JPH08319362A - Production of composite material of organic polymer and metal oxide - Google Patents

Abstract

PURPOSE: To produce a composite material of an organic polymer and a metal oxide which is useful as a variety of molding materials, electric and electronic parts, machine parts, sport goods, film, fiber and the 7 like because the organic polymer is improved in its thermal and mechanical characteristics such as stiffness by easily and arbitrarily micro-dispersing superfine particles of a metal oxide in a solid organic polymer that does not swell with the metal alkoxide. CONSTITUTION: An organic polymer of less than 1wt.% of swelling coefficient at equilibrium in tetraethoxysilane at 25 deg.C is swollen in a swelling solution such as an organic solvent or water, then the swollen organic polymer is impregnated with a solution containing a metal alkoxide. Then, the metal alkoxide is subjected to hydrolysis and condensation reaction to convert the alkoxide to the metal oxide whereby the objective composite material of an organic polymer and a metal oxide is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite of an organic polymer and a metal oxide in which fine particles of a metal oxide are dispersed in an organic polymer solid without macroaggregation or phase separation. More specifically, it has excellent mechanical properties such as heat resistance, chemical resistance, adhesiveness, and high rigidity, and is useful for various molding materials, films, fibers, etc. of composites composed of organic polymers and metal oxides. It relates to a manufacturing method.

[0002]

2. Description of the Related Art A method for blending inorganic fine particles such as silica, alumina, titania, calcium carbonate, etc. for the purpose of improving mechanical properties such as heat resistance and rigidity of an organic polymer is already known, and many of them are known. It has been put to practical use as an organic polymer. In order to efficiently carry out the reinforcement by this method, it is important to enhance the adhesion and affinity with the organic polymer.

When fine particles having a small particle size are used, it has been studied to uniformly disperse the finest particles as much as possible, because the affinity of the interface is improved by increasing the surface area. However, there is a problem that the finer the particles, the stronger the cohesiveness of the particles, and rather, the larger the particle size and the lower the various properties.

On the other hand, a method of compounding an organic polymer and a metal oxide using a so-called sol-gel reaction, which is a metal oxide obtained by subjecting a metal alkoxide to a hydrolysis polycondensation reaction, has been studied in some organic polymer systems. Has been done. In this method, metal alkoxide is uniformly dispersed in organic polymer,
This is an in-situ polymerization method, and it is expected that the metal oxide particles of nano-order to micron-order can be homogeneously dispersed and the affinity between the resin and the metal oxide can be improved.

For example, polyethylene glycol (J. Non-Cryst. Solids, Vol. 82, p. 210, 1986) has been reported so far.
Year), polytetramethylene oxide (Polymer, Volume 30,
2001 p. 1989), polyvinyl alcohol (J. Appl. P
olym. Sci., 39, 371, 1990), polyetherketone (J. Appl. Polym. Sci., 40, 1177, 1990),
Polymethylmethacrylate (Polymer, 33, 1486, 1
992)

Poly (p-phenylene vinylene) precursor (Polymer, Volume 32, 605, 1991), Polyimide (Poly
mer J., Vol. 24, p. 107, 1992), polyurethane resin (JP-A-6-136321), and ketone resin (JP-A-5-36321).
-331353).

However, in all of these methods, since the metal alkoxide is homogeneously dispersed in the organic polymer solid, it is essential to prepare a homogeneous sol solution consisting of the organic polymer, the metal alkoxide and the organic solvent. Therefore, there are problems that a large amount of solvent is required and it is difficult to adapt to an organic polymer having poor solubility such as polypropylene.

On the other hand, butadiene rubber (Polym. Pre., Jp
n., 43, 3151 1994) and polydimethylsiloxane elastomer (Makromol. Chem., 185, 2609 1984).
Chem., 187, 2861, 1986, Polyme.
r, Vol. 26, p. 2069 (1985 etc.) etc., the organic polymer is soaked in a tetraethoxysilane solution and sufficiently swelled, and then it is added with an acid and a basic catalyst. A method of holding in an aqueous solution to form a composite is disclosed.

However, this method is intended for rubbers and elastomers having a good swelling property for tetraethoxysilane, and is generally used for other thermoplastic organic polymers having little swelling property for tetraethoxysilane. I couldn't adapt to it.

[0010]

The problems to be solved by the present invention include a method of mixing and filling a pre-prepared inorganic filler, and a homogeneous solution obtained by dissolving an organic polymer and a metal alkoxide in an organic solvent. Provided is a method for producing a composite in which fine particles of a metal oxide are microscopically dispersed in an organic polymer solid that does not have a property of swelling with a metal alkoxide without using a method of forming a composite. Especially.

[0011]

Means for Solving the Problems As a result of intensive research to solve the above problems, the present inventors have found that an organic polymer solid that does not have the property of swelling with a metal alkoxide is
After pre-swelling the organic polymer solid with an organic solvent, it is impregnated with a metal alkoxide or a solution containing it, and then
By subjecting the metal alkoxides to a hydrolysis polycondensation reaction in an organic polymer solid, it is possible to easily obtain a composite of an organic polymer and a metal oxide in which a metal oxide is finely dispersed in an organic polymer solid. They have found the present invention and completed the present invention.

