JP2818110B2 - Organic conductive polymer paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic conductive polymer paint which is easily cured by ultraviolet light or visible light.

[0002]

2. Description of the Related Art Organic conductive polymers are electronic devices utilizing the properties of semiconductors, electrochromic materials utilizing changes in absorption wavelength during oxidation-reduction, electrode materials and electrochemically active materials for batteries, and antistatic. Are being put into practical use as conductive fillers such as electromagnetic wave shielding materials.

In particular, polythiophene, polypyrrole, polyaniline and the like are stable in the air and have a conductivity of 100.
Some are S / cm or more, and are organic conductive polymers suitable for practical use. These organic conductive polymers are 1S / c
In order to obtain a conductivity of m or more, a process called doping for forming a complex of a dopant and an organic conductive polymer is performed.
Although it is relatively easy to dope a gas such as iodine or arsenic pentafluoride as a dopant such as polypyrrole or polythiophene, the dopant is desorbed from the organic conductive polymer with time and the conductivity is reduced. In the method of doping an anion by an electrochemical method, the conductivity is relatively stable, but there is a disadvantage that the doping step is complicated and not suitable for mass synthesis.

[0004] In the case of polyaniline, stable conductivity is exhibited when an inorganic or organic protonic acid is used as a dopant. Japanese Patent Application Laid-Open No. 1-131288 discloses a method for dissolving such a doped polyaniline or aniline derivative polymer in a solvent to obtain a coating having excellent transparency. However, the polymer of the doped polyaniline or aniline derivative can be prepared by special solvents such as N, N'-dimethylformamide, N-methyl-
It is soluble only in 2-pyrrolidone and the like. In addition, the above-mentioned doped polyaniline coating film has a problem that the coating film strength is low, the solvent resistance and the chemical resistance are low, and when the protonic acid as a dopant flows out upon contact with the solvent or upon contact with alkali. However, there is a problem that the dopant is desorbed to lower the conductivity. There is also an attempt to disperse a polymer of polyaniline or an aniline derivative without dissolving the polymer in a paint binder to form a paint. However, if the polymer is not sufficiently dispersed in the binder, a coating film having high conductivity and transparency is obtained. Cannot be obtained, and a paint having high surface hardness and excellent conductivity and transparency has not been obtained.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and uses an aniline-based polymer, has high transparency and high surface hardness, and is particularly resistant to solvents and chemicals. It is an object of the present invention to provide an organic conductive polymer coating which can provide an organic conductive layer having excellent alkali resistance and also has excellent storage stability of the coating.

[0006]

The (meth) acrylate compound used in the present invention is not particularly limited as long as polymerization is initiated by actinic rays such as ultraviolet rays or visible rays, and crosslinks and cures. 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 Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, tris- (2-hydroxyethyl) -isocyanurate (meth) Acrylate,
2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane, 3-phenoxy-2-
Examples include propanoyl acrylate, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether, and tetramethylolmethanetetra (meth) acrylate.

[0007] In addition to the above, it is preferable that at least one (meth) acrylate compound having a urethane bond in the molecule is further included, whereby the scratch resistance is further improved, and such a (meth) acrylate compound is preferred as the (meth) acrylate compound. Examples thereof include urethane prepolymers of pentaerythritol triacrylate hexamethylene diisocyanate, pentaerythritol triacrylate isophorone diisocyanate, and pentaerythritol triacrylate tolylene diisocyanate.

Further, in addition to the above, examples of the (meth) acrylate compound include polyester (meth) acrylate compounds having an ester bond as a main chain and having at least two (meth) acryloyl groups in a molecule. .
These components cure to form a highly crosslinked structure, and the resulting organic conductive layer has high surface hardness and abrasion resistance.

The aniline polymer used in the present invention is:
Any conventionally known conductive aniline-based polymer of aniline or an aniline derivative monomer can be used without particular limitation. Commercially available products include, for example, Vericon, manufactured by Allied Signal.

The aniline derivative monomer includes aniline, N-methylaniline, N-ethylaniline, diphenylaniline, o-toluidine, m-toluidine,
2-ethylaniline, 3-ethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2,6-
Dimethylaniline, 2,6-diethylaniline, 2-methoxyaniline, 4-methoxyaniline, 2,4-dimethoxyaniline, o-phenylenediamine, m-phenylenediamine, 2-aminobiphenyl, N, N-diphenyl-p- Phenylenediamine and the like.

