JPH06240180A - Electrically conductive coating composition - Google Patents

Abstract

PURPOSE:To obtain an electrically conductive coating composition capable of forming a coating film having excellent hardness, alkali resistance, transparency and electrical conductivity. CONSTITUTION:The electrically conductive coating composition is composed of 100 pts.wt. of a (meth)acrylate compound having >=2 (meth)acryloyl groups, 5-30 pts.wt. of an aniline-based electrically conductive polymer and 0.1-10 pts.wt. of a photo-polymerization initiator sensitized by actinic ray. A coating film having excellent hardness, alkali resistance, transparency and electrical conductivity can be produced from the composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive coating composition, and more particularly to a conductive coating composition capable of obtaining a coating having excellent hardness, alkali resistance, transparency and conductivity.

[0002]

2. Description of the Related Art In recent years, conductive polymers such as polyaniline, polythiophene, and polypyrrole have been used in electronic devices that utilize the properties of semiconductors, electrochromic materials that utilize changes in absorption wavelength during redox, and batteries. It is being put to practical use as a conductive filler such as an electrode material, an electrochemically active material, an antistatic material and an electromagnetic wave shielding material.

In order to impart metallic conductivity to these conductive polymers, a doping treatment is performed to form a complex between the dopant and the conductive polymer. When the conductive polymer is polyaniline, an inorganic / organic protonic acid is used as a dopant and exhibits stable conductivity, but it is difficult to dissolve in a solvent and thus has a drawback of poor workability in manufacturing a paint.

In order to solve the above drawbacks, Japanese Patent Laid-Open No. 1-13
In 1288, a conductive paint obtained by dissolving finely cut polyaniline in a specific solvent is proposed, but the hardness of the obtained coating is low, and when it comes into contact with alkali, it is a dopant. There is a drawback that the conductivity of the coating film is lowered due to the outflow or elimination of acid.

[0005]

SUMMARY OF THE INVENTION In view of the above drawbacks, the present invention aims to provide a conductive coating composition capable of obtaining a coating having excellent hardness, alkali resistance, transparency and conductivity. To do.

[0006]

The (meth) acrylate compound used in the present invention is a compound having two or more (meth) acryloyl groups, and examples thereof include ethylene glycol di (meth) acrylate and 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) -isocyanuric acid ester (meth) acrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (methacryloxydiethoxy) phenyl] propane , 3-phenoxy-2-propanoyl acrylate,
1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether and the like can be mentioned.

The aniline-based conductive polymer used in the present invention is not particularly limited as long as it is a polymer of an aniline-based monomer and has conductivity.

Examples of the aniline-based monomer include
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-
Examples thereof include dimethoxyaniline, o-phenylenediamine, m-phenylenediamine, 2-aminobiphenyl, N, N-diphenyl-p-phenylenediamine.

As a method for polymerizing the aniline-based monomer, for example, a flask equipped with a stirrer and a dropping funnel is used.
Examples include a method in which a predetermined amount of water, a solvent such as dimethylformamide (DMF), an aniline-based monomer and an acid are supplied and dissolved, and a predetermined amount of an oxidizing agent is added to the resulting solution, and oxidative polymerization is performed with stirring.

Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, and organic acids such as p-toluenesulfonic acid.

Examples of the oxidizing agent include persulfate,
Hydrogen peroxide, peroxides such as permanganate, lead dioxide,
Examples thereof include dichromate, oxides such as manganese dioxide, and Lewis acids such as iron chloride.

The amount of the aniline-based conductive polymer added is
When the amount is small, the conductivity of the obtained coating is lowered, and when the amount is large, the hardness and alkali resistance of the obtained coating are lowered. Therefore, it is 5 per 100 parts by weight of the (meth) acrylate compound.
Limited to ~ 30 parts by weight.

The photopolymerization initiator used in the present invention is a compound having a property of being sensitized by actinic rays such as ultraviolet rays and visible rays.

