small. 8
When baked at 00 ° C. for 2 hours, no ash was found in nylon-6, and the presence of ash was confirmed in the acrylic resin, but the remaining amount could not be obtained in a very small amount.

(Example 34) 5 sheets of acrylic resin were used.
It was immersed in 0 ° C. methanol for 20 minutes. About 22% by weight
An increase in weight was observed. Then, after immersing in a solution of tetrabutoxytitanium and acetylacetone (molar ratio = 1: 2) at room temperature for 4 hours, the solution was taken out of the solution, the surface was washed with methanol, and dried at room temperature for about 15 hours. Furthermore,
Heat treatment was carried out at 80 ° C. for 24 hours to obtain a composite of acrylic resin and titanium oxide. FIG. 36 shows the distribution of Ti in the cross section of the composite obtained by the EPMA measurement. A composite having a morphology with the maximum concentration of titania on the surface has been obtained. 8
When it was calcined at 00 ° C. for 2 hours, 3.5% by weight of ash was found.

(Example 35) A polyvinyl chloride sheet was immersed in acetone at 30 ° C for 30 minutes. A weight gain of about 150% by weight was observed. Then, after immersing in a solution of tetraethoxy titanium and acetic acid (molar ratio = 2: 1) for 4 hours at room temperature, the solution was taken out of the solution, the surface was washed with methanol, and dried at room temperature for about 15 hours. 2 at 80 ° C
Heat treatment was performed for 4 hours to obtain a composite of polyvinyl chloride and titanium oxide. FIG. 37 shows the distribution of Ti in the cross section of the composite obtained by the EPMA measurement. A composite having a morphology with the maximum concentration of titania on the surface has been obtained. When baked at 800 ° C. for 2 hours, 3.5% by weight of ash was found.

(Example 36) Nylon-6 sheet 4
It was immersed in a mixed solution of 1.2 mol / l ammonia water and methanol (weight ratio = 2: 1) at 0 ° C. for 2 hours. About 9
A weight gain of wt% was seen. Next, after holding in a TMOS vapor atmosphere heated to 100 ° C. for 3 hours, it was taken out and dried at room temperature for 2 hours. Further, heat treatment was carried out at 80 ° C. for 24 hours to obtain a composite of nylon-6 and silica. FIG. 38 shows S of the cross section of the composite obtained by EPMA measurement.
The distribution of i is shown. A composite having a morphology having a maximum silica concentration on the surface is obtained. When baked at 800 ° C. for 2 hours, 0.5% by weight of ash was found.

Example 37 An impregnating solution containing 10 g of TMOS, 10 g of acetone and 1.2 g of water was prepared, and immediately after the preparation of the impregnating solution, a polyvinyl chloride sheet was immersed for 2 hours (30 ° C.). A weight gain of 63% by weight was observed. The resin was taken out, dried at room temperature for 2 hours, and then heat-treated at 80 ° C. for 24 hours to obtain a composite of polyvinyl chloride and silica. FIG. 39 shows S of the cross section of the composite obtained by EPMA measurement.
The distribution of i is shown. When baked at 800 ° C. for 2 hours, 21% by weight of ash was found.

(Example 38) 4.6 g of distilled water was added to the impregnating liquid.
(Example 38) With respect to the case of addition, the same examination as in Example 37 was conducted. FIG. 40 shows the distribution of Si in the cross section of the composite obtained by the EPMA measurement. Incidentally, when water is not added, silica is a composite in a form in which it is almost uniformly distributed, and the sloped form of the composite obtained by adding water to the impregnating liquid is greatly different. I understand. When baked at 800 ° C for 2 hours, the ash content is 3
% By weight.

Example 39 The impregnating solution used in Example 37 was stirred at 30 ° C. for 2 hours, and then a polyvinyl chloride sheet was allowed to stand for 2 hours (30 ° C.). The resin was taken out, dried at room temperature for 2 hours, and then heat-treated at 80 ° C. for 24 hours to obtain a composite of polyvinyl chloride and silica. FIG. 41 shows the distribution of Si in the cross section of the composite obtained by the EPMA measurement. When baked at 800 ° C for 2 hours, 1
8 wt% ash was found. By using the impregnating liquid in which TMOS was reacted for 2 hours, the gradient morphology of the composite was changed.

