JPH08100060A - Antistatic agent using conductive organic polymer composition - Google Patents

Abstract

PURPOSE: To obtain a conductive compsn. which can form an antistatic film almost independent of moisture and excellent in water resistance and transparency by dissolving or dispersing, in a solvent, polyaniline or its deriv. and a specific protonic acid dopant in the doped state. CONSTITUTION: This antistatic agent is a conductive org. polymer compsn. which comprises polyaniline or its deriv. and a dopant satisfying the relation: (mol.wt. of dopant)/N=350-2,000 (wherein N is the number of protonic acid groups having acid dissociation constants pKa of 4.0 or lower in one molecule), has a conductivity of 10<-9> S/cm or higher, and is a dispersion or a soln. in the doped state. Pref. examples of the dopant are compds. represented by formulas I to VII (wherein R<1> to R<4> , R<7> , R<1> ' to R<4> ', and R<7> ' are each H, etc.; R<5> is a 20-40C alkyl, etc.; R<6> is a 5-20C alkyl, etc.; R is 1-5; K' is 0-4; K+K' is 5; m, m', and m" are each 0-5; (p) is 1-5; and q and q' are each 1-6).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a conductive organic polymer composition containing polyaniline and / or a derivative thereof dispersed or dissolved in a general-purpose organic solvent and an aqueous solvent in a doped state (a state in which a dopant coexists). It relates to the antistatic agent used. Since the organic polymer composition used in the present invention is dispersed or dissolved in a solvent in a dope state, a solution or dispersion of the composition can be directly applied to the metal surface and dried.
The obtained conductive thin film is useful for antistatic treatment of resin molded products, films, synthetic papers, fibers and the like.

[0002]

2. Description of the Related Art Highly insulating materials such as resin molded products, plastic films, synthetic papers and fibers are charged with static electricity due to friction, peeling, etc. and often cause serious troubles. Need to be processed.
Conventional measures include i) applying an ionic surfactant and ii) adding a conductive filler (carbon black or the like). However, for ionic antistatic agents,
i) Conductivity decreases under low humidity and the antistatic ability is insufficient, ii) It is difficult to reduce the surface resistance to 10 ⁸ (Ω / □) or less, iii) Poor water resistance, etc. In addition, the conductive filler has drawbacks such as i) the base material is blackened and the transparency is deteriorated, and ii) the strength and hardness of the base material are lowered to impair the original physical properties. There is a need for antistatic agents that overcome these drawbacks. On the other hand, it is expected that the above problems can be solved by developing an antistatic agent for plastic films, synthetic papers and fibers by using a conductive organic polymer such as polyaniline, polypyrrole and polythiophene. However, in general, the chargeable organic polymer is infusible and
Since it is insoluble in general-purpose organic solvents and aqueous solvents, it has poor processability and has been a major obstacle to application development.

Regarding polyaniline, a method (JP-A-3-28229) that allows processing because polyaniline in a dedoped state is soluble in a certain polar organic solvent has been proposed. For example, there is a problem that two steps are required, a step of molding the undoped polyaniline and a step of further doping with a protonic acid.

A method for solubilizing doped polyaniline (WO92-22911) has also been proposed, but a harmful and highly corrosive solvent is used, and an excessive corrosive protonic acid dopant is used. There are many problems in industrially using polyaniline.

A method of dissolving polyaniline in a doped state in a polar organic solvent to which ammonia or a volatile amine is added (Japanese Patent Laid-Open No. 3-285983) has also been proposed. Or, there is a problem that amine gas is generated.

A self-doping type water-soluble polyaniline in which a sulfonic acid group serving as a dopant is directly bonded to a polymer skeleton has been proposed (JP-A-5-178989), but the production process is complicated and there is a problem in cost. It was

As a method for forming a film of polyaniline on a substrate, a method of chemically oxidatively polymerizing aniline or a derivative thereof in the presence of a target substrate (JP-A-2-695) is used.
25) was proposed, but it was not suitable for industrial large-scale production.

[0008]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have earnestly studied to develop an inexpensive conductive polyaniline which can be dispersed or dissolved in a general-purpose organic solvent and an aqueous solvent in a doped state. It has been found that the derivative can be dissolved or dispersed in a solvent in the doped state. Further, it has been found that the conductive thin film formed from the solution or dispersion of the polyaniline composition of the present invention can be applied to an antistatic film having low humidity dependency, excellent water resistance and transparency.

[0009]

That is, according to the present invention, polyaniline and / or its derivative (A), and (dopant molecular weight) / N = 350 to 2000 (where N = 1 has an acid dissociation constant pKa of 4. The number of protonic acid groups is 0 or less), and the conductivity is 10 or less.
^-9 (S / cm) or more, the present invention relates to an antistatic agent using a conductive organic polymer composition characterized by being dispersed or dissolved in a doped state, and the conductive organic polymer composition. An antistatic agent characterized by using a conductive organic polymer composition in which a preferred dopant used in the product is at least one selected from the following formulas (1) to (7): The present invention relates to a resin molded product, a plastic film, a synthetic paper, a fiber and the like containing the antistatic agent.

