JPH0885768A - Antistatic transparent plastic plate and its production - Google Patents

Abstract

PURPOSE: To obtain an antistatic transparent plastic plate uniformly coated with a conductive layer formed by easily curing by irradiation with ultraviolet or visible light and being excellent in hardness, solvent resistance and chemical resistance by using specified components. CONSTITUTION: This plate is produced by forming a conductive layer made from a photocurable conductive coating material comprising 100 pts.wt. (meth) acrylate compound (A) having at least two (meth) acryloyl groups in the molecule, 0.1-30 pts.wt. aniline polymer (B), 1-100 pts.wt. alkyl (meth) acrylate (C), and 0.01-10 pts.wt. photopolymerization initiator (D) on a transparent plastic plate substrate. An example of the preparation of the photocurable conductive coating material comprises mixing the component B with the component C and optionally an organic solvent, adding the component A and the component D to the mixture, and further mixing the resultant mixture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic transparent plastic plate and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conductive polymers are electronic devices that utilize the properties of semiconductors, electrochromic materials that utilize the change in absorption wavelength during redox, battery electrode materials and electrochemically active substances, antistatic and electromagnetic waves. It is being put to practical use as a conductive filler such as a shield material. In particular, polythiophene, polypyrrole, polyaniline and the like are stable in air and have a conductivity of 100 S / cm or more, and are conductive polymers suitable for practical use.

In order to obtain a high conductivity of 1 S / cm or more, these conductive polymers are subjected to a treatment called doping for forming a complex between the dopant and the conductive polymer. As a dopant for polypyrrole, polythiophene, etc., a method of doping a gas such as iodine, arsenic pentafluoride, etc. is relatively easy, but there is a drawback that the dopant is separated from the conductive polymer with time and conductivity is lowered. It was Further, a method of performing anion doping by an electrochemical method is also performed. In this case, the conductivity is relatively stable, but there is a drawback that the process is complicated and it is not suitable for mass synthesis.

In the case of polyaniline, as a dopant,
Since it uses an inorganic / organic protonic acid, it exhibits stable conductivity, but it is usually insoluble in a solvent, and thus there is a problem in workability in forming a coating film. Further, even if processed, sufficient conductivity could not be obtained with a small amount of compounding. Therefore, a method of forming a coating film of a specific polyaniline soluble in a solvent using a binder such as polyester has been disclosed (JP-A-1-131288).

However, when such a polyaniline is used as a coating film, there have been problems that the coating film strength is weak and solvent resistance and chemical resistance are poor. In particular, polyaniline is
The acid as a dopant is washed away when it comes into contact with the solvent,
There has been a problem that the dopant is released and becomes an insulator when it comes into contact with alkali. Further, the sparingly soluble polyaniline requires a special solvent, and a technique of using an appropriate dispersant for dispersing the solvent-insoluble polyaniline in the solvent has not been disclosed so far.

In order to improve the hardness and solvent resistance of plastic substrates and the like, paints that are easily cured by ultraviolet rays or visible rays have been proposed (Japanese Patent Laid-Open No. 60-60166). However, since this paint uses an inorganic conductor, it is difficult to disperse it, a large amount of dispersant and a long dispersion time are required, and the storage stability of the paint is poor due to re-aggregation even after dispersion. There was a problem.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to easily cure by irradiation of ultraviolet rays or visible rays to form a conductive layer, and to provide a transparent surface. It is an object of the present invention to provide an antistatic transparent plastic plate which has no coating unevenness and has a conductive layer having excellent hardness, solvent resistance and chemical resistance, and a method for producing the same.

[0008]

In the antistatic transparent plastic plate of the present invention, a conductive layer made of a photocurable conductive paint is formed on a transparent plastic plate base material.

The above-mentioned photo-curable conductive coating material comprises a (meth) acrylate compound (a), an aniline polymer (b), a (meth) acrylic acid alkyl ester resin (c) and a photopolymerization initiator (d). As a constituent.

