JPH09278938A - Production of composite material of active energy ray-curable resin with metal oxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composite material excellent in transparency, surface hardness, heat resistance, etc., by finely dispersing a metal oxide into a resin by a specific method using a reactive monomer of an active energy ray-curable resin and a metal alkoxide. SOLUTION: A homogeneous solution containing (A) a reactive monomer of an active energy ray-curable resin (preferably an acrylic monomer or oligomer such as polyester acrylate) and (B) a metal alkoxide (preferably a silicon alkoxide and/or titanium alkoxide) is applied to a substrate or cast into the substrate and the component A is polymerized by irradiation with active energy ray and the component B is polymerized by heating. A photoreaction initiator having absorption band of 200-500nm is preferably used as a photoreaction initiator usually combinedly in order to polymerize the component A. A concentration of a metal oxide in the objective composite material is preferably 2-40wt.% and particle diameter of the metal oxide is preferably <=5μm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has excellent transparency, surface hardness, heat resistance and mechanical strength in which a metal oxide is finely dispersed in an active energy ray-curable resin in a nano-order to a micron-order. The present invention relates to a method for producing a composite of an active energy ray-curable resin and a metal oxide, which is useful as a film, a coating film, a sealant and the like.

[0002]

2. Description of the Related Art Active energy ray curable resins are widely used as coating agents, paints, sealants, etc. because of their extremely short curing time and good work efficiency. However, the resin is often a soft resin, the problem that the surface hardness and heat resistance is insufficient, and, in a resin system having sufficient hardness, it is hard and brittle, and thus has poor mechanical strength, There are problems such as cracks, and their applications and usage conditions are limited.

On the other hand, a method for improving hardness and heat resistance by dispersing and mixing metal oxide particles such as silica and titania into an active energy ray-curable resin has already been known. When the resin is reinforced with these metal oxide particles, the point of improvement is to disperse the particles having the smallest particle size as uniformly as possible.

However, the smaller the particle size, the easier it becomes to aggregate and form secondary particles, and therefore the particle size becomes large on the contrary, and there is a problem that the dispersibility and the adhesion are deteriorated. It has not been realized to improve efficiently. In addition, there is a problem that the properties required for applications such as paints and coating agents are impaired because the transparency is significantly reduced due to the influence of secondary particles, and the smaller the particle size of the metal oxide, the more exponential the cost. There was a growing problem.

[0005]

The problems to be solved by the present invention include excellent transparency, surface hardness, and heat resistance in which metal oxides are finely dispersed in the active energy ray-curable resin in the order of nanometer to micrometer. To provide a method for producing a composite of an active energy ray-curable resin and a metal oxide, which has properties and mechanical strength and is useful as a film, a coating film, a sealant and the like.

[0006]

Means for Solving the Problems That is, according to the present invention, after applying or molding a homogeneous solution containing a reactive monomer of an active energy ray-curable resin and a metal alkoxide, the active energy ray is irradiated to activate the active energy ray. A method for producing a composite of an active energy ray-curable resin and a metal oxide, which comprises polymerizing a metal alkoxide by heating a reactive monomer of the ray-curable resin.

The method for producing a composite of an active energy ray-curable resin and a metal oxide according to the present invention is based on the fact that the content of the metal oxide is 2 to 40% by weight and the reaction of the active energy ray-curable resin. A solution containing a metal alkoxide is impregnated from the surface of a reactive monomer or a partially cured product of the reactive monomer, and the reactive monomer and / or the metal alkoxide are reacted before the solution is uniformly impregnated. A method for producing a composite of an active energy ray-curable resin and a metal oxide, wherein the concentration of the metal oxide is continuously changed in the thickness direction of the composite obtained by .

Further, in the method for producing a composite of an active energy ray-curable resin and a metal oxide of the present invention, the maximum / minimum value of the concentration of the metal oxide in the obtained composite is 1.5. The production method characterized by the above, or the size of the metal oxide particles contained in the obtained composite is less than 0.2 μm. The size of the metal oxide particles contained is particularly 0.2 to 5 μm, and the method for producing a composite of an active energy ray-curable resin and a metal oxide according to claim 5, also. Including.

The method for producing a composite of an active energy ray-curable resin and a metal oxide of the present invention uses an acrylate-based monomer as a reactive monomer of the active energy ray-curable resin used, Further, a production method characterized by using a reaction initiator having an absorption band in a wavelength range of 200 to 500 nm, and a production method characterized by using a silicone alkoxide and / or a titanium alkoxide as a metal alkoxide to be used. Is also included.