[0010]

Embedded image (In the formula, R ¹ is hydrogen, or an alkyl group, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group, an aryloxy having 1 to 15, preferably 2 to 12 carbon atoms. And R ^{1 ′} is hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an alkylthioalkyl group, an aryl group, an alkylaryl group or an arylalkyl group. , An alkylsulfinyl group, an alkoxyalkyl group, an aryloxyalkyl group, an alkylsulfonyl group, an alkoxycarbonyl group, a carboxyl group, a nitrile group, a hydroxy group, a nitro group or a halogen, and when there are plural, they may be the same or different. . and preferred R ^{1 '} Is hydrogen, an alkyl group, an alkoxy group, an alkylthio group, an alkylthioalkyl group, an aryl group, an alkylsulfinyl group, an alkoxyalkyl group, an alkoxycarbonyl group, a carboxyl group, a nitrile group, a hydroxy group, more preferably hydrogen, an alkoxy group, Alkylthio group, alkylthioalkyl group,
An alkylsulfinyl group, an alkoxyalkyl group, an alkoxycarbonyl group, a carboxyl group, a nitrile group, and a hydroxy group. k is 1 to 5, preferably 2 to 4
Is an integer from 0 to 4, and k'is an integer from 0 to 4, and k + k '
= 5. )

[0011]

[Chemical 9] (In the formula, R ² and R ^{2 ′} may be the same or different and may be hydrogen, or an alkyl group having 5 to 15 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxy group. An alkyl group or an aryloxyalkyl group, preferably R ² ,
R ^{2 ′} represents an alkyl group having 5 to 15 carbon atoms, an alkylthioalkyl group, an alkoxyalkyl group, or an aryloxyalkyl group. m and m'represent an integer of 0 to 5. Preferably, m + m 'is 1-8. )

[0012]

[Chemical 10] (In the formula, R ³ and R ^{3 ′} may be the same or different and each is hydrogen or an alkyl group having 5 to 20 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl. Group, an aryloxyalkyl group, preferably R ³ ,
R ^{3 ′} is an alkyl group having 7 to 20 carbon atoms, an alkylthioalkyl group, an alkoxyalkyl group, or an aryloxyalkyl group. m, m ′, and m ″ represent integers from 0 to 5. Preferred m + m 'is 1 to 8, preferred m''is 2
From 5. n represents an integer of 1 to 5. )

[0013]

[Chemical 11] (In the formula, R ⁴ represents hydrogen or an alkyl group, an alkenyl group, an alkoxy group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group or an aryloxyalkyl group having 5 to 20 carbon atoms, Preferred R ⁴ is an alkyl group having 7 to 20 carbon atoms, an alkoxy group, an alkylthioalkyl group, an alkoxyalkyl group or an aryloxyalkyl group.
R ^4'is hydrogen or an alkyl group having 5 to 20 carbon atoms,
Alkenyl group, alkylthioalkyl group, aryl group,
Alkylaryl group, arylalkyl group, an alkoxyalkyl group, an aryloxyalkyl group, preferably R ^{4 'represents} an alkyl group having 20 to 7 carbon atoms, alkylthioalkyl group, an alkoxyalkyl group, an aryloxyalkyl group. m, m ′, and m ″ represent integers from 0 to 5. Preferred m + m 'is 1 to 8, preferred m''is 2
From 5. )

[0014]

[Chemical 12] (In the formula, R ⁵ represents an alkyl group having 20 to 40 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group or an aryloxyalkyl group.
⁵ represents an alkyl group having 20 to 40 carbon atoms, an alkylthioalkyl group, an alkoxyalkyl group, or an aryloxyalkyl group. )

[0015]

[Chemical 13] (In the formula, R ⁶ represents an alkyl group having 5 to 20 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group or an aryloxyalkyl group, and preferred R ⁶
Represents an alkyl group having 7 to 20 carbon atoms, an alkylthioalkyl group, an alkoxyalkyl group, and an aryloxyalkyl group. p represents an integer of 1 to 5, preferably 2 to 5. )

[0016]

Embedded image (In the formula, M represents a monovalent cation (excluding proton) such as sodium ion, potassium ion and ammonium ion. R ⁷ and R ^{7 ′} are hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group and an alkylthio group. Indicates an alkyl group, aryl group, alkylaryl group, arylalkyl group, alkylsulfinyl group, alkoxyalkyl group, aryloxyalkyl group, alkylsulfonyl group, alkoxycarbonyl group, carboxyl group, nitrile group, hydroxy group, nitro group or halogen. ,
When there are a plurality of them, they may be the same or different. Preferred R ⁷ and R ^{7 ′} are hydrogen, an alkyl group, an alkoxy group, an alkylthio group, an alkylthioalkyl group, an alkylsulfinyl group, an alkoxyalkyl group, an aryloxyalkyl group, an alkylsulfonyl group, an alkoxycarbonyl group, a carboxyl group, a nitrile group, A hydroxy group, a nitro group or halogen is shown. q and q'represent an integer of 1 to 6. )

