JPH0841321A - Organic polymer composition, thin conductive film made thereof and production of thin film - Google Patents

Abstract

PURPOSE:To obtain an organic polymer composition which is solvent-soluble in a doped state by mixing a polyaniline (derivative with a specified dopant. CONSTITUTION:This composition is obtained by mixing a polyaniline (derivative) with 1-3 equivalents of a dopant being a compound represented by formula I or II [wherein R<1> is H, alkyl, alkoxy (carbonyl), polyoxyalkylenecarbonyl, alkenyl, alkylthioalkyl, aryl, alkylaryl, arylalkyl or the like; R<2> to R<4> are each alkylene or phenylene; m is 2-5; and n1 and n2 are each 1-50]. This composition is dissolved in a lowly corrosive and lowly toxic solvent such as an ether, a ketone or an alcohol, and the solution is applied to a substrate and dried to obtain a thin conductive film of a conductivity of 10<-9>S/cm or above.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an organic polymer composition containing polyaniline and / or its derivative soluble in an organic solvent in a doped state (a state in which a dopant coexists), and a conductive thin film produced from the composition. And a conductive thin film obtained. Since the organic polymer composition of the present invention is soluble in a solvent in a dope state, a molded product such as a film or sheet can be produced by a simple method such as coating a solution of the composition on a substrate and drying. it can. Further, the obtained thin film is useful as an antistatic film or a transparent conductive film.

[0002]

2. Description of the Related Art A conductive organic polymer containing electrolyte ions as a dopant is obtained by chemical oxidative polymerization of aromatic compounds such as aniline, pyrrole and thiophene using a chemical oxidant. can get. However, since an organic polymer is generally infusible and insoluble in an aqueous solvent and an organic solvent, it is difficult to mold and process, which has been a major obstacle to application and development.

Regarding polyaniline, there is a method (JP-A-3-28229) for processing a molded article by utilizing the fact that dedoped polyaniline (polyaniline having no dopant) is soluble in a certain polar organic solvent. Proposed. However, according to this method, two steps, that is, a step of obtaining a molded body from dedoped polyaniline and a step of adding a dopant to the obtained molded body are necessary, which is complicated.

A method for solubilizing doped polyaniline (polyaniline coexisting with a dopant) (WO92-229)
No. 11) is proposed. However, this method has problems such as the use of a harmful and highly corrosive solvent and the use of excess corrosive protic acid as a dopant.

Also proposed is a method of dissolving doped polyaniline in a polar organic solvent added with ammonia or a volatile amine (JP-A-3-285983). However, this method also has a problem that harmful ammonia or amine gas is generated when the solvent is removed after molding.

Further, a self-doping type water-soluble polyaniline in which a sulfonic acid group serving as a dopant is directly bonded to a polymer skeleton (JP-A-5-178989) is also proposed. However, this polyaniline has a problem in terms of cost because the manufacturing process is complicated.

On the other hand, as a method for forming a thin film of polyaniline, a method of chemically oxidatively polymerizing aniline or a derivative thereof in the presence of a substrate (Japanese Patent Laid-Open No. 2-69525) has been proposed. However, this method was not suitable for industrial large-scale production. As described above, there are many problems in industrially using polyaniline.

[0008]

Means for Solving the Problems The inventors of the present invention have earnestly studied to develop an inexpensive organic polymer composition soluble in a general-purpose solvent in a doped state and a conductive thin film formed therefrom, and as a result, The present invention has been completed by finding that the dopant can make the polyaniline and / or its derivative soluble in the solvent in the doped state.

That is, the present invention relates to polyaniline and / or
Or a derivative thereof, and general formula (I):

[0010]

[Chemical 4]

(In the formula, R ^{1 s} may be the same or different and each represents hydrogen, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a polyoxyalkylenecarbonyl group, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group. , An arylalkyl group, an alkoxyalkyl group, an alkylthio group, an alkylthio group,
An alkylsulfinyl group, an alkylsulfonyl group, a carboxyl group, a nitrile group, a hydroxyl group, a nitro group or halogen, and m represents an integer of 2 to 5) and a general formula (II):

[0012]

[Chemical 5]

(Wherein R ² , R ³ and R ⁴ may be the same or different, an alkylene group or a phenylene group respectively, and n ₁ and n ₂ may be the same or different, each from 1 to The invention relates to an organic polymer composition containing at least one of the compounds represented by the formula 50) as a dopant, a conductive thin film containing the composition, and a method for producing the conductive thin film.

