JP2010001327A - Antistatic coating and antistatic material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic coating excellent in the maintenance of its electroconductivity. <P>SOLUTION: This antistatic coating contains an electroconductive polymer and a dopant, or a dope-joined electroconductive polymer obtained by dope-joining with the dopant, a binder resin, a phosphate ester compound expressed by formula (I): (C<SB>n</SB>H<SB>2n+1</SB>O)<SB>m</SB>P(O)(OH)<SB>3-m</SB>[wherein, (n) is an integer of 1 to 24; and (m) is 1 or 2] and/or an antioxidant having a radical-capturing function, and the antistatic material having a substrate material and an antistatic layer obtained by using the above antistatic coating on the substrate material is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antistatic paint and an antistatic material using the same.

The protective film (protective film) used for a polarizing plate etc. has an antistatic layer on PET film etc. as a base material, for example. For the antistatic layer, a paint obtained by mixing a quaternary ammonium salt with a binder resin is generally used.
Although such a paint is excellent in transparency, it has a large environmental dependency, and therefore the resistance value in a dry state increases and the antistatic property is inferior. Studies on antistatic coatings in which a polymer is mixed with a binder resin are underway.
A conductive polymer can usually combine with a dopant having an acid group such as a sulfonic acid group to exhibit conductivity.

However, the present inventors have found that the conductivity of the conductive polymer antistatic coating is often deactivated by impurity ions (for example, ammonium ions) or active oxygen in the air.
In particular, when the antistatic coating has a thickness of 0.1 μm or less, the tendency is prominent, and the resistance value increases with time.
Then, an object of this invention is to provide the antistatic coating material excellent in electroconductivity maintenance.

  As a result of diligent research to solve the above-mentioned problems, the present inventor has found that a conductive polymer and a dopant, a doped junction conductive polymer doped by a dopant, a binder resin, a phosphate ester compound having a specific structure, and / or The present inventors have found that a composition containing an antioxidant having a radical scavenging function can be an antistatic paint excellent in maintaining conductivity, and completed the present invention.

That is, this invention provides the following 1-8.
1. Conductive polymers and dopants or the doped junction conductive polymers are joined doped with a dopant, and a binder resin, formula _{(I) :( C n H 2n} + 1 O) m P (O) (OH) 3-m ( wherein Wherein n is an integer of 1 to 24, and m is 1 or 2.) An antistatic paint containing a phosphoric acid ester compound and / or an antioxidant having a radical scavenging function.
2. 2. The antistatic paint according to 1 above, wherein a total ratio of the conductive polymer, the dopant, and the doped junction conductive polymer / a mass ratio of the phosphate compound is 100/5 to 100/500.
3. 3. The antistatic paint according to 1 or 2 above, wherein n is an integer of 1 to 4.
4). The antistatic coating material according to any one of the above 1 to 3, wherein a mass ratio of the total amount of the conductive polymer, the dopant, and the doped junction conductive polymer / the antioxidant is 100/1 to 100/10.
5). The antistatic coating material according to any one of 1 to 4 above, wherein a mass ratio of the total amount of the conductive polymer, the dopant, and the doped junction conductive polymer / the binder resin is 100 / 2,000 to 100/50.
6). 6. The antistatic paint according to any one of 1 to 5, wherein the antioxidant is a hindered phenol compound.
7). The antistatic paint according to any one of 1 to 6 above, wherein the surface resistance after drying is 1 × 10 ⁴ to 1 × 10 ¹² Ω / □.
8). The antistatic material which has a base material and the antistatic layer obtained by using the antistatic coating material in any one of said 1-7 on the said base material.

  The antistatic paint of the present invention and the antistatic material of the present invention are excellent in maintaining electrical conductivity.

The present invention will be described in detail below.
The antistatic paint of the present invention comprises a conductive polymer and a dopant, or a doped bonded conductive polymer doped with a dopant, a binder resin, and a formula (I): (C _n H _{2n + 1} O) _m P (O) (OH) _3-m (wherein n is an integer of 1 to 24 and m is 1 or 2) and / or an antioxidant having a radical scavenging function It is an antistatic paint.

The conductive polymer will be described below.
The conductive polymer that can be contained in the antistatic paint of the present invention is not particularly limited. Examples thereof include polyaniline, polypyrrole, polythiophene, poly (p-phenylene), poly (p-phenylene vinylene) and derivatives thereof.
Of these, polyaniline and polyaniline derivatives are preferred from the standpoint of superior conductivity.
A conductive polymer can be used individually or in combination of 2 types or more, respectively. The production of the conductive polymer is not particularly limited. For example, a conventionally well-known thing is mentioned.