[0010]

The invention will be used in more detail below. The active energy ray-curable resin used in the present invention is an infrared ray, a visible ray, an ultraviolet ray or an electron beam, which is capable of undergoing a polymerization reaction of a reactive monomer.
In the present invention, a reactive monomer and / or a partially reactive polymer of the monomer, which undergo a curing reaction upon irradiation with an active energy ray, are used.

As the reactive monomer and the partially reactive polymer,
Specifically, acrylic-based monomers and oligomers such as polyester acrylate, urethane acrylate, polyether acrylate, epoxy acrylate, polybutadiene acrylate, silicone acrylate, and alkyl acrylate, liquid polybutadiene compounds,

Reactive monomers of commercially available active energy ray-curable resins such as unsaturated polyester compounds, radical polymerizable compounds such as polyene-polythiol compounds, aminoalkyd resins, cationic polymerizable compounds such as epoxy type and vinyl ether type Although partial reaction polymers can be used, acrylic monomers and oligomers are particularly preferable.

In order to react the reactive monomer of the active energy ray-curable resin, a photoreaction initiator is usually used together. As the photoreaction initiator used in the present invention, a radical-type or cation-type photoreaction initiator usually used in the above-mentioned active energy ray-curable resin system is used, and specifically, for example, a benzophenone derivative, Radical photoinitiators such as benzoin ether, benzyl dimethyl ketal, hydroxyalkylphenone, and acylphosphine side, and cationic photoinitiators such as onium salts and related compounds, aryldiatinium salts, and iron arene complexes. You can

Particularly, a photoreaction initiator having an absorption band in the wavelength range of 200 to 500 nm is preferable. When the wavelength is less than 200 nm, it is difficult to effectively irradiate active energy rays because the absorption of resin or air component becomes significant, and when the wavelength exceeds 500 nm, the thermal stability and light stability of the homogeneous sol solution become poor. Inferiority and overlapping with the wavelength range of thermal vibration of the resin cause problems such as heat generation, which is not preferable.

The amount of the reaction initiator added varies depending on the type of the reaction initiator used and the type of the reactive monomer, and cannot be specified unconditionally, but it is usually based on 100 parts by weight of the reactive monomer. 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight are used. If it is less than 0.1 part by weight, the reaction of the reactive monomer is insufficient, and if it exceeds 10 parts by weight, it becomes an impurity and impairs the heat resistance and mechanical properties of the composite, which is not preferable.

As the metal alkoxide used in the present invention, a silicone alkoxide type monomer represented by the following general formula 1 and a partially hydrolyzed polycondensate zone thereof having a polymerization degree of about 2 to 10 and / or a mixture thereof are used. .

(General formula 1) R _4-n M (OR) _n (wherein M is Si, R is an alkyl group having 1 to 6 carbon atoms, n
Represents an integer of 3 or 4. )

As the metal atom of M, in addition to Si, T
i is preferably used, and in addition, Sn, Al, Zr
It is also possible to use one of the above or a mixture of two or more thereof.

The composite of the present invention can be obtained by the following method. After coating a homogeneous sol solution consisting of a metal alkoxide, a reactive monomer and a reaction initiator on the substrate or injecting it into the mold, the metal alkoxide is polycondensed into a metal oxide, and then an active energy ray is applied. A method of polymerizing reactive monomers by irradiation.

Alternatively, a homogeneous sol solution consisting of a metal alkoxide, a reactive monomer and a reaction initiator is injected into a mold or coated on a substrate, and the active monomer is irradiated to polymerize the reactive monomer. Then, it can be obtained by a method of polycondensing a metal alkoxide to form a composite.

The homogeneous sol solution containing the metal alkoxide and the reactive monomer may contain an organic solvent or water. Since the polycondensation reaction of the metal alkoxide is caused by hydrolysis, water is essential for the progress of the reaction. Water is preferably contained in the sol solution of the metal alkoxide and the reactive antimer, but it is also possible to utilize moisture in the air.

In particular, when a highly reactive metal alkoxide such as titanium alkoxide is used, a partial polymer of a metal alkoxide is used, or when complexing is performed in a thin film form, the use of moisture in the air is used. In many cases, it is not necessary to add water to the sol solution.
The amount of water added to the sol solution is 0 to 8 times the molar amount of the metal alkoxide, and is used in a range that does not cause the heterogeneous phase separation of the sol solution.