In order to disperse or dissolve polyaniline in the doped state, the selection of the protonic acid dopant is important. A suitable dopant should have a solvent-solvent partial structure having a certain spatial extent in addition to the protonic acid group. Depending on the dopant, the formula weight of one unit of polyaniline when protonated is 181. In order to disperse or dissolve the polyaniline main chain having low solubility by doping, it is estimated that the formula weight per protonic acid group of the dopant is 181 or more. As a result of various searches for dopants in accordance with such a policy, the present inventors have found that (dopant molecular weight) / n = 350 to 2
It has been found that a dopant satisfying 000 (N = the number of protonic acid groups having an acid dissociation constant pKa in one molecule of 4.0 or less) is suitable. The value of 350 is approximately twice that of 181 for polyaniline. If this value is 2000 or more, steric hindrance due to the dopant hinders electron conduction between the main chains of polyaniline, resulting in a decrease in conductivity. A protonic acid group having an acid dissociation constant pKa of more than 4 is insufficient in proton addition to polyaniline, and the resulting composition has low conductivity.

The value of (molecular weight of dopant) / N is preferably 400 to 2000, and more preferably 46.
0-2000, most preferably 520-2000
However, the polyaniline in the doped state is easily dispersed or dissolved in the solvent in this order.

Specific examples of suitable dopants include the protonic acid compounds represented by the above formulas (1) to (7). These are all organic sulfonic acids having a molecular weight of several hundreds. In the dopants represented by the formulas (1) to (6), RX is an organic group having a relatively low polarity and is useful for dispersing or dissolving polyaniline mainly in a general-purpose organic solvent. The dopant has a sulfonate moiety of hydrophilic group and is useful mainly for dispersion or dissolution in an aqueous solvent.

The aniline or its derivative used in the oxidative polymerization may be one kind or two or more kinds, but has a structure represented by the following formula.

[Chemical 15] (In the formula, r is an integer from 0 to 5. R ⁸ may be the same or different and each is hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an alkanoyl group, an alkylthio group, an aryloxy group, an alkylthioalkyl group or an aryl group. , An alkylaryl group, an arylalkyl group, an alkylsulfinyl group, an alkoxyalkyl group, an alkylsulfonyl group, a carboxyl group, a halogen group, a cyano group, a haloalkyl group, a nitroalkyl group, or a cyanoalkyl group.)

As specific examples, 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-cycloloaniline, 2-bromoaniline,
Examples include 5-chloro-2-methoxyaniline and 3-phenoxyaniline.

Ammonium peroxodisulfate, hydrogen peroxide, ferric chloride, etc. are used as the oxidizing agent, and ammonium peroxodisulfate is preferably used, but it is not particularly limited.

As a method of obtaining polyaniline used in the present invention, a method of adding an oxidizing agent and a solution of a protic acid or a solution of an oxidizing agent to a solution or suspension of aniline or an aniline derivative and a protic acid can be mentioned. For the polymerization, usual polymerization conditions are applied. For example, the reaction temperature is between −10 ° C. and 40 ° C., the reaction time is within the range of 30 minutes to 48 hours, and the reaction mixture is stirred under normal pressure. The protonic acid added during oxidative polymerization is not limited as long as the acid dissociation constant pKa value is 4.0 or less, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, benzenesulfonic acid, p-toluene, etc. Examples thereof include organic acids such as sulfonic acid, m-nitrobenzoic acid and trichloroacetic acid, and polymer acids such as polystyrene sulfonic acid, polyvinyl sulfonic acid and polyvinyl sulfuric acid.

The obtained polyaniline is dedoped by treatment with a base such as aqueous ammonia to be dedoped polyaniline. However, it can be treated again with a desired protonic acid to obtain doped polyaniline. At the time of oxidative polymerization, a desired protonic acid may be added to dope, or may be added to dedoped polyaniline to obtain doped polyaniline.

The dopant is preferably 1 equivalent to polyaniline. Excess dopant is undesirable as it can induce corrosion.

The organic solvent in which the polyaniline composition used in the present invention can be dispersed or dissolved can be used without particular limitation, as long as it is one generally used as a general-purpose solvent. For example, ethers such as tetrahydrofuran and dioxane, alcohols such as methanol, ethanol, isopropyl alcohol and 2-n-butoxyethanol,
Nitriles such as acetonitrile, ketones such as acetone, carboxylic acids such as formic acid, acetic acid and propionic acid, aromatic hydrocarbons such as xylene and toluene, halogenated hydrocarbons such as chloroform, N-methylpyrrolidone and dimethylformamide. A polar solvent such as dimethyl sulfoxide can be used. Furthermore, the aqueous solvent in which the polyaniline composition used in the present invention can be dispersed or dissolved,
It means water or a mixed solvent of an organic solvent miscible with water. The ratio of water and organic solvent is not particularly limited. Examples of the organic solvent include tetrahydrofuran, ethers such as dioxane, alcohols such as methanol, ethanol, isopropyl alcohol, 2-n-butoxyethanol, nitriles such as acetonitrile, ketones such as acetone, formic acid, acetic acid, Carboxylic acids such as propionic acid and polar solvents such as N-methylpyrrolidone, dimethylformamide and dimethylsulfoxide can be used. In any case, those having low corrosiveness and toxicity are preferable.