The doped junction conductive polymer will be described below.
The doped junction conductive polymer that can be contained in the antistatic paint of the present invention is a conductive polymer having a dopant bonded thereto.
The conductive polymer as the basic skeleton of the doped junction conductive polymer is not particularly limited. Examples thereof include polyaniline, polypyrrole, polythiophene, poly (p-phenylene), poly (p-phenylene vinylene) and derivatives thereof.
Of these, polyaniline and polyaniline derivatives are preferred as materials for the antistatic coating because they are easy to handle during synthesis and are inexpensive. Hereinafter, polyaniline and a polyaniline derivative may be collectively referred to as “polyanilines”.
Further, when the doped junction conductive polymer is a polyaniline, it can be uniformly dispersed in the binder resin, and the electric resistance after drying can be lowered.

The production of the doped junction conductive polymer is not particularly limited. A manufacturing method in the case where the doped junction conductive polymer is a polyaniline (hereinafter sometimes referred to as “doped junction polyaniline”) will be described.
As a method for producing doped junction polyaniline, for example, polyaniline is polymerized in a mixed solution containing an aniline monomer, a dopant, a protonic acid, water, and an oxidizing agent, and then doped with the dopant. The method of obtaining is mentioned. An anionic surfactant can be favorably used as the dopant, and among them, one preferred embodiment includes sulfosuccinic acid and alkylbenzenesulfonic acid and / or alkylnaphthalenesulfonic acid.
Specifically as a manufacturing method of dope junction polyaniline, for example, the mixing process which mixes an aniline monomer, a dopant, a protonic acid, and water, and the liquid mixture obtained by the mixing process are -20-5 degreeC. Then, an oxidizing agent is added and stirred to polymerize the aniline monomer to obtain a polyaniline that is dope-bonded with the dopant, thereby producing a production method.

First, the mixing process will be described.
The mixing step is a step of mixing the aniline monomer, the dopant, the protonic acid, and water. The mixing method is not particularly limited as long as it is a method capable of obtaining a mixed liquid of the above components.
The aniline monomer is aniline, an aniline derivative or a mixture thereof, and a compound represented by the following formula (1) is preferable.

上記式（１）中、ｎは０〜５の整数を表す。
Ｒ¹は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルカノイル基、アルキルチオ基、アリールオキシ基、アルキルスルフィニル基、アルキルチオアルキル基、アリール基、アルキルアリール基、アリールアルキル基、アルコキシアルキル基、アルキルスルホニル基、カルボキシ基、ハロゲン基、シアノ基、ハロアルキル基、ニトロアルキル基またはシアノアルキル基であり、水素原子、アルキル基であるのが好ましい。複数のＲ¹は、同一であっても異なっていてもよい。

In said formula (1), n represents the integer of 0-5.
R ¹ is hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkanoyl group, an alkylthio group, an aryloxy group, an alkylsulfinyl group, an alkylthioalkyl group, an aryl group, alkylaryl group, arylalkyl group, an alkoxyalkyl group, an alkyl A sulfonyl group, a carboxy group, a halogen group, a cyano group, a haloalkyl group, a nitroalkyl group or a cyanoalkyl group, preferably a hydrogen atom or an alkyl group. The plurality of R ¹ may be the same or different.

Specific examples of the compound represented by the formula (1) include aniline, o-toluidine, m-toluidine, o-ethylaniline, m-ethylaniline, o-ethoxyaniline, m-butylaniline, m -Hexylaniline, m-octylaniline, 2,3-dimethylaniline, 2,5-dimethylaniline, 2,5-dimethoxyaniline, o-cyanoaniline, 2,5-dichloroaniline, 2-bromoaniline, 5-chloro 2-methoxyaniline, 3-phenoxyaniline and the like. These may be used alone or in combination of two or more.
In addition to the aniline monomer, other monomers may be used as long as the object of the present invention is not impaired.

The dopant used in the production of the doped junction conductive polymer is not particularly limited. For example, sulfosuccinic acid; alkylbenzene sulfonic acid; alkyl naphthalene sulfonic acid; halogen compounds such as iodine, bromine, chlorine, iodine; proton acids such as sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, borohydrofluoric acid; Salts; Lewis acids such as aluminum trichloride, iron trichloride, molybdenum chloride, antimony chloride, arsenic pentafluoride, antimony pentafluoride; organic carboxylic acids such as acetic acid, trifluoroacetic acid, polyethylene carboxylic acid, formic acid, benzoic acid; Various salts of these organic carboxylic acids; phenols such as phenol, nitrophenol and cyanophenol; various salts of these phenols; benzenesulfonic acid, polyethylenesulfonic acid, anthraquinonesulfonic acid, alkylsulfonic acid (for example, dodecylsulfonic acid), Camphorsulfonic acid, copper Organic sulfonic acids such as Russianine tetrasulfonic acid, porphyrin tetrasulfonic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, naphthalene sulfonic acid condensate; various salts of these organic sulfonic acids; polymer acids such as polyacrylic acid; polyethylene oxide dodecyl Polyalkylene oxide phosphates such as ether phosphates and polyethylene oxide alkyl ether phosphates; various salts of these phosphates; sulfates such as lauryl sulfate, cetyl sulfate, stearyl sulfate, lauryl ether sulfate; Various salts of these sulfates are listed.
The dopants can be used alone or in combination of two or more.