When the amount of the aniline-based polymer is small, the conductivity of the resulting coating film becomes insufficient. When the amount is large, the protective effect of the crosslinked binder on the aniline-based polymer is reduced, and the scratch resistance and chemical resistance are reduced. The content is 0.1 to 30 parts by weight with respect to 100 parts by weight of the (meth) acrylate compound because the properties and the solvent resistance are reduced.

The photopolymerization initiator used in the present invention may be any as long as it has a property of initiating the polymerization of the above (meth) acrylate compound by actinic rays such as ultraviolet rays and visible rays. Sulfides such as sodium methyl dicarbamate sulfide, tetramethylthiuram monosulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide and disulfide; thioxanthone, ethylthioxanthone, 2-chlorothioxanthone, diethylthioxanthone, diisopropylthioxanthone Thioxanthone derivatives such as; hydrazone,
Diazo compounds such as azoisobutyronitrile and benzenediazonium; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone, benzylanthraquinone, t
-Butylanthraquinone, 2-methylanthraquinone,
Aromatic carbonyl compounds such as 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzyldimethylketal, methylphenylglyoxylate; 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone , Α-hydroxy-α, α'-dimethyl-acetophenone, 2,
Acetophenone derivatives such as 2-diethoxyacetophenone and 2,2-dimethoxyacetophenone; dialkylamino such as 2-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate and isopropyl 4-diethylaminobenzoate Benzoic acid esters; benzoyl peroxide, di-t
Peroxides such as -butyl peroxide, dicumyl peroxide, cumene hydroperoxide; acridine derivatives such as 9-phenylacridine, 9-p-methoxyphenylacridine, 9-acetylaminoacridine, benzacridine; Phenazine derivatives such as dimethylbenzphenazine, 9-methylbenzphenazine, 10-methoxybenzphenazine;
Quinosaline derivatives such as 4 ', 4 "-trimethoxy-2,3-diphenylquinosaline; 2,4,5-triphenylimidazoyl dimer; halogenated ketones; acylated phosphorus such as acylphosphine oxide and acylphosphonate And the like.

Examples of those activated by visible light include 2-nitrofluorene, 2,4,6-tris (trichloromethyl) -1,3,5-triazine,
3,3'-carbonylbiscoumarin, thiomicheller ketone and the like.

The alkyl (meth) acrylate resin used in the present invention is used for dispersing the aniline polymer of the organic conductive polymer coating of the present invention in a (meth) acrylate compound. Examples of the alkyl (meth) acrylate-based resin include homo- or copolymers of alkyl (meth) acrylates. Examples of the alkyl (meth) acrylate include, for example, methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like, and the above-mentioned alkyl (meth) acrylate homopolymer or copolymer is poly (meth) acrylate )
Methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, poly (meth) butyl acrylate, poly (meth) acrylate 2-ethylhexyl,
A butyl (meth) acrylate / methyl (meth) acrylate copolymer may, for example, be mentioned.

As the molecular weight of the alkyl (meth) acrylate resin decreases, the dispersibility of the obtained aniline polymer decreases, and the transparency of the obtained organic conductive layer decreases.
The conductivity is reduced, and the effect of increasing the viscosity of the organic conductive polymer paint is not exhibited, so that the coatability is reduced. If it is large, the paint viscosity becomes too high and the coatability is reduced. One million is preferable, and more preferably 300,000 to 800,000.

When the amount of the alkyl (meth) acrylate resin is reduced, the dispersing effect is lost and the transparency and conductivity of the obtained organic conductive layer are reduced. The amount is limited to 10 to 100 parts by weight based on 100 parts by weight of the (meth) acrylate compound.

The organic solvent used in the present invention may be any solvent which does not dissolve the aniline polymer but dissolves the (meth) acrylate compound and the alkyl (meth) acrylate resin. Although not limited, those having a low boiling point or those having high volatility have a problem that the viscosity of the coating material changes due to evaporation during coating, and those having a high boiling point require a long time for the drying step. Therefore, a solvent having a boiling point of about 70 to 160 ° C. is preferable. For example, cyclohexanone, 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, And anisole.