When a conductive thin film is formed from the polyaniline composition used in the present invention, it can be mixed with another matrix polymer compound. As such a matrix polymer compound, polyester, polystyrene, polyethylene, polyamide, polyimide, polyvinyl chloride, polyvinyl acetate, polypropylene, epoxy resin, phenol resin, silicone resin, styrene-butadiene copolymer, polybutadiene, fluorine resin, Polysiloxane, polycarbonate, polyacrylonitrile,
Examples thereof include polymethyl methacrylate and ABS resin.

For example, when the polymer compound is polyester, a large amount of ester bond is contained in the side chain of the dopant, or when the polymer compound is polyamide, a large amount of amide bond is contained in the side chain of the dopant. It is possible to improve the compatibility of the doped polyaniline with the matrix polymer compound. Further, the mixing ratio of the doped polyaniline or its derivative and the matrix polymer compound is such that the conductivity after thinning is 10 ^−9.
There is no particular limitation as long as it is (S / cm) or more. The method for mixing the polyaniline composition used in the present invention and the matrix polymer compound is not particularly limited, but it is preferable to mix them in a dispersed or solution state. For example, the dispersion or solution of the polyaniline in the doped state and the solution of the polymer compound are mixed, or a solvent is added at once to disperse or dissolve the polyaniline.

A conductive thin film is obtained by applying a dispersion or solution containing polyaniline used in the present invention to a substrate and drying it. The base material to which the doped polyaniline or its derivative is applied is a resin molded product, a plastic film, a synthetic paper, a fiber or the like. A resin molded product uses a thermoplastic and / or thermosetting resin,
A molded product obtained by shaping with heat and / or a solvent includes a film, a synthetic paper, and a fiber in a broad sense, but in the present invention, a shape other than these is meant.
In addition, a product obtained by further processing the primary molded product as a material is also included. For example, the material of the resin molded product is not particularly limited unless it is attacked by a solvent that disperses or dissolves polyaniline, and specifically, polyester, polystyrene, polyethylene, polyamide, polyvinyl chloride, polyvinyl acetate, polypropylene, styrene. -Butadiene copolymer, polybutadiene, polysiloxane, polycarbonate, polyacrylonitrile, polymethylmethacrylate, ABS resin and the like are mentioned, and the shape is not limited. Examples of the material of the plastic film include polyester, polyethylene, polypropylene, polyamide and polycarbonate. Examples of synthetic paper include polyester and polypropylene type. The fibers include natural fibers, chemical fibers, synthetic fibers, inorganic fibers, etc., and specifically, natural fibers such as cotton, wool, silk, etc., chemical fibers such as rayon, polyester, polyamide, acrylic, polyethylene, polypropylene, polyurethane. And synthetic fibers such as glass, carbon and other inorganic fibers.

The method for forming a thin film on the surface of the base material is not particularly limited, and the base material is dipped in a dispersion or solution of polyaniline or a mixed dispersion or solution of polyaniline and a matrix polymer, followed by brush coating. Roller coat,
It can be easily applied by a method such as spray coating and then dried, and can be applied to a large-area, long-sized substrate.
The thickness of the thin film is not particularly limited and is determined from the required surface resistance value and the conductivity of the polyaniline composition. When coating polyaniline having the same conductivity, the thickness and the surface resistance value are in inverse proportion to each other.

The conductive thin film obtained from polyaniline used in the present invention has the following features and is very useful as an antistatic film for resin molded products, plastic films, synthetic papers, fibers and the like. i) Less dependent on humidity,
ii) Excellent transparency, iii) Since it is a thin film on the surface, it does not impair the original mechanical properties of the substrate, iv) High water resistance,
In particular, it has high washing resistance as an antistatic agent for fibers, v) It has a relatively high electric conductivity, and has an arbitrary surface resistance (10 ³ to 10 ¹⁰ Ω /
□) is possible.

[0032]

According to the present invention, a solution of polyaniline dispersed or dissolved in a dope state can be directly coated on a substrate and the solvent can be removed to form a thin film. The thin film thus prepared has high conductivity and stability, and is a resin molded product, a plastic film, specifically a film for transparent recording (for transparent thermal recording, transparent electrostatic recording, etc.). , Ceramic release film, chip carrier film, OHP film, floppy disk film, micro X-ray film, dry film, dry heat OHP film, trading film, conductive packaging film, magnetic tape film. It is preferably used for a clean room (floor, wall, ceiling, etc.) film, a film for other photosensitive materials and the like, as well as an antistatic agent for synthetic paper, natural and synthetic and semi-synthetic fibers. It is also possible to form a thin film after mixing with another polymer material in the dispersion or solution.