  Among these, sulfosuccinic acid and alkylbenzene sulfonic acid and / or alkyl naphthalene sulfonic acid are used from the viewpoint that a dope-bonded conductive polymer having excellent compatibility with binder resin (particularly polyester resin) and low electric resistance can be obtained. Use in combination is preferred. In particular, it is preferably made of sulfosuccinic acid and alkylnaphthalenesulfonic acid from the viewpoint of excellent conductivity.

Sulfosuccinic acid is a compound represented by the following formula (2).

In formula (2), R ² and R ³ are each an alkyl group, preferably an alkyl group having 4 to 20 carbon atoms, and more preferably an alkyl group having 6 to 12 carbon atoms from the viewpoint of availability.
As sulfosuccinic acid, what is marketed in the form of sulfosuccinate (for example, sodium salt) can also be used.

Alkylbenzenesulfonic acid is a compound represented by the following formula (3).

In the formula (3), R ⁴ is an alkyl group having 1 to 20 carbon atoms. Generally, alkylbenzenesulfonic acid having an alkyl group having 10 to 14 carbon atoms and a salt thereof are commercially available. The most common dodecyl group is preferable from the viewpoint of price. Examples of the alkyl benzene sulfonic acid include p-toluene sulfonic acid and dodecyl benzene sulfonic acid. Although dodecylbenzenesulfonic acid has a linear type and a branched type, both can be used in the same manner. As dodecylbenzenesulfonic acid, those commercially available in the form of sulfonates can also be used.

式（４）中、Ｒ⁵は、炭素数１〜２０のアルキル基であり、炭素数２〜１２のアルキル基が好ましく、入手が容易であることから炭素数４〜１２のアルキル基がより好ましい。通常市販では、塩の形で扱われており、同様に使用可能である。 Alkylnaphthalenesulfonic acid is a compound represented by the following formula (4).

In the formula (4), R ⁵ is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 2 to 12 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms because it is easily available . Usually, it is handled in the form of a salt on the market and can be used in the same manner.

  The molar ratio of sulfosuccinic acid to alkylbenzene sulfonic acid and / or alkyl naphthalene sulfonic acid (addition of sulfo succinic acid / alkyl benzene sulfonic acid and alkyl naphthalene sulfonic acid) at the time of addition of the dopant is determined as follows. 10/90 to 90/10, more preferably 20/80 to 80/20, and more preferably 30/70 to 50/50. More preferably.

  The dopant content is preferably such that the molar ratio of the aniline monomer to the dopant (aniline monomer / dopant) is 100/20 to 100/200, and is an amount that is 100/40 to 100/100. Is more preferable. When the content of the dopant is within this range, the conductivity is excellent (the surface resistance value is small) and the mixing property with the binder resin (particularly the polyester resin) is excellent.

The protonic acid is not particularly limited as long as it is a protonic acid that can be used for producing polyaniline. For example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and perchloric acid; organic acids such as p-toluenesulfonic acid, m-nitrobenzoic acid and trichloroacetic acid; polymer acids such as polystyrenesulfonic acid, polyvinylsulfonic acid and polyvinylsulfuric acid Is mentioned.
Since the synthesis of polyaniline proceeds on the acidic side, the amount of protonic acid added is preferably such that the above-mentioned mixed solution has a pH of 0-4.

Next, the polymerization process will be described.
In the polymerization step, after the mixed liquid obtained in the mixing step is set to -20 to 5 ° C, an oxidant is added and stirred to polymerize the aniline monomer, and the polyaniline doped with the dopant (dope-bonded polyaniline) ).
In the polymerization step, the polymerization can be carried out even at a relatively high temperature such as at room temperature, but the reaction is fast and gel particles and the like are liable to occur, so the mixed solution obtained in the mixing step was set to -20 to 5 ° C. It is preferred to carry out the polymerization later. The polymerization time is not particularly limited, but for example, it is preferable to perform polymerization for about 5 to 48 hours in the above temperature range.
The cooling method is not particularly limited. For example, if ethylene glycol or the like is added to a normal water bath, cooling at 0 ° C. or less is possible.

The oxidizing agent used in the production of the doped junction polyaniline is not particularly limited as long as it is an oxidizing agent that can be used in the production of polyaniline. For example, ammonium persulfate, hydrogen peroxide, ferric chloride and the like can be mentioned.
The addition amount of the oxidizing agent is preferably 0.5 to 1.5 mol with respect to 1 mol of the aniline monomer.