When water is added to the sol solution, it is possible to advance the polycondensation reaction of the metal alkoxide in a homogeneous sol solution and apply it before the entire solution gels. Is. It is also possible to use a homogeneous sol solution containing no water, in which the polycondensation reaction of the metal alkoxide is allowed to proceed while stirring the solution in a moist atmosphere and slowly absorbing moisture from the surface of the solution.

Further, in order to accelerate the reaction of the metal alkoxide, it is preferable to use heat treatment or the like in combination during the reaction, or to perform it as a final treatment step. When a metal alkoxide that is easily reacted by light, such as titanium alkoxide or zirconia alkoxide, is used in combination,
Upon irradiation with active energy rays, the reaction of the metal alkoxide also proceeds at the same time, and an extremely homogeneous complex is obtained.

The organic solvent contained in the homogeneous sol solution is used for homogenizing the sol solution containing the metal alkoxide, the reactive monomer, the reaction initiator and water, and the organic solvent compatible with these is used. . Suitable organic solvents differ depending on the type of reactive monomer or metal alkoxide used, and therefore cannot be specified unconditionally, but for example, diethyl ether, dioxane, ethers such as tetrahydrofuran (THF), dimethylformamide (DMF), etc. , Dimethylacetamide (DMA), N-methylpyrrolidone (NM
P), etc., amide type, ethyl acetate, methyl acetate, etc. ester type,

Ketones such as acetone and 2-butanone (MEK), methanol, ethanol, 2-propanol,
Alcohols such as butanol, hydrocarbons such as hexane and cyclohexane, aromatics such as toluene, xylene, m-cresol, benzene and nitrobenzene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and dichloroethane, dimethyl. Silicone type such as polysiloxane and cyclomethicone, amine type such as triethylamine, diethylamine and pyridine,

In addition, dimethyl sulfoxide (D
MSO), acetonitrile, carbon disulfide, organic solvent such as methyl ethyl cellosolve, or acetylacetone,
2,4-Pentadione and other diketones, methyl acetoacetate and ethyl acetoacetate and other ketoesters, lactic acid and methyl lactate and other hydroxycarboxylic acid systems, 4-hydroxy-4
Organic solvents such as keto alcohols such as methyl-2-pentanone and amino alcohols such as monoethanolamine and diethanolamine can be used alone or in combination.

In the present invention, it is possible to use an acidic catalyst or a basic catalyst together as a reaction catalyst for the polycondensation reaction of metal alkoxide. As the acidic catalyst, 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,
Basic substances such as dimethylamine, ethylenediamine and butylamine are used. In any case, it is preferable to use as little amount as possible within a range that does not significantly inhibit the curing reaction of the reactive monomer.

The concentration of the metal oxide contained in the composite of the present invention is usually preferably 2 to 40% by weight. If it is less than 2% by weight, the effect of the compounding intended by the present invention becomes insufficient,
On the other hand, if it exceeds 40% by weight, the composite becomes brittle and cracks easily occur, which is not preferable.

The particle size of the metal oxide dispersed in the composite of the present invention varies depending on the type of the metal oxide or resin used and the purpose of use, and cannot be specified unconditionally, but is usually 10 μm or less, The range is preferably 5 μm or less. When it exceeds 10 μm, the mechanical properties of the composite are deteriorated, which is not preferable. The minimum value of particle size is not particularly specified.
Although particles having a size of up to about 5 nm can be confirmed by observation with an electron microscope, particles having a particle size smaller than this may be present in the composite.

The transparency of the composite differs depending on the particle size of the metal oxide dispersed in the composite. For example, 0.2μ
When the particle size is larger than m, an opacified or clouded complex is obtained, and when the particle size is less than 0.2 μm, a transparent complex is obtained. Therefore, it is possible to obtain a composite having a changed transparency by changing the particle size of the metal oxide in the composite.
This property is particularly useful when using a transparent resin such as an acrylic resin.

The composite in the present invention is not only in the form in which the concentration of the metal oxide is uniformly distributed in the composite,
It includes a component-graded composite in which the metal oxide concentration in the composite is changed in a tilted manner, particularly from the composite surface toward the thickness direction. As the component-graded composite, the maximum concentration of the metal oxide contained in the composite is 5 to 100% by weight, the minimum value is 0 to 30% by weight, and the ratio of the maximum value to the minimum value (maximum The value / minimum value is 1.5 or more, preferably 2 or more. The component gradient composite of the present invention can be obtained, for example, by the following method.

(1) After coating a reactive monomer or a partially cured product of a reactive monomer on a substrate or injecting it into a mold, a liquid containing a metal alkoxide is applied from the surface of the monomer. Before the metal alkoxide is impregnated and the metal alkoxide is homogeneously impregnated, the active monomer is irradiated to completely react the reactive monomer to form a graded structure of the metal alkoxide concentration inside the resin. A method of obtaining a complex having a concentration gradient of a metal oxide by advancing the polycondensation reaction.

(2) An anhydrous sol solution containing a reactive monomer and a metal alkoxide is coated on a substrate and kept in a wet atmosphere to locally cause a reaction of the metal alkoxide near the surface of the coating film. Further, the convection of the sol solution generated inside the coating film is used to form a concentration gradient of the metal oxide inside the coating film. Then, a gradient composite is obtained by irradiating an active energy ray to completely cure the reactive monomer.

(3) A sol solution containing a reactive monomer, a reaction initiator and a metal alkoxide is applied on a substrate, the metal alkoxide is partially evaporated from the surface of the coating film, and then an active energy ray is irradiated. To completely cure the reactive monomer. Then, a method of advancing the polycondensation reaction of the metal alkoxide to obtain a complex having a concentration gradient of the metal oxide can be mentioned.

The term "partially cured product of the reactive monomer" as used herein means that the reactive monomer of the active energy ray-curable resin is irradiated with an active energy ray at a dose or less to completely cure the reactive monomer. It is a partially cured product obtained by partially reacting with and can be impregnated with a liquid containing a metal alkoxide.

The degree of curing of the partially cured product varies depending on the type of the reactive monomer used and the composition of the liquid containing the metal alkoxide, and cannot be specified unconditionally.
Usually, those irradiated with a dose of 95% or less of the dose required to completely cure the reactive monomer are used.

Irradiation doses above 95% usually lead to
The liquid containing the metal alkoxide is not efficiently impregnated. In addition to the metal alkoxide, the liquid containing the metal alkoxide can optionally contain water, an organic solvent, an acidic catalyst or a basic catalyst, and further a reactive monomer and a reaction initiator. is there.

As a method of impregnating with a liquid containing a metal alkoxide, a method of applying a liquid or a partially cured product when a partially cured product of a reactive monomer in a state of not being dissolved in a liquid containing a metal alkoxide is used. It is possible to carry out the impregnation operation by, for example, a method of immersing the product in a liquid.

Depending on the type and amount of the organic solvent, the rate of permeation into the coating film varies, and the gradient morphology of the obtained composite changes. When water or a catalyst is included, the degree of polymerization of the metal alkoxide changes over time, and the impregnation rate of the metal alkoxide that permeates into the coating film also changes over time. It is possible to

In addition, the ambient temperature and humidity for performing the impregnation operation,
It is also possible to change the inclination form by controlling the atmospheric condition. In the method (1) described above, it is also possible to preliminarily and homogeneously impregnate a reactive monomer or a partially cured product thereof with a metal alkoxide, and in this case, the metal alkoxide is not contained and the reactivity is reduced instead. It is also possible to obtain a composite having a concentration gradient structure of a metal oxide by a method of impregnating with a solution containing a monomer.

In the method (2), it is preferable to add a metal alkoxide polymerization catalyst to a wet atmosphere in which an anhydrous sol solution is held, and it is particularly preferable to use a basic catalyst atmosphere such as ammonia. Further, convection of the sol solution in the coating film is considered to be caused by the heat of vaporization when the solvent evaporates from the coating liquid surface is caused by the temperature of the coating film surface lower than the temperature of the substrate surface, solvent casting temperature, atmosphere, The type of solvent used is an important factor.

Since each of these factors has a plurality of factors that are inherent and interrelated, it is impossible to unambiguously determine the manufacturing conditions of the target composite having a concentration gradient structure of the metal oxide. However, the casting temperature is usually from -10 ° C.
50 ° C. is preferred. When it exceeds 50 ° C., the casting speed becomes high, and a homogeneous composite body is easily formed. Further, if it is lower than -10 ° C, the humidity is lowered, which is not preferable.