The organic conductive polymer paint of the present invention has the above-mentioned constitution, but in addition to the above, an ultraviolet absorber,
Antioxidants, thermal polymerization inhibitors and the like may be added as necessary, and these can be used as known ones. Examples of the ultraviolet absorber include a salicylic acid-based ultraviolet absorber and a benzophenone-based ultraviolet absorber. Agents, benzotriazole-based UV absorbers, cyanoacrylate-based UV absorbers, and the like.Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the thermal polymerization inhibitor include hydroquinone and p-methoxyphenol.

The photopolymerization initiator may be co-existed with an amine compound which promotes photopolymerization in order to prevent a decrease in the photopolymerization rate due to oxygen inhibition. There is no particular limitation as long as it is non-volatile, such as an amine or an aromatic amine.
Amino group-containing photopolymerization initiators such as diethanolaminobenzoate and Michler's ketone, which are used as the above photopolymerization initiator, such as triethanolamine and methyldiethanolamine, can also be used as the above amine compound.

When the amount of the amino compound is small, the photopolymerization rate of the (meth) acrylate compound with respect to actinic rays is reduced, the crosslinking is insufficient, and the resulting coating film is insufficiently cured. Even if a large amount is added, the photopolymerization rate is saturated, so the (meth) acrylate compound 100
It is preferably 0.01 to 10 parts by weight based on parts by weight.

As a method for producing the aniline-based polymer, for example, an oxidizing agent solution is dropped into this solution while dissolving the aniline or the aniline derivative monomer and an acid in water, dimethylformamide (DMF) or the like and stirring the solution. And oxidative polymerization.

In the above oxidative polymerization method, the concentration of aniline or aniline derivative monomer is 0.1 to 0.1% based on water and DMF.
1 mol / liter is suitable. Examples of the acid include inorganic protic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as p-toluenesulfonic acid. 1N is appropriate.

The oxidizing agent includes, for example, persulfate,
Examples include hydrogen peroxide, permanganate, lead dioxide, dichromate, manganese dioxide, iron chloride and the like. The appropriate concentration of the oxidizing agent is 0.1 to 1 mol / liter with respect to water and DMF.

The alkyl (meth) acrylate resin is produced by a known solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk polymerization method or the like.

In the production of the organic conductive polymer coating, the (meth) acrylic acid alkyl ester-based resin and the aniline-based polymer are added to an organic solvent, mixed and finely dispersed, and the average particle size of the aniline-based polymer is determined. Is preferably 0.4 μm or less. Next, the (meth) acrylate compound,
Photopolymerization initiator and the like are added, and the mixture is further mixed. For the mixing, a device usually used for sufficiently dispersing the fine powder in a binder, for example, a sand mill, a ball mill, an attritor, a high-speed rotary stirrer, a three-roll, or the like is used.

The organic conductive polymer coating is, for example, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polysulfone,
Polyphenylene sulfide, polyether sulfone,
It is applied to a resin film or sheet such as a fluororesin, a resin molded body, glass or ceramics, a metal plate coated with a resin, etc., and the resulting coating film is irradiated with actinic rays, photopolymerizable, and crosslinked. And cured to obtain a conductive coating.

As the above-mentioned actinic rays, those usually used for photocuring are suitably used. Examples thereof include those using a (ultra) high-pressure mercury lamp, a halogen lamp, a xenon lamp as a light source, a nitrogen laser, a He-Cd laser, An Ar laser or the like is used.

The organic conductive polymer coating of the present invention can be obtained by adding a silane coupling agent and / or a titanate coupling agent to the organic conductive polymer coating of the present invention.

The silane coupling agent improves the dispersibility of the aniline polymer in a (meth) acrylate compound or an organic solvent. For example, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-
Examples thereof include aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, polyethylene oxide-modified silane monomer, polymethylethoxysiloxane, and hexamethyldisilazane.

The above-mentioned titanium coupling agent is also used for the same purpose. For example, isopropyl triisostearoyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2 , 2'-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, isopropyltridecylbenzenesulfonyl titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, isopropyltrio Kutanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl isostearyl diacryl titanate, isopropyl tri ( Dioctyl phosphate)
Titanate, isopropyltricumylphenyl titanate, isopropyltri (N-aminoethyl-aminoethyl) titanate and the like can be mentioned.

The above-mentioned coupling agent may be treated by adding dropwise or spraying it to the particulate aniline polymer with stirring, or dissolving the above-mentioned coupling agent in a solvent, stirring and mixing, and then adding the solvent. The particles may be treated by removing them by drying. Also dissolve the coupling agent in the organic solvent of the organic conductive polymer coating of the present invention,
The polyaniline particles may be stirred and mixed, and the amount of these coupling agents to be added is such that when the amount is small, the adhesion to the surface of the aniline-based polymer particles is insufficient and the transparency of the obtained conductive layer is reduced. Is reduced, so that 0.1 to 100 parts by weight of the (meth) acrylate compound
10 parts by weight are added.

[0032]

Next, embodiments of the present invention will be described. Hereinafter, "parts" means "parts by weight".

(Example 1) (Preparation of aniline polymer) p-toluenesulfonic acid 16
0 g (0.8 mol) was dissolved in 1000 ml of deionized water, and this was divided into 500 ml each.
36.5 liters (0.4 mol) of aniline was added to one side, and 91 g of ammonium peroxodisulfate was dissolved to the other side. Next, the aniline-containing p-toluenesulfonic acid aqueous solution was charged into a separable flask reaction vessel equipped with a cooling tube, a stirrer, and a dropping funnel, and while suppressing the temperature rise in a water bath, ammonium peroxodisulfate-containing p-toluenesulfonic acid aqueous solution was added. 500 ml was dropped over 30 minutes, and stirring was continued for 3 hours. Next, 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 Polymer Dispersion) Aniline polymer obtained above: 20 parts Polymethyl methacrylate (polymethyl methacrylate): 40 parts (manufactured by Negami Kogyo; Hyperl HPA, weight average molecular weight (Mw)) : 500,000) Xylene: 140 parts The above composition was dispersed with an attritor for 8 hours to obtain an aniline polymer dispersion. When the aniline polymer particles of this dispersion were observed with an electron microscope, the average particle size was 0.01 μm or less.

(Preparation of Organic Conductive Polymer Coating Material) Aniline-based polymer dispersion obtained above: 100 parts Dipentaerythritol hexaacrylate: 100 parts (manufactured by Nippon Kayaku: DPHA) 2,4-diethylthioxanthone : 0.1 part ("Kayacure DETX" manufactured by Nippon Kayaku) Ethyl 4-dimethylaminobenzoate: 0.1 part Xylene: 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive polymer paint. .

(Formation of Organic Conductive Layer) The organic conductive polymer coating was coated on a polymethyl methacrylate plate with a bar, cured with a high-pressure mercury lamp at an irradiation dose of 1000 mJ / cm ² , and cured to a thickness of 2 μm. A layer was formed.

(Example 2) The aniline polymer dispersion obtained in Example 1: 100 parts 6-functional urethane acrylate: 100 parts (manufactured by Kyoeisha Yushi Kagaku Kogyo; UA-306T) 2,4-diethylthioxanthone: 0. 1 part Ethyl 4-dimethylaminobenzoate 0.1 part Xylene 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive polymer paint. As in Example 1, an organic conductive layer having a thickness of 2 μm was obtained. I got

(Example 3) The aniline polymer dispersion obtained in Example 1: 100 parts Polyester acrylate: 100 parts (manufactured by Toagosei Chemical Industry; M-9050) 2,4-diethylthioxanthone: 0.1 part Ethyl 4-dimethylaminobenzoate: 0.1 part Xylene: 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive polymer paint, and a 2 μm-thick organic conductive layer was obtained in the same manner as in Example 1. I got

(Example 4) The aniline polymer dispersion obtained in Example 1: 100 parts Tetramethylol methanetetraacrylate: 100 parts (Shin-Nakamura Chemical Co .; A-TMMT) 2,4-diethylthioxanthone: 0 0.1 part Ethyl 4-dimethylaminobenzoate: 0.1 part Xylene: 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive polymer coating material. An organic conductive layer was obtained.

Example 5 The aniline polymer dispersion obtained in Example 1: 2 parts Tetramethylol methanetetraacrylate: 100 parts 2,4-diethylthioxanthone: 0.1 part Ethyl 4-dimethylaminobenzoate: 0.1 part Xylene: 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive polymer coating, and a 2 μm-thick organic conductive layer was obtained in the same manner as in Example 1.