(Example 40) A polyvinyl chloride sheet was immersed in an impregnating solution of TMOS and toluene (weight ratio = 1: 1) in an amount of 30.
It was soaked at 24 ° C. for 24 hours. A weight gain of about 50% by weight was observed. Then, the polymer was taken out of the solution, and the surface solution was wiped off thoroughly and kept in a 0.2 mol / l hydrochloric acid aqueous solution for about 5 hours. After drying at room temperature for 15 hours,
Heat treatment was performed at 80 ° C. for 24 hours to obtain a composite of polyvinyl chloride and silica. The thickness of the composite was about 600 μm. Scanning electron microscopy (SE
M), 600-800n near the surface
m silica particles are observed, and the inside of the surface is about 150 μm, 200-400 nm inside, and 150-20 near the center.
0 nm silica particles were observed.

(Example 41) A polyvinyl chloride sheet was impregnated with TMOS and toluene (weight ratio = 1: 1) in an amount of 30.
It was soaked at 24 ° C. for 24 hours. A weight gain of about 50% by weight was observed. Then, the polymer was taken out of the solution, the surface solution was wiped off thoroughly, and the polymer was kept in an aqueous ammonia solution of 0.6 mol / l for about 5 hours. After drying at room temperature for 15 hours, heat treatment was performed at 80 ° C. for 24 hours to obtain a composite of polyvinyl chloride and silica. The thickness of the composite is about 600 μm
Met. When the silica particles in the composite were observed with a scanning electron microscope (SEM), it was 20-10 near the surface.
0 nm silica particles can be seen, about 100 μm from the surface, 100-200 nm inside, 200-3 near the center.
00 nm silica particles were observed.

Example 42 A polyvinyl chloride sheet was immersed in a solution of acetone and acetic acid (weight ratio = 10: 1) at 30 ° C. for 1 hour. A weight gain of about 130% by weight was observed. Then, it was immersed in an impregnating solution of TMOS and acetone (weight ratio = 1: 1) at 30 ° C. for 16 hours, the polymer was taken out of the solution, and the solution on the surface was wiped off thoroughly, and the solution was immersed in a 0.7 mol / l aqueous ammonia solution. Hold for about 5 hours. Furthermore, after drying at room temperature for 15 hours, heat treatment was performed at 80 ° C. for 24 hours to obtain a composite of polyvinyl chloride and silica.
When the silica particles in the composite were observed with a scanning electron microscope (SEM), it was 150 in the layer from the surface to 20 μm.
Fine silica particles with a size of not more than nm were observed, a layer of giant particles of 500-1000 nm was present inside the layer, and a layer of silica particles of 80-200 nm was observed near the center.

[0140]

The present invention provides a molding material, electric / electronic parts,
Useful as various materials such as machine parts, automobile parts, sports equipment, films, fibers, etc., excellent in heat resistance properties, mechanical properties such as breaking strength, and adhesiveness, and transparency can be changed as desired. It is possible to provide an excellent method for producing a complex of an organic polymer in which a metal oxide has a continuous component concentration gradient structure and a metal oxide.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing various forms of a complex of an organic polymer in which metal oxide particles have a component gradient structure and a metal oxide, which are produced by the production method of the present invention. Each of a to h represents one form of the inventive complex. The vertical axis of each of a to h represents the concentration of the metal oxide, and the horizontal axis represents the distance (thickness) of the cross section of the organic polymer.

FIG. 2 is a diagram showing a result of measurement of Si distribution in a cross section of the composite of nylon-6 and silica obtained in Example 1 by EPMA.

FIG. 3 is a diagram showing the measurement results of Si distribution in a cross section of the composite of nylon-6 and silica obtained in Example 3 by EPMA.

FIG. 4 is a diagram showing a result of measurement of Si distribution in a cross section of a composite of nylon-6 and silica obtained in Example 4 by EPMA.

FIG. 5 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of nylon-6 and silica obtained in Example 5 by EPMA.

FIG. 6 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of nylon-6 and silica obtained in Example 6 by EPMA.

FIG. 7 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of nylon-6 and silica obtained in Example 7 by EPMA.

FIG. 8 is a diagram showing the measurement results of Si distribution in a cross section of the composite of nylon-6 and silica obtained in Example 8 by EPMA.