[0033]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. The evaluation methods used in the present invention are shown below.

Surface resistance: Measured with a specific resistance measuring device manufactured by Takeda Riken Co., Ltd. under the conditions of an applied voltage of 500 V and 25 ° C.

Electrification decay time: Using a static day meter made by ETS, USA, sandwiching the sample between the electrodes in an atmosphere of 23 ° C. and 15% RH and applying a voltage of 5.0 kV, the applied voltage became 5.0 kV. The electrode was grounded at that point, and the decay time t99 from grounding until the applied voltage reached 0.05 kV was measured.

Adhesion: A substrate was cut on the surface of the thin film with a cutter knife, cellophane tape was applied, and then the film was peeled off, and the number of remaining 100 cells was counted.

Pencil hardness: According to JIS-K-5401, a pencil scratch test material was used and tested for scratches under a load of 200 g.

Water resistance: The substrate coated with the thin film was dipped in water and the surface resistance before dipping was compared when the substrate was left at room temperature.

[0039]

[Synthesis Example 1] 15 g of aniline, 270 g of distilled water and 36 g of concentrated hydrochloric acid were added, and while maintaining the temperature at 0 ° C, a solution of 24.5 g of ammonium persulfate in 70 g of distilled water was added dropwise over 1 hour, followed by stirring for 4 hours. did. Filtered off, washed with water,
After washing with methanol and ether, vacuum drying was performed to obtain 12.4 g of polyaniline. 10 g of the obtained polyaniline was added to 1000 g of 3% aqueous ammonia, and the mixture was stirred at room temperature for 2 hours, filtered, washed with water, washed with methanol and washed with ether. After vacuum drying, 6.5 g of dedoped polyaniline (emeraldine base) was obtained. N
-Dissolved in methylpyrrolidone and measured GPC,
The polystyrene equivalent number average molecular weight was 27,000 and the weight average molecular weight was 99,000.

[0040]

Synthesis Example 2 In a 300 ml three-necked flask equipped with a stirrer, a distillate withdrawal tube and a thermometer, 27.8 g of dimethyl 5-sulfosodium isophthalate, 207.8 g of diethylene glycol-mono-n-butyl ether and an esterification catalyst were used. , Zinc acetate 0.067g, 21
The reaction was carried out at 0 ° C for 8 hours. As the reaction progressed, the white suspension became a transparent homogeneous liquid, and a calculated amount of methanol was distilled. Further, unreacted diethylene glycol-mono-n-butyl ether was distilled at 220 ° C. and 70 mmHg for 2 hours.

[0041]

Synthesis Example 3 1 g of the diester compound obtained in Synthesis Example 2
20 g of an ion exchange resin (Organo Co., Arborist 15) was added to 30 ml of the HF solution, and the mixture was stirred at room temperature for 15 minutes. After filtering off with a glass filter, the ion exchange resin was washed again with 30 ml of THF and combined with the filtrate. 0.0
Titration with a 2N aqueous sodium hydroxide solution confirmed quantitatively conversion to sulfonic acid at the sodium sulfo group. THF was distilled off and the residue was dried to give ¹ H-N
The structure of formula (9) was confirmed by MR and IR.

[0042]

Embedded image 0.10 g of the undoped polyaniline obtained in Synthesis Example 1 and the sulfonic acid type diester compound (molecular weight 534)
When 0.30 g was added to 8 ml of THF and ultrasonic irradiation was performed, a uniform dark green solution was obtained in 3 hours. When this solution was filtered through a glass filter, the amount of insoluble matter remaining on the filter was extremely small. This doped polyaniline THF solution was applied onto polyethylene terephthalate film and dried at 120 ° C. for 1 hour to give a film thickness of 1 μm.
A thin film of m was obtained. When the thin film obtained was measured by the two-terminal method, the conductivity σ was 12 (S / cm). In the same manner, doped polyaniline was dissolved in 2-n-butoxyethanol to form a thin film. Conductivity σ = 9 (S
/ Cm).

[0043]

[Synthesis Example 4] Similarly, the compounds of formulas (10) to (14) were subjected to ion exchange treatment, and after confirming the structure, ultrasonic irradiation was performed in an equivalent amount of dedoped polyaniline and THF to obtain a uniform dark green solution. After filtration, the doped polyaniline THF solution was coated on polyethylene terephthalate film,
It was dried at 0 ° C. for 1 hour to obtain a thin film having a film thickness of 1 μm. The conductivity of the obtained thin film was measured by the two-terminal method. The results are shown in Table 1.