In a preferred embodiment, the method for producing a doped junction conductive polymer further includes a washing step after the polymerization step. By washing, the residue of the oxidant, excess proton acid, and dopant can be flowed, and the doped junction conductive polymer can be purified. The washing step can be performed by a known method. For example, after completion | finish of superposition | polymerization, methanol and acetone are added, the method of depositing polyaniline, and filtering is mentioned.
A doped junction conductive polymer can be manufactured by the above manufacturing method.
A doped junction conductive polymer obtained by polymerizing a monomer in the presence of a dopant as described above is preferable because it can be uniformly dispersed in a binder resin (particularly a polyester resin).

The weight average molecular weight of the state in which the doped junction conductive polymer is not dope-bonded is preferably 50,000 or more from the viewpoint that electric resistance can be lowered (conductivity can be improved). From the point of being able to lower the electrical resistance and excellent in the mixing property with the binder resin, the weight average molecular weight of the dope-bonded conductive polymer in the undoped state is more preferably 50,000 to 1,000,000, More preferably, it is 100,000 to 300,000.
In the present specification, the weight average molecular weight of the doped junction conductive polymer in the undoped state is obtained by dissolving the produced doped junction conductive polymer in dimethylformamide (DMF), adding ammonia water, and then dedoping. Using a gel permeation chromatography (GPC) method, the weight average molecular weight of the polyaniline in an undoped state was measured and calculated with a UV detector. Polystyrene was used as a standard sample.
The doped junction conductive polymers can be used alone or in combination of two or more.
In the present invention, a conductive polymer and a doped junction conductive polymer can be used in combination.

The dopant will be described below.
The dopant that the antistatic coating material of the present invention can contain is not particularly limited. For example, the same thing as the above is mentioned.
Of these, sulfosuccinic acid, alkylbenzene sulfonic acid, and alkylnaphthalene sulfonic acid are preferred from the viewpoint of excellent conductivity maintenance, excellent compatibility with binder resins (particularly polyester resins), low electrical resistance, and excellent conductivity. The combined use of sulfosuccinic acid and alkylbenzenesulfonic acid and / or alkylnaphthalenesulfonic acid is more preferred. The dopants can be used alone or in combination of two or more.
In the present invention, a dopant is used for the conductive polymer. The amount of the dopant is preferably 20 to 200 parts by mass and more preferably 40 to 100 parts by mass with respect to 100 parts by mass of the conductive polymer from the viewpoint of excellent conductivity.
The dopant can also be used for a doped junction conductive polymer.

The phosphoric acid ester compound will be described below.
The phosphoric acid ester compound that can be contained in the antistatic coating material of the present invention is a compound represented by the following formula (I).
Formula _{(I) :( C n H 2n} + 1 O) m P (O) (OH) 3-m
In the formula, n is an integer of 1 to 24, and m is 1 or 2.
In the present invention, the phosphate ester compound traps ionic impurities such as ammonium ions present in the environment (for example, in the atmosphere) where the antistatic paint of the present invention is placed, and the ionic impurities bind to the dopant. Thus, it has a function of preventing the conductivity of the conductive polymer or the doped junction conductive polymer from being deactivated.

In the formula, the alkyl group represented by C _n H _{2n + 1} has 1 to 24 carbon atoms (n), and is excellent in maintaining conductivity, so that the number of carbon atoms (n) is 1 to 1. 4 is preferred. The alkyl group may be linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group.
In the formula, m is 1 or 2. The phosphoric acid ester compound can be used as a mixture of phosphoric acid monoester (m: 1) and phosphoric acid diester (m: 2). A commercial item can be used for the phosphoric acid ester compound as a mixture of phosphoric acid monoester and phosphoric acid diester.
Examples of the phosphoric acid ester compound include methyl phosphate, ethyl phosphate, butyl phosphate, 2-ethylhexyl phosphate, oleyl phosphate, tetracosyl phosphate, and the like. Of these, methyl phosphate, ethyl phosphate, and butyl phosphate are preferred from the viewpoint of being nonvolatile and excellent in maintaining conductivity. The phosphoric ester compounds can be used alone or in combination of two or more.

  The amount of the phosphate ester compound is preferably 100/5 to 100/500 from the viewpoint that the total amount of the conductive polymer, the dopant and the doped junction conductive polymer / the mass ratio of the phosphate ester compound is more excellent in maintaining the conductivity. 100/10 to 100/200 is more preferable.

The antioxidant having a radical scavenging function will be described below.
The antioxidant that can be contained in the antistatic coating material of the present invention has a radical scavenging function.
In the present invention, the antioxidant traps radicals such as oxygen radicals present in the environment (for example, in the atmosphere) where the antistatic paint of the present invention is placed, and the conductivity of the conductive polymer or doped junction conductive polymer is increased. It has a function to prevent deactivation.