Preferred R ¹ of the general formula (I) includes an alkyl group having 1 to 15 carbon atoms, an alkoxy group, an alkoxycarbonyl group, an alkoxyalkyl group and a polyoxyalkylenecarbonyl group. Among them, an alkoxycarbonyl group having 1 to 15 carbon atoms, an alkoxy group, an alkoxyalkyl group and a polyoxyalkylenecarbonyl group are particularly preferable. Among them, the general formula (III):

[0015]

[Chemical 6]

(In the formula, R ⁵ and R ⁵ 'may be the same or different and each has 1 to 10 carbon atoms, preferably 2 to 8 alkyl group, alkenyl group, alkylthioalkyl group, aryl group, alkylaryl. A sulfonic acid represented by a group, an arylalkyl group or an alkoxyalkyl group) is particularly preferable because the doped polyaniline to which it is added exhibits particularly high solubility in a general-purpose solvent such as tetrahydrofuran or 2-butoxyethanol.
In addition, as a preferable compound, in the general formula (I), m is 2, R ¹ is an ester group having 1 to 15 carbon atoms, an alkoxy group, an alkoxycarbonyl group, an alkoxyalkyl group and / or a polyoxyalkylenecarbonyl group, particularly Examples thereof include sulfonic acids having an alkoxycarbonyl group or a polyoxyalkylenecarbonyl group.

Preferred R ² , R ³ and R ⁴ of the general formula (II) include an alkylene group having 1 to 10 carbon atoms and a phenylene group, respectively. Among them, an alkylene group having 2 to 10 carbon atoms as R ² , a phenylene group as R ³ , and an alkylene group having 2 to 10 carbon atoms as R ⁴ are particularly preferable. R ² , R ³ and R ⁴ are each an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, an alkylthio group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkylsulfinyl group, an alkoxyalkyl. It may be substituted with one or more substituents selected from the group consisting of groups, alkylsulfonyl groups, alkoxycarbonyl groups, nitro groups and halogens. Preferable substituents for R ² , R ³ and R ⁴ include an alkyl group having 1 to 20 carbon atoms and an alkoxy group, respectively.

As a specific example of the particularly preferred compound (II), in the general formula (II), R ² and R ⁴ are both alkylene groups having 5 to 10 carbon atoms, R ³ is an m-phenylene group, and n ₂ is Polymeric acids having an integer of 10 to 40 and a ratio of n ₁ / n ₂ of 0.1 to 1 can be mentioned. The compounds represented by formula (I) or (II) may be used alone or in combination of two or more.

Another component of the organic polymer of the present invention, polyaniline and / or its derivative, has the following general formula (IV):

[0020]

[Chemical 7]

(In the formula, R ⁶ 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, an aryl group or an alkylaryl group. , Arylalkyl group, alkylsulfinyl group, alkoxyalkyl group, alkylsulfonyl group, alkoxycarbonyl group, amino group, alkylamino group, dialkylamino group, arylthio group, arylsulfinyl group, arylsulfonyl group, carboxyl group, halogen, cyano group , A haloalkyl group, a nitroalkyl group or a cyanoalkyl group, and p is 0 to
It is obtained by oxidative polymerization of aniline or a derivative thereof represented by (integral of 5).

Preferred R ⁶ is hydrogen or C 1-5.
Alkyl group, alkoxy group, aryl group, cyano group,
Examples include halogen and aryloxy groups.

Specific examples 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,
Examples include 5-chloro-2-methoxyaniline and 3-phenoxyaniline. These anilines or their derivatives can be used alone or in combination of two or more.

The polyaniline and / or its derivative used in the present invention can be obtained by oxidative polymerization of one or more kinds of the above-mentioned aniline and its derivative represented by the formula (IV). For example, aniline and /
Alternatively, it can be obtained by adding a solution of an oxidizing agent and a protic acid or a solution of an oxidizing agent to a solution or suspension of the derivative (IV) and the protic acid. For the polymerization, a usual polymerization method can be adopted, and the polymerization conditions are also the usual conditions. 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 under normal pressure,
The mixture is allowed to stir.

As the oxidizing agent used in the oxidative polymerization,
Examples thereof include ammonium peroxodisulfate, hydrogen peroxide, ferric chloride and the like. However, it is not limited to these. Preferably used,
Ammonium peroxodisulfate may be mentioned.