The (meth) acrylate compound (a)
Is a polymer having at least two or more (meth) acryloyl groups in the molecule, and is preferably one in which the polymerization is initiated by active rays such as ultraviolet rays or visible rays. For example, ethylene glycol di (meth) acrylate, Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate , Tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris- (2-hydroxyethyl) -isocyanuric acid ester ( (Meth) acrylate, 2,2-bis (4
-Acryloxydiethoxyphenyl) propane, 2,2
-Bis (4-methacryloxydiethoxyphenyl) propane, 3-phenoxy-2-propanoyl acrylate, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether, tetramethylolmethane tetra (meth) acrylate Etc.

Further, the above-mentioned (meth) acrylate compound (a) has an acrylic urethane oligomer having a urethane bond in the molecule, or an ester bond as a main chain (meth).
By adding a polyester acrylate having at least two acryloyl groups in the molecule, a highly crosslinked structure can be obtained, and the hardness and scratch resistance of the resulting coating film can be further improved.

Examples of the acrylic urethane oligomer include pentaerythritol triacrylate hexamethylene diisocyanate, pentaerythritol triacrylate isophorone diisocyanate and pentaerythritol triacrylate tolylene diisocyanate.

As the aniline polymer (b), a conventionally known aniline polymer having conductivity can be used.

In the above photocurable conductive coating composition, if the addition amount of the aniline polymer (b) is small, the conductivity of the coating film obtained is insufficient, and if it is large, scratch resistance, chemical resistance, and resistance to chemicals are increased. Since the solvent property decreases, it is limited to 0.1 to 30 parts by weight with respect to 100 parts by weight of the (meth) acrylate compound (a).

Examples of the method for preparing the aniline polymer (b) include a method in which an aniline monomer and an acid are dissolved in water or dimethylformamide and the like, and an oxidant solution is added dropwise while stirring to perform oxidative polymerization.

The aniline-based monomer is aniline or a derivative thereof, and examples thereof include aniline, N-methylaniline, N-ethylaniline, diphenylaniline, o-toluidine, m-toluidine, 2-ethylaniline and 3-ethyl. Aniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 2,6-diethylaniline, 2-methoxyaniline, 4-methoxyaniline, 2,4-dimethoxyaniline, o-phenylene Diamine, m-phenylenediamine, 2-aminobiphenyl, N, N-diphenyl-p-
Examples thereof include phenylenediamine.

Examples of the acid include inorganic protonic acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as p-toluenesulfonic acid, and the acid concentration is preferably 0.1 to 1N.

Examples of the oxidizing agent include persulfate, hydrogen peroxide, permanganate, lead dioxide, dichromate, manganese dioxide, iron chloride and the like. The concentration of these oxidizing agents is 0.1 to water or dimethylformamide.
1 mol / l is preferred.

The (meth) acrylic acid alkyl ester resin (c) is used as a dispersant for dispersing the aniline polymer (b) in the (meth) acrylate compound (a). ) Examples of the alkyl acrylate resin (c) include homopolymers or copolymers of alkyl (meth) acrylate.

Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Examples thereof include butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate.

The homopolymer or copolymer of the above-mentioned (meth) acrylic acid alkyl ester can be prepared by a known polymerization method, for example,
It can be produced by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method or the like.

When the molecular weight of the (meth) acrylic acid alkyl ester resin (c) is small, the effect of thickening is not exhibited and the coatability of the paint is deteriorated. Since the workability deteriorates, 100,000 to 1
It is preferably, 000,000, and more preferably 300,000 to 800,000.

When the amount of the (meth) acrylic acid alkyl ester resin (c) added to the above-mentioned photocurable conductive coating material is small, the dispersion effect is not exhibited and the transparency of the obtained coating film is lowered and the coating film is increased. The viscous effect is not exhibited, the coatability is deteriorated, and the scratch resistance is deteriorated when the amount is increased. Therefore, the amount is limited to 1 to 100 parts by weight, preferably 2 parts by weight, relative to 100 parts by weight of the (meth) acrylate compound (a). ˜50 parts by weight.

The photopolymerization initiator (d) is preferably one having a property of initiating the polymerization of the (meth) acrylate compound (a) by an actinic ray such as an ultraviolet ray or a visible ray.