9 is a diagram showing the results of measurement of Si distribution in a cross section of a composite of nylon-6 and silica obtained in Example 9 by EPMA. FIG.

10 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of nylon-6 and silica obtained in Example 10 by EPMA. FIG.

11 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of vinyl chloride and silica obtained in Example 11 by EPMA. FIG.

FIG. 12 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of vinyl chloride and silica obtained in Example 12 by EPMA.

13 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of vinyl chloride and silica obtained in Example 13 by EPMA. FIG.

FIG. 14 is a diagram showing a result of measurement of Si distribution in a cross section of a composite of the acrylic resin and silica obtained in Example 14 by EPMA.

FIG. 15 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of the acrylic resin and silica obtained in Example 15 by EPMA.

16 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of the acrylic resin and silica obtained in Example 16 by EPMA. FIG. An enlarged view near the surface is also shown.

FIG. 17 is a diagram showing the measurement results of Si distribution in the cross section of the composite of nylon-66 and silica obtained in Example 17 by EPMA.

FIG. 18 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of polypropylene and silica obtained in Example 18 by EPMA.

FIG. 19 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of the polyacetal and silica obtained in Example 19 by EPMA.

20 is a diagram showing the measurement results of Si distribution in the cross section of the composite of polyvinylidene fluoride and silica obtained in Example 20 by EPMA. FIG.

21 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of the polybutylene terephthalate and silica obtained in Example 21 by EPMA. FIG. An enlarged view near the surface is also shown.

22 is a diagram showing the measurement results of Si distribution in the cross section of the composite of polybutylene terephthalate and silica obtained in Example 22 by EPMA. FIG.

23 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of polyethylene terephthalate and silica obtained in Example 23 by EPMA. FIG.

FIG. 24 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of polyethylene terephthalate and silica obtained in Example 24 by EPMA.

25 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of polyethylene terephthalate and silica obtained in Example 25 by EPMA. FIG.

FIG. 26 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of the thermoplastic polyester elastomer and tin oxide obtained in Example 26 by EPMA.

FIG. 27 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of the thermoplastic polyester elastomer obtained in Example 27 and silica by EPMA.

28 is a diagram showing the measurement results of Si distribution in the cross section of the composite of nylon-6 and silica obtained in Example 28 by EPMA. FIG.

FIG. 29 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of vinyl chloride and silica obtained in Example 29 by EPMA.

30 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of vinyl chloride and silica obtained in Example 30 by EPMA. FIG.

31 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of vinyl chloride and alumina obtained in Example 31 by EPMA. FIG.

FIG. 32 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of the carboxylic acid-modified polypropylene obtained in Example 32 and silica by EPMA.

FIG. 33 Si of the cross section of the composite of the styrene-based copolymer and silica obtained in Example 33, taken by EPMA.
It is a figure which shows the measurement result of distribution.

FIG. 34 is a diagram showing a result of measurement of Si distribution in a cross section of a composite by EPMA of a sample obtained by coating silica on nylon-6 obtained in Comparative Example 4.

FIG. 35 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite by EPMA, of the sample obtained by coating silica on the acrylic resin obtained in Comparative Example 5.

36 is a diagram showing the results of measurement of the Ti distribution in the cross section of the composite of the acrylic resin and titania obtained in Example 34 by EPMA. FIG.

37 is a diagram showing the results of measurement of the Ti distribution in the cross section of the composite of polyvinyl chloride and titania obtained in Example 35 by EPMA. FIG.

38 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of nylon-6 and silica obtained in Example 36 by EPMA. FIG. An enlarged view near the surface is also shown.

FIG. 39 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of polyvinyl chloride and silica obtained in Example 37 by EPMA.

FIG. 40 is a diagram showing the result of measurement of the Si distribution in the cross section of the composite of polyvinyl chloride and silica obtained in Example 38 by EPMA.

41 is a diagram showing the results of measurement of the Si distribution in the cross section of the composite of polyvinyl chloride and silica obtained in Example 39 by EPMA. FIG.