The protonic acid added during the oxidative polymerization can be used without any particular limitation as long as it has an acid dissociation constant pKa value of 4.0 or less. For example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, benzenesulfonic acid, p-toluenesulfonic acid, m-nitrobenzoic acid, organic acids such as trichloroacetic acid, polystyrenesulfonic acid, polyvinylsulfonic acid,
Polymeric acids such as polyvinyl sulfuric acid may be mentioned, but are not limited to these.

The organic polymer composition of the present invention can be obtained by adding a dopant during the oxidative polymerization of aniline and / or its derivative. Alternatively, the doped polyaniline obtained by using a protonic acid is dedoped by treating it with a base such as aqueous ammonia, and the desired dopant is added again to the dedoped polyaniline to obtain the organic polymer composition of the present invention. You can also

The amount of the dopant is polyaniline and / or
Alternatively, it may be added in an equivalent amount to the derivative or added in excess. Preferably polyaniline and /
Alternatively, it is 1 to 3 equivalents relative to the derivative.

The solvent in which the organic polymer composition of the present invention can be dissolved can be used without particular limitation as long as it is a solvent generally used in general. For example, ethers such as tetrahydrofuran, alcohols such as methanol and ethanol, nitriles such as acetonitrile,
Examples thereof include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as xylene and toluene, halogenated hydrocarbons such as chloroform, and organic solvents such as polar solvents such as N-methylpyrrolidone, dimethylformamide and dimethyl sulfoxide. The solvent used is preferably one that is less corrosive and less toxic.

A film from the organic polymer composition of the present invention,
When a molded product such as a sheet is produced, it can be mixed with another matrix polymer compound. As such a matrix polymer compound, polyester, polystyrene, polyethylene, polyamide, polyvinyl chloride,
Examples thereof include polyvinyl acetate, polypropylene, styrene-butadiene copolymer, polybutadiene, polysiloxane, polycarbonate, polyacrylonitrile, polymethylmethacrylate, and ABS resin.

For example, when the matrix polymer compound to be mixed is polyester, a large amount of ester bonds are contained in the side chains of the dopant, and when the matrix polymer compound is polyamide, amide bonds are contained in the side chains of the dopant. By containing a large amount, the compatibility of the doped polyaniline with the matrix polymer compound can be enhanced. The mixing ratio of the doped polyaniline and / or its derivative and the matrix polymer compound is such that the conductivity after thinning is 10 as described later.
There is no particular limitation as long as it is ^-9 S / cm or more.

The method of mixing the organic polymer composition of the present invention and the matrix polymer compound is not particularly limited, but it is preferable to mix them in a solution state. For example, a method of mixing the composition of the present invention in a doped state and a solution of a matrix polymer compound, a method of adding each of them to a solvent at one time and dissolving them, etc.

A conductive thin film is obtained by applying a solution containing the composition of the present invention onto a substrate and drying it. There is no particular limitation on the substrate used. For example, polymer compounds such as polyester and polyethylene, metals such as gold and platinum, and glass are used. The thickness of the base material is also not particularly limited and is appropriately selected depending on the purpose of use.

The conductivity of the thin film thus obtained is 10 ⁻⁹
It is preferably S / cm or more. A more preferable electric conductivity is 10 ⁻⁶ S / cm or more. The film thickness of the thin film is not particularly limited and may be appropriately selected depending on the purpose of use. Generally 1
0 μm to 10 ⁻⁴ μm is preferable.

[0035]

The feature of the organic polymer composition of the present invention resides in that a compound in which a substituent having a structure highly compatible with a solvent is bonded to benzenesulfonic acid is used as a dopant for polyaniline and / or its derivative. In other words, the doped polyaniline and / or its derivative can be solubilized by spreading the side chain of the compound in the solvent and mixing with the solvent molecule. Only by using this special dopant, it is possible to provide an organic polymer composition containing a conductive polyaniline and / or a derivative thereof that can be dissolved in a general-purpose solvent, and a thin film having good conductivity can be easily obtained. Be able to manufacture.

[0036]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Reference Example 1 In a 500 ml three-necked flask equipped with a stirrer, a cooler, a distillate withdrawal port and a thermometer, 20.9 g of 5-sulfosodium isophthalate dimethyl, 41.0 g of dimethyl isophthalate, neopentyl glycol 399. 2.4 g and 1.16 g of sodium acetate as a reaction catalyst were added to give 2
The reaction was carried out at 00 ° C for 4 hours. As the reaction progressed, the white suspension became a transparent homogeneous liquid, and a calculated amount of methanol was distilled. Further, unreacted neopentyl glycol was distilled off at 200 ° C. and 80 mmHg for 1.5 hours.

33.4 g of the above mixture and 6.3 mg of antimony oxide as a polycondensation catalyst were added to a glass reactor equipped with a stirrer, a nitrogen introducing pressure reducing tube and a thermometer, and the inside of the reactor was sufficiently replaced with nitrogen gas. After heating, the pressure reduction was started from 260 ° C. and reduced to 0.3 mmHg over 30 minutes. The final temperature was 275 ° C. When GPC was performed using N-methylpyrrolidone as a solvent, the number average molecular weight was 3,100 in terms of polystyrene.

Reference Example 2 300 equipped with a stirrer, a distillate withdrawal pipe and a thermometer
In a 3-ml 3-necked flask, 27.8 g of dimethyl 5-sulfosodium isophthalate and diethylene glycol-mono-
Add 207.8 g of n-butyl ether and 0.067 g of zinc acetate as an esterification catalyst, and add 8 at 210 ° C.
Reacted for 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 off at 220 ° C. and 70 mmHg for 2 hours.

Reference Example 3 6.5 g of the oligomeric compound synthesized in Reference Example 1 was dissolved in 40 ml of methyl ethyl ketone, and 400 ml of 12% hydrochloric acid was added with stirring. After stirring for 1 hour, the resulting white turbid matter was filtered through a glass filter and further washed 3 times with 35 ml of 12% hydrochloric acid. After washing, it was dried under reduced pressure at room temperature for 1 day. After drying, part of the solution was made into an aqueous solution and titrated with a 0.02N sodium hydroxide aqueous solution to quantitatively confirm that the sulfosodium group was converted into a sulfonic acid group.

Reference Example 4 20 g of an ion exchange resin (Amberlyst 15) was added to 15 ml of a THF (tetrahydrofuran) solution containing 1 g of the diester compound synthesized in Reference Example 2 and stirred at room temperature for 15 minutes. After filtering off with a glass filter, the ion exchange resin was washed again with 16 ml of THF and combined with the filtrate.
Titration was performed with a 0.02 N sodium hydroxide aqueous solution to quantitatively confirm that the sulfosodium group was converted to a sulfonic acid group.

Example 1 300 ml three-necked flask equipped with a stirrer and a thermometer
5.0 g of the sulfonic acid residue-containing oligomeric compound of Reference Example 3 and 0.5 g of aniline were mixed and dispersed in 100 ml of distilled water and cooled to 0 ° C. 10 ml of an aqueous solution of 0.6 g of ammonium peroxodisulfate, which is a polymerization oxidant, was cooled to 0 ° C. in advance and added dropwise over 10 minutes.
After the reaction mixture was kept at 0 ° C. and stirred for 10 hours, the produced dope polyaniline was filtered off and washed with water. It was dried under reduced pressure at room temperature for one day to obtain 3.8 g of doped polyaniline. When the obtained target product was compression-molded into pellets and measured by the four-terminal method, the conductivity σ was 2.1 S / cm. When 0.5 g of powdered polyaniline was added to 10 ml of THF and ultrasonic irradiation was performed, a uniform dark green solution was obtained. When this solution was filtered through a G4 glass filter, the amount of insoluble matter remaining on the filter was extremely small. 0.3 g of this polyaniline was treated with 30 ml of 3% ammonia water at room temperature for 2 hours, filtered, washed with water and dried to obtain dedoped polyaniline. When undoped polyaniline was dissolved in NMP (N-methylpyrrolidone) and measured by GPC, the number average molecular weight was 18,000 and the weight average molecular weight was 9 in terms of polystyrene.
It was 0000.

Example 2 The THF solution of the doped polyaniline obtained in Example 1 and the THF solution of the Byron resin RV-280 manufactured by Toyobo Co., Ltd. were mixed at various ratios and applied on a polyethylene terephthalate film to form a thin film ( The film thickness was 1 μm), and the conductivity was measured. The results are shown in Fig. 1. Optical thin film (400
No phase separation was observed in any case. Doped polyaniline ratio is 15, 2
At 0, 30, 50% by weight, the adhesion of the thin film is 10
At 0%, the pencil hardness was 2H. The test methods were as follows.

