JPH08283425A - Component gradient composite of organic polymer and metal oxide and its production - Google Patents

Abstract

PURPOSE: To obtain the subject component gradient composite favorable in terms of effectively manifesting such characteristics as to be seen in the case of high content of the metal oxide as a component, less apt to develop cracks, and having such good moldability as not to cause only the surface layer thereof when heated or after change in its properties with the lapse of time. CONSTITUTION: This composite essentially comprises an organic polymer component and a metal oxide component A, having such component gradient structure that the content of the metal oxide component A in the composite lies continuously changed from the surface of the composite toward the depth, being 5-100wt.% and 0-50wt.% in the regions presenting higher content levels including the maximum and lower levels including the minimum, respectively, and the content ratio in these regions stands at >=1.5. This composite is obtained by the following process: a homogeneous solution containing the organic polymer and a metal alkoxide is applied on an organic polymer or inorganic base material and held in an aerial atmosphere containing water and/or a polymerization catalyst for the metal alkoxide followed by drying and then heat treatment.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composite of a metal oxide obtained by a hydrolysis / polycondensation reaction of a metal alkoxide and an organic polymer, in which the content of the metal oxide is inclined in the thickness direction of the composite. The present invention relates to a gradient composite of an organic polymer and a metal oxide having different regions, and a method for producing the same.

[0002]

2. Description of the Related Art Various methods have been studied so far in order to modify the performance of organic polymers, and a plurality of organic polymers are blended to prepare a resin having novel properties, It is widely practiced to prepare a molded product having desired properties by compounding it with a reinforcing material.

[0003] For example, in blending composites of organic polymers, organic polymers exhibiting compatibility are searched for, and a homogeneous composite is formed by a method such as melt mixing, or incompatible organic polymers are micro-converted. Organic polymers have been modified according to the purpose of use by blending by devising mixing conditions so as to have a specific dispersion structure including a phase separation structure.

On the other hand, physical property modification by mixing and dispersing a reinforcing material in an organic polymer has been extensively studied. Specifically, it is widely practiced to mix organic or inorganic fibrous substances such as aramid fiber, pulp, glass fiber, and carbon fiber, and powdered inorganic materials such as calcium carbonate, silica, and alumina with organic polymers. There is.

In particular, compounding by mixing with an inorganic material has been widely studied as an easy high-performance modifying means because the excellent heat resistance and mechanical properties of the inorganic material can be utilized. However, in the case of an inorganic material, it is not possible to control the dispersion state microscopically due to the difference in essential properties from the organic polymer material in terms of its heat insolubility, chemical insolubility, high specific gravity, and surface characteristics. It is not simple, and is generally compounded for the purpose of obtaining a bulk composite material that is as homogeneous as possible.

That is, in order to enhance the modifying effect, a material having a smaller shape and having good wettability with the matrix polymer is selected as the reinforcing inorganic material, and a predetermined amount thereof is dispersed as homogeneously as possible. This is an important factor in compounding. However, even in this case, there is a problem that as the inorganic material becomes finer particles, it becomes more difficult to disperse it homogeneously, and the energy and cost become high.

Therefore, in order to obtain a high-performance composite material of an organic material and an inorganic material, which is composed of an organic material and a particulate inorganic material, is microscopically homogeneous and has a controlled dispersion structure, Such a method of simply mixing an inorganic material in the form of fine particles with an organic polymer is quite difficult and requires the development of a new technique.

The present inventors have conducted research and development on a novel composite material of an organic material and an inorganic material effective for such a purpose. One example thereof is a micro hybrid composite material of a metal oxide obtained from a metal alkoxide and an organic polymer.

The complex is prepared by subjecting a metal alkoxide to hydrolysis and polycondensation in-situ in an organic polymer matrix to obtain a nano-order to a micro-order.
Der metal oxide particles are highly wettable in an organic polymer and are uniformly dispersed and compounded, and are a composite of an organic material and an inorganic material, which have excellent properties including mechanical properties. It is a material.