Among the above photopolymerization initiators (d), those which are activated by ultraviolet rays include, for example, sodium methyldithiocarbamate sulfide, tetramethylthiuram monosulfide, diphenylmonosulfide, dibenzothiazoyl monosulfide and disulfide. Sulfides such as; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone and diisopropylthioxanthone; (di) azo compounds such as hydrazone, azobisisobutyronitrile and benzenediazonium; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Aromatic carbonyls such as benzophenone, dimethylaminobenzophenone, Michler's ketone, benzylanthraquinone, t-butylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzyldimethylketal, and methylphenylglyoxylate. Compound;
Acetophenones such as 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxyethoxy-α, α'-dimethylacetophenone, 2,2-diethoxyacetophenone and 2,2-dimethoxyacetophenone. Derivatives; dialkylaminobenzoic acid esters such as 2-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate and isopropyl 4-diethylaminobenzoate;
Peroxides such as benzoyl peroxide, butyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide; 9
-Phenylacridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine, benzacridine and other acridine derivatives; 9,10-dimethylbenzphenazine, 9-methylbenzphenazine, 10-methoxybenzphenazine and other phenazine derivatives; 6 ，
Quinoxaline derivatives such as 4 ′, 4 ″ -trimethoxy-2,3-diphenylquinoxaline; 2,4,5-triphenylimidazoyl dimer; halogenated ketones; acylated phosphorus such as acylphosphine oxide and acylphosphonate A compound etc. are mentioned.

Further, as the one which is activated by visible light, for example, 2-nitrofluorene, 2,4,6-tris (trichloromethyl) -1,3,5-triazine,
3,3′-carbonylbiscoumarin, thiomichler ketone and the like can be mentioned.

An amine compound may be added in order to prevent sensitivity deterioration due to oxygen inhibition of the photopolymerization initiator (d). Such an amine compound is not particularly limited as long as it is a non-volatile compound such as an aliphatic amine or an aromatic amine, and for example, triethanolamine, methyldiethanolamine or the like is used, and further, the dialkylaminobenzoic acid ester is used. A photopolymerization initiator containing an amino group such as Michler's ketone can also be used as the amine compound.

When the amount of the photopolymerization initiator (d) added in the photocurable conductive coating composition is small, the photopolymerization rate is low and the coating film obtained is insufficiently cured. Since the polymerization rate becomes saturated and does not increase further, it is limited to 0.01 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylate compound (a).

If necessary, an organic solvent, an ultraviolet absorber, an antioxidant, a thermal polymerization inhibitor, etc. may be added to the photocurable conductive coating material.

As the above-mentioned organic solvent, one having a low boiling point or one having a strong volatility has a problem that the viscosity of the coating material changes due to evaporation during coating, and a solvent having a high boiling point requires a long time for drying. About 70 to 160 ° C. is preferable, and examples thereof include cyclohexane, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), diethylene glycol dimethyl ether, butyl acetate, isopropyl acetone, methyl ethyl ketone, toluene, xylene, anisole and the like. To be

Examples of the ultraviolet absorber include salicylic acid-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers, and the antioxidant includes phenol-based, phosphoric acid-based, and sulfur-based ultraviolet absorbers. Antioxidants may be mentioned, and as the thermal polymerization inhibitor,
Examples thereof include hydroquinone and p-methoxyphenol.

As a method for preparing the photocurable conductive coating material of the present invention, an organic solvent may be added to the aniline polymer (b) and the (meth) acrylic acid alkyl ester resin (c), if necessary. After the above-mentioned mixing, the (meth) acrylate compound (a), the photopolymerization initiator (d) and the like are further added and mixed.

The equipment used in the step of mixing the photocurable conductive coating material is an equipment usually used for dispersing or blending the fine powder in order to sufficiently disperse the fine powder in the coating material, for example, a sand mill, a ball mill or an atto. A lighter, a high-speed rotary stirring device, a triple roll, etc. are used. The average particle size of the aniline-based polymer after mixing is preferably 0.4 μm or less.

Examples of the transparent plastic plate base material include vinyl chloride resin, acrylic resin, ABS
Resin, polycarbonate, polyethylene terephthalate, polyether ether ketone, polyphenylene sulfide, polyether sulfone, polysulfone,
Examples include plastic plates or sheets of polyimide, polyetherimide, fluororesin, and the like.