Claims (13)

[Claims] 1. A component concentration, characterized in that a metal alkoxide is impregnated into an organic polymer solid so as to have a concentration gradient, and then the metal alkoxide is subjected to a polycondensation reaction to be immobilized as a metal oxide. A method for producing a composite of an organic polymer having a graded structure and a metal oxide. 2. A solid organic polymer is immersed in a metal alkoxide or a solution containing a metal alkoxide, and the immersion operation is completed before the metal alkoxide is uniformly impregnated in the organic polymer, whereby the organic polymer internal The method for producing a composite of an organic polymer having a component concentration gradient structure and a metal oxide according to claim 1, wherein a concentration gradient structure of the metal alkoxide is formed in the. 3. A solid organic polymer is immersed in a solution containing a metal alkoxide and water, and a solid organic polymer is impregnated with the metal alkoxide, whereby a concentration gradient structure of the metal alkoxide is formed inside the organic polymer. 2. The method for producing a composite of an organic polymer having a component concentration gradient structure and a metal oxide according to claim 1, wherein 4. A solid organic polymer is immersed in a metal alkoxide or a solution containing a metal alkoxide to impregnate the solid organic polymer with the metal alkoxide, and then part of the metal alkoxide is removed from the organic polymer. To form a metal alkoxide concentration gradient structure inside the organic polymer, and then subject the metal alkoxide to a polycondensation reaction, which is a composite of an organic polymer having a component concentration gradient structure and a metal oxide. Body manufacturing method. 5. A solid organic polymer is uniformly impregnated with a metal alkoxide, and then the organic polymer is impregnated with water and / or an acidic catalyst or a basic catalyst so as to have a concentration gradient. A method for producing a composite of an organic polymer having a component concentration gradient structure and a metal oxide, which comprises performing a condensation reaction. 6. A solid organic polymer swollen with a swelling liquid in advance is used, and the organic polymer having a gradient structure of component concentration and the metal oxide according to any one of claims 2 to 5. And a method for producing a complex with. 7. A solid organic polymer impregnated with a metal alkoxide is immersed in an aqueous solution containing water and / or an acidic catalyst or a basic catalyst, and water and / or an acidic catalyst or a basic catalyst is added to the organic polymer. 7. The method according to claim 1, wherein the metal alkoxide in the organic polymer is subjected to a polycondensation reaction to immobilize the metal alkoxide to immobilize it as a metal oxide. 8. A solid organic polymer impregnated with a metal alkoxide is held in a steam atmosphere containing an acidic catalyst or a basic catalyst to react the metal alkoxide inside the organic polymer to obtain a metal oxide. The method according to claim 1, wherein the method is fixed. 9. A solid organic polymer is immersed in a mixed solvent consisting of an organic solvent for swelling the organic polymer and water and / or a solution of an acidic catalyst or a basic catalyst to swell the organic polymer. In addition, the organic polymer is impregnated with water and / or an acidic catalyst or a basic catalyst, and then the organic polymer is immersed in a metal alkoxide or a solution containing the metal alkoxide to carry out a polycondensation reaction of the metal alkoxide. And a method for producing a composite of an organic polymer having a gradient structure of component and a metal oxide. 10. As the organic polymer, polyamide, polyolefin, polyester, polyvinyl chloride, acrylic resin, polystyrene copolymer, thermoplastic elastomer,
At least one selected from polyacetals and fluororesins is used, and the composite of an organic polymer having a component concentration gradient structure and a metal oxide according to any one of claims 1 to 9 is used. Production method. 11. The ratio of the maximum value and the minimum value of the local concentration of the metal oxide distributed in the composite of the obtained organic polymer and the metal oxide is 1.5 or more. The method for producing a composite of an organic polymer having a component concentration gradient structure according to any one of claims 1 to 9 and a metal oxide, which is characterized in that. 12. The organic polymer according to claim 11, wherein the obtained composite of the organic polymer and the metal oxide has a gradient structure of the component concentration of the metal oxide in the thickness direction of the composite. And a method for producing a complex of a metal oxide. 13. A solid organic polymer impregnated with a metal alkoxide is impregnated with an acidic catalyst or a basic catalyst so as to have a concentration gradient, and a polycondensation reaction of the metal alkoxide is carried out to form an organic polymer in the organic polymer. 1. A method for producing a composite of an organic polymer having a component concentration gradient structure and a metal oxide, wherein the dispersed metal oxide has a shape in which the particle size is continuously changed.