JPH0241337A - Resin composition and film containing polytungstic acid - Google Patents

Abstract

PURPOSE:To obtain a resin composition having protonic conductivity, EC characteristics, high refractive index, ultraviolet-shielding property, etc., and giving a practical high-performance film by uniformly dispersing a polytungstic acid (derivative) in a base polymer. CONSTITUTION:The objective resin composition is composed of (A) a polytungstic acid and/or its derivative, preferably a condensed polytungstic acid containing peroxo or peroxide ion (having carbon atom as a hetero atom) or its derivative (modified with carbide, ethoxide, etc., of a metal such as niobium or talc), (B) a water-soluble polymer or emulsion as a base polymer and preferably further (C) water or water and a hydrophilic solvent and optionally a crosslinking agent and a photo-polymerization initiator. The ratio A/B is (0.05-2)/1 and (A+B)/(A+B+C)X100 is 5-70wt.%. The objective film is produced from the resin composition.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to a functional material containing polytungstic acid having various properties such as proton conductivity, EC properties, high refractive index, and ultraviolet blocking properties. This invention relates to resin compositions and films.

[Conventional technology and problems]

Polytungstic acid has various properties such as proton conductivity, EC properties, high refractive index, and UV protection.
Applications to electrochromic display elements, resist materials, etc. have been proposed (JP-A-60-251130, JP-A-61-275376, JP-A-62-36008, etc.).

Here, a thin film (normal thickness is 0.5 mm) is applied onto a substrate using a wet method.
3 μm or less), but 0
．． There was a problem that it was impossible to make the film thicker than about 5 μm, and even if it could be formed, cranking would occur and it could not be used as a practical material.

Furthermore, since such polytungstic acid cannot be formed into a film by itself, that is, without a base material, there is a problem that a practical functional film that takes advantage of the properties of polytungstic acid cannot be obtained.

[Means for solving problems]

As a result of intensive studies to solve the above problems, the present inventors have created a practical resin composition that maximizes the properties and functions of polytungstic acid by incorporating a base polymer into the polytungstic acid. and a film thereof was obtained.

That is, the present invention provides a resin composition containing (al polytungstic acid and/or a derivative thereof and a (bl base polymer) and a film thereof. In the present invention, polytungstic acid, which is a component fa), is: It is crosslinked by heat or irradiation such as ultraviolet rays, X-rays, or electron beams,
In particular, condensed polytungstic acids containing peroxo or peroxide ions, or containing carbon as a heteroatom and peroxo or peroxide ions are preferably used.

Such condensed polytungstic acid is usually represented by the following general formula.

WO, -ZCO,・￥HzOz ・,2HzO (here, χ, 2, and O are respectively 0≦χ≦0.25.0.05≦7
≦1.0.16= ;! ≦3.5 theal. ) Further, the derivative of polytungstic acid refers to polytungstic acid modified with metal carbide such as niobium (Nb) or tantalum (Ta) or metal ethoxide.

The base polymer of the BL component in the present invention is not particularly limited as long as it is water-soluble, and water-soluble polymers and emulsions are used, and water-soluble polymers are preferred.

Specific examples of such water-soluble polymers include natural polymers such as
Examples of semi-synthetic polymers include starch, pectin, dextran, gelatin, casein, and collagen.
Methylcellulose, ethyl.

Examples include cellulose, ethylhydroxyethylcellulose, methylhydroxypropylcellulose, soluble starch, methylstarch, alginate, etc. Synthetic polymers include polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, and polyethylene. Examples include glycol, polyethylene oxide, and the like.

The emulsion is not particularly limited, but water-soluble emulsions are preferred, such as polyhydroxynykyl acrylate, vinyl chloride, vinyl acetate, etc.
Examples include acrylic copolymer, ethyl acrylate-butyl acrylate copolymer, methyl methacrylate-butadiene copolymer, and polyvinyl acrylate.

In the present invention, the preferred blending ratio (weight ratio) of polytungstic acid and/or its derivative as the component (a) and the base polymer as the component ('b) is (al/(bl)
=0.05/1 to 2/1, particularly preferably (a)
/ (bl = 0.2/1 to 1/1. By setting the blending ratio within the above range, the (a) component and the (bl component) are uniformly dispersed, resulting in a uniform product having the function of the al component. A composition is obtained.

In the present invention, it is preferable that the composition further contains a solvent as the fc) component. By using such a solvent, component (a) and component fb) of the present invention can be more uniformly dispersed.

As such a solvent, water or a mixture of water and an organic solvent is used. Here, examples of the organic solvent include alcohols, monoether monoalcohols, dimethylformamide, dioxane, tetrahydrofuran, ketones, etc., which are compatible with water, and one or more of these may be used in combination. be able to.

The amount of solvent used in this case mainly depends on the molecular weight and type of the base polymer used as component (b), but
Preferably ((a) ten mountains)) / ((a)+(bl
+(JXloo is used in an amount of 5 to 70% by weight, particularly preferably 10 to 60% by weight. Within the above range, the composition can be formed into a film on bloody stool.

In the present invention, the component (d) further includes a photocrosslinking agent,
A photopolymerization initiator can also be included as component (e).

Here, as the photocrosslinking agent, monomers and oligomers containing one or more polymerizable carbon-carbon double bonds in one molecule are preferable, such as acrylamide and N.