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

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

Example 3 0.3 g of the sulfonic acid residue-containing diester compound obtained in Reference Example 4 and 0.1 g of dedoped polyaniline having a number average molecular weight of 28,000 and a weight average molecular weight of 131,000 were used as T.
When added to 8 ml of HF and irradiated with ultrasonic waves, a uniform dark green solution was obtained in 3 hours. When this solution was filtered through a G4 glass filter, the amount of insoluble matter remaining on the filter was extremely small. This dope polyaniline THF solution is coated on a polyethylene terephthalate film,
It was dried at 120 ° C. for 1 hour to obtain a thin film having a film thickness of 1 μm.
When the thin film obtained is measured by the two-terminal method, the conductivity σ
Was 12 S / cm.

Example 4 The THF solution of the doped polyaniline obtained in Example 3 and the THF solution of the Byron resin RV-280 manufactured by Toyobo Co., Ltd. were mixed at various ratios and applied on a polyethylene terephthalate film to form a thin film ( The film thickness was 1 μm), and the conductivity was measured. The results are shown in Fig. 1. Optical thin film (400
No phase separation was observed in any case. Doped polyaniline ratio is 10, 1
In the case of 5, 20, 30 and 50% by weight, the adhesion of the thin film was 100% and the pencil hardness was 2H.

[0048]

Since the organic polymer composition of the present invention is soluble in a general-purpose organic solvent in the dope state, it is used as a solution,
The solution can be applied directly on the substrate and the solvent can be removed to form a film or a thin film. As described above, when the composition of the present invention is used, a conductive organic polymer film can be easily obtained, and is suitable for use as an antistatic material or a transparent conductive film. It is also possible to form a film or a thin film after mixing with another polymer material in a solution.

[Brief description of drawings]

FIG. 1 is a graph showing changes in conductivity with respect to the weight ratio of doped polyaniline obtained in Examples 2 and 4.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location H01B 1/12 G 5/14 Z // C08G 63/688 NNK

Claims (8)

[Claims] 1. Polyaniline and / or a derivative thereof, and a compound represented by the general formula (I): (In the formula, R ¹ may be the same or different and each is hydrogen or an alkyl group, an alkoxy group, an alkoxycarbonyl group, a polyoxyalkylenecarbonyl group, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl. Group, alkoxyalkyl group, alkylthio group, alkylsulfinyl group,
Alkylsulfonyl group, carboxyl group, nitrile group,
A hydroxyl group, a nitro group or a halogen, and m
Represents an integer of 2 to 5) and a compound represented by the general formula (II): (In the formula, R ² , R ³ and R ⁴ may be the same or different, each may be an alkylene group or a phenylene group, and n ₁ and n ₂ may be the same or different, each being an integer of 1 to 50. The organic polymer composition containing at least one of the compounds represented by the formula) as a dopant. 2. At least one of R ² , R ³ and R ⁴ is an alkyl group, alkenyl group, alkoxy group, alkylthio group, alkylthioalkyl group, aryl group, alkylaryl group, arylalkyl group, alkylsulfinyl group, alkoxy. The organic polymer composition according to claim 1, which comprises one or more substituents selected from the group consisting of an alkyl group, an alkylsulfonyl group, an alkoxycarbonyl group, a nitro group and a halogen. 3. The dopant has the general formula (III): (In the formula, R ⁵ and R ^{5 ′} may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkylthioalkyl group, an aryl group, an alkylaryl group, an arylalkyl group or an alkoxyalkyl group. The organic polymer composition according to claim 1, which is a compound represented by 4. The dopant according to general formula (II)
R²And R^FourIs an alkylene group, R³Is m-phenyle
Group, n₂Is an integer from 10 to 40, and n ₁/ N₂But
The organic acid according to claim 1, which is a polymer acid of 0.1 to 1.
Polymer composition. 5. A conductive thin film containing the organic polymer composition according to claim 1. 6. The conductive thin film according to claim 5, which has a conductivity of 10 ⁻⁹ S / cm or more. 7. The conductive thin film according to claim 5, which is obtained by applying a solution containing the organic polymer composition according to any one of claims 1 to 4 onto a substrate and drying the solution. . 8. A method for producing a conductive thin film, which comprises applying a solution containing the organic polymer composition according to any one of claims 1 to 4 onto a substrate and drying the solution.