Among the above photopolymerization initiators, examples of photopolymerization initiators sensitized by ultraviolet rays include sulfides such as sodium methyldithiocarbamate sulfide, diphenyl monosulfide, dibenzothiazoyl monosulfide, and dibenzothiazoyl disulfide. Compounds: thioxanthone, 2-ethylthioxanthone, 2-
Thioxanthone compounds such as chlorothioxanthone and 2,4-diethylthioxanthone; (di) azo compounds such as hydrazone, azobisisobutyronitrile and benzenediazonium; benzoin, benzoin methyl ether, benzoin ethyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone , Benzylanthraquinone, t-butylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, and other aromatic carbonyl compounds; methyl p-dimethylaminobenzoate,
Dialkylaminobenzoic acid ester compounds such as ethyl p-dimethylaminobenzoate, butyl p-dimethylaminobenzoate and isopropyl p-diethylaminobenzoate;
Peroxides such as benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide; 9-phenylacridine, 9
Acridine compounds such as -p-methoxyphenylacridine, 9-acetylaminoacridine and benzacridine; phenazine compounds such as 9,10-dimethylbenzphenazine, 9-methylbenzphenazine and 10-methoxybenzphenazine; 6,4 ', 4 "-Trimethoxy-
A quinoxaline compound such as 2,3-diphenylquinoxaline; a 2,4,5-triphenylimidazoyl dimer; a halogenated ketone; an acylated phosphorus compound such as an acylphosphinoxide and an acylphosphonate.

Further, as a photopolymerization initiator sensitized by visible light, 2-nitrofluorene, 2,4,6-triphenylpyrylium tetrafluoroboron salt, 2,4,6-tris (trichloromethyl) -1,3,5-triazine,
3,3′-carbonylbiscoumarin, thiomichler ketone and the like can be mentioned.

When the amount of the above-mentioned photopolymerization initiator added decreases, the sensitivity of the reaction system to actinic rays decreases, and the photopolymerization reactivity of the (meth) acrylate compound decreases, and when it increases, the sensitivity of the reaction system to actinic rays decreases. Although the hardness is improved, the hardness of the obtained coating is lowered, so that it is limited to 0.1 to 10 parts by weight with respect to 100 parts by weight of the (meth) acrylate compound.

The composition of the conductive coating composition of the present invention is as described above, but an ultraviolet absorber, an antioxidant, a thermal polymerization inhibitor, etc. may be added within a range that does not impair the physical properties.

In the conductive coating composition of the present invention 2, the range of the addition amount of the aniline type conductive polymer in the composition of the conductive coating composition of the present invention is changed, and further, the sulfone group, the carboxyl group and the phosphinico are added. It is a conductive coating composition to which a (meth) acrylate compound having any one of the groups is added.

The amount of the aniline-based conductive polymer added is
When the amount is small, the electroconductivity of the obtained coating film is reduced, and when the amount is large, the hardness and transparency of the obtained coating film are reduced. Therefore, the amount is 5 to 100 relative to 100 parts by weight of the (meth) acrylate compound.
Limited to parts by weight.

Among the (meth) acrylate compounds having any one of the above-mentioned sulfone group, carboxyl group and phosphinico group, examples of the (meth) acrylate compound having a sulfone group include: The compound etc. which are represented by Formula (1) or (2) are mentioned.

[0021]

[Chemical 1]

In the formula, R ¹ and R ² are -C (CH ₃ ) ₂ CH ₂ -,-
(CH ₂ ) _j −, — (CH ₂ O) _k — and — (CH ₂ CH ₂ O) _m — represent any one group, and j, k and m are 0 or 1 to
Indicates a positive integer of 15.

Having the above-mentioned carboxyl group (meth)
Examples of the acrylate compound include acrylic acid and methacrylic acid.

Having the above phosphinico group (meth)
Examples of the acrylate compound include compounds represented by the general formula (3).

[0025]

[Chemical 2]

In the formula, R ³ and R ⁴ are represented by any one of the general formulas (4) and (5), and may be the same or different, and either one may be a hydroxyl group. Good.

[0027]

[Chemical 3]

In the formula, R ⁵ , R ⁶ and R ⁷ are hydrogen atoms,
Represents a methyl group or a halogenated methyl group, in which different groups may be present or may be the same group, and n is 0
Alternatively, a positive integer of 1 to 8 is shown.

[0029]

[Chemical 4]

In the formula, R ⁸ represents a hydrogen atom, a methyl group or a halogenated methyl group, and p, q and r are 0 or 1-
Indicates a positive integer of 8.

Examples of the halogenated methyl group include a chloromethyl group and a bromomethyl group.

When the addition amount of the (meth) acrylate compound having any one of the above-mentioned sulfone group, carboxyl group and phosphinico group is small, the conductivity of the obtained coating film is lowered, and when it is increased, it is obtained. (Meth) acrylate compound 1 because the transparency of the coating decreases.
It is limited to 1 to 30 parts by weight with respect to 00 parts by weight.

The electroconductive coating composition of the present invention and the electroconductive coating composition of the present invention 2 are mixed in a liquid state and applied on a substrate for use.