According to the present invention, the organic polymer solid is not mixed and pre-prepared with an inorganic filler such as silica, and the process for preparing a homogeneous solution of the organic polymer, metal alkoxide and organic solvent is not performed. The present invention relates to a method for producing a composite of an organic polymer in which metal oxide particles are microscopically dispersed in an organic polymer solid and a metal oxide, and particularly, as the organic polymer solid, a non-rubber resin or the like. It is effective for organic polymer solids that hardly swell in the metal alkoxides.

That is, the present invention swells an organic polymer having an equilibrium swelling rate of 1% by weight or less when immersed in a tetraethoxysilane solution at 25 ° C. with a swelling solution containing an organic solvent and / or water. And then impregnating an impregnating solution containing metal alkoxides into the swollen organic polymer, followed by hydrolytic polycondensation reaction of the metal alkoxides to fix as metal oxides. A method for producing a composite of a polymer and a metal oxide.

In the production method of the present invention, the organic polymer used is particularly a solid organic polymer selected from polyamide, acrylic resin, polyvinylidene chloride resin, polypropylene, polyester and phenoxy resin, and metal alkoxides used. Is a method for producing a composite of an organic polymer and a metal oxide, which uses a silicon alkoxide, a partial hydrolysis-condensation product of a silicon alkoxide, or a mixture thereof.

Further, according to the present invention, the swollen organic polymer is dipped in the impregnating liquid to impregnate the organic polymer with the metal alkoxide, and the vapor of the impregnating liquid containing the metal alkoxide is swollen. The method for producing a composite of an organic polymer and a metal oxide is characterized in that the metal alkoxide is impregnated in the organic polymer by bringing it into contact with the organic polymer.

Further, in the production method of the present invention, the swelling liquid contains an acidic catalyst or a basic catalyst, the impregnating liquid containing a metal alkoxide contains water and / or an acidic catalyst or a basic catalyst, and After impregnating an organic polymer with metal alkoxides, the organic polymer is held in a steam atmosphere to promote a hydrolysis polycondensation reaction of the metal alkoxide, and further, in a steam atmosphere, an organic solvent is added. And / or a method for producing a composite of an organic polymer and a metal oxide, which comprises an acidic catalyst or a basic catalyst.

Further, according to the present invention, an organic polymer having an equilibrium swelling ratio of 1% by weight or less when immersed in a tetraethoxysilane liquid at 25 ° C. is added with a swelling liquid containing an organic solvent and / or water. The swelling of the organic polymer and the impregnation operation of the metal alkoxide are simultaneously performed with the impregnating liquid containing the metal alkoxide, which is selected from the silicon alkoxide, the partial hydrolysis-condensation product of the silicon alkoxide, or a mixture thereof, and the metal alkoxide is not The method includes a method for producing a composite of an organic polymer and a metal oxide, which comprises fixing the metal alkoxides by stopping the same operation before homogeneously permeating the inside of the polymer.

According to the production method of the present invention, an organic polymer in which the particle size of the metal oxide particles contained in the obtained composite of the organic polymer and the metal oxide is 0.01 μm to less than 0.2 μm. A method for producing a complex with a metal oxide, and a method for producing a complex with an organic polymer in which the particle diameter of the metal oxide particles contained is 0.2 to 5 μm.

Further, according to the present invention, the composite of the metal oxide and the organic polymer obtained by the production method of the present invention is partially performed in the thickness direction of the organic polymer solid, and at least a part of the metal oxide is formed. A composite of an organic polymer and a metal oxide, characterized in that it contains a region not composited with the metal oxide, and the particle size of the metal oxide particles in the composite region of the metal oxide is 0.2.
A composite of an organic polymer and a metal oxide, wherein the composite has a size of at least μm, is opaque or semitransparent in the composite region, and is transparent in the region not composited with the metal oxide. It includes.

The present invention will be described in detail below. As the organic polymer solid used in the present invention, a commercially available solid organic polymer having a small content of adsorbed metal alkoxide can be used. In particular, it is effective for organic polymer solids having an equilibrium swelling ratio of 1% by weight or less when immersed in a tetraethoxysilane solution at 25 ° C.

Concretely, polyamide such as nylon-6, acrylic resin such as polymethylmethacrylate or a copolymer of polymethylmethacrylate and polymethacrylic acid, polyvinylidene chloride resin, polypropylene, polyester such as polybutylene terephthalate. Examples thereof include organic polymer solids composed of a simple substance such as a phenoxy resin, or a mixture or copolymer thereof. These organic polymers are used in solid forms such as sheets, films, fibers, lots, pellets, microspheres, powders and various three-dimensional molded products.

The metal alkoxides in the present invention are represented by the general formula R _4-n M (OR) _n (M is a silicon atom, R is an alkyl group having 1 to 6 carbon atoms, and n is 4 or 3). A silicon alkoxide-based monomer, a partially hydrolyzed low condensate thereof having a degree of polymerization of about 2 to 10 or a mixture thereof is used. Others, molecular weight 2000-10000
No. 0 ladder type silicone compound or metal hydroxide is used.
It is also possible to use Sn, Zr, Al, Br, Tl, In, Mg, Ba and the like alone or in combination of two or more.