However, if the proportion of the metal oxide component in the composite is excessively increased, a good composite material can be obtained due to the difference in the essential characteristics between the organic polymer to be composited and the metal oxide. It's gone. That is, if the metal oxide content is high, cracks are likely to occur, become brittle, have poor formability, and are deformed such as warped and distorted. On the other hand, if the metal oxide content is very small, desired composite physical properties cannot be obtained.

[0011]

The problem to be solved by the present invention is to obtain a good complex capable of effectively exhibiting the properties up to the high content region of the metal oxide. Specifically, a component-graded composite of an organic polymer and a metal oxide, and a process for producing the same, which has good moldability such that cracks hardly occur, and peeling of only the surface layer does not occur due to heating or aging To provide the law.

[0012]

[Means for Solving the Problems] The inventors of the present invention have made diligent research to obtain a composite having an excellent property in a wide composition range in a composite composed of an organic polymer and a metal oxide. It has been completed.

That is, the present invention is a composite of an organic polymer component, an organic polymer containing at least two components of a metal oxide component (A) and a metal oxide, which is deep from the surface of the complex. 5 to 100% by weight, where the content of the metal oxide component (A) in the composite has a graded component structure and the content is the highest, and the content is the lowest. It is a component gradient composite of an organic polymer and a metal oxide, which is characterized in that the content ratio in the place is 0 to 50% by weight, and the content ratio in the high place and the low place is 1.5 or more.

The component gradient composite of the organic polymer and the metal oxide of the present invention is specifically described in the metal oxide component (A).
Is a component-graded composite of an organic polymer and a metal oxide, which is obtained by hydrolysis / polycondensation of a metal alkoxide or its low condensate in the presence of an organic polymer component. .

The component gradient composite of the organic polymer and the metal oxide of the present invention is specifically, the metal oxide component (A).
Is present on at least one surface of the composite in excess of the average content of the composite as a whole.

Furthermore, in the component gradient composite of the organic polymer and the metal oxide of the present invention, the metal oxide component (A) has a mean content of the metal oxide component (A) of not more than the average content of the whole composite on at least one surface. It is a component-graded composite of an organic polymer and a metal oxide, characterized by being present in a ratio.

In addition, the component gradient composite of the organic polymer and the metal oxide of the present invention has a thickness (in which the content of the metal oxide component (A) continuously changes in the depth direction of the composite ( d1) is a component gradient composite of an organic polymer and a metal oxide, characterized in that it is larger than the thickness (d2) showing the highest content of the metal oxide component (A).

Furthermore, the component-gradient composite of the organic polymer and metal oxide of the present invention is characterized in that the size of the metal oxide in the composite is 0.01 to 5 μm in average diameter. The component gradient composite of a polymer and a metal oxide, and the size of the metal oxide in the composite have an average diameter of 0.01 to 0.5 μm.
And a component gradient composite of an organic polymer and a metal oxide.

In the gradient composite of the organic polymer and the metal oxide of the present invention, the metal oxide component is hydrolyzed / polycondensed of the metal alkoxide or its low condensate in the presence of the organic polymer component. And a metal alkoxide or a condensate thereof is represented by the general formula 1, which is a gradient composite of an organic polymer and a metal oxide.

(General formula 1)

Embedded image (In the formula, M represents a silicon atom, R represents C _m H _{2m + 1} , m represents an integer of 1 to 4, and n represents an integer of 1 to 10.)

Further, the component gradient composite of an organic polymer and a metal oxide of the present invention is characterized in that the organic polymer component is a thermosetting resin, and the component gradient composite of an organic polymer and a metal oxide. It is the body.

The component gradient composite of an organic polymer and a metal oxide according to the present invention is a component gradient composite of an organic polymer and a metal oxide, wherein the organic polymer component is a thermoplastic resin. Is.

In the present invention, a homogeneous solution comprising an organic polymer, a metal alkoxide, a common solvent thereof and / or a polymerization catalyst for the metal alkoxide is applied onto an organic polymer or an inorganic substrate, and water and / or Alternatively, a component gradient composite of an organic polymer and a metal oxide is characterized in that it is dried and heat-treated after being held in an atmosphere containing a metal alkoxide polymerization catalyst and / or an organic solvent in the air. It includes a method.