The method for producing an antistatic transparent plastic plate according to the second aspect of the present invention is to form a coating film by applying a photocurable conductive paint on the transparent plastic film.
Step 2, a second step of transferring and laminating the coating film formed in the first step onto a transparent plastic substrate, and irradiating the coating film with actinic rays such as ultraviolet rays or visible rays to cure the coating to form a conductive layer. And the third step.

As a method for applying the above-mentioned photo-curable conductive coating material onto a plastic plate base material, for example, a general coating method such as a spray method, a bar coating method, a doctor blade method, a roll coating method or a dipping method is used. Is used.

In order to transfer and laminate the above-mentioned coating film, a method is adopted in which the coating film and the transparent plastic plate are superposed so that they are in contact with each other, and heat and pressure are applied to laminate them. Peel off the plastic film.

The transparent plastic film may be a film having a smooth surface, and examples thereof include a polyolefin film, a polyester film, and a polyester biaxially stretched film. If the smoothness of the film surface is good, the smoothness of the conductive layer surface is also good,
An antistatic transparent plastic plate having excellent smoothness can be obtained.

When the thickness of the conductive layer becomes thin, the conductivity becomes insufficient, and when it becomes thick, the transparency decreases.
It is preferably 5 to 5 μm.

Examples of the active light source for curing the above photocurable conductive coating material include, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, and He-Cd.
A laser, an Ar laser or the like is used.

When the irradiation amount of the above-mentioned actinic rays is small, the curing of the coating film is insufficient and the coating strength such as scratch resistance and hardness is lowered, and when the irradiation amount is large, the coating film is strongly colored and the transparency is high. As the integrated exposure amount at 365 nm becomes 50,
It is preferably 5,000 mJ / cm ² .

Next, the present invention 3 will be described. The method for producing an antistatic transparent plastic plate according to the third aspect of the present invention is
The first step of forming a coating film by coating the above photocurable conductive coating material on a transparent plastic film, irradiating the coating film with actinic rays such as ultraviolet rays or visible rays to cure the coating film and forming a conductive layer. A second step, a third step of forming a thermoplastic transparent resin layer on a transparent plastic plate substrate,
It comprises a fourth step of laminating the transparent resin layer on the plastic plate base material and a conductive layer on the plastic film so as to be in contact with each other, and a fifth step of peeling the plastic film.

As the plastic film and the photocurable conductive paint, the same ones as used in the present invention are used.

In the first step of forming the above-mentioned coating film, the present invention 2 is used.
The same method as the first step of the above is used to form the second conductive layer.
In the steps, the same method as in the second step of the present invention 2 is adopted.

In the third step, a thermoplastic transparent resin layer is formed on the plastic plate base material in order to improve the adhesion between the plastic plate base material and the conductive layer. Examples of the plastic plate base material include the same plastic plate base materials as used in the present invention.

A saturated polyester resin is preferably used for forming the transparent resin layer. As the saturated polyester resin, it is preferable to use a copolymer of several polyvalent carboxylic acids and several polyhydric alcohols. Examples of the polycarboxylic acid include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid; dicarboxylic acids,
Aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like can be mentioned.

As the polyhydric alcohol, ethylene glycol, 1,2-propylene glycol, 1,
4-butanediol, 1,5-pentanediol, 1,
6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, 1,
4-cyclohexane dimethanol, an ethylene oxide addition agent of bisphenol A, etc. are mentioned.

Examples of commercially available saturated polyester resins include "Chemit" manufactured by Toray Industries, Inc., "Byron" manufactured by Toyobo Co., Ltd., "Vitel" manufactured by Goodyear Co., Ltd., and the like.

When the softening point of the saturated polyester resin is low, the tackiness is strong and the handling becomes difficult. When the softening point is high, the temperature rises during lamination, which may cause thermal deformation of the substrate. . The softening point here is a value measured by the ring and ball method.

The transparent resin layer is formed by applying the saturated polyester resin on the plastic plate by the same application method as in the present invention.

In the fourth step, the transparent resin layer on the plastic plate base material and the conductive layer on the plastic film are laminated so as to be in contact with each other. As a stacking method,
A method of laminating by applying heat and pressure can be mentioned.