The amount of the metal alkoxide used cannot be unconditionally specified because it varies depending on the type of the metal alkoxide used and the organic polymer solid, but the organic polymer 1 is usually used.
It is preferable to use the metal oxide finally obtained in an amount of 0.5 to 50 parts by weight based on 00 parts by weight.
If the amount of the metal oxide is less than 0.5 parts by weight, the concentration of the metal oxide in the composite will be small, and the effect of the present invention will not be clear. If the amount of the metal oxide exceeds 50 parts by weight, the composite will be fragile. Appears.

As the organic solvent used in the present invention, when used in the swelling liquid in the pretreatment step, an organic solvent and a mixed organic solvent which are compatible with the impregnating liquid and can swell the used organic polymer are used. . When used in an impregnating solution containing metal alkoxides, organic solvents and mixed organic solvents that can be mixed homogeneously with metal alkoxides are used.

Further, for the purpose of increasing the impregnation amount of the metal alkoxides, it is possible to use an organic solvent capable of partially dissolving the organic polymer in the swelling or impregnation treatment step. These organic solvents cannot be unconditionally specified because they vary depending on the type of organic polymer or metal alkoxide used, but for example, ethers such as diethyl ether, dioxane, tetrahydrofuran (THF),

Dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone (N
MP) etc., amides such as ethyl acetate and methyl acetate, ketones such as acetone and 2-butanone (MEK), alcohols such as methanol, ethanol, 2-propanol and butanol, hydrous such as hexane and cyclohexane. Carbon type, aromatic type such as toluene, xylene, m-cresol, benzene, nitrobenzene,

Carbon tetrachloride, chloroform, halogens such as dichloromethane and dichloroethane, silicones such as dimethylpolysiloxane and cyclomethicone, amines such as triethylamine, diethylamine and pyridine, dimethylsulfoxide (DMSO),
Acetonitrile, carbon disulfide, organic solvents such as methyl ethyl cellosolve, or acetylacetone,

Diketone compounds such as 2,4-heptadione,
Ketoesters such as methyl acetoacetate and ethyl acetoacetate, hydroxycarboxylic acid compounds such as lactic acid and methyl lactate,
It is possible to use keto alcohols such as 4-hydroxy-4-methyl-2-pentanone and amino alcohol solvents such as monoethanolamine and diethanolamine, alone or in combination.

The acidic catalyst used in the present invention includes various organic and inorganic acids such as formic acid, acetic acid and hydrochloric acid, and the basic catalyst includes various basic substances such as ammonia, triethylamine, dimethylamine, ethylenediamine and butylamine. It can be used.

In the present invention, metal alkoxides are prepared without mixing and filling preliminarily prepared inorganic fillers and without using a homogeneous solution obtained by dissolving an organic polymer and metal alkoxides in a solvent. The present invention relates to a method for producing a composite of a metal oxide and an organic polymer solid by subjecting a polymer to a hydrolysis polycondensation reaction in the organic polymer. The outline of the method for compounding the metal oxide and the organic polymer according to the present invention is shown below.

In the present invention, the organic polymer solid is pre-swelled with a swelling liquid composed of an organic solvent and / or water as a pretreatment step, and then the metal alkoxide or the metal alkoxide and the organic solvent are added to the swollen product. A composite of a metal oxide and an organic polymer is obtained by impregnating an impregnating liquid consisting of (1) and then subjecting the contained metal alkoxides to a hydrolysis polycondensation reaction to form a metal oxide. .

Here, it is also possible to combine the swelling liquid and the impregnating liquid containing the metal alkoxide, and perform the swelling and the impregnation at the same time. However, this method may cause a problem that the metal oxide concentration in the finally obtained composite decreases. The swelling liquid in the present invention is a solution that swells the organic polymer solid used and is compatible with the impregnating liquid, and contains an organic solvent, and / or water, and further an acidic catalyst or a basic catalyst. Used. The swelling liquid is preferably one capable of swelling the organic polymer solid used by 1% by weight or more, particularly 5% by weight or more.

The impregnating liquid in the present invention is a homogeneous solution containing metal alkoxides, and may contain an organic solvent and / or water, and / or an acidic catalyst or a basic catalyst in addition to the metal alkoxides. It is possible. The pretreatment step is a step of preliminarily swelling the organic polymer solid with the swelling liquid, and by performing this step, the impregnation operation of the impregnating liquid is efficiently performed in the subsequent impregnation step.

The swollen product of the organic polymer solid can be obtained by a method of immersing the organic polymer solid in the swelling liquid or a method of bringing the organic polymer solid into contact with the vapor of the swelling liquid. Further, by adding water and / or a catalyst to the swelling liquid in advance, it is possible to improve the amount of metal oxide finally immobilized.

The impregnation step is a step of introducing metal alkoxides into the organic polymer solid swollen material. As a method of impregnating the organic polymer solid swollen material with the metal alkoxide, a method of immersing the organic polymer solid swollen material in an impregnating solution containing the metal alkoxide, or an organic polymer solid swollen material in the vapor of the impregnating solution. Can be carried out by a method of contacting. The amount of metal alkoxide impregnated depends on the composition of the swelling liquid,
And / or the composition can be changed depending on the composition of the impregnating liquid, and the preparation can be performed by the impregnation conditions such as the immersion time and the immersion temperature.