The antioxidant having a radical scavenging function is not particularly limited. Examples include hindered phenol compounds, amine compounds, thioester radical trap agents, sulfur-containing metal complex radical trap agents, and phosphorus radical trap agents.
Among these, a hindered phenol compound is preferable from the viewpoint of excellent radical scavenging function and superior conductivity maintenance.

Examples of hindered phenol compounds include nonylphenol, mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, butylhydroxyanisole (BHA), 2,4-dimethyl-6-t-butylphenol. 2,6-di-t-butyl-p-cresol (BHT), 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,4,6-tri -t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 4-t-butylcatechol (TBC), 2,5-di-t-butylhydroquinone, 2,5-di-t-amyl Phenolic radical trapping agents such as hydroquinone and propyl gallate; 4,4'-methylenebis (2,6-di-t-butylphenol), polybutylated bisphenol, 4,4'-thiobis (3-methyl-6-t-butylphenol) ) And other bisphenol type radical trapping agents; 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl) Ru-4-hydroxybenzyl) benzene, 1,1,3′-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, tetrakis [methylene-3- (3,5-di-t- And polyphenol type radical trapping agents such as butyl-4-hydroxyphenyl) propionate] methane (Tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)] methane).
Moreover, as a commercial item of a hindered phenol-type compound, brand name Irganox 1010 (made by Ciba Specialty Chemical Co., Ltd.) can be used, for example.

Moreover, as an amine compound, an amine antioxidant is mentioned as an antioxidant with an oxygen radical trap effect, for example.
Examples of amine antioxidants include aniline / acetone condensation products (generic name RD), p-phenidine / acetone condensation products (general name AW), and diphenylamine / acetone condensation products (general name BLE). Amine / ketone condensation products; aromatic secondary amines.
Examples of aromatic secondary amines include octylated diphenylamine (generic name AD), alkylated diphenylamine (generic name ODA), 4,4′-bis (dimethylbenzyl) diphenylamine (generic name CD), and phenyl-α-. Diarylamine compounds such as naphthylamine (generic name PA); diphenyl-p-phenylenediamine (generic name DP), mixed diaryl-p-phenyleneamine (generic name TP, 630), dinaphthyl-p-phenylenediamine (generic name) Diaryl-p-phenylenediamine compounds such as White); N-isopropyl-N′-phenyl-p-phenylenediamine (generic names BIONA, 3C), N-1,3-dimethylbutyl-N′-phenyl-p -Phenylenediamine (generic name 6C), N- (3-methacrylo Alkyl-aryl-p-phenylene such as (Luoxy-2-hydroxypropyl) -N'-phenyl-p-phenylenediamine (generic name G-1), N- (methacryloyl) -N'-phenyl-p-phenylenediamine Examples include diamines.

Of these, hindered phenol compounds are preferred from the viewpoints of excellent radical scavenging function and superior electrical conductivity, and among them, polyphenol type radical trapping agents are more preferred.
Antioxidants can be used alone or in combination of two or more.

  The amount of the antioxidant is preferably 100/1 to 100/10 from the viewpoint that the total amount of the conductive polymer, the dopant and the doped junction conductive polymer / the mass ratio of the antioxidant is excellent in maintaining the conductivity. 100/2 to 100/5 is more preferable.

The binder resin will be described below.
The binder resin contained in the antistatic paint of the present invention is not particularly limited. For example, a polyester resin is mentioned. Specific examples include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and amorphous polyester resin. These may be used alone or in combination of two or more.
Among these, an amorphous polyester resin is preferable from the viewpoint of excellent compatibility with the conductive polymer and / or the doped junction conductive polymer.

  Examples of the amorphous polyester include an amorphous polyester resin that is soluble in an organic solvent, in which a third component is added to a polyethylene terephthalate skeleton. Specifically, Byron manufactured by Toyobo Co., Ltd. is preferable.

  Mixing of the conductive polymer and / or the dope-bonded conductive polymer into the binder resin may be performed by adding a normal plastic compounding agent to the binder resin and the conductive polymer and / or the dope-bonded conductive polymer, for example, This can be done by using a kneader or the like. When an amorphous polyester resin is used as the binder resin, the amorphous polyester resin is soluble in a solvent such as methyl ethyl ketone (MEK) or toluene. Therefore, the amorphous polyester resin is dissolved or dispersed in the solvent. The binder resin can be mixed with the conductive polymer and / or the doped junction conductive polymer by adding the conductive polymer and / or the doped junction conductive polymer to the solution.

  From the viewpoint that the amount of the binder resin is excellent in adhesion to the base film and is excellent in maintaining the conductivity, the total amount of the conductive polymer, the dopant and the doped bonded conductive polymer / the mass ratio of the binder resin is 100/2. It is preferable that it is 000-100 / 50, and it is more preferable that it is 100 / 1,000-100 / 100.

  The antistatic coating material of the present invention preferably further contains a solvent from the viewpoint that the viscosity can be lowered and workability can be improved. Solvents include toluene, methyl ethyl ketone (MEK), acetone, methanol, ethanol, isopropanol, toluene, xylene, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) Etc. These may be used alone or in combination of two or more. Among these, toluene and MEK are preferable from the viewpoint of compatibility with other components and excellent volatility.

  The amount of the solvent can be freely set in order to obtain an optimum film thickness in accordance with the workability when applying the antistatic paint and the performance (resistance value, strength, etc.) of the coating film. For example, the amount of the solvent with respect to 100 parts by mass of the binder resin can be 100 to 100,000 parts by mass.

  The antistatic paint of the present invention, if necessary, within a range that does not impair the object of the present invention, for example, an antioxidant other than a filler, a reaction retarding agent, an antioxidant, an antioxidant having a radical scavenging function, It can contain additives such as pigments (dyes), plasticizers, thixotropic agents, ultraviolet absorbers, flame retardants, surfactants, dispersants, dehydrating agents, and adhesion-imparting agents.

  The antistatic paint of the present invention is not particularly limited for its production. For example, a binder resin is dissolved or dispersed in a solvent in advance to obtain a binder resin solution, and the obtained binder resin solution is oxidized with a conductive polymer and a dopant, or a doped junction conductive polymer, a phosphate ester compound and / or a radical scavenging function. The antistatic coating material of the present invention can be produced by mixing with an inhibitor and an additive that can be used as required.

The surface resistance after drying the antistatic coating of the present invention is preferably 1 × 10 ⁴ to 1 × 10 ¹² Ω / □, and is preferably 1 × 10 ⁶ to 1 × 10 ¹⁰ Ω / □. More preferred.
In the present invention, the surface resistance was measured using a resistance measuring instrument (manufactured by Dia Instruments, Hiresta IP and HR probe).

Next, the antistatic material of the present invention will be described.
The antistatic material of this invention is an antistatic material which has a base material and the antistatic layer obtained by using the antistatic coating material of this invention for the said base material.

The base material used for the antistatic material of the present invention is not particularly limited. For example, a film is mentioned and a transparent film is preferable. Specific examples include films of polyester, nylon, polyolefin, and the like. Among these, a polyester film is preferable from the viewpoint of excellent adhesion to the antistatic layer, and a polyethylene terephthalate film (PET film) is more preferable.
The antistatic paint used for the antistatic material of the present invention is not particularly limited as long as it is the antistatic paint of the present invention.

The method for producing the antistatic material of the present invention includes, for example, a method having an application step of applying an antistatic paint to a base material and a drying step of drying the antistatic paint applied to the base material. Examples thereof include a two-layer extrusion method with a prevention paint, a sandwich method by injection molding, and heat fusion of two films.
A manufacturing method including an application process for applying an antistatic paint to a base material and a drying process for drying the antistatic paint applied to the base material will be described below.
First, in the coating process, for example, the process of applying the antistatic coating to the substrate includes, for example, spin coating method, gravure printing, screen printing, brush coating method, spray coating method, wire bar method, blade method, roll coating method, dipping Law.
In the case of employing spin coating in the present invention, one preferred embodiment is to set the number of rotations per minute to 2,000 and rotate for 20 seconds.

In the drying step after the coating step, the antistatic coating material applied to the substrate is dried to form an antistatic layer, which can be used as the antistatic material of the present invention. The drying temperature is preferably 80 to 100 ° C.
The thickness of the antistatic layer is preferably from 0.01 μm to 2 mm, more preferably from 0.05 μm to 0.5 μm, from the viewpoint of cost and production speed.
The antistatic material of the present invention can be produced by the method as described above.

The antistatic material of the present invention will be described below with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 1 schematically shows a cross section of an example of the antistatic material of the present invention.
In FIG. 1, an antistatic material 100 of the present invention includes a base material 101 and an antistatic layer 103 on the base material 101. Further, the antistatic material 100 can have an adhesive layer 111 on the opposite side of the antistatic layer 103. The antistatic layer 103 is formed, for example, by applying an antistatic paint (not shown) on a substrate 101 such as a PET film and drying it, and can impart an antistatic function to the substrate 101.

FIG. 1 shows that the surface layer 107, which is the surface of the antistatic layer 103, is affected by an external factor 109 in an environment where the antistatic material 100 of the present invention is placed.
The inventors of the present application speculate that the deterioration of the antistatic layer 103 due to the influence of the external factor 109 is a cause of the decrease in conductivity over time. Further, when the antistatic layer 103 becomes thin, it is considered that the entire antistatic layer 103 is affected by the external factors 109 and the antistatic layer 103 is likely to deteriorate.
Examples of the external cause include ionic impurities such as ammonium ions and radicals such as oxygen radicals.