In the fifth step, the antistatic transparent plastic plate of the third aspect of the present invention is obtained by peeling the plastic film from the laminate obtained in the fourth step.

Next, the present invention 4 will be described. A method for manufacturing an antistatic transparent plastic plate of the present invention 4 is
The first step of applying the above photocurable conductive coating material onto a transparent plastic film (f ₁ ) to form a coating film, and irradiating the coating film with actinic rays such as ultraviolet rays or visible rays to cure the coating film. Second step of forming conductive layer, third step of forming thermoplastic transparent resin layer on transparent plastic film (f ₂ ).
Process, a fourth process of laminating the transparent resin layer on a transparent plastic plate substrate, a fifth process of peeling the plastic film (f ₂ ) from the transparent resin layer, the transparent resin layer and the conductive layer And a sixth step of laminating the plastic film (f ₁ ) so that they are in contact with each other, and a seventh step of peeling the plastic film (f ₁ ).

The plastic films (f ₁ ) and (f
_{As 2} ) and the photocurable conductive coating, the same coating as that used in the present invention is used.

In the first step of forming the above coating film, the present invention 2 is used.
The same method as the first step of the above is used to form the second conductive layer.
In the steps, the same method as in the second step of the present invention 2 is adopted.

In the third step, a thermoplastic transparent resin layer is formed on the transparent plastic film (f ₂ ).
The same saturated polyester resin as in the third aspect of the invention is preferably used for the transparent resin layer, and is formed by the same coating method as in the third aspect of the invention.

In the fourth step, the transparent resin layer formed in the third step is laminated on the transparent plastic plate base material, and in the fifth step, the transparent resin layer is transferred to the plastic film (f ₂ ) Is peeled off. Examples of the laminating method include a method of laminating by applying heat and pressure.

In the sixth step, the transparent resin layer and the conductive layer are laminated so as to be in contact with each other, and in the seventh step, the plastic film (f ₁ ) is peeled off, whereby the present invention can be carried out. An antistatic transparent plastic plate is obtained. . Examples of the laminating method include a method of laminating by applying heat and pressure.

[0059]

【Example】

[Synthesis of aniline-based polymer] p-toluenesulfonic acid 1
60 g (0.8 M) was dissolved in 1000 ml of deionized water to prepare the same sulfonic acid aqueous solution. This is 500m
Divide into 1 liter each, and one side has 36.5 ml aniline (0.4
M) was added, and 91 g of ammonium peroxodisulfate was dissolved in the other. A separable flask reaction vessel equipped with a cooling tube, a stirrer and a dropping funnel was charged with the aniline-containing sulfonic acid aqueous solution, and 500 ml of ammonium peroxodisulfate-containing sulfonic acid aqueous solution was added dropwise over 30 minutes while suppressing the temperature rise in a water bath. Stirring was continued for 3 hours. The precipitate was collected by filtration and sufficiently washed with methanol to obtain a green aniline polymer powder (average particle size: 0.3 μm).

[Preparation of aniline-based polymer dispersion] -Synthetic aniline-based polymer 20 parts by weight-Polymethylmethacrylate 40 parts by weight "Hyper HPA" manufactured by Negami Kogyo Co., Ltd. (Mw: 500,000) -Xylene 140 parts by weight Each component was dispersed with an attritor for 8 hours to obtain an aniline polymer dispersion (A). The particle size of the polyaniline particles in this dispersion liquid (A) was 0.0 when observed with an electron microscope.
It was 1 μm or less.

(Example 1) [Preparation of photo-curable conductive paint] 100 parts by weight of aniline polymer dispersion (A) • 100 parts by weight of dipentaerythritol hexaacrylate Nippon Kayaku Co., Ltd. “DPHA” Polymerization initiator 2,4-diethylthioxanthone 0.1 parts by weight "Kayacure DETX" manufactured by Nippon Kayaku Co., Ltd. Ethyl 4-dimethylaminobenzoate 0.1 parts by weight Xylene 150 parts by weight The above components are stirred with an attritor for 20 minutes. Thus, a photocurable conductive coating material was obtained.