On the other hand, in order to promote the polycondensation reaction of the metal alkoxides impregnated in the organic polymer solid swollen material and promote the immobilization as a metal oxide, a post-treatment after impregnating the metal alkoxides As the step, a method such as immersing the organic polymer solid swollen material in an aqueous solution, spraying an atomized aqueous solution, or holding it in a steam atmosphere can be performed.

By adding an organic solvent and / or a catalyst to the aqueous solution, it is possible to improve the immobilization rate of the metal oxide and control the particle size of the metal oxide particles. Furthermore, in order to accelerate the reaction of the metal alkoxides, it is effective to use a treatment such as heating or ultraviolet irradiation in combination during the reaction or to perform it as a final treatment step.

In the present invention, in addition to a composite in which metal oxide particles are microscopically homogeneously dispersed in an organic polymer solid, the composition of the swelling liquid or the impregnating liquid, and the impregnation conditions such as temperature and time can be changed. Thus, it is possible to obtain a composite having a form in which the compounding with the metal oxide is partially performed in the thickness direction of the organic polymer solid and at least a part of the compound includes a region not compounded with the metal oxide. is there.

For example, a method of terminating the impregnation operation when the organic polymer solid is impregnated with the impregnating liquid to a desired thickness, or a method of swelling and impregnating the swelling liquid and the impregnating liquid containing metal alkoxides together. Is performed simultaneously, the same operation is stopped before the metal alkoxides are uniformly impregnated in the organic polymer, and the metal alkoxides are immobilized.

Further, in the present invention, when the metal alkoxides are impregnated and then contacted with an aqueous solution containing a catalyst such as ammonia or hydrochloric acid to be immobilized on the metal oxide, the kind and concentration of the catalyst are changed. It is possible to control the particle size of the metal oxide.

As a result, a composite of a metal oxide and an organic polymer having different particle sizes can be prepared. In particular, when a transparent resin such as an acrylic resin is used, the particle size of the metal oxide is remarkable. It is possible to obtain a complex of an organic polymer and a metal oxide in which the complexed portion is opaque or translucent and the non-complexed portion is transparent by controlling the temperature.

In the present invention, by using a small amount of an organic silane compound such as aminoalkoxysilane, epoxyalkoxysilane, vinylalkoxysilane, and mercaptoalkoxysilane, it is possible to improve the affinity between the organic polymer and the metal oxide. is there.

[0043]

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 A 0.5 mm thick film-shaped nylon-6 (manufactured by Ube Industries, Ltd .: UBE Nylon 1022B) was placed in a swelling liquid consisting of methanol and distilled water (4: 1, weight ratio). It was dipped and left at room temperature for 3 days. A weight gain of 16% by weight was seen. Further, methanol and tetramethoxysilane (hereinafter abbreviated as TMOS:
The silicon alkoxide was sufficiently impregnated by immersing it in an impregnation liquid of Tokyo Chemical Industry Co., Ltd. (special grade reagent) (2: 1, weight ratio) at room temperature for 6 days. The weight increase was 23% by weight.

Then, after keeping in a steam atmosphere (23 ° C.) of ammonia water of 0.6 mol / l for 1 day,
Heat treatment was performed in vacuum at 24 ° C. for 24 hours to obtain a composite of nylon-6 and silica. The appearance of the composite was completely the same as that of nylon-6 alone.

The presence of Si was confirmed by fluorescent X-ray. When the composite was baked at 800 ° C for 2 hours, it was about 8.
There was 9% by weight of residual silica. When Si in the thickness direction of the cross section was detected with an electron beam microanalyzer (EPMA), it was found that silica was homogeneously dispersed. When the silica particles in the cross section of the composite were observed with a scanning electron microscope (SEM), the particle size was 20 to 80 nm.

The dynamic viscoelasticity was measured at 30 ° C. and 1
When Young's modulus at 00 ° C was measured, each was 400
It was 0 MPa and 1000 MPa. On the other hand, nylon-
In case of 6 units, Young's modulus is 3000 MPa and 7 respectively
It was 00 MPa. The fluorescent X-ray is model 3030 manufactured by Rigaku Corporation and EPMA is E manufactured by Shimadzu Corporation.
PM-810, SEM is S-manufactured by Hitachi Ltd.
Model 800 was used.

In the EPMA measurement, the output was 15 kV-50 nA, and the Si Kα ray was detected by 7.124Å. The SEM sample used was one in which the fractured cross section was sputtered with platinum after being immersed in liquid nitrogen for 10 minutes.
The dynamic viscoelasticity was measured by using DMA-200 manufactured by Seiko Denshi Kogyo Co., Ltd. at a temperature of 1 Hz after heating at 2 ° C./min.

Comparative Example 1 Nylon-6 used in Example 1 was immersed in a solution of TMOS and tetraethoxysilane (hereinafter abbreviated as TEOS, a special grade reagent manufactured by Tokyo Chemical Industry Co., Ltd.) at 25 ° C. for 7 days. The degree of swelling was less than 0.1% by weight. Then, the sample was immersed in distilled water for 5 hours, then at room temperature for 24 hours, and further at 80 ° C. in vacuum for 24 hours.
Heat treatment was performed for an hour. When baked at 800 ° C. for 2 hours, neither silica was left at all, and a composite of nylon-6 and silica could not be obtained.