The method for producing a component-gradient composite of an organic polymer and a metal oxide according to the present invention is characterized in that the metal oxide component is hydrolyzed from a metal alkoxide or a low condensate thereof in the presence of an organic polymer component. An organic polymer obtained by being uniformly dispersed in an organic polymer component by polycondensation, wherein the metal alkoxide is a silicon alkoxide represented by the general formula 1 or a low condensate thereof. It is a method for producing a component-gradient composite with a metal oxide.

(General formula 1)

[Chemical 4] (In the formula, M represents a silicon atom, R represents C _m H _{2m + 1} , m represents an integer of 1 to 4, and n represents an integer of 1 to 10.)

Further, the method for producing a component gradient composite of an organic polymer and a metal oxide of the present invention is the same or different basic as a polymerization catalyst for a metal alkoxide contained in an atmosphere and / or a homogeneous solution. It includes a method for producing a component-graded complex of an organic polymer and a metal oxide, which is characterized by using a substance.

That is, the present invention provides a composite of an organic polymer and a metal oxide containing at least one organic polymer and a metal oxide, wherein the metal oxide component contained is inside the composite. Exists in different concentrations and forms a component gradient structure in which the metal oxide component concentration continuously changes in the depth direction from the surface of the composite,

The concentration of the metal oxide component in the composite is 5-100% by weight at the highest concentration and 0-50 at the lowest concentration.
The present invention relates to a component gradient composite of an organic polymer and a metal oxide, which is characterized by having a weight percentage and a content ratio of a high portion and a low portion of 1.5 or more. It is mainly composed of a component gradient composite of an organic polymer and a metal oxide, which is composed of a metal oxide obtained by polycondensing a metal alkoxide or a low condensate thereof in the presence of a polymer and an organic polymer.

In the composition gradient composite of the organic polymer and the metal oxide, at least one surface of the composite is
Those in which the metal oxide component is present in excess of the average metal oxide concentration of the composite, or those in which the metal oxide component is below the average metal oxide concentration of the composite on at least one surface are included. Further, the component gradient composite of the organic polymer and the metal oxide includes one having a metal oxide concentration gradient larger than the thickness having the highest metal oxide content in the depth direction.

Further, the component gradient composite of the organic polymer and the metal oxide includes one in which the size of the metal oxide contained in the composite is 0.01 μm to 5 μm in average diameter. Further, the component gradient composite of the organic polymer and the metal oxide,
The form includes a coating film, a thread, a film, a spherical shape, and a molded body having various shapes such as a block.

The present invention is basically based on the fact that the metal oxide has a region which continuously changes in the depth direction while maintaining homogeneity in the organic polymer except in the depth direction. Therefore, simply by irregular aggregation or phase separation, those having regions with different metal oxide concentrations discontinuously,
It is different from that having a uniform coating film having a constant metal oxide content formed on the surface of the substrate by coating.

The organic polymer that can be used in the present invention includes
Polycondensation of a metal alkoxide in the presence of an organic polymer, as long as it is possible to form a homogeneous composite of an organic polymer and a metal oxide, is not particularly limited,
Specifically, for example, a thermosetting resin such as a phenol resin, an epoxy resin, an acrylic resin, an alkyd resin, a melamine resin, and a urea resin, a thermoplastic resin such as nylon, a polyester, an acrylic resin, or polybutadiene or SBS. It is possible to use various rubber-based resins and the like, and particularly thermosetting resins, especially epoxy resins, acrylic resins, alkyd resins, and melamine resins are preferable.

From the viewpoint of ease of production, it is desirable to use an organic polymer or a precursor resin thereof that dissolves or swells in a homogeneous solution consisting of a metal alkoxide, a condensate thereof, or a solvent and the like.

As the metal alkoxide in the present invention, the silicon alkoxide represented by the general formula 1 and / or its condensate is used. As other metal alkoxides, metal alkoxides such as Ti, Al, and Zr can be used, but when an alkoxide of Si or a mixture with other metal alkoxides containing Si as a main component is used, hydrolysis and heavy metal alkoxides are used. The reaction rate of condensation is slow, which is particularly preferable in controlling the concentration gradient.

The component-graded composite of the organic polymer and the metal oxide in the present invention has a content (hereinafter sometimes simply referred to as a metal oxide content) in the composite of the metal oxide component (A). .) Is 5 to 100% by weight, and the lowest part is preferably 0 to 50% by weight.