[0044]

[Chemical 17]

[0045]

Embedded image

[0046]

[Chemical 19]

[0047]

Embedded image

[0048]

[Chemical 21]

[0049]

[Table 1]

[0050]

[Synthesis Example 5] 0.10 g of the undoped polyaniline obtained in Synthesis Example 1 and the sulfonic acid type compound 0.
When 23 g was added to 15 ml of 2-n-butoxyethanol and irradiated with ultrasonic waves, a uniform dark green solution was obtained in 3 hours. When this solution is filtered through a glass filter,
The amount of insoluble matter remaining on the filter was extremely small.

[0051]

[Synthesis Example 6] 0.10 g of the undoped polyaniline obtained in Synthesis Example 1 and the sulfonic acid type compound 0.
When 23 g was added to 15 ml of toluene and ultrasonic irradiation was performed, a uniform dark green solution was obtained in 3 hours. When this solution was filtered through a glass filter, the amount of insoluble matter remaining on the filter was extremely small.

[0052]

[Synthesis Example 7] 2,2'-dinaphthylmethane-6,6'-
2.5 g of disulfonic acid sodium salt was dissolved in a mixed solution of 10 ml of distilled water and 70 ml of methanol, 37.5 g of an ion exchange resin (Amberlyst 15) was added, and the mixture was stirred at room temperature for 1 hour.
Stir for 5 minutes. 0.02 after filtering with a glass filter
Titration with a specified aqueous sodium hydroxide solution quantitatively confirmed that the sodium sulfo group was converted into a sulfonic acid group. The solvent was distilled off, the residue was dried, and ¹ H-NM was used.
The structure was confirmed by R and IR. 2.4 g of 2,2′-dinaphthylmethane-6,6′-disulfonic acid thus obtained and 2,
2.7 g of 2'-dinaphthylmethane-6,6'-disulfonic acid sodium salt was added to 10 ml of distilled water to dissolve it, and 3
The mixture was stirred for 0 minutes at room temperature to reach ionic equilibrium and used as a dopant solution.

[0053]

[Synthesis Example 8] 13 ml of the solution of the dopant (molecular weight 450) of Synthesis Example 7 and 0.5 g of aniline were put and cooled to 0 ° C.
A small amount of ferrous sulfate was added. Ammonium persulfate 1.2
A solution prepared by dissolving g in 4 ml of water was cooled to 0 ° C. in advance and added dropwise over 10 minutes. The reaction mixture was kept at 0 ° C. and stirred for 20 hours. The produced doped polyaniline was dissolved in water and dialyzed for 2 days (Spectrum
Spectra / Pore 7, FE-0521-05, manufactured by Medical Industries). A part of the solution was vacuum dried to determine the solid content concentration, and the obtained polyaniline was compression-molded into pellets, and the conductivity σ = 2.2 × 10 ⁻³ (S / cm).
0.1 g of this polyaniline was added to 10 ml of 3% ammonia water.
At room temperature for 2 hours, filtered, washed with water and dried to obtain dedoped polyaniline. NMP with undoped polyaniline
When dissolved in, and subjected to GPC, the number average molecular weight was 12,000 and the weight average molecular weight was 23,000 in terms of polystyrene.

[0054]

Comparative Example 1 Dodecylbenzenesulfonic acid (molecular weight 32
6) 0.18 g and 0.1 g of the undoped polyaniline obtained in Reference Example 1 were added to 10 ml of toluene and subjected to ultrasonic irradiation for 3 hours, but polyaniline was hardly dissolved and precipitated. The same result was obtained when the solution was changed to THF, chloroform, or 2-n-butoxyethanol.

[0055]

Example 1 TH of the doped polyaniline obtained in Synthesis Example 3
F solution and THF of TOYOBO byron resin RV-280
The solutions are mixed in various ratios, coated on polyethylene terephthalate film to form a thin film (film thickness 1 μm),
The conductivity was measured. The results are shown in FIG. When the thin film was observed with an optical microscope (400 times), no phase separation was observed at any ratio. Doped polyaniline ratio is 1
In the case of 5, 20, 30, and 50 wt%, the adhesion of the thin film was 100% and the pencil hardness was 2H.

[0056]

Example 2 The aqueous solution of the doped polyaniline obtained in Synthesis Example 8 and an aqueous dispersion of the Byron resin MD1200 manufactured by Toyobo Co., Ltd. were mixed at various ratios, and the mixture was coated on a polyethylene terephthalate film to form a thin film (film thickness 1 μm). The conductivity was measured. The results are shown in FIG. Optical thin film (4
(00 times), no phase separation was observed at any ratio. The ratio of doped polyaniline is 10, 2
When 0, 30, 50 wt%, the adhesion of the thin film is 100
%, Pencil hardness was 2H.