(Example 2) The thickness used in Example 1 is 0.5.
mm nylon-6 film with methanol and TMO
The silicon alkoxide was impregnated by immersing it in an impregnating liquid of S (1: 1, weight ratio) at room temperature for 6 days. Weight increase is 1
It was 0% by weight. Then, after keeping in a steam atmosphere (23 ° C.) of ammonia water of 0.6 mol / l for 1 day,
Heat treated in vacuum at 80 ° C for 24 hours to give nylon-6
A silica-silica composite was obtained. The appearance of the composite is nylon-6
It was exactly the same as the simple substance.

The presence of Si was confirmed by fluorescent X-ray. When the composite was baked at 800 ° C for 2 hours, it was about 1.
There was 3% by weight of residual silica. When Si in the thickness direction of the cross section was detected by EPMA, it was found that the silica was homogeneously dispersed.

(Comparative Example 2) Nylon used in Example 1
To a solution prepared by dissolving 1 g of 6 in 20 g of m-cresol, 0.14 g of distilled water and 0.3 g of TMOS were sequentially added dropwise. After reacting at 60 ° C. for 7 hours, it was coated on a glass substrate, dried with hot air at 80 ° C. for 24 hours, and then vacuum dried at 200 ° C. for 1 hour to cast the solvent. The obtained coating film was a film having an inferior appearance that was opaque and non-uniform.

On the other hand, the precipitate obtained by precipitating the solution before coating in methanol was dried with hot air at 80 ° C. for 2 hours, and 200 ° C.
After vacuum drying for 1 hour, melt press molding was performed at 260 ° C. The film was colored dark brown, and a film having a good appearance was not obtained.

Example 3 A sheet-shaped acrylic resin (Acrylite 001 manufactured by Mitsubishi Rayon Co., Ltd.) was immersed in a swelling solution of methanol, acetone and distilled water (5: 1: 2, weight ratio) at room temperature for 2 days. did. There was a weight gain of about 18% by weight. Then, methanol, acetone, TMOS (1
It was immersed in an impregnating solution (0: 1: 6, weight ratio) for 2 days to sufficiently impregnate the silicon alkoxide.

Acrylic resin becomes rubbery, 62% by weight
There was an increase in weight. Furthermore, after keeping it in a saturated steam atmosphere of 0.5 mol / l ammonia water for 1 day,
After heat treatment for 24 hours, a composite of acrylic resin and silica was obtained. The composite has excellent transparency and a parallel light transmittance of about 9
It was 8%.

The presence of Si was confirmed by fluorescent X-ray. When the composite was baked at 800 ° C for 2 hours, it was about 7.
There was a residual amount of silica of 8% by weight. When Si in the thickness direction of the cross section was detected by EPMA, it was found that the silica was homogeneously dispersed. When silica particles were observed using SEM, the particle size of silica was 50 to 100 nm.
The light transmittance is NDH turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd.
It was measured using a -300 model.

Comparative Example 3 The acrylic resin used in Example 3 was immersed in a TEOS solution at 25 ° C. for 7 days. The degree of swelling was less than 0.1% by weight. The sample was then immersed in distilled water for 5 hours, then at room temperature for 24 hours and then for 8 hours.
Heat treatment was performed at 0 ° C. for 24 hours. After firing at 800 ° C. for 2 hours, there was no residual silica and a composite of acrylic resin and silica could not be obtained.

Example 4 The sheet-shaped acrylic resin used in Example 3 was immersed in an impregnating solution of methanol and TMOS (1: 1, weight ratio) for 10 days to sufficiently impregnate the silicate. Acrylic resin becomes rubber-like, 110% by weight
An increase in weight was observed. Then, after keeping in a saturated steam atmosphere of 0.35 mol / l of ammonia water for 1 day,
Heat treatment was performed at 80 ° C. for 24 hours to obtain a composite of acrylic resin and silica. The composite had excellent transparency and a light transmittance of about 96%.

The presence of Si was confirmed by fluorescent X-ray. When the composite was baked at 800 ° C for 2 hours, it was about 16
There was a residual amount by weight of silica. When Si in the thickness direction of the cross section was detected by EPMA, it was found that silica was homogeneously dispersed in the entire film. Figure 1 shows the EPMA results.

Example 5 The sheet-shaped acrylic resin used in Example 3 was immersed in an impregnating solution of methanol and TMOS (1: 1, weight ratio) for 3 days to impregnate the silicon alkoxide. There was a weight gain of 17.5% by weight. Then, after soaking in distilled water for 5 hours, heat treatment was performed at 80 ° C. for 24 hours to obtain a composite of an acrylic resin and silica.
When the fracture surface of the composite was observed, the surface was opaque but the inside was transparent. The parallel light transmittance of the obtained composite film was about 54%.

When Si in the thickness direction of the cross section was detected by EPMA, it was a layer in which silica was dispersed in a substantially uniform concentration up to about 60 μm from the surface, and silica was not detected inside the layer. When the silica particles in the cross section were observed by SEM, the particle size of silica was 100 to 500 nm. Further, when the composite was calcined at 800 ° C. for 2 hours, the amount of silica remaining was about 2.4% by weight.

(Examples 6 and 7) In Example 5, after impregnating silicon alkoxide, 0.3 mol / l of ammonia water (Example 6) and 0.9 mol / l of ammonia water ( Similar examination was carried out for the case of immersion in Example 7) for 5 hours. When the fracture surface of the composite was examined, Example 7 was transparent in its entirety, but in Example 6, the surface was opalescent and the inside was transparent. When the parallel light transmittance of the obtained composite film was measured, it was about 85% in Example 6 and about 96% in Example 7.