If the metal oxide content in the highest portion is less than 5% by weight, the effect of complexing is insufficient, and if the metal oxide content in the lowest portion exceeds 50% by weight, it is complex. This is not preferable because the body becomes brittle, cracks and the like are likely to occur, and the total thickness of the composite must be extremely thin.

The ratio of the highest metal oxide content to the lowest metal oxide content must be 1.5 or more, preferably 2 or more. If the ratio is less than 1.5, the effect as a component gradient composite is insufficient. Further, when the thickness (d1) in which the metal oxide concentration changes in a gradient in the depth direction is larger than the thickness (d2) of the region showing the highest metal oxide content, the effect as a graded composite material is more enhanced. It is clear.

The size of the metal oxide in the present invention is 0.01 μm to 5 μm in diameter. In particular, when the size of the metal oxide is 0.01 μm to 0.5 μm and the organic polymer used is transparent, the composite of the present invention has a transparent to translucent appearance. When the size of the metal oxide is 0.5 μm to 5 μm, it has a semitransparent to opaque appearance.

In any case, in the component gradient composite composed of a metal oxide and an organic polymer obtained by polycondensing a metal alkoxide or a condensate thereof in the presence of an organic polymer,
Compared to mixing and dispersing the metal oxide particles produced in advance and the organic polymer, the particle size of the metal oxide particles can be controlled to a very small particle size.

As the conventional particles for reinforcing addition of silica or the like, particles having a diameter of about 1 to 2 μm are the limit in view of possibility of homogeneous dispersion and cost. When smaller particles are used, it is often difficult to uniformly disperse or control them due to the difference in density with the organic polymer and the aggregation of the particles.

In the present invention, it is possible to obtain a component-gradient composite in which the average particle diameter of the metal oxide is homogeneously contained up to the nanometer size and the dispersion structure is controlled.
The size of the metal oxide in the present invention is given a numerical value of 0.01 μm because it is difficult to capture a particle size of 0.01 μm or less by measurement with a scanning electron microscope or the like. It doesn't matter if it is small.
However, when the average particle diameter is 5 μm or more, it becomes difficult to obtain a homogeneous component gradient composite.

As a method for obtaining a component gradient composite of an organic polymer and a metal oxide of the present invention, the finally obtained component gradient composite is maintained at a microscopically homogeneous dispersion and at the same time the depth of the composite is increased. Any material may be used as long as it has a region where the metal oxide concentration continuously changes in the depth direction, and is not particularly limited by the manufacturing method.

However, to give an example of a specific production method thereof, for example, an organic polymer component and a metal alkoxide or a condensate thereof, and / or water, and / or a catalyst, and / or an organic solvent are used as raw materials. , Hydrolysis and polycondensation of metal alkoxides that are heterogeneous in the depth direction of the finally obtained complex when performing hydrolysis / polycondensation of metal alkoxide, curing reaction of resin, and / or solvent casting The operation is performed to generate.

More specifically, of the above raw materials, specific raw material components (for example, metal alkoxide, basic catalyst and water)
It is possible to develop a gradient metal oxide concentration distribution by imparting the concentration distribution of (1) to the depth direction or performing external stimulation (for example, heating) from one direction.

For example, a homogeneous solution comprising an organic polymer, a metal alkoxide or a condensate thereof, a common solvent thereof and / or a polymerization catalyst of a metal alkoxide is coated on a substrate, and water and / or a metal alkoxide is polymerized. By holding the catalyst and / or the organic solvent in an atmosphere containing air and then performing drying and heat treatment, a gradient of the metal oxide concentration in the coating film can be exhibited.

In the present invention, the same or different acids or basic substances are used as the polymerization catalyst for the metal alkoxide contained in the atmosphere or in the homogeneous solution. In particular, various amine compounds and basic substances such as ammonia are used. It is preferable to use it for making fine particles of the metal oxide in the gradient composite and controlling the gradient of the component.

In the present invention, the organic solvent contained in the atmosphere is preferably one that is homogeneously miscible with the solution containing an organic polymer or the like, and is of a different type from the organic solvent already contained in the solution. Is particularly preferable.