[0057]

Example 3 TH of the doped polyaniline obtained in Synthesis Example 3
F solution and THF of TOYOBO byron resin RV-280
The solution was mixed so that the proportion of doped polyaniline was 20 wt% to prepare a solution having a solid content of 1%. It was coated on a polyethylene terephthalate film with a bar coater to form a thin film. Transmission electron microscope, film thickness is 0.0
It was measured to be 1 μm. Surface resistance Rs = 1.3 × 10 ⁹
(Ω / □), and the charge decay time was 0.48 seconds. Similarly, from this solution, the surface resistance was changed to form a thin film, and the transmittance (550 mm) of each was measured. The results are shown in FIG.

[0058]

Example 4 Similarly, a THF solution of doped polyaniline doped with a dopant derived from the formulas (10) to (14) and a THF solution of Byron resin RV-280 manufactured by Toyobo Co., Ltd. are mixed so that the proportion of the doped polyaniline is 40 wt%. The mixture was mixed to prepare a solution having a solid content of 1% to form a thin film. Further, the aqueous solution of the doped polyaniline obtained in Synthesis Example 8 and the aqueous dispersion of the BYRON resin MD1200 manufactured by Toyobo Co., Ltd. were mixed so that the weight ratio of the doped polyaniline was 30%, and 1
% Solution was prepared and made into a thin film. Table 2 shows the results.

[0059]

[Table 2]

[0060]

Example 5 A mixed THF solution of the doped polyaniline obtained in Synthesis Example 3 and the Byron resin RV-280 manufactured by Toyobo Co., Ltd. was coated on a polyethylene terephthalate film with a bar coater to have a surface resistance R S = 1.1 × 10 ¹⁰ , 2 0.0 x 10
A thin film of ⁸ , 7.2 × 10 ⁴ (Ω / □) was formed. Each of the thin film-coated polyethylene terephthalate films was placed in an atmosphere of relative humidity of 15, 50, and 65% for 24 hours, and the surface resistance was measured under the conditions. The results are shown in FIG. As a reference example, the result of coating a conventional ionic antistatic agent (Sunstat 2012A manufactured by Sanyo Kasei) on a polyethylene terephthalate film is shown by a dotted line in the same figure. The above surface resistance RS = 7.2 × 10 ⁴ (Ω /
FIG. 4 shows the time-dependent change in the surface resistance of the polyethylene terephthalate film (□) coated with the thin film after the immersion treatment in distilled water. Further, the above surface resistance RS
= 1.1 × 10 ¹⁰ , 2.0 × 10 ⁸ , 7.2 × 10 ⁴
The polyethylene terephthalate film coated with a thin film of (Ω / □) was left in air at 230 ° C. for 1 minute, but the surface resistance was not changed in any of the samples.

[0061]

[Example 6] A mixed THF solution (polyaniline 20 wt%, solid content 1 wt%) of the doped polyaniline obtained in Synthesis Example 3 and Toyobo Co., Ltd. Byron resin RV-280 was bar-coated on a polypropylene plate (100 mm x 100 mm x 5 mm). Surface resistance RS = 8.1 × 10 ⁸ (Ω /
A thin film of □) was prepared. The charge decay time was 0.54 seconds. Synthetic paper coated with thin film, relative humidity 15, 50,
After being placed in a 65% atmosphere for 24 hours, the surface resistance was measured and found to be the same under all conditions. Further, it was immersed in distilled water at room temperature for 24 hours, but no change was observed in the surface resistance.

[0062]

Example 7 A mixed THF solution (polyaniline 20 wt%, solid content 1 wt%) of the doped polyaniline obtained in Synthesis Example 3 and Toyobo Byron resin RV-280 was applied on Toyobo polyester synthetic paper crisper with a bar coater. Coating was performed to form a thin film having a surface resistance RS = 4.3 × 10 ⁸ (Ω / □). The charge decay time was 0.41 seconds. After the thin film-coated synthetic paper was placed in an atmosphere of relative humidity of 15, 50, and 65% for 24 hours, the surface resistance was measured, and the value was the same under all conditions. Furthermore, it was immersed in distilled water at room temperature for 24 hours and ii) left in air at 230 ° C. for 1 minute, but the surface resistance did not change before and after the treatment in any case.

[0063]

Example 8 Cotton yarn, wool yarn, polyester yarn, and nylon yarn are dipped in a THF solution (20% by weight of polyaniline, solid content 1%) of the doped polyaniline of Synthesis Example 3 and Byron resin RV-280 manufactured by Toyobo Co., Ltd., and 120 It was dried at 0 ° C for 10 minutes. After repeating this operation three times, the charge decay time of each fiber was measured and compared with that of the untreated fiber (Table 3). Further, the charge decay time after soaking each fiber in distilled water at room temperature for 24 hours is also shown.

[0064]

[Table 3] It was confirmed by observation with an electron microscope that the polyaniline thin film uniformly covered the fiber surface.

[Brief description of drawings]

FIG. 1 shows the results of measuring the electrical conductivity of the thin film (film thickness 1 μm) coated polyethylene terephthalate film obtained in Examples 1 and 2 of the present invention.

FIG. 2 shows the results of measuring the surface resistance and the light transmittance of the thin film-coated polyethylene terephthalate obtained in Example 3 of the present invention.