[Preparation of Coating Film] The conductive coating material was applied onto a polyethylene terephthalate (hereinafter referred to as PET) film (“Tetron film HP7” manufactured by Teijin Ltd., thickness 25 μm) with a bar coater to give a film thickness of 2 μm. And dried to form a coating film. The dried coating film was thermocompression-bonded and laminated on an acrylic resin plate at a temperature of 90 ° C. and a pressure of 4 kg / cm ² to form a conductive layer. Next, this conductive layer was irradiated with a high-pressure mercury lamp to irradiate it with a light amount of 1000 mJ / cm ² and cured, and then the PET film was peeled off to obtain a film thickness
An antistatic transparent plastic plate having a conductive layer of μm was obtained.

Example 2 In place of dipentaerythritol hexaacrylate, a hexafunctional urethane acrylate (“UA-306T” manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) was used.
A photo-curable conductive coating material was obtained in the same manner as in Example 1 except that parts by weight were used, and this photo-curable conductive coating material was then used to form an acrylic resin plate in the same manner as in Example 1. An antistatic transparent plastic plate having a conductive layer having a film thickness of 2 μm was obtained.

(Example 3) Photocuring was carried out in the same manner as in Example 1 except that 100 parts by weight of polyester acrylate ("M-9050" manufactured by Toagosei Kagaku Kogyo Co., Ltd.) was used in place of dipentaerythritol hexaacrylate. After obtaining the type conductive coating material, this photocurable conductive coating material was used to form a film having a thickness of 2 on the acrylic resin plate in the same manner as in Example 1.
An antistatic transparent plastic plate having a conductive layer of μm was obtained.

Example 4 Instead of dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate (“A-TMM” manufactured by Shin-Nakamura Chemical Co., Ltd.) was used.
T ") except that 100 parts by weight was used, a photocurable conductive coating material was obtained in the same manner as in Example 1, and the photocurable conductive coating material was used to prepare an acrylic resin in the same manner as in Example 1. An antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm on the resin plate was obtained.

Example 5 A photocurable conductive coating material was obtained in the same manner as in Example 4 except that the amount of the aniline polymer dispersion liquid (A) used was changed to 20 parts by weight. Using the photo-curable conductive paint, an antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm on an acrylic resin plate was obtained in the same manner as in Example 1.

(Example 6) [Preparation of aniline polymer dispersion] Synthetic aniline polymer (synthetic product of Example 1) 20 parts by weight Polymethylmethacrylate 80 parts by weight "Hyper HPA manufactured by Negami Kogyo Co., Ltd." (Mw: 500,000) -Xylene 100 parts by weight The above components were dispersed in an attritor for 8 hours to obtain an aniline polymer dispersion liquid (B). When the particle size of the polyaniline particles in this dispersion liquid (B) was observed with an electron microscope, it was 0.0
It was 1 μm or less. Then, a photocurable conductive coating material was obtained in the same manner as in Example 1 except that 100 parts by weight of the aniline polymer dispersion liquid (B) was used instead of the synthetic aniline polymer (A). Then, using this photocurable conductive coating material, an antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm on an acrylic resin plate was obtained in the same manner as in Example 1.

(Example 7) [Preparation of aniline-based polymer dispersion] -Aniline-based polymer 20 parts by weight "Versicon (Powder)" manufactured by Allied Signal (average particle size 0.1 to 0.2 µm) -Poly Methyl methacrylate 40 parts by weight "Hyper HPA" manufactured by Negami Kogyo Co., Ltd. (Mw: 500,000) -Xylene 140 parts by weight The above components were dispersed for 8 hours with an attritor to obtain an aniline polymer dispersion (C).

Then, in place of the synthetic aniline polymer (A), 100 parts by weight of the aniline polymer dispersion (C) was used in the same manner as in Example 1, and the photocurable conductive coating material was used. Then, using this photocurable conductive paint, a film thickness of 2 was formed on the acrylic resin plate in the same manner as in Example 1.
An antistatic transparent plastic plate having a conductive layer of μm was obtained.

Example 8 Example 7 was repeated except that the amount of the aniline polymer dispersion liquid (C) used was 2 parts by weight.
After obtaining a photo-curable conductive coating material in the same manner as described in (1) above, using this photo-curable conductive coating material, an antistatic transparent plastic having a conductive layer with a film thickness of 2 μm on an acrylic resin plate as in Example 1 was used. A plate was obtained.