As a method for producing the above conductive coating composition, for example, a predetermined amount of a (meth) acrylate compound, an aniline type conductive polymer, a photopolymerization initiator and the like are supplied to a dissolver, an attritor, a triple roll or the like. And a method of stirring.

When producing the above conductive coating composition,
For example, a solvent such as methyl ethyl ketone may be added.

As a method for obtaining a coating film using the above-mentioned conductive coating composition, for example, a coating composition layer is formed on the surface of a substrate by a method such as a spray method, a bar coating method, a doctor blade method, a dipping method or the like. A method of irradiating the layer with an actinic ray to cure it.

The base material is not particularly limited,
Examples thereof include resins such as vinyl chloride, polycarbonate, polymethacrylate, and acrylonitrile-butadiene-styrene copolymer; glass molded products and the like.

Examples of the light source of the above actinic rays include a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, a helium-cadmium laser, an argon laser and the like.

When the irradiation intensity of the above-mentioned actinic rays becomes weak, the reactivity of photopolymerization is lowered and the hardness of the obtained coating is lowered,
Since the reactivity of photopolymerization does not improve even if the strength becomes higher than a predetermined strength, it is preferably 500 to 2000 mJ / cm ² .

If the irradiation time of the above-mentioned actinic rays is shortened, the reactivity of photopolymerization is lowered and the hardness of the obtained coating film is lowered.
Since the reactivity of photopolymerization does not improve even if the time is longer than a predetermined time, it is preferably 1 to 60 minutes.

[0041]

EXAMPLES Next, examples of the present invention will be described. In addition,
"Parts" means "parts by weight". Example 1 (1) Production of aniline-based conductive polymer dispersion solution A separable flask equipped with a stirrer was charged with 160 parts of p-toluenesulfonic acid and 1000 ml of deionized water,
It was dissolved with stirring to obtain a p-toluenesulfonic acid aqueous solution. The obtained p-toluenesulfonic acid aqueous solution was added to 50
0 ml was divided into two equal parts, 36.5 parts of aniline was supplied to one side, and ammonium peroxodisulfate 91 was supplied to the other side.
Parts were supplied and dissolved to obtain an aniline-containing p-toluenesulfonic acid aqueous solution and an ammonium peroxodisulfate-containing p-toluenesulfonic acid aqueous solution.

The obtained aniline-containing p-toluenesulfonic acid aqueous solution was supplied to a separable flask equipped with a stirrer, a cooling tube and a dropping funnel, and the resulting ammonium peroxodisulfate was stirred while suppressing the temperature rise in a water bath. Containing p
-Toluenesulfonic acid aqueous solution was added dropwise with a dropping funnel over 30 minutes, and stirring was continued for further 3 hours to obtain a precipitate. The obtained precipitate was collected by filtration and washed with methanol to obtain a green powder of an aniline-based conductive polymer.

50 parts of the obtained aniline-based conductive polymer and 150 parts of ethyl cellosolve were supplied to a disperser and dispersed for 24 hours to obtain an aniline-based conductive polymer dispersion solution having a solid content concentration of 25% by weight. .

(2) Production of conductive coating composition 40 parts of the obtained aniline-based conductive polymer dispersion solution, 100 parts of pentaerythritol triacrylate, 4 parts of benzophenone and 1 part of Michler's ketone were supplied to a separable flask equipped with a stirrer. Then, the mixture was stirred to obtain a conductive coating composition.

(3) Production of coating film The obtained conductive coating composition was bar-coated on an acrylic plate, and a high pressure mercury lamp beam 1000 was applied to the bar-coated portion.
Irradiation with mJ / cm ² was carried out for curing to obtain a film having a thickness of 4 μm.

(4) Evaluation of coating film Using the obtained coating film, a hardness test was carried out to evaluate the hardness, and an alkali resistance test was carried out to evaluate the alkali resistance. The results obtained are shown in Table 1. .

The above hardness test was carried out according to JIS K 5400. That is, a pencil having a hardness of 9H to 6B is 9
The surface of the coating was scratched 5 times by changing the position, and the hardness of the pencil when the number of breakage of the coating reached less than 2 out of 5 times was examined.

The alkali resistance test is based on ASTM D
It carried out based on 257. That is, the obtained coating is 10
% Sodium hydroxide aqueous solution and kept at a temperature of 30 ° C. for a predetermined time (immediately after 10 minutes, after 20 minutes, after 10 minutes
Surface specific resistance value (Ω / after 0 minute and 200 minutes)
□) was measured.