The solvent used is a hydrophilic organic solvent of 30
% Or more, the boiling point is 50 to 50%.
Those at 200 ° C. are preferably used. When the hydrophilic solvent is not contained, the reaction of the metal alkoxide occurs only on the surface of the coating film, so that there is a problem that a continuous tilted structure cannot be obtained or the obtained metal oxide particles become large. Not good for

If the boiling point of the solvent used is less than 50 ° C.,
Casting is likely to end before the graded structure is developed, which is not preferable. On the other hand, when the boiling point exceeds 200 ° C., on the contrary, the casting speed becomes too slow and the graded structure does not appear. In addition, the coating liquid is cooled and on a hot plate,
It is also effective to cast with a temperature difference between the substrate surface and the casting surface.

In the case of the above method (3) of evaporating the metal alkoxide from the surface of the coating film, the metal alkoxide to be used preferably has a boiling point of 200 ° C. or less. Specific examples include tetramethoxysilane and tetraethoxysilane.

[0047]

The present invention will be specifically described below with reference to examples. (Example 1 and Comparative Example 1) Epoxy acrylate-based reactive monomer (200EA; manufactured by Kyoeisha Chemical Co., Ltd.) 10
g, photoreaction initiator (1173; manufactured by Ciba-Geigy Co., Ltd.) 0.3 g, MS-51 (partial polymer of tetramethoxysilane, manufactured by Mitsubishi Chemical Co., Ltd.) 8 g, methanol 5
After the sol solution of g was stirred to form a homogeneous solution, it was applied on a glass plate and cast at room temperature (25 ° C, 50%).

One hour after the start of casting, the resin was completely cured by irradiation with ultraviolet rays. Then 24 at 80 ℃
Heat treatment was performed for an hour to obtain a composite. A coating film excellent in transparency was obtained without generation of cracks. The amount of silica obtained from the ash content after firing the obtained composite at 800 ° C. for 2 hours was about 28% by weight. The surface hardness was measured and found to be 6 gf / μm ² . A surface hardness of a cured product obtained by curing an epoxy acrylate-based reactive monomer (200EA; manufactured by Kyoeisha Chemical Co., Ltd.) containing no MS-51 by UV irradiation in the same manner as in Example 1 was 0.6 gf / μm ^2. Met. (Comparative Example 1) For the surface hardness, a micro surface hardness tester DUH-200 manufactured by Shimadzu Corporation was used. The ultraviolet ray was generated by using a 160 W high-pressure mercury lamp as a light source.

Example 2 10 g of polyester acrylate-based reactive monomer (9 EGA), photoinitiator (1
173) 0.3 g, tetramethoxysilane (TMOS;
(Tokyo Kasei Kogyo Co., Ltd.) 4g, methanol 5g, distilled water 2g After stirring the sol solution to make a homogeneous solution, 25
The mixture was allowed to stir at ℃ for about 2 days. Then, it was applied onto a glass plate and cast at room temperature (25 ° C., 50%).

One hour after the start of casting, the resin was completely cured by irradiating it with ultraviolet rays using a 160 W high pressure mercury lamp as a light source. Then, heat treatment was performed at 80 ° C. for 24 hours to obtain a composite. A coating film excellent in transparency was obtained without generation of cracks. The amount of silica obtained from the ash content after firing the obtained composite at 800 ° C. for 2 hours was about 10.5% by weight.

(Example 3 and Comparative Example 2) 3 g of a mixture of an acrylate-based reactive monomer and a reaction initiator (Dicure Clear SD-17; manufactured by Dainippon Ink and Chemicals, Inc.)
And MS-51 (0.3 g) were stirred to form a homogeneous sol solution. Apply the sol solution onto the polycarbonate and
After spin coating at 00 rpm for 20 seconds, 125
The acrylate was cured by irradiating it with ultraviolet rays using a W high-pressure mercury lamp as a light source. Further, heat treatment was performed at 80 ° C. for 24 hours to obtain a composite. A homogeneous transparent coating having a film thickness of about 8 μm was obtained. When the pencil hardness of the coating film was examined, the composite was 2
H is D-Cure Clear S that does not include MS-51
The UV cured product of D-17 resin alone (Comparative Example 2) is HB.
Met. It can be seen that the coating film hardness has improved.

(Example 4 and Comparative Example 3) Mixture of acrylate and reaction initiator (Dicure Clear SD-17)
3 g, MS-51 0.6 g, tetraethoxy titanium (T
A solution of 0.2 g of a 1: 2 complex of ETi; manufactured by Merck Ltd. and acetylacetone (produced by Kanto Kagaku Co., Ltd.) was stirred to prepare a homogeneous sol solution. The sol solution was applied to a glass plate and irradiated with ultraviolet rays to cure the acrylate. Further, heat treatment was performed at 80 ° C. for 24 hours to obtain a composite. A good coating film with good transparency having a film thickness of about 0.5 mm was obtained.

When the cross section of the composite was observed with a scanning electron microscope (SEM), it was observed that particles having a particle size of 50 to 100 nm were uniformly dispersed. About 2 at 800 ℃
The remaining amount of silica and titania determined from the ash content after time calcination was about 10% by weight. On the other hand, in Comparative Example 3 which was treated in the same manner as in Example 4 except that the TETi complex was not added, cracks occurred after irradiation with ultraviolet rays, and a good coating film could not be obtained. The SEM is S-80 manufactured by Hitachi, Ltd.
0 was used, and the sample was sputtered with Pt for about 3 nm.

(Example 5 and Comparative Example 4) A mixture of polyester urethane acrylate and a reaction initiator (Dicure Coat 8714A; manufactured by Dainippon Ink and Chemicals, Inc.) 5
g, MS-51 0.7g solution was stirred to make a homogeneous sol solution. The sol solution was applied to a glass plate, spin-coated at 400 rpm for 20 seconds, and irradiated with ultraviolet rays using a 80 W metal halide lamp as a light source to cure the acrylate. Further, heat treatment was performed at 80 ° C. for 24 hours to obtain a composite. A homogeneous transparent coating with a film thickness of about 150 μm was obtained.

When the cross section of the composite was observed by SEM, it was observed that silica particles having a particle diameter of 50 to 200 nm were uniformly dispersed. The silica amount obtained from the ash content after calcining at 800 ° C. for 2 hours was about 6% by weight. When a tensile test was performed, the tensile strength was 4.5 (Kg / mm ² ), the elongation was 30%, and the elastic modulus was 130 (Kg / mm ² ). When dynamic viscoelasticity was measured, the tan δ peak temperature was 100 ° C.

On the other hand, in Comparative Example 4 obtained in the same manner as in Example 5 except that MS-51 was not included, the tensile strength was 4.0 (K
g / mm ² ), elongation 27%, elastic modulus 100 (Kg /
mm ² ). Moreover, when dynamic viscoelasticity measurement was performed, the tan δ peak temperature was 83 ° C. It can be seen that the glass transition temperature is greatly improved. The tensile test was performed using an autograph 2000 manufactured by Shimadzu Corporation with a sample length of 1 cm and a tensile speed of 1 mm / min, and dynamic viscoelasticity was measured using a DMS-200 manufactured by Seiko Electronic Co., Ltd. It was measured at a temperature rate of 2 ° C./min and 1 Hz.

(Example 6 and Comparative Example 5) Polyester urethane acrylate (Dicure Coat 8714A) was applied to a substrate and irradiated with ultraviolet rays (120 W high pressure mercury lamp light source) for about 3 seconds to obtain a semi-cured product. The resin was completely cured by irradiation for 30 seconds. The semi-cured product is placed in TMOS and acetone (mixing weight ratio = 10: 1) for about 1 hour (30
℃) soaked. After taking out from the TMOS solution and washing the surface with methanol, it was immersed in a 0.5 mol / l aqueous ammonia solution for 1 hour (30 ° C.).

Next, the resin was completely cured by irradiating it with ultraviolet rays and then heat-treated at 80 ° C. for 24 hours to obtain a composite. A homogeneous transparent composite was obtained. FIG. 1 shows the distribution of Si in the vicinity of the surface of the composite of resignation command 6 obtained by an electron beam microanalyzer (EPMA). The X axis represents the distance from the surface toward the inside of the composite, and the Y axis represents the Si concentration. An inclined structure is formed in which the surface has a strong silica concentration, the silica concentration decreases toward the inside, and the silica concentration becomes zero within about 50 μm. The maximum concentration of silica is about 12% by weight and the minimum value is zero.

As Comparative Example 5, the resin was sufficiently irradiated with ultraviolet rays (30 seconds) and completely cured, and then the same treatment as in Example 6 was carried out to form a composite with silica. FIG. 2 shows an EPMA spectrum near the surface of the composite obtained in Comparative Example 5. It can be seen that almost no silica was introduced. The maximum concentration of silica is about 0.8% by weight. For EPMA measurement, an EPM-810 manufactured by Shimadzu Corporation was used, and output was 15 kV-50 nA, resolution was 1 μm, and 100 μ.
m / min scan speed, detection is Si Kα ray (7.12
6 ohm strong).

Example 7 Polyester acrylate-based reactive monomer (9EGA) 10 g, photoinitiator (1
173) 0.3 g, TMOS 4 g, methanol 5 g,
A sol solution of 2 g of distilled water was stirred to form a homogeneous solution, which was applied on a glass plate and cast at room temperature (25 ° C, 50%). Thirty hours after the start of casting, the resin was completely cured by irradiation with ultraviolet rays. Then, heat treatment was performed at 80 ° C. for 24 hours to obtain a composite. A coating film excellent in transparency was obtained without generation of cracks.

The amount of silica obtained from the ash content after firing the obtained composite at 800 ° C. for 2 hours was about 8% by weight. The results of examining the Si distribution in the cross section of the composite by EPMA are shown in FIG. A gradient composite having a low silica concentration on the surface and an increasing silica concentration toward the inside was obtained. It is presumed that the tilted structure as shown in FIG. 3 was developed because TMOS was evaporated from the surface during solvent casting and ultraviolet irradiation. The surface temperature is 50- during UV irradiation.
It was 60 ° C. The ultraviolet rays were irradiated for about 30 seconds using a 160 W high pressure mercury lamp as a light source.

[0062]

INDUSTRIAL APPLICABILITY The present invention is a composite of a metal oxide and an active energy ray-curable resin, which is useful as a film, a paint, a sealant, etc. and has excellent transparency, surface hardness, heat resistance and mechanical properties. Can be provided.

[Brief description of drawings]

FIG. 1 is a diagram showing an EPMA measurement result of Si in a cross section of a complex of an active energy ray-curable resin and silica obtained in Example 6.

FIG. 2 is a diagram showing an EPMA measurement result of Si in a cross section of a composite of an active energy ray-curable resin obtained in Comparative Example 5 and silica.

FIG. 3 is a diagram showing EPMA measurement results of Si in a cross section of a composite of an active energy ray-curable resin and silica obtained in Example 7.

Claims (8)

[Claims] 1. A reactive monomer of an active energy ray-curable resin is formed by coating or molding a homogeneous solution containing a reactive monomer of an active energy ray-curable resin and a metal alkoxide, and then irradiating with an active energy ray. A method for producing a composite of an active energy ray-curable resin and a metal oxide, wherein the metal alkoxide is polymerized by heating. 2. The method for producing a composite of an active energy ray-curable resin and a metal oxide according to claim 1, wherein the content of the metal oxide is 2 to 40% by weight. 3. A solution containing a metal alkoxide is impregnated from the surface of a reactive monomer of an active energy ray-curable resin or a partially cured product of the reactive monomer, and before the solution is uniformly impregnated. And an active energy ray-curable resin obtained by reacting a reactive monomer and / or a metal alkoxide, wherein the concentration of the metal oxide continuously changes in the thickness direction of the composite. Method for producing complex with metal oxide. 4. A composite of an active energy ray-curable resin and a metal oxide according to claim 3, wherein the maximum / minimum value of the concentration of the metal oxide is 1.5 or more. Manufacturing method. 5. The active energy ray curable resin and the metal oxide according to claim 1, wherein the size of the metal oxide particles contained is less than 0.2 μm. A method for producing a complex with an object. 6. The method for producing a composite of an active energy ray-curable resin and a metal oxide according to claim 5, wherein the size of the metal oxide particles contained is 0.2 to 5 μm. . 7. An acrylate-based monomer is used as a reactive monomer of an active energy ray-curable resin, and a reaction initiator having an absorption band in a wavelength range of 200 to 500 nm is used. The method for producing a composite of an active energy ray-curable resin according to any one of claims 1 to 6 and a metal oxide. 8. A composite of an active energy ray curable resin and a metal oxide according to claim 1, wherein a silicone alkoxide and / or a titanium alkoxide is used as the metal alkoxide. Manufacturing method.