When Si in the thickness direction of the cross section was detected by EPMA, both of the composites were layers in which silica was dispersed in a substantially uniform concentration up to about 64 μm from the surface, and silica was not detected in the inside. . When the silica particles of the cross section were observed by SEM, the particle size of silica was 50 to 300 nm in Example 6, and 20 to 100 n in Example 7.
It was m. Further, when the composite was calcined at 800 ° C. for 2 hours, the amount of residual silica was about 3.9% by weight in Example 6 and about 4.7% by weight in Example 7.

(Embodiment 8) In the fourth embodiment, the TMOS
The same examination was performed when the immersion time of the methanol and the impregnating liquid was 5 days. The weight increase after impregnation with the impregnation liquid was about 98% by weight. The obtained composite had excellent transparency and the parallel light transmittance was about 97%.

When Si in the thickness direction of the cross section was detected by EPMA, it was a layer in which silica was dispersed at a substantially uniform concentration up to about 300 μm from the surface, and from this, the inside (about 40 μm) was formed.
No silica was detected in m). The results of EPMA are shown in FIG. When the composite was baked at 800 ° C. for 2 hours, about 17% by weight of silica remained.

Example 9 A sheet-shaped acrylic resin was impregnated with methanol and TMOS (1: 1, weight ratio) in an impregnating solution.
It was immersed at 3 ° C. for 3 days and impregnated with silicon alkoxide. There was a weight gain of about 50% by weight. Then 0.0
After immersing in a 4 mol / l hydrochloric acid aqueous solution for 5 hours, 80
It heat-processed at 24 degreeC for 24 hours, and the composite of acrylic resin and silica was obtained. When the fracture surface of the composite was observed, the surface was opaque but the inside was transparent. The parallel light transmittance of the obtained composite film was about 16%.

When Si in the thickness direction of the cross section was detected by EPMA, it was a layer in which silica was dispersed at a substantially uniform concentration up to about 170 μm from the surface, and silica was not detected inside the layer. The results of EPMA are shown in FIG. S
When the silica particles in the cross section were observed by EM, the particle size of silica was 200 to 1000 nm. 80 complex
When baked at 0 ° C. for 2 hours, there was about 7.5% by weight of residual silica.

Example 10 A 0.5 mm thick polypropylene (Noblen MH-8) film was immersed in a swelling solution of methanol and distilled water (2: 1, weight ratio) at 80 ° C. for 3 days.
Let it soak for an hour. A weight gain of about 24% by weight was observed.
Then, it was immersed in an impregnating solution of TMOS and methanol (1: 1, weight ratio) at room temperature for about 5 hours, then kept at 25 ° C and 35% room temperature for 5 hours, and further at 80 ° C for 5 hours and 150 ° C.
Was heat-treated for 2 hours to obtain a composite of polypropylene and silica.

The presence of Si was confirmed by fluorescent X-ray.
When the composite was calcined at 800 ° C. for 2 hours, there was about 2.4 wt% residual silica. When Si in the thickness direction of the cross section was detected by EPMA, it was found that silica was homogeneously dispersed throughout the film.

Comparative Example 4 The polypropylene used in Example 10 was immersed in the TEOS solution for 7 days, and the swelling degree was 0.1% by weight or less. Next, the sample was immersed in distilled water for 5 hours, left at room temperature for 24 hours, and further heat-treated at 80 ° C. for 5 hours and 150 ° C. for 2 hours. After firing at 800 ° C. for 2 hours, there was no residual silica and a composite of polypropylene and silica could not be obtained.

(Example 11) In Example 10, instead of using a swelling solution of methanol and distilled water (2: 1, weight ratio) in the pretreatment step, methanol and ammonia water (0.
74 mol / l) (2: 1, weight ratio) of swelling liquid
It was immersed at 0 ° C. for 3 hours. The weight increase was about 25% by weight. Then, the same treatment as in Example 5 was performed to obtain a polypropylene / silica composite.

The presence of Si was confirmed by fluorescent X-ray. When the composite was baked at 800 ° C for 2 hours, it was about 6.
There was 1% by weight of residual silica. When Si in the thickness direction of the cross section was detected by EPMA, it was found that the silica was homogeneously dispersed. The results of EPMA are shown in FIG.

When the viscoelasticity was measured, the elastic modulus was 25.
The temperature was 3.6 GPa at 100 ° C and 863 MPa at 100 ° C, and the peak temperature of tan δ observed near the room temperature range was 59 ° C. The elastic modulus at 25 ° C. of the polypropylene alone was 2.1 GPa, 425 MPa at 100 ° C., and the tan δ peak was 40 ° C. It can be seen that the elastic modulus and heat resistance are improved.

A tensile test was conducted to measure the yield stress and elastic modulus.
Was. Yield stress is 8.3Kg / mm², The elastic modulus is 202 kg / mm²so
there were. The yield stress of polypropylene alone is 6.7K.
g / mm ², Modulus of elasticity is 147 Kg / mm²Met. Also, epoki
For Si resin (Chiragaigi Co., Ltd. Araldite)
When the adhesiveness was measured, the shear required for peeling
The force was 60-80 Kg. In addition, polypropylene
In the case of a single substance, it was 14 kg. For epoxy adhesive
It can be seen that the adhesiveness to it is significantly improved.