A conductive polymer generates radicals when a dopant is bonded to the polymer, and exhibits conductivity due to its movement. The environment where the antistatic material mainly composed of the conductive polymer is placed is a general place where oxygen and various impurities in the air exist. The mechanism of deterioration of the antistatic layer is that the radical of the conductive polymer is bonded to the oxygen radical and disappears, and a basic ion such as a small amount of ammonium ion in the air is combined with a dopant having oxygen, It is presumed to be caused by undoping. In particular, when the antistatic layer is thin, it tends to be affected by external factors, and thus measures for preventing deterioration are required.
Note that the above mechanism is the inventor's inference, and even different mechanisms are within the scope of the present invention.
On the other hand, the antistatic material of the present invention can be deactivated with time even when the antistatic layer is thinned to 0.1 μm or less by using the antistatic paint of the present invention. Excellent conductivity and maintenance of conductivity.

In the antistatic material of the present invention, the conductive polymer and / or the dope-bonded conductive polymer is uniformly dispersed in the binder resin, and the electrical resistance is low and the electrical conductivity is excellent. Moreover, it is excellent in the adhesiveness of a base material (especially PET film) and an antistatic layer. Furthermore, the light transmittance is high and there is no problem of bleeding.
The antistatic material of the present invention includes, for example, packaging materials such as electronic parts and electronic materials, protective films; interiors such as cosmetic materials or curtains used in places where dust is a problem such as medical institutions and clean rooms. Material: It is suitably used as a housing for home appliances.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Evaluation The film having an antistatic coating film obtained as described below was evaluated for appearance (mixability of the dope-bonded conductive polymer and binder resin), PET adhesion, and surface resistance by the following evaluation method. The results are shown in Table 2.

(1) Appearance The film having the antistatic coating film is visually observed. “O” indicates that the coating is transparent and uniformly applied, and “B” indicates that the coating is uniform but cloudy. “B” means that the antistatic paint is aggregated and a coating film cannot be formed, and “C” is given.

(2) PET Adhesive The antistatic coating was applied onto a PET film having a thickness of 25 μm using a spin coater and then dried in an oven at 100 ° C. for 1 minute to form an antistatic layer on the PET film. The obtained antistatic layer was subjected to a cross-cut peel test. After making 100 mm grids (10 rows x 10 rows) on the antistatic layer with a cutter knife and attaching them completely with cellophane tape on the grid, the cellophane tape is momentarily peeled off and cannot be peeled off. The number of remaining grids was checked.

(3) Surface resistance About the obtained antistatic material, the surface resistance of the antistatic layer at 100 V under the conditions of 25 ° C. and 50% RH was measured using a resistance measuring instrument (manufactured by Dia Instruments, Hiresta IP and HR probe). It was measured. The obtained surface resistance value is defined as surface resistance 1.
Further, a deterioration promotion test was conducted in which the obtained antistatic material was placed in an oven at 80 ° C. for 1 week. Using the antistatic material obtained after the deterioration promotion test, the surface resistance of the antistatic layer was measured in the same manner as described above. The obtained surface resistance value is defined as surface resistance 2.
The logarithms of the obtained surface resistance values 1 and 2 were taken, and the difference between the logarithms was shown as the resistance value difference.
The evaluation standard for the resistance difference is that the conductivity is maintained well when the resistance difference is within the first power.

2. Production of doped junction conductive polymer (Synthesis Example 1)
Each component of Formulation 1 shown in Table 1 was placed in a 500 ml flask with the amount (part by mass) shown in the same table and mixed. After cooling this mixed liquid to 0 ° C. in a water bath, Formulation 2 (mixed liquid of 2.7 parts by mass of ammonium persulfate and 20 parts by mass of water) was added and stirred, and oxidative polymerization was performed for 12 hours.
Next, methanol was added to precipitate polyaniline, and the solid obtained by filtration was washed with a large amount of distilled water to obtain polyaniline bonded with a sulfonic acid group as a dope bonded conductive polymer. The obtained polyaniline was dispersed in toluene to produce a dispersion containing 5% by mass of polyaniline bonded with a sulfonic acid group. Let the obtained dispersion liquid be dope junction conductive polymer dispersion liquid.

  Further, 0.1 g of the obtained dope-bonded conductive polymer dispersion was taken and dissolved in 10 g of dimethylformamide, and then dedoped by adding 2 drops of 0.1% aqueous ammonia. Then, the weight average molecular weight of polyaniline filtered with a filter was measured by GPC.