Comparative Example 1 [Preparation of aniline-based polymer dispersion] Synthetic aniline-based polymer (synthetic product of Example 1) 20 parts by weight Xylene 180 parts by weight Disperse with the above composition for 8 hours with an attritor. Then, an aniline-based polymer dispersion liquid (D) was obtained. Then, instead of the synthetic aniline-based polymer (A), the aniline-based polymer dispersion liquid (D)
After obtaining a photocurable conductive coating material in the same manner as in Example 1 except that 100 parts by weight of was used, the photocurable conductive coating material was used to prepare an acrylic resin plate on the acrylic resin plate in the same manner as in Example 1. An antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm was obtained.

Comparative Example 2 A photocurable conductive coating material was obtained in the same manner as in Example 1 except that the amount of the aniline polymer dispersion liquid (A) used was changed to 5 parts by weight. Using the photo-curable conductive paint, an antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm on an acrylic resin plate was obtained in the same manner as in Example 1.

Comparative Example 3 A photocurable conductive coating material was obtained in the same manner as in Example 1 except that the amount of the aniline polymer dispersion liquid (A) used was changed to 500 parts by weight. Using the photo-curable conductive paint, an antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm on an acrylic resin plate was obtained in the same manner as in Example 1.

(Example 9) The photocurable conductive coating material obtained in Example 1 was bar-coated on an acrylic resin plate and irradiated with a high-pressure mercury lamp at a light amount of 1000 mJ / cm ² to cure it. A coating film having a film thickness of 2 μm was formed to obtain an antistatic transparent plastic plate.

(Example 10) An antistatic transparent plastic plate was obtained in the same manner as in Example 9 except that the photocurable conductive coating material obtained in Example 2 was used.

(Example 11) An antistatic transparent plastic plate was obtained in the same manner as in Example 9 except that the photocurable conductive coating material obtained in Example 3 was used.

(Example 12) An antistatic transparent plastic plate was obtained in the same manner as in Example 9 except that the photocurable conductive coating material obtained in Example 4 was used.

(Example 13) An antistatic transparent plastic plate was obtained in the same manner as in Example 9 except that the photocurable conductive coating material obtained in Example 5 was used.

(Example 14) An antistatic transparent plastic plate was obtained in the same manner as in Example 9 except that the photocurable conductive coating material obtained in Example 6 was used.

(Example 15) An antistatic transparent plastic plate was obtained in the same manner as in Example 9 except that the photocurable conductive coating material obtained in Example 7 was used.

(Example 16) An antistatic transparent plastic plate was obtained in the same manner as in Example 9 except that the photocurable conductive coating material obtained in Example 8 was used.

(Example 17) [Preparation of composition for transparent resin layer] 30 parts by weight of saturated polyester resin ("Chemit R-99" manufactured by Toray Industries, Inc.) 14 parts by weight of methyl ethyl ketone ・ 56 parts by weight of toluene By mixing, a transparent resin layer composition was prepared.
The conductive coating material obtained in Example 1 was applied and dried on a PET film by using a bar coater so that the film thickness after drying was 2 μm to form a coating film, which was then dried with a high pressure mercury lamp at 100 ° C.
A conductive layer was formed by irradiating with a light amount of 0 mJ / cm ² . Separately, the above transparent resin layer composition was applied onto an acrylic resin plate using a bar coater so that the film thickness after drying was 2 μm and dried to form a transparent resin layer. The conductive layer is formed on the transparent resin layer at a temperature of 90 ° C. and a pressure of 4 kg / cm.
² was thermocompression bonded and transfer laminated. Finally, from the conductive layer to P
The ET film was peeled off to obtain an antistatic transparent plastic plate having a conductive layer having a film thickness of 2 μm.

Example 18 As a composition for a transparent resin layer, a saturated polyester resin (“Chemit R-2 manufactured by Toray Industries, Inc.
Example 74 except that 30 parts by weight of 74 ") were used.
In the same manner as described above, an antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm was obtained.