For the tensile test and the adhesion test, an autograph manufactured by Shimadzu Corporation was used. The tensile test is 5 mm with a length of 10 mm, a width of 3 mm and a thickness of 0.5 mm.
It was measured at a speed of / minute. For the adhesion test, two test pieces having a width of 10 mm were prepared, and the shear peel strength of a sample in which an epoxy resin was attached to 20 mm and which was superposed and adhered was measured. After adhering, the sample was left at room temperature for 3 days and then heat-treated at 80 ° C. for 5 hours to be cured.

Example 12 A 0.5 mm sheet of polyvinyl chloride (3001 manufactured by Mitsubishi Plastics Co., Ltd.) was immersed in a swelling solution of acetone and distilled water (2: 1, weight ratio) at 30 ° C. for 1 day. . There was a weight gain of about 20% by weight. Then, after soaking in an impregnating solution of TMOS and acetone (1: 1, weight ratio) for 6 hours (30 ° C.), it is kept at 20 ° C. and 35% room temperature for 5 hours, and further heat treated at 80 ° C. for 24 hours. A composite of polyvinyl chloride and silica was obtained.

The presence of Si was confirmed by fluorescent X-ray. When the composite was baked at 800 ° C for 2 hours, it was about 15
There was a residual amount by weight of silica. When Si in the thickness direction of the cross section was detected by EPMA, it was found that the silica was homogeneously dispersed.

Comparative Example 5 The polyvinyl chloride used in Example 12 was immersed in a TEOS solution for 7 days, but the swelling degree was 0.1% by weight or less. Then, the sample was immersed in distilled water for 5 hours, left at room temperature for 24 hours, and further heat-treated at 80 ° C. for 24 hours. It was calcined at 800 ° C. for 2 hours, but no residual silica was found. No composite of polyvinyl chloride and silica was obtained.

(Example 13) A nylon-6 film was immersed in a swelling solution of methanol and distilled water (2: 1, weight ratio) at 80 ° C.
And soaked for 3 hours. A weight gain of about 24% by weight was observed. Then TMOS and methanol (5: 1, weight ratio)
After being immersed in the impregnating liquid of above at 30 ° C. for about 5 hours, the solution is further added to 0.1.
It was kept for 1 day in a saturated steam atmosphere of 5 mol / l ammonia water. Then, it was vacuum dried at room temperature of 25 ° C. and 35% for 5 hours and at 80 ° C. for 24 hours to obtain a composite of nylon-6 and silica.

The presence of Si was confirmed by fluorescent X-ray. When the composite was baked at 800 ° C for 2 hours, about 5.
There was 4% by weight of residual silica. When Si in the thickness direction of the cross section was detected by EPMA, it was found that silica was homogeneously dispersed in the entire film. The EPMA results are shown in FIG.

Example 14 Polybutylene terephthalate (PBT; manufactured by Dainippon Ink and Chemicals, Inc., PLANAC-
The sheet of 128) was immersed in chloroform at 60 ° C. for 3 hours. A weight gain of about 28% was seen. Then
After immersing in an impregnating solution of TMOS and chloroform (10: 1, weight ratio) at 30 ° C. for about 10 hours, it was further kept for 1 day in a saturated steam atmosphere of 0.6 mol / l ammonia water.

Then, the mixture was allowed to stand at room temperature of 25 ° C. and 35% for 5 hours, and heat-treated at 80 ° C. for 24 hours and at 150 ° C. for 2 hours to obtain a PBT / silica composite. The presence of Si was confirmed by fluorescent X-ray. When the composite was calcined at 800 ° C. for 2 hours, there was about 3% by weight of residual silica. When Si in the thickness direction of the cross section was detected by EPMA, it was found that silica was homogeneously dispersed in the entire film.

(Comparative Example 6) The PBT used in Example 14 was immersed in the TEOS solution for 7 days, and the swelling degree was 0.1% by weight or less. Then, the sample is immersed in distilled water for 5 hours, left at room temperature for 24 hours, and then at 80 ° C.
Heat treatment was performed for 5 hours at 150 ° C. for 2 hours. 800 ° C
After firing for 2 hours, there was no residual silica at all. PB
No composite of T and silica was obtained.

(Example 15) A polyvinyl chloride sheet was immersed in a swelling solution of acetone and distilled water (2: 1, weight ratio) at 50 ° C.
And soaked for 3 hours. There was a weight gain of about 20% by weight.
Then, after immersing in an impregnating liquid of toluene and tetraethoxytin (special grade reagent manufactured by Kanto Chemical Co., Inc.) (2: 1, weight ratio) for 6 hours (30 ° C.), 5 ° C. at 20 ° C. and 35% room temperature. Hold for 80 hours at 80 ℃, then 150 ℃
Heat treatment was performed for 2 hours to obtain a composite of polyvinyl chloride and tin oxide.

The presence of Sn was confirmed by fluorescent X-ray. When the composite was calcined at 800 ° C. for 2 hours, the amount of remaining tin oxide was about 3% by weight. When Si in the thickness direction of the cross section was detected by EPMA, it was found that tin oxide was homogeneously dispersed. FIG. 6 shows the result of EPMA measurement. Incidentally, EP
The MA measurement was performed with an output of 15 kV-50 nA and was detected by Sn Lα ray 3.600.

[0086]

INDUSTRIAL APPLICABILITY The present invention can easily and optionally disperse finely divided metal oxide fine particles into an organic polymer solid that does not have the property of swelling with a metal alkoxide to give the organic polymer. A method for producing a composite of an organic polymer and a metal oxide, which improves mechanical properties such as heat resistance and rigidity and is useful for various molding materials, electric / electronic parts, mechanical parts, sports equipment, films, fibers, etc. Can be provided.

[Brief description of drawings]

FIG. 1 is a view showing a measurement result of a composite of an organic polymer and a metal oxide obtained in Example 4 by EPMA (electron beam microanalyzer).

FIG. 2 is a view showing a result of measurement by a EPMA (electron beam microanalyzer) of a composite of an organic polymer and a metal oxide obtained in Example 8.

FIG. 3 is a view showing a result of measurement with a EPMA (electron beam microanalyzer) of a composite of an organic polymer and a metal oxide obtained in Example 9.

FIG. 4 is a view showing a result of measurement with a EPMA (electron beam microanalyzer) of a composite of an organic polymer and a metal oxide obtained in Example 11.

FIG. 5 is a view showing a result of measurement with a EPMA (electron beam microanalyzer) of a composite of an organic polymer and a metal oxide obtained in Example 13.

FIG. 6 is a diagram showing the results of measurement by an EPMA (electron beam microanalyzer) of the composite of organic polymer and metal oxide obtained in Example 15.

Claims (14)

[Claims] 1. An organic polymer having an equilibrium swelling rate of 1% by weight or less when immersed in a tetraethoxysilane solution at 25 ° C. is swollen with a swelling solution containing an organic solvent and / or water, and then, An organic polymer and a metal, wherein the swollen organic polymer is impregnated with an impregnating solution containing metal alkoxides, and then the metal alkoxides are hydrolyzed and polycondensed to be immobilized as metal oxides. A method for producing a complex with an oxide. 2. The organic polymer according to claim 1, wherein the organic polymer is a solid substance of an organic polymer selected from polyamide, acrylic resin, polyvinylidene chloride resin, polypropylene, polyester and phenoxy resin. And a method for producing a complex of a metal oxide. 3. The metal alkoxide is a silicon alkoxide, a partial hydrolysis-condensation product of a silicon alkoxide, or a mixture thereof.
Or a method for producing a composite of the organic polymer and the metal oxide according to 2 above. 4. The organic polymer is impregnated with a metal alkoxide by immersing the swollen organic polymer in an impregnation liquid. A method for producing a composite of an organic polymer and a metal oxide. 5. The organic polymer is impregnated with the metal alkoxide by bringing the vapor of the impregnating liquid containing the metal alkoxide into contact with the swollen organic polymer. 3. A method for producing a composite of an organic polymer and a metal oxide as described in 1. 6. The method for producing a composite of an organic polymer and a metal oxide according to claim 1, wherein the swelling liquid contains an acidic catalyst or a basic catalyst. . 7. The organic polymer according to any one of claims 1 to 3, wherein the impregnating liquid containing the metal alkoxide contains water and / or an acidic catalyst or a basic catalyst. A method for producing a complex with an object. 8. The method according to claim 1, wherein the organic alkoxide is impregnated in the organic polymer and then held in a steam atmosphere to accelerate the hydrolysis polycondensation reaction of the metal alkoxide. A method for producing a composite of an organic polymer and a metal oxide according to any one of the above. 9. The method for producing a composite of an organic polymer and a metal oxide according to claim 8, wherein the steam atmosphere contains an organic solvent and / or an acidic catalyst or a basic catalyst. 10. An organic polymer having an equilibrium swelling ratio of 1% by weight or less when immersed in a tetraethoxysilane liquid at 25 ° C., a swelling liquid consisting of an organic solvent and / or water, and a silicon alkoxide or silicon. The swelling of the organic polymer and the impregnation operation of the metal alkoxide are simultaneously performed with the impregnating liquid containing the metal alkoxide, which is selected from the partial hydrolyzed condensate of the alkoxide or a mixture thereof, and the metal alkoxide is contained inside the organic polymer A method for producing a complex of an organic polymer and a metal oxide, characterized in that the same operation is stopped before the metal is uniformly permeated into the solution to immobilize the metal alkoxide. 11. The organic polymer according to any one of claims 1 to 10, wherein the metal oxide particles contained have a particle size of 0.01 μm to less than 0.2 μm. A method for producing a complex with an object. 12. The particle size of the contained metal oxide particles is 0.2 to 5 μm.
A method for producing a composite of an organic polymer and a metal oxide according to any one of 1. 13. A composite of a metal oxide and an organic polymer, which is obtained by the production method according to claim 1, is partially performed in a thickness direction of the organic polymer solid, A composite of an organic polymer and a metal oxide, comprising at least a part of a region that is not composited with a metal oxide. 14. The metal oxide particles in the composite area with the metal oxide have a particle size of 0.2 μm or more, are opaque or semitransparent in the composite area, and are not composite with the metal oxide. The composite of an organic polymer and a metal oxide according to claim 13, which has a morphology that is transparent in the region.