Each component shown in Table 1 is as follows.
Aniline monomer: Reagent, manufactured by Kanto Chemical Co., Ltd. Sodium sulfosuccinate; di-2-ethylhexyl sodium sulfosuccinate, Lipar 860K, manufactured by Lion Akzo, solid content 35% by mass
-Sodium butylnaphthalenesulfonate: Perex NBL, manufactured by Kao Corporation, solid content 35% by mass
-Hydrochloric acid: Reagent, manufactured by Aldrich, 6N hydrochloric acid,
・ Toluene: Reagent, manufactured by Aldrich ・ Ammonium persulfate: Reagent, manufactured by Aldrich

3. Preparation of antistatic paint The components shown in Table 2 were mixed uniformly using the amounts (parts by mass) shown in the same table to obtain an antistatic paint.

4). Manufacture of laminated body A PET film (thickness 25 μm) is placed on a spin coater, 1.0 g of the obtained antistatic coating is applied on the PET film, and the spin coater is rotated for 20 seconds at a setting of 2,000 revolutions per minute. Then, an antistatic coating was applied to the PET film to obtain a film having a coating film of the antistatic coating.

Details of the components shown in Table 2 are as follows.
-Doped bonded conductive polymer dispersion: Doped bonded conductive polymer dispersion prepared as described above-Binder resin solution: 30 parts by mass of amorphous polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) dissolved or dispersed in 70 parts by mass of methyl ethyl ketone Solution obtained by the following: maleic anhydride: reagent, manufactured by Aldrich, Inc., phosphoric acid: reagent, manufactured by Aldrich, Inc., phosphate ester compound 1: methyl phosphate, reagent, manufactured by Aldrich, Inc., phosphate compound 2: ethyl phosphate [(C ₂ H ₅ O) _m P (O) (OH) _3-m , m = 1, 2], trade name JP-502, manufactured by Johoku Chemical Industry Co., Ltd. ・ Phosphate ester compound 3: dibutyl phosphate, trade name DBP, Johoku Chemical Industry Co., Ltd. -Antioxidant 1: Hindered phenol-based antioxidant (Irganox 1010, compound name tetrakis [methylene-3- (3,5- -t- butyl-4-hydroxyphenyl) propionate] methane, produced by Ciba Specialty Chemicals Co.)
Antioxidant 2: Amine-based radical trapping agent (N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, trade name: NOCRACK 6C, manufactured by Ouchi Shinsei Chemical Co., Ltd.)

As is clear from the results shown in Table 2, Comparative Examples 1 and 2 that did not contain a phosphoric acid ester compound were inferior in maintaining conductivity. Further, in Comparative Example 3 containing no phosphoric acid ester compound and containing phosphoric acid, the composition was agglomerated and an antistatic coating film could not be formed on the film. This is presumably because phosphoric acid was bonded to the doped junction conductive polymer to become a dopant, and the doped junction conductive polymer and the binder resin were not compatible.
On the other hand, Examples 1 to 12 have a low surface resistance, a small increase in surface resistance after the deterioration acceleration test with respect to the initial surface resistance, and excellent electrical conductivity. In particular, Example 10 containing a phosphoric ester compound and an antioxidant has the same surface resistance after the initial test and after the deterioration acceleration test, and is excellent in maintaining the electrical conductivity.
In Examples 1 to 12, the doped junction conductive polymer and the binder resin are uniformly mixed, and the appearance is excellent.

FIG. 1 is a cross-sectional view schematically showing a cross section of an example of the antistatic material of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Antistatic material of this invention 101 Base material 103 Antistatic layer 107 Surface layer 109 External factor 111 Adhesive layer

Claims (8)

Conductive polymers and dopants or the doped junction conductive polymers are joined doped with a dopant, and a binder resin, formula _{(I) :( C n H 2n} + 1 O) m P (O) (OH) 3-m ( wherein Wherein n is an integer of 1 to 24, and m is 1 or 2.) An antistatic paint containing a phosphoric acid ester compound and / or an antioxidant having a radical scavenging function.   2. The antistatic paint according to claim 1, wherein the total amount of the conductive polymer, the dopant, and the doped junction conductive polymer / the mass ratio of the phosphate ester compound is 100/5 to 100/500.   The antistatic paint according to claim 1 or 2, wherein the n is an integer of 1 to 4.   The antistatic paint according to any one of claims 1 to 3, wherein a mass ratio of the total amount of the conductive polymer, the dopant, and the doped junction conductive polymer / the antioxidant is 100/1 to 100/10.   The antistatic paint according to any one of claims 1 to 4, wherein a mass ratio of the total amount of the conductive polymer, the dopant, and the doped junction conductive polymer / the binder resin is 100 / 2,000 to 100/50.   The antistatic paint according to any one of claims 1 to 5, wherein the antioxidant is a hindered phenol compound. The antistatic paint according to any one of claims 1 to 6, wherein the surface resistance after drying is 1 x 10 ⁴ to 1 x 10 ¹² Ω / □.   The antistatic material which has a base material and the antistatic layer obtained using the antistatic coating material in any one of Claims 1-7 on the said base material.

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