N-dimethylacrylamide, acroylmorpholine,
N-methylacrylamide, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropylacrylamide, N,N'-methylenebisacrylamide, N-vinylpyridine, N-vinyl-2-pyrrolidone,
Diethylaminoethanol, dimethylaminoethyl methacrylate, Diaseptone acrylamide, N-methylolacrylamide, 2-acrylamido-2-methylpropanesulfonic acid, sodium p-styrenesulfonate,
Methoxytetraethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, β-(meth)acryloyloxyethylhydrogen succinate, β-(meth)acryloyloxyethylhydrogen phthalate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, pentaglycerol tri(meth)acrylate,
pentaerythritol tri- or tetra(meth)acrylate, dipentaerythritol tri-, tetra-, penta- or hexa(meth)acrylate, hexa(meth)acrylate of ε-caprolactone adduct of dipentaerythritol, epoxy-based (meth)acrylate oligomer, Examples include urethane-based (meth)acrylate oligomers and polyester-based (meth)acrylate oligomers.
These can be used alone or in combination of two or more.

Further, as the photopolymerization initiator, various photopolymerization initiators known as polymerization initiators and aggravating agents for ultraviolet curable coatings are used.

Specific examples of the photopolymerization initiator include anthraquinone, methylanthraquinone, anthraquinone series such as sodium anthraquinone 2,6-disulfonate, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2-
Methylbenzoin, benzophenone, Michler's ketone, 1-hydroxycyclohexylphenyl ketone, benzyl, benzyl dimethyl ketal, 2,2-jethoxyacetophenone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone,
Examples include anthracene, 1.1-dichloroacetophenone, methylorthobenzoylbenzoate, and those used in combination with small amounts of stimulant aids such as amines.

The resin composition of the present invention contains the (a) component and the (bl component, and if necessary, the (dl component and +81 component).
It is obtained by dissolving it in component C) and mixing it uniformly.

The present invention also provides a film made of the above-mentioned resin composition, specifically a film made by removing the solvent from the above-mentioned composition by evaporation.

Such a film is prepared by coating the above composition on a base material such as a plastic film such as polyethylene terephthalate or a glass plate, and then heating the composition at 80 to 120°C for 5 to 30°C.
By heating for about a minute and evaporating the solvent, a film can be obtained as a single film on or peeled from the substrate.

The thickness of such a film is not limited, but is usually several μm to
Films of several orders of magnitude can be obtained.

Further, in the present invention, the resin composition can be impregnated into a base material such as a nonwoven fabric to form a sheet or a shaped article.

In the present invention, photochromism can be developed by irradiating the film with light energy such as ultraviolet rays. That is, in detail, 100 to 5000n
+J/d, preferably 500-3000+++J
By irradiating the film with ultraviolet light at /-, the colorless film develops a blue color, and then returns to colorless when left to stand.

〔Effect of the invention〕

According to the present invention, since polytungstic acid is uniformly dispersed in the base polymer, an extremely practical and highly functional film can be obtained without impairing the properties of polytungstic acid.

Therefore, it can be effectively used in various fields such as light control materials, recording materials, sensors, and automobiles.

More specifically, ECD related, polymer solid electrolyte,
It can be applied to applications such as light control film, humidity sensor film, UV cut film, ion conductive film, and high refractive index film.

〔Example〕

Example I 60 parts by weight of polyvinyl alcohol was dissolved in 50 parts by weight of water, and polytungstic acid (W(h・0.63
50 parts by weight of H,0□.1.851(,0) and 50 parts of water were added, and the mixture was mixed and stirred at room temperature to obtain a uniform resin composition.

The formulation of the resulting composition is shown in the table.

This composition was applied onto a base material (polyethylene terephthalate film) using an applicator to form a coating film, which was heated and dried at 100° C. for 10 minutes, and then peeled off from the base material to obtain a film.

Example 2 A film of the present invention was obtained in the same manner as in Example 1, except that polyvinylpyrrolidone was used instead of polyvinyl alcohol.

The properties of these films were evaluated by the following method, and the results are shown in the tables and figures.

[Film forming property]

・Elastic modulus and elongation---JIS K-714
Appearance - - - - - - - - - - - - Optical microscopy [Photochromism] The obtained transparent film was irradiated with ultraviolet rays using a high-pressure mercury lamp (1
0100O/cIll).

○-・--1-- It developed a blue color, and then returned to transparency when left at room temperature.

×−・−・−・No color development.

[UV power/pigeon properties] The results of measuring the transmittance in the range of 200 to 500 nm using a spectrophotometer are shown in the figure.

[Comparative example]

10 parts by weight of polytungstic acid was dissolved in 40 parts by weight of water, and this solution was spin-coded onto a glass plate.
It was dried at 120°C for 5 minutes and then cured at 120°C for 1 hour.

Although the thickness of this coating film was 0.5 μm or more, cranking occurred and it could not be peeled off from the base material.
It could not be obtained as a stand-alone film.

4,

[Brief explanation of the drawing]

The figure is a graph showing the UV cut properties of the film of the present invention. Patent applicant: Nitto Electric Industry Co., Ltd. Representative: Goro Kamai (nwt)

Claims (5)

[Claims] (1) A resin composition containing (a) polytungstic acid and/or its derivative, and (b) a base polymer. (2) The polytungstic acid or its derivative is (a) containing peroxo or peroxide ions, or (b) condensed polytungstic acid or its derivative containing carbon as a heteroatom and peroxo or peroxide ion. Claim 1
The resin composition described. (3) The resin composition according to claim 1, wherein the base polymer is a water-soluble polymer or an emulsion. (4) A film comprising the resin composition according to claim 1. (5) The resin composition according to claim 1, further comprising water or water and a hydrophilic solvent.