FIG. 3 shows the results of measuring the humidity dependence of the surface resistance of the thin film-coated polyethylene terephthalate film obtained in Example 5 of the present invention and the conventional ionic antistatic agent (Sunstat 2012A). Show.

FIG. 4 shows the results of measuring the surface resistance value of the thin film-coated polyethylene terephthalate film obtained in Example 5 of the present invention after immersion in distilled water.

Claims (12)

[Claims] 1. Polyaniline and / or its derivative (A), and (dopant molecular weight) / N = 350 to 2
000 (N = 1, the number of proton dissociation constants pKa in one molecule is 4.0 or less) of a protonic acid dopant (B), having a conductivity of 10 ⁻⁹ (S / cm) or more and being doped. An antistatic agent using a conductive organic polymer composition characterized by being dispersed or dissolved in a state. 2. An antistatic agent using the conductive organic polymer composition according to claim 1, wherein the dopant is represented by the formula (1). Embedded image (In the formula, R ¹ is hydrogen, or an alkyl group having 1 to 15 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group,
It represents an alkoxyalkyl group or an aryloxyalkyl group, and when there are a plurality of groups, they may be the same and different. R
^{1 'is} hydrogen, an alkyl group, an alkenyl group, an alkoxy group,
Alkylthio group, alkylthioalkyl group, aryl group, alkylaryl group, arylalkyl group, alkylsulfinyl group, alkoxyalkyl group, aryloxyalkyl group, alkylsulfonyl group, alkoxycarbonyl group, carboxyl group, nitrile group, hydroxy group, nitro group Or, it represents halogen, and when there are plural halogen atoms, they may be the same or different. k represents an integer of 1 to 5, k ′ represents an integer of 0 to 4, and k + k ′ = 5. ) 3. An antistatic agent using the conductive organic polymer composition according to claim 1, wherein the dopant is represented by the formula (2). Embedded image (In the formula, R ² and R ^{2 ′} may be the same or different and may be hydrogen, or an alkyl group having 5 to 15 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxy group. (Alkyl group and aryloxyalkyl group are shown. M and m ′ are integers from 0 to 5.) 4. An antistatic agent using the conductive organic polymer composition according to claim 1, wherein the dopant is represented by the formula (3). Embedded image (In the formula, R ³ and R ^{3 ′} may be the same or different and may be hydrogen or an alkyl group having 5 to 20 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxy group. Indicates an alkyl group or an aryloxyalkyl group, m, m ′, m ″
Represents an integer of 0 to 5. n represents an integer of 1 to 5. ) 5. An antistatic agent using the conductive organic polymer composition according to claim 1, wherein the dopant is represented by the formula (4). [Chemical 4] (In the formula, R ⁴ is hydrogen or an alkyl group having 5 to 20 carbon atoms, an alkenyl group, an alkoxy group, an alkylthio group,
Alkylthioalkyl group, aryl group, alkylaryl group, arylalkyl group, alkylsulfinyl group,
Represents an alkoxyalkyl group or an aryloxyalkyl group, wherein R ^4'is hydrogen or an alkyl group having 5 to 20 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group, aryl An oxyalkyl group is shown.
m, m ′, and m ″ represent integers from 0 to 5. ) 6. An antistatic agent using the conductive organic polymer composition according to claim 1, wherein the dopant is represented by the formula (5). Embedded image (In the formula, R ⁵ represents an alkyl group having 20 to 40 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group or an aryloxyalkyl group.) 7. An antistatic agent using the conductive organic polymer composition according to claim 1, wherein the dopant is represented by the formula (6). [Chemical 6] (In the formula, R ⁶ represents an alkyl group having 5 to 20 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyalkyl group or an aryloxyalkyl group, and p is 1 to 5
Indicates an integer. ) 8. An antistatic agent using the conductive organic polymer composition according to claim 1, wherein the dopant is represented by the formula (7). [Chemical 7] (In the formula, M represents a monovalent cation (excluding proton) such as sodium ion, potassium ion and ammonium ion. R ⁷ and R ^{7 ′} are hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group and an alkylthio group. Indicates an alkyl group, aryl group, alkylaryl group, arylalkyl group, alkylsulfinyl group, alkoxyalkyl group, aryloxyalkyl group, alkylsulfonyl group, alkoxycarbonyl group, carboxyl group, nitrile group, hydroxy group, nitro group or halogen. ,
If a plurality of them exist, they may be the same and different. q,
q'represents an integer of 1 to 6. ) 9. An antistatic agent for molded resin products, which comprises at least one conductive organic polymer composition according to claim 1. 10. At least 1 according to claims 1-7 or 8.
Antistatic agent for plastic films using one kind of conductive organic polymer. 11. At least 1 according to claims 1-7 or 8.
An antistatic agent for synthetic paper using one kind of conductive organic polymer. 12. At least 1 according to claims 1-7 or 8.
Antistatic agent for fibers using one kind of conductive organic polymer.