The component-graded composite of the organic polymer and metal oxide of the present invention can be used for various molded products such as coating films, threads, films and fine particles, and molding raw materials. It is also possible to prepare it in a system containing other inorganic fibers such as metal and glass and / or organic fibers such as cellulose and aramid and / or powders thereof.

In the component gradient composite of the organic polymer and the metal oxide of the present invention, for example, although the average concentration of the metal oxide in the entire composite is very low, 5 to 100 is present on at least one surface portion. It is possible to have a metal oxide concentration as high as wt% and a structure in a dispersed state in which the concentration gradually decreases from the surface portion to the inside.

Therefore, in this case, only the surface portion has characteristics due to the higher metal oxide concentration, for example, high hardness, excellent solvent resistance and heat resistance, but the layer is limited to a constant thickness from the surface. As a result, a deterioration factor such as a crack is not seen, and since the components are graded toward the inside, peeling of only the surface layer does not occur due to heating or aging, and a stable composite material The property can be expressed. On the contrary, it is also possible that the metal oxide concentration inside is higher than that at the surface portion, or that the concentration distribution of the multi-layer is more complicated.

[0051]

EXAMPLES Next, the present invention will be further described with reference to examples. In the examples,% is based on weight unless otherwise specified.

(Example 1) Acrylic resin (manufactured by Dainippon Ink and Chemicals, Inc .: Acridic A-405) 3
0 g (resin content 57%; xylene, butanol solution), melamine resin (Dainippon Ink and Chemicals, Inc .: Super Beckamine G-821) 6.5 g (resin content 60%;
Isobutyl solution), epoxy resin (Dainippon Ink and Chemicals, Inc .: Epiclon 1050) 2.5 g, tetramethoxysilane (hereinafter referred to as TMOS: special grade reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 10 g, and dehydrated tetrahydrofuran (THF; Kanto Chemical Co., Ltd. special grade reagent) 20g
A homogeneous solution consisting of

Drop on the substrate (nylon-66 plate),
After leaving it in a saturated steam atmosphere with an ammonia concentration of 0.09 mol / l for about 5 hours, it is further heated to 28 ° C. and 50% of about 1%.
Left for days. A heat treatment was carried out at 80 ° C. for 2 hours and further at 150 ° C. for 1 hour to obtain an acrylic resin / silica-based coating film (about 40 μm thick).

Electron beam microanalyzer (EPMA)
FIG. 1 shows the result of scanning the distribution of Si in the cross section of the coating film from the surface using. From the results shown in FIG. 1, it can be seen that a strong Si distribution is seen on the surface side and the Si concentration continuously changes over the depth direction of about 40 microns.

Further, the Si concentration distribution in the depth direction is
It was found that a uniform Si concentration was maintained in the direction perpendicular to the depth direction by showing the same distribution even when measured at several different positions on the same coating film. From the above results, the obtained coating film has a silica-containing layer having a concentration higher than the average metal oxide concentration of the entire coating film on the surface portion, is homogeneous in the depth direction and the direction orthogonal to the depth direction, and Was confirmed to be a composite (coating film) having a continuous concentration change. here,

Thickness of concentration gradient region = about 23 μm, concentration gradient region thickness / total thickness = 0.54 concentration gradient region thickness / maximum concentration region thickness = about 9 maximum metal oxide concentration / minimum metal oxide concentration = 28% by weight
/3.5% by weight = 7.3.

This component-gradient composite has a slight turbidity, and the cross section of the coating film was observed using a scanning electron microscope (SEM). As a result, silica fine particles having a diameter of 0.2 to 0.4 μm were observed. Was observed. The state of distribution of the silica particles was uniform, but it was highly distributed near the surface of the coating film and decreased as it went inside the coating film.

EPMA is E manufactured by Shimadzu Corporation.
Using PM-810 type, output 15kV-50nA, resolution 1-1.5 micron, scan speed 10 micron / min, detection is Si Kα ray (7.126 angstrom-
I went there. Further, as the SEM, an S-800 type Ohmstrong SEM manufactured by Hitachi, Ltd. was used, and about 3
The observation was performed on a sample obtained by sputtering platinum of nm.