Example 2 A coating film was obtained in the same manner as in Example 1 except that 20 parts of the aniline-based conductive polymer dispersion solution was used, and the obtained coating film was evaluated in the same manner as in Example 1, The results obtained are shown in Table 1.
It was shown to.

Comparative Example 1 A coating film was obtained in the same manner as in Example 1 except that 200 parts of the aniline-based conductive polymer dispersion solution was used, and the obtained coating film was evaluated in the same manner as in Example 1, The obtained results are shown in Table 1.

Comparative Example 2 A coating film was obtained in the same manner as in Example 1 except that 5 parts of the aniline-based conductive polymer dispersion solution was used, and the obtained coating film was evaluated in the same manner as in Example 1, The obtained results are shown in Table 1.

[0052]

[Table 1]

Example 3 (1) Production of Conductive Coating Composition and Production of Film 40 parts aniline-based conductive polymer dispersion solution obtained in the same manner as in Example 1 (10 parts aniline-based conductive polymer) , Pentaerythritol triacrylate 100 parts, 2-acryloyloxyethyl acid acid phosphate (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., product name: light ester PA) 1
Parts, benzophenone 4 parts, Michler's ketone 1 part, and methyl ethyl ketone 100 parts are supplied to a separable flask equipped with a stirrer and stirred to obtain a conductive coating composition, and the obtained conductive coating composition is used in the same manner as in Example 1. To obtain a coating.

(2) Evaluation of coating film Using the obtained coating film, the total light transmittance (%) and the haze value (%) were measured to evaluate the transparency, and the surface resistivity (Ω) was evaluated.
/ □) was measured to evaluate the conductivity, and the obtained results are shown in Table 2.
It was shown to.

Total light transmittance (%) and haze value (%)
Was measured according to ASTM D 1003, and the surface specific resistance value (Ω / □) was measured according to ASTM D257.

Example 4 A coating film was obtained in the same manner as in Example 3 except that 3 parts of 2-acryloyloxyethyl acid phosphate was used.
The obtained coating film was evaluated in the same manner as in Example 3, and the obtained results are shown in Table 2.

Example 5 A coating film was obtained in the same manner as in Example 3 except that 20 parts of 2-acryloyloxyethyl acid phosphate was used, and the obtained coating film was evaluated and evaluated in the same manner as in Example 3. The obtained results are shown in Table 2.

Example 6 In place of 2-acryloyloxyethyl acid phosphate, 3-acrylamido-2-methylpropanesulfonic acid (manufactured by Nitto Kagaku Co., Ltd., trade name: TABS-Q) was used.
A coating film was obtained in the same manner as in Example 3 except that parts were used, and the obtained coating film was evaluated in the same manner as in Example 3. The obtained results are shown in Table 2.

Example 7 Example 3 was repeated except that 3 parts of acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Unichemical Co., trade name: Phosmer PE) was used instead of 2-acryloyloxyethyl acid phosphate. A coating film was obtained in the same manner, the obtained coating film was evaluated in the same manner as in Example 3, and the obtained results are shown in Table 2.

Comparative Example 3 A coating film was obtained in the same manner as in Example 3 except that 50 parts of 2-acryloyloxyethyl acid phosphate was used, and the obtained coating film was evaluated in the same manner as in Example 3 and obtained. The obtained results are shown in Table 2.

[0061]

[Table 2]

[0062]

Since the constitution of the conductive coating composition of the present invention is as described above, a coating film having excellent hardness and alkali resistance can be obtained by applying it on a substrate. The coating composition has one of a sulfone group, a carboxyl group and a phosphinico group (meth).
Since the acrylate compound is added, a coating having excellent transparency and conductivity can be obtained by applying the acrylate compound on the substrate.

Claims (2)

[Claims] 1. A 100 parts by weight of a (meth) acrylate compound having two or more (meth) acryloyl groups, 5 to 30 parts by weight of an aniline-based conductive polymer, and a photopolymerization initiator sensitized by an actinic ray. 1 to 10 parts by weight of a conductive coating composition. 2. Any one of 100 parts by weight of a (meth) acrylate compound having two or more (meth) acryloyl groups, 5 to 100 parts by weight of an aniline-based conductive polymer, a sulfone group, a carboxyl group and a phosphinico group. 1 to 30 parts by weight of a (meth) acrylate compound having one group and a photopolymerization initiator sensitized by an actinic ray 0.1 to 0.1
A conductive coating composition comprising 10 parts by weight.