(Example 6) (Preparation of aniline polymer dispersion liquid) The aniline polymer obtained in Example 1: 20 parts Polymethyl methacrylate: 80 parts Xylene: 100 parts The above composition was stirred with an attritor for 20 minutes. An organic conductive polymer paint was obtained, and a 2 μm-thick organic conductive layer was obtained in the same manner as in Example 1. When the aniline polymer particles of this dispersion were observed with an electron microscope, the average particle size was 0.01 μm or less.
it was under.

(Preparation of Organic Conductive Polymer Coating Material) The above aniline polymer dispersion: 100 parts Dipentaerythritol hexaacrylate: 100 parts 2,4-diethylthioxanthone: 0.1 part Ethyl 4-dimethylaminobenzoate: 0 .1 part Xylene: 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive polymer paint, and a 2 μm-thick organic conductive layer was obtained in the same manner as in Example 1.

(Comparative Example 1) (Preparation of aniline polymer dispersion liquid) An aniline polymer dispersion solution obtained by dispersing the aniline polymer obtained in Example 1 in an attritor for 8 hours with the above composition: 20 parts xylene: 180 parts I got (Preparation of Organic Conductive Polymer Coating) Above aniline polymer dispersion: 100 parts Dipentaerythritol hexaacrylate: 100 parts 2,4-diethylthioxanthone: 0.1 part Ethyl 4-dimethylaminobenzoate: 0.1 part Xylene: 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive polymer paint, and a 2 μm-thick organic conductive layer was obtained in the same manner as in Example 1.

(Comparative Example 2) The aniline polymer dispersion obtained in Example 1: 5 parts Dipentaerythritol hexaacrylate: 100 parts 2,4-diethylthioxanthone: 0.1 part Ethyl 4-dimethylaminobenzoate: 0.1 part Xylene: 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive polymer coating, and a 2 μm-thick organic conductive layer was obtained in the same manner as in Example 1.

(Comparative Example 3) The aniline polymer dispersion obtained in Example 1: 500 parts Dipentaerythritol hexaacrylate: 100 parts 2,4-diethylthioxanthone: 0.1 part Ethyl 4-dimethylaminobenzoate: 0.1 part Xylene: 150 parts The above composition was stirred with an attritor for 20 minutes to obtain an organic conductive paint, and a 2 μm-thick organic conductive layer was obtained in the same manner as in Example 1.

Example 7 (Preparation of Organic Conductive Polymer Coating) Aniline polymer of Example 1: 10 parts γ-methacryloxypropyltrimethoxysilane: 5 parts (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) DPHA: 100 parts 2,4-diethylthioxanthone: 1 part Ethyl 4-dimethylaminobenzoate: 1 part Polymethyl methacrylate (weight average molecular weight 500,000): 50 parts (manufactured by Negami Kogyo; Hyperl HP) Xylene: 600 The team was added to the attritor. This was dispersed for 8 hours while stirring to prepare an organic conductive polymer paint. The aniline polymer in this coating was observed with an electron microscope and found to have an average particle size of 0.01 μm or less.

(Formation of Organic Conductive Layer) An organic conductive layer having a thickness of 2 μm was obtained in the same manner as in Example 1 using the above-mentioned conductive polymer paint.

Example 8 An organic conductive layer was obtained in the same manner as in Example 7 except that 5 parts of γ-methacryloxypropyltrimethoxysilane in Example 7 was changed to 0.3 part.

Example 9 5 parts of γ-methacryloxypropyltrimethoxysilane of Example 7 was replaced with isopropyl triisostearoyl titanate (manufactured by Ajinomoto; KR-TT).
S) An organic conductive layer was obtained in the same manner as in Example 7, except that the amount was changed to 5 parts.

Example 10 An organic conductive layer was obtained in the same manner as in Example 7 except that 5 parts of γ-methacryloxypropyltrimethoxysilane in Example 7 was changed to 0.3 parts of isopropyl triisostearoyl titanate. .

Example 11 An organic conductive layer having a thickness of 2 μm was obtained in the same manner as in Example 7 except that 10 parts of the aniline polymer in Example 7 was changed to 0.5 part.

Example 12 An organic conductive layer having a thickness of 2 μm was obtained in the same manner as in Example 7 except that 10 parts of the aniline polymer of Example 7 was changed to 25 parts.

(Example 13) An organic conductive layer was formed in the same manner as in Example 7 except that 5 parts of γ-methacryloxypropyltrimethoxysilane in Example 7 was changed to 5 parts of γ-glycidoxypropyltrimethoxysilane. Prepared.

Example 14 An organic conductive material was prepared in the same manner as in Example 1 except that 5 parts of γ-methacryloxypropyltrimethoxysilane in Example 7 was changed to 0.3 part of γ-glycidoxypropyltrimethoxysilane. Layer obtained.

Example 15 An organic conductive layer was formed in the same manner as in Example 7 except that 5 parts of γ-methacryloxypropyltrimethoxysilane in Example 7 was changed to 5 parts of tetraisopropylbis (dioctylphosphite) titanate. Obtained.

Example 16 5 parts of γ-methacryloxypropyltrimethoxysilane of Example 7 was replaced with tetraisopropylbis (dioctylphosphite) titanate 0.3
An organic conductive layer was obtained in the same manner as in Example 1 except that the parts were changed.

(Example 17) (Preparation of aniline polymer dispersion) Aniline polymer: 20 parts (manufactured by Allied Signal; Versicon) Polymethyl methacrylate: 40 parts Xylene: 140 parts The composition was dispersed by an attritor for 8 hours to prepare an aniline polymer dispersion.

(Preparation of Organic Conductive Polymer Coating) Above aniline polymer dispersion: 100 parts DPHA: 100 parts 2,4-diethylthioxanthone: 0.1 part Ethyl 4-dimethylaminobenzoate: 0.1 part Xylene : 150 parts Preparation of organic conductive polymer paint of the above composition, Example 1
In the same manner as in the above, an organic conductive layer having a thickness of 2 μm was obtained.

(Example 18) An organic conductive layer was obtained in the same manner as in Example 17, except that 100 parts of the aniline polymer dispersion and 2 parts of the aniline polymer dispersion were used.

Comparative Example 4 An organic conductive layer was obtained in the same manner as in Example 7, except that 5 parts of γ-methacryloxypropyltrimethoxysilane were changed to 0.05 part of γ-methacryloxypropyltrimethoxysilane.

Comparative Example 5 An organic conductive layer was obtained in the same manner as in Example 7, except that 5 parts of γ-methacryloxypropyltrimethoxysilane were changed to 20 parts of γ-methacryloxypropyltrimethoxysilane.

Comparative Example 6 An organic conductive layer was obtained in the same manner as in Example 7 except that 5 parts of γ-methacryloxypropyltrimethoxysilane was changed to 0.05 part of isopropyl triisostearoyl titanate.

Comparative Example 7 An organic conductive layer was obtained in the same manner as in Example 7 except that 5 parts of γ-methacryloxypropyltrimethoxysilane was changed to 20 parts of isopropyl triisostearoyl titanate.

The organic conductive layers prepared in Examples 1 to 18 and Comparative Examples 1 to 7 were evaluated for surface resistivity, total light transmittance, and surface hardness. The results are shown in Tables 1 and 2.

[0065]

[Table 1]

[0066]

[Table 2]

The above evaluation method is as follows. The surface resistivity is based on ASTM D257, the total light transmittance is based on ASTM D1003, and the surface hardness is
It was based on JIS-K5400 using a pencil hardness tester.

[0068]

As described above, the organic conductive polymer coating of the present invention has the above-described constitution, and is easily cured by ultraviolet light or visible light. The formed organic conductive layer has a high surface hardness and a high transparency. It has excellent storage stability and high storage stability of paint, and is suitably used as an antistatic material related to a semiconductor manufacturing process.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09D 4 / 02,4 / 06,133 / 06-133 / 12,1 79/02

Claims (2)

(57) [Claims] (1) A (meth) acrylate compound having at least two or more (meth) acryloyl groups in a molecule.
0 parts by weight, 0.1 to 30 parts by weight of aniline polymer, 10 to 100 parts by weight of alkyl (meth) acrylate resin, 0.01 to 10 parts by weight of photopolymerization initiator, and 100 to 1000 parts by weight of organic solvent Organic conductive polymer paint characterized by comprising 2. A (meth) acrylate compound 10 having at least two (meth) acryloyl groups in the molecule.
0 parts by weight, 0.1 to 30 parts by weight of aniline polymer, 10 to 100 parts by weight of alkyl (meth) acrylate resin, 0.1 to 10 parts by weight of silane coupling agent and / or titanate coupling agent , Photopolymerization initiator
Organic conductive polymer paint characterized by comprising 01 to 10 parts by weight and 100 to 1000 parts by weight of an organic solvent.