(Example 2) Under the production conditions of Example 1, 20 g of methanol was used instead of 20 g of THF,
Furthermore, instead of casting the homogeneous solution in saturated steam of ammonia water, a case was examined in which the casting was performed in an atmosphere of 25 ° C. and 50%. A coating film having excellent transparency was obtained.
The results of EPMA measurement are shown in FIG. It can be seen that the composition is a gradient composite having a high metal oxide concentration on the substrate side.

Thickness of concentration gradient region = 40 μm, concentration gradient region thickness / total thickness = 0.7 concentration gradient region thickness / maximum concentration region thickness = 10 maximum metal oxide concentration / minimum metal oxide concentration = 11.5% by weight /4.5% by weight = 2.5.

The component gradient composite was transparent, and it was observed by SEM observation that fine particles having a diameter of about 0.04 to 0.1 μm were uniformly dispersed in the micro range.

Comparative Example 1 A homogeneous solution obtained by adding 5 g of distilled water to the homogeneous solution of Example 1 was used.
A sample was created by the same method as above and examined. EPM
The result of A measurement is shown in FIG. It can be seen that there is no slope in the silica concentration, and the silica is uniformly distributed.

Thickness of concentration gradient region = 0 μm, maximum metal oxide concentration / minimum metal oxide concentration = 12% by weight
/ 11 wt% = 1.1 The composite is transparent and has a diameter of 0.06 to 0.15 by SEM observation.
It was confirmed that the fine particles of μm were uniformly dispersed.

(Comparative Example 2) A sample was prepared and examined in the same manner as in Example 1 when the ammonia concentration in Example 1 was set to 0.5 mol / l. The result of EPMA measurement is shown in FIG. It can be seen that there is no slope in the silica concentration, and the silica is uniformly distributed.

The thickness of the concentration gradient region = 0 μm, the maximum metal oxide concentration / the minimum metal oxide concentration = 13.5 wt% / 12.5 wt% = 1.1, and the composite was a transparent body.

(Example 3) The same homogeneous solution as in Example 1 was dropped on a nylon-66 plate, and a saturated steam atmosphere of a mixed solution of 0.06 mol / l ammonia water and methanol at a ratio of 10: 3 (weight ratio) was used. After standing at 22 ° C. for about 10 hours under the same conditions, the same treatment as in Example 1 was performed to obtain a coating film (about 75 μm thick) made of an acrylic resin / silica system. The result of EPMA measurement is shown in FIG. It can be seen that a graded composite having an extremely high silica concentration on the surface side of the coating film was obtained.

Concentration gradient region thickness = 40 μm, concentration gradient region thickness / total thickness = 0.53 concentration gradient region thickness / maximum concentration region thickness = 13.3 maximum metal oxide concentration / minimum metal oxide concentration = 30% by weight
/ 3% by weight = 10 The graded composite exhibits turbidity, and it was observed by SEM observation that particles having a diameter of about 0.3 to 2 μm were uniformly dispersed in the micro range.

Example 4 A homogeneous solution obtained by adding 0.06 g of triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd., special grade reagent) to the same homogeneous solution as in Example 1 was used. Solvent casting and heat treatment were performed under various conditions to obtain an acrylic resin / silica coating film (about 120 μm thick). The result of EPMA measurement is shown in FIG. It can be seen that the gradient composite has a high silica concentration on the surface side of the coating film.

Concentration gradient region thickness = 70 μm, concentration gradient region thickness / total thickness = 0.58 concentration gradient region thickness / maximum concentration region thickness = 17.5 maximum metal oxide concentration / minimum metal oxide concentration = 40% by weight
/7.5% by weight = 5.3

Compared to the composite of Example 3, the concentration gradient of the metal oxide is gentle. The graded complex has a slight turbidity, and the diameter is about 60-200n in SEM observation.
It was observed that the fine particles of m were uniformly dispersed in the micro range. Compared to the composite of Example 3, dispersed particles having a smaller particle size were obtained.

Example 5 Bisphenol type epoxy resin (manufactured by Dainippon Ink and Chemicals, Inc .: Epicron 8)
50) 10 g and an aliphatic polyamine-based epoxy curing agent (manufactured by Dainippon Ink and Chemicals, Inc .: Epicron B-05
3) A mixed solution of 2 g and 5 g of THF was mixed and stirred at room temperature for 26 hours, and then 5 g of TMOS was uniformly mixed. The obtained homogeneous sol solution is applied to the substrate and the room temperature (18 ° C., 4
0%) was solvent cast and heat treated at 80 ° C. for 5 hours and 150 ° C. for 3 hours to obtain a composite of an epoxy resin and silica. The result of EPMA measurement is shown in FIG. It can be seen that the gradient composite has a form in which the silica concentration is maximum within about 50 μm on the surface of the coating film.

Concentration gradient region thickness = 170 μm, concentration gradient region thickness / total thickness = 0.7, concentration gradient region thickness / maximum concentration region thickness = 8.5, maximum metal oxide concentration / minimum metal oxide concentration = 26. 5% by weight / 10.0% by weight = 2.65
Met. The gradient composite was homogeneous and transparent, and it was observed by SEM observation that fine particles having a diameter of about 30 to 200 nm were uniformly dispersed in a micro range.

(Example 6) 15 g of alkyd resin (manufactured by Dainippon Ink and Chemicals, Inc .: Beckosol 1343)
A mixed solution of 5 g of butylated melamine resin (manufactured by Dainippon Ink and Chemicals, Inc .: Super Beckamine G-821-60), 10 g of ethanol, and 5 g of TMOS was stirred to obtain a homogeneous sol solution. The obtained homogeneous sol solution was applied to a substrate, solvent cast was performed in an atmosphere of ammonia water of 0.4 mol / l (30 ° C.), and then at 80 ° C. for 5 hours.
Heat treatment was performed at 150 ° C. for 1 hour to obtain a complex of alkyd resin and silica. The result of EPMA measurement is shown in FIG. It can be seen that the surface of the coating film is a graded composite in which the silica concentration is maximized. The slope was formed over the entire film thickness (about 120 μm) and was milky.

Concentration gradient region thickness = 120 μm, concentration gradient region thickness / total thickness = 1, concentration gradient region thickness / maximum concentration region thickness = 120 or more, maximum metal oxide concentration / minimum metal oxide concentration = 62 wt% / 14 % By weight = 4.4.

[0075]

Industrial Applicability The component gradient composite of an organic polymer and a metal oxide obtained by the present invention contains metal oxides of various sizes (μm order to about 10 nm) in the organic polymer. Since it is dispersed very uniformly and the content concentration of the metal oxide has a distribution in the thickness direction of the complex, for example, the average of the metal oxide in the entire complex is present on the surface or inside. It is possible to produce a complex having a portion having a metal oxide concentration higher (lower) than the concentration, and having physical properties peculiar to an organic polymer complex containing a high (or low) metal oxide concentration, and a metal Since the oxide concentration changes in a gradient, it is possible to provide a stable composite material that does not cause peeling between the surface layer surface and the inside due to heating or aging like a general coating film.

[Brief description of drawings]

FIG. 1 is a diagram showing a Si distribution measurement result by an electron beam microanalyzer (EPMA) in a thickness direction of a component gradient composite (coating film) of an organic polymer and a metal oxide obtained in Example 1. .

FIG. 2 is a diagram showing a Si distribution measurement result by EPMA in a thickness direction of a component gradient composite (coating film) of an organic polymer and a metal oxide obtained in Example 2.

FIG. 3 is a diagram showing a Si distribution measurement result by EPMA in a thickness direction of a composite (coating film) of an organic polymer and a metal oxide obtained in Comparative Example 1.

FIG. 4 is a diagram showing a Si distribution measurement result by EPMA in a thickness direction of a composite (coating film) of an organic polymer and a metal oxide obtained in Comparative Example 2.

FIG. 5 is a diagram showing the Si distribution measurement result by EPMA in the thickness direction of the component gradient composite (coating film) of the organic polymer and metal oxide obtained in Example 3.

FIG. 6 is a diagram showing the Si distribution measurement result by EPMA in the thickness direction of the component gradient composite (coating film) of the organic polymer and metal oxide obtained in Example 4.

FIG. 7 is a diagram showing the Si distribution measurement results by EPMA in the thickness direction of the component gradient composite (coating film) of the organic polymer and metal oxide obtained in Example 5.

FIG. 8 is a diagram showing Si distribution measurement results by EPMA in the thickness direction of a component gradient composite (coating film) of an organic polymer and a metal oxide obtained in Example 6.

Claims (16)

[Claims] 1. A composite of an organic polymer and a metal oxide containing an organic polymer component and at least two components of a metal oxide component (A), the metal oxide being in a depth direction from the surface of the composite. Has a component gradient structure in which the content of the metal oxide component (A) in the composite continuously changes, and is 5 to 100% by weight at the highest content and 0 at the lowest. 5
A component gradient composite of an organic polymer and a metal oxide, which has a content ratio of 0% by weight and a high content and a low content of 1.5 or more. 2. The metal oxide component (A) is obtained by hydrolysis / polycondensation of a metal alkoxide or its low condensate in the presence of an organic polymer component. A gradient composite of the described organic polymer and metal oxide. 3. The metal oxide component (A) is present on at least one surface of the composite in excess of the average content of the composite as a whole. A gradient composite of an organic polymer and a metal oxide. 4. The metal oxide component (A) is present on at least one surface of the composite at a ratio not higher than the average content of the composite as a whole. Gradient composite of organic polymer and metal oxide. 5. The thickness (d) in which the content of the metal oxide component (A) continuously changes in the depth direction of the composite.
1) is larger than the thickness (d2) showing the highest content of the metal oxide component (A).
A gradient composite of the described organic polymer and metal oxide. 6. The size of the metal oxide in the composite has an average diameter of 0.01 to 5 μm.
5. A gradient composite of the organic polymer according to any one of 5 and a metal oxide. 7. The composition gradient composite of an organic polymer and a metal oxide according to claim 6, wherein the size of the metal oxide in the composite has an average diameter of 0.01 to 0.5 μm. body. 8. The organic polymer according to any one of claims 2 to 7, wherein the metal alkoxide or its condensate is represented by the general formula 1. Component gradient complex. Embedded image (In the formula, M represents a silicon atom, R represents C _m H _{2m + 1} , m represents an integer of 1 to 4, and n represents an integer of 1 to 10.) 9. The component gradient composite of an organic polymer and a metal oxide according to claim 1, wherein the organic polymer component is a thermosetting resin. 10. The component gradient composite of an organic polymer and a metal oxide according to claim 1, wherein the organic polymer component is a thermoplastic resin. 11. A homogenous solution of an organic polymer, a metal alkoxide and a common solvent thereof is applied onto an organic polymer or an inorganic base material, and a water and / or metal alkoxide polymerization catalyst is placed in the air. A method for producing a component gradient composite of an organic polymer and a metal oxide, which comprises performing drying and heat treatment after holding in an atmosphere in which the composition is contained. 12. The gradient of components between an organic polymer and a metal oxide according to claim 11, wherein an air atmosphere containing a water and / or metal alkoxide polymerization catalyst further contains an organic solvent. Method of manufacturing composite. 13. The component gradient of an organic polymer and a metal oxide according to claim 12, wherein the organic solvent contained in the atmosphere is different from the organic solvent used for preparing the homogeneous solution. Method of manufacturing composite. 14. A metal alkoxide polymerization catalyst is further contained in a homogeneous solution of an organic polymer, a metal alkoxide and their common solvent.
13. A method for producing a component-gradient composite of an organic polymer and a metal oxide according to any one of 13 to 13. 15. The organic compound according to claim 11, wherein the polymerization catalyst of the metal alkoxide contained in the air atmosphere or in the homogeneous solution is the same or different basic substance. A method for producing a component gradient composite of a polymer and a metal oxide. 16. The organic polymer according to any one of claims 11 to 15, wherein the metal alkoxide is a silicon alkoxide represented by the general formula 1 or a low condensate thereof. Ingredients Gradient composite manufacturing method. Embedded image (In the formula, M represents a silicon atom, R represents C _m H _{2m + 1} , m represents an integer of 1 to 4, and n represents an integer of 1 to 10.)