(Example 19) The conductive coating material obtained in Example 17 was applied and dried on a PET film (f ₁ ) using a bar coater so that the film thickness after drying was 2 μm to form a coating film. After that, a light amount of 1000 mJ / cm ² was irradiated with a high pressure mercury lamp to form a conductive layer. Separately, the composition for transparent resin layer obtained in Example 17 was applied on a PET film (f ₂ ) using a bar coater so that the film thickness after drying was 2 μm and dried to form a transparent resin layer. . Next, this transparent resin layer is overlaid on the conductive layer, and the temperature is 90 ° C. and the pressure is 4
Thermocompression bonding was performed at kg / cm ² , and transfer lamination was performed. Finally, the PET film (f ₁ ) was peeled off from the conductive layer to obtain an antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm.

(Example 20) As a composition for a transparent resin layer, a saturated polyester resin ("Chemit R-9" manufactured by Toray Industries, Inc.
9 ”) was used in the same manner as in Example 19 to obtain an antistatic transparent plastic plate having a conductive layer with a film thickness of 2 μm.

[Evaluation of Performance of Antistatic Transparent Plastic Plate] The following performance evaluation was performed on the antistatic transparent plastic plates obtained in the above Examples and Comparative Examples.
The results are shown in Tables 1 and 2. (1) Surface resistivity The surface resistivity was measured according to ASTM D257. (2) Total light transmittance Total light transmittance was measured according to ASTM D1003. (3) Surface hardness Measured with a pencil hardness meter according to JIS-K5400. (4) Appearance The antistatic transparent plastic plates obtained in Examples 1 to 8 and 17 to 20 were excellent in surface smoothness.

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[Table 1]

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[Table 2]

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EFFECT OF THE INVENTION The antistatic transparent plastic plate of the present invention has the above-mentioned constitution and is provided with a conductive layer having excellent transparency, surface hardness, solvent resistance and chemical resistance. It is preferably used as a material. The method for producing an antistatic transparent plastic plate according to the second, third and fourth aspects of the present invention has the above-mentioned configuration, and the transparency and surface of the photocurable conductive coating material are easily cured by curing the coating film with an ultraviolet ray or a visible ray. A conductive layer having excellent hardness, solvent resistance, and chemical resistance can be formed.

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Claims (4)

[Claims] 1. A transparent plastic plate substrate,
(A) 100 parts by weight of a (meth) acrylate compound having at least two or more (meth) acryloyl groups in the molecule, (b) 0.1 to 30 parts by weight of an aniline polymer,
(C) 1- (meth) acrylic acid alkyl ester resin
An antistatic transparent plastic plate, characterized in that a conductive layer made of a photocurable conductive coating material having 100 parts by weight and 0.01 to 10 parts by weight of (d) a photopolymerization initiator is formed. 2. A first step of forming a coating film by applying the photocurable conductive paint used in claim 1 on a transparent plastic film, the coating film on a transparent plastic plate base material. And a third step of irradiating the coating with actinic rays such as ultraviolet rays or visible rays to cure the coating to form a conductive layer. Method. 3. The first step of forming a coating film by applying the photocurable conductive coating composition used in claim 1 on a transparent plastic film, the coating film having an activity such as ultraviolet rays or visible light rays. A second step of irradiating and curing a light beam to form a conductive layer, a third step of forming a thermoplastic transparent resin layer on a transparent plastic plate base material, and a transparent resin layer on the plastic plate base material A method for producing an antistatic transparent plastic plate, comprising a fourth step of laminating the plastic film so as to be in contact with the conductive layer and a fifth step of peeling the plastic film. 4. On a transparent plastic film (f ₁ ),
A first step of applying a photocurable conductive coating material used in claim 1 to form a coating film, irradiating the coating film with actinic rays such as ultraviolet rays or visible rays to cure the coating film to form a conductive layer. Second
Process, a third process of forming a thermoplastic transparent resin layer on a transparent plastic film (f ₂ ), a fourth process of laminating the transparent resin layer on a transparent plastic plate substrate, the transparent resin A fifth step of peeling the plastic film (f ₂ ) from the layer, a sixth step of laminating the conductive layer and the transparent resin layer so as to be in contact with each other, and a seventh step of peeling the plastic film (f ₁ ) A method for producing an antistatic transparent plastic plate, which comprises: