JP5492413B2 - Conductive polyaniline composition and method for producing the same - Google Patents

Description

  The present invention relates to a conductive polyaniline composition and a method for producing the same. More specifically, the present invention relates to a conductive polyaniline composition that is easy to manufacture and handle, has high heat resistance, and provides a molded article having extremely excellent electrical characteristics, and a method for manufacturing the same.

  Polyaniline is a well-known material as one of conductive polymers. In addition to its electrical properties, polyaniline has the advantage that it can be synthesized relatively easily from aniline, which is an inexpensive material, and exhibits excellent stability against air and the like in a state of conductivity.

Regarding the conductive polyaniline composition, Patent Document 1 discloses a conductive material containing a compound having a protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent immiscible with water and a phenolic hydroxyl group. A polyaniline composition is described. By the method described in this document, a highly conductive polyaniline molded product can be obtained easily.
However, it cannot be said that the heat resistance of the obtained molded body is necessarily high. For example, when exposed to a high temperature of about 160 ° C. for about 1 day, the conductivity tends to decrease.
International Publication No. 2005/052058 Pamphlet

  An object of this invention is to provide the electroconductive polyaniline composition which gives the molded object which shows the outstanding heat resistance, and its manufacturing method in view of the said problem.

In order to achieve the above object, as a result of intensive research conducted by the present inventors, in the composition of Patent Document 1 described above, when a compound having a phenolic hydroxyl group containing two or more aromatic rings is used, the conductive property It was found that a polyaniline molded article having a high temperature and excellent heat resistance was obtained, and the present invention was completed.
According to this invention, the following electroconductive polyaniline composition and its manufacturing method are provided.
1. Or a protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent substantially immiscible with water, and a compound having two or more aromatic rings and having a phenolic hydroxyl group, or A conductive polyaniline composition consisting essentially of
2. 2. The conductive polyaniline composition according to 1, wherein the compound having a phenolic hydroxyl group is a compound represented by the following formula (1).
Ar-X-Ar '(1)
[Wherein, X is a single bond, a group containing an oxygen atom, a nitrogen atom, or a group containing a carbon atom, and one or two are present in the compound. When two are present, the two Xs may be the same or different. Ar and Ar ′ are aromatic ring groups, and both may be the same or different. Ar and / or Ar ′ has at least one hydroxyl group. Ar and Ar ′ may have one or more substituents selected from the group consisting of a halogen atom, a nitro group, a nitrile group, an amino group, a cyano group, and a carbonyl group. ]
3. 2. The conductive polyaniline composition according to 1, wherein the compound having a phenolic hydroxyl group is a compound in which a hydroxyl group is bonded to a polycyclic aromatic ring.
4). Conductive polyaniline in which a compound having two or more aromatic rings and having a phenolic hydroxyl group is added to a protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent substantially immiscible with water A method for producing the composition.
5. 5. The method for producing a conductive polyaniline composition according to 4, wherein the compound having a phenolic hydroxyl group is a compound represented by the following formula (1) or a compound in which a hydroxyl group is bonded to a polycyclic aromatic ring.
Ar-X-Ar '(1)
[Wherein, X is a single bond, a group containing an oxygen atom, a nitrogen atom, or a group containing a carbon atom, and one or two are present in the compound. When two are present, the two Xs may be the same or different. Ar and Ar ′ are aromatic ring groups, and both may be the same or different. Ar and / or Ar ′ has at least one hydroxyl group. Ar and Ar ′ may have one or more substituents selected from the group consisting of a halogen atom, a nitro group, a nitrile group, an amino group, a cyano group, and a carbonyl group. ]
6). The electroconductive molded object obtained by drying the electroconductive polyaniline composition in any one of said 1-3.

  ADVANTAGE OF THE INVENTION According to this invention, the electroconductive polyaniline composition which gives the molded object which shows the outstanding heat resistance, while being highly conductive is provided.

  The conductive polyaniline composition of the present invention has a protonated substituted or unsubstituted polyaniline complex dissolved in an organic solvent substantially immiscible with water, two or more aromatic rings, and phenolic And a compound having a hydroxyl group.

  Examples of organic solvents that are substantially immiscible with water (water-immiscible organic solvents) used in the composition of the present invention include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin; methylene chloride, chloroform, Halogen-containing agents such as carbon tetrachloride, dichloroethane, tetrachloroethane; ester solvents such as ethyl acetate, and the like. Among these, toluene, xylene, chloroform, trichloroethane, and ethyl acetate are preferable in that the solubility of the polyaniline complex is excellent.

As the protonated substituted or unsubstituted polyaniline complex (hereinafter referred to as polyaniline complex) used in the composition of the present invention, a substituted or unsubstituted polyaniline (hereinafter simply referred to as polyaniline) is represented by the following formula (I). Those obtained by protonation with the organic protonic acid or a salt thereof (hereinafter referred to as organic protonic acid (I) or a salt thereof) shown are preferable in terms of conductivity and solubility.
M (YARn) m (I)

In the present invention, the weight average molecular weight of the substituted or unsubstituted polyaniline is preferably a high molecular weight body of 10,000 g / mol or more. Thereby, the intensity | strength and ductility of the electroconductive article obtained from a composition can be improved. There is no particular upper limit for the weight average molecular weight, polyaniline having a weight average molecular weight of about several million g / mol can be produced, and the conductive polyaniline composition of the present invention can also be produced. However, from the viewpoint of dissolution, the weight average molecular weight is preferably about 10,000,000 or less.
The molecular weight of polyaniline is measured by gel permeation chromatography (GPC).
Examples of the substituent of the substituted polyaniline include linear or branched hydrocarbon groups such as a methyl group, an ethyl group, a hexyl group, and an octyl group, an alkoxyl group such as a methoxy group and a phenoxy group, an aryloxy group, and a CF ₃ group. And halogen-containing hydrocarbon groups.

In the above formula (I), M is a hydrogen atom or an organic or inorganic free radical. Examples of the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group. Examples of the inorganic free radical include sodium, lithium, potassium, cerium, and ammonium.
Y is an acidic group, for example, —SO ₃ ^— group, —PO ₃ ^2- group, —PO ₄ (OH) ^— group, —OPO ₃ ^2- group, —OPO ₂ (OH) ^— group, —COO. ^- group and the like. Among these, high acidity, -SO ₃ in terms easily doped ^- group.
A is a hydrocarbon group which may contain a substituent, for example, a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, a substituent such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, menthyl and the like. Including optionally substituted cycloalkyl groups, dicyclohexyl groups such as bicyclohexyl, norbornyl, adamantyl or the like or polycycloalkyl groups, phenyl, tosyl, thiophenyl, pyrrolinyl, pyridinyl, furanyl and the like An aryl group containing an aromatic ring, naphthyl, anthracenyl, fluorenyl, 1,2,3,4-tetrahydronaphthyl, indanyl, quinolinyl, indonyl and the like may be condensed diaryl group or polyaryl group, alkylaryl group, etc. Is mentioned.
R is each independently —R ¹ , —OR ¹ , —COR ¹ , —COOR ¹ , —CO (COR ¹ ), or —CO (COOR ¹ ). Here, R ¹ is a hydrocarbon group which may contain a substituent having 4 or more carbon atoms, a silyl group, an alkylsilyl group, or a — (R ² O) x—R ³ group, — (OSiR ³ ₂ ) x—. OR ³ (R ² is an alkylene group, R ³ is a hydrocarbon group which may be the same or different, and x is an integer of 1 or more). Examples of when R ¹ is a hydrocarbon group include linear or branched butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, pentadecyl, eicosanyl, etc. Can be mentioned.
n is an integer of 2 or more, and m is the valence of M.
As the compound represented by the formula (I), dialkylbenzenesulfonic acid, dialkylnaphthalene sulfonic acid, sulfophthalic acid ester, and a compound represented by the following formula (II) can be preferably used from the viewpoint of easy doping.
M (YCR ⁴ (CR ⁵ ₂ COOR ⁶ ) COOR ⁷ ) _p (II)
In the above formula (II), M is a hydrogen atom or an organic or inorganic free radical as in the case of the formula (I). Examples of the organic free radical include a pyridinium group, an imidazolium group, and an anilinium group. Examples of the inorganic free radical include sodium, lithium, potassium, cerium, and ammonium.

Y is an acidic group, for example, —SO ₃ ^— group, —PO ₃ ^2- group, —PO ₄ (OH) ^— group, —OPO ₃ ^2- group, —OPO ₂ (OH) ^— group, —COO. ^- group and the like, -SO ₃ ^- group.

R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group or an R ⁸ ₃ Si— group (wherein R ⁸ is a hydrocarbon group, and three R ⁸ may be the same or different). ). Examples of the hydrocarbon group when R ⁴ and R ⁵ are hydrocarbon groups include a linear or branched alkyl group having 1 to 24 carbon atoms, an aryl group containing an aromatic ring, and an alkylaryl group. The hydrocarbon group when R ⁸ is a hydrocarbon group is the same as in the case of R ⁴ and R ⁵ .

R ⁶ and R ⁷ are each independently a hydrocarbon group or — (R ⁹ O) _q —R ¹⁰ group [wherein R ⁹ is a hydrocarbon group or a silylene group, and R ¹⁰ is a hydrogen atom or a hydrocarbon, A group or R ¹¹ ₃ Si— (R ¹¹ is a hydrocarbon group, three R ¹¹ may be the same or different), and q is an integer of 1 or more. Examples of the hydrocarbon group when R ⁶ and R ⁷ are hydrocarbon groups include a linear or branched alkyl group having 1 to 24 carbon atoms, an aryl group containing an aromatic ring, and an alkylaryl group. Among these, those having 4 or more carbon atoms are preferable from the viewpoint of obtaining a polyaniline complex that is easily dissolved in an organic solvent immiscible with water. Specific examples of the hydrocarbon group when R ⁶ and R ⁷ are hydrocarbon groups include a linear or branched butyl group, pentyl group, hexyl group, octyl group, decyl group and the like.

In R ⁶ and R ⁷ , when R ⁹ is a hydrocarbon group, the hydrocarbon group includes a linear or branched alkylene group having 1 to 24 carbon atoms, an arylene group containing an aromatic ring, an alkylarylene group, an aryl An alkylene group and the like; The hydrocarbon group in R ⁶ and R ⁷ when R ¹⁰ and R ¹¹ are hydrocarbon groups is the same as in the case of R ⁴ and R ⁵ , and q is 1 to 10. preferable.

（式中、Ｙは−ＳＯ_３基等の酸性基である）Specific examples of the case where R ⁶ and R ⁷ are — (R ⁹ O) _q —R ¹⁰ groups include groups represented by the following formulas.

(Wherein Y is an acidic group such as —SO ₃ group)

  p is the valence of M.

The organic protonic acid (II) or a salt thereof is more preferably a sulfosuccinic acid derivative represented by the following formula (III) (hereinafter referred to as sulfosuccinic acid derivative (III)) from the viewpoint of conductivity and solubility.
M (O ₃ SCH (CH ₂ COOR ¹² ) COOR ¹³ ) _m (III)
In the above formula (III), M and m are the same as in the above formula (I).

R ¹² and R ¹³ are each independently a hydrocarbon group or — (R ¹⁴ O) _r —R ¹⁵ group [wherein R ¹⁴ is a hydrocarbon group or a silylene group, and R ¹⁵ is a hydrogen atom or a hydrocarbon, A group or an R ¹⁶ ₃ Si— group (wherein R ¹⁶ is a hydrocarbon group, three R ¹⁶ may be the same or different), and r is an integer of 1 or more].

The hydrocarbon group when R ¹² and R ¹³ are hydrocarbon groups is the same as R ⁶ and R ⁷ .

In R ¹² and R ¹³ , the hydrocarbon group in the case where R ¹⁴ is a hydrocarbon group is the same as R ⁹ described above. In R ¹² and R ¹³ , the hydrocarbon group in the case where R ¹⁵ and R ¹⁶ are hydrocarbon groups is the same as R ⁴ and R ⁵ described above.

  r is preferably from 1 to 10.

Specific examples in the case where R ¹² and R ¹³ are — (R ¹⁴ O) _q —R ¹⁵ groups are the same as those of — (R ⁹ O) _q —R ¹⁰ in R ⁶ and R ⁷ .

In the case where R ¹² and R ¹³ are hydrocarbon groups, the hydrocarbon group is the same as R ⁶ and R ⁷ and is a butyl group from the viewpoint of obtaining a polyaniline complex that is easily dissolved in an organic solvent immiscible with water. Hexyl group, 2-ethylhexyl group, decyl group and the like are preferable.

The organic protonic acid or a salt thereof has a function of protonating polyaniline, and exists as a dopant (counter anion) in the polyaniline complex. That is, in the composition of the present invention, two types of compounds function as dopants: an organic protonic acid or a salt thereof, and a compound having two or more aromatic rings and a phenolic hydroxyl group.
In the polyaniline complex, the composition ratio of the polyaniline and the organic protonic acid or a salt thereof is not particularly limited, but the molar ratio of the monomer unit of the polyaniline / the organic protonic acid or the salt thereof is usually from the viewpoint of obtaining high conductivity. 2 to 4, preferably 2 to 2.5.

  The polyaniline complex can be produced by a chemical oxidative polymerization method or an electrolytic polymerization method. For specific manufacturing conditions, the above-mentioned International Publication No. 2005/052058 may be referred to.

The compound having two or more aromatic rings and having a phenolic hydroxyl group (hereinafter sometimes referred to as a phenolic compound) is not particularly limited as long as it has aromaticity. For example, benzene ring, naphthalene What has 2 or more aromatic rings, such as a ring, anthracene ring, a pyridine ring, a pyrrole ring, and has 1 or more phenolic hydroxyl groups can be used.
As such a compound, a compound represented by the following formula (1) can be preferably used.

Ar-X-Ar '(1)
[Wherein, X is a single bond, a group containing an oxygen atom, a nitrogen atom, or a group containing a carbon atom, and Ar and Ar ′ are aromatic ring groups, which may be the same or different. Ar and / or Ar ′ has at least one hydroxyl group. Ar and Ar ′ may have one or more substituents selected from the group consisting of a halogen atom, a nitro group, a nitrile group, an amino group, a cyano group, and a carbonyl group. ]

X is a single bond, an oxygen atom, —NH—, —NHCO—, —COO—, —CO—, —COCH ₂ —, —OCO—, —CH ₂ —, —C ₂ H ₄ —, —C ₃ H _6- and the like can be mentioned. From the standpoint of obtaining heat resistance and high electrical conductivity, preferred examples of X include an oxygen atom.
One or two X can be present in the phenolic compound. When two are present, the two Xs may be the same or different. As such, for example, a single bond and -CH 2 as X _- fluorene structure having a like.
Of the substituents on Ar and Ar ′, examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and an isobutyl group.
Examples of other substituents for Ar and Ar ′ include halogen, amino group, cyano group, nitro group, nitrile group, and carbonyl group.
A plurality of substituents on Ar or Ar ′ may be bonded to each other to form a ring. Examples of the ring structure include a cyclohexyl ring, a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, and a pyrrole ring.

  Moreover, as a preferable phenolic compound other than the compound of the formula (1) in which two aromatic rings are bonded through X, a phenolic compound in which a hydroxyl group is added to a polycyclic aromatic ring such as a naphthalene ring or an anthracene ring is used. Can be mentioned. Such a compound is preferable in that it exhibits heat resistance and high conductivity. Examples of such a compound include α-naphthol and β-naphthol.

As the phenolic compound, phenoxyphenol (2-phenoxyphenol, 3-phenoxyphenol, or 4-phenoxyphenol) or naphthol is particularly preferable from the viewpoint of obtaining heat resistance and high conductivity.
The phenolic compound used in the present invention functions as a dopant and contributes to the development of high conductivity. In addition, since the molecular weight is large, the boiling point is high and it is difficult to volatilize. Therefore, it is considered that the decrease in conductivity is suppressed even when used at high temperatures.

The polyaniline composition of the present invention can be produced by adding (b) a phenolic compound to (a) the polyaniline complex dissolved in a water-immiscible organic solvent.
The proportion of the (a) polyaniline complex in the water-immiscible organic solvent depends on the type of the water-immiscible organic solvent, but is usually 900 g / L or less, preferably 0.01 to 300 g / L or less. It is. If the content of the polyaniline complex is too high, the solution state cannot be maintained, and it becomes difficult to handle the molded body, the uniformity of the molded body is impaired, and consequently the electrical properties and mechanical strength of the molded body. , Resulting in a decrease in transparency. On the other hand, if the content of the polyaniline complex is too small, only a very thin film can be produced when the film is formed by the method described later, which may make it difficult to produce a uniform conductive film.

A phenolic compound is added to a solution in which the polyaniline complex is dissolved in a water-immiscible organic solvent. Specifically, the phenolic compound may be added in a solid state or in a liquid state, or may be added in a state dissolved or suspended in a water-immiscible solvent. Preferably, an appropriate solvent addition method is selected so as to be in a dissolved state even after the addition.
The molar concentration of the phenolic compound in the entire polyaniline composition is preferably in the range of 0.01 mol / L to 5 mol / L. In this range, particularly excellent conductivity can be obtained. In particular, the range is preferably from 0.2 mol / L to 2 mol / L.

In addition, you may add another resin material, an inorganic material, a hardening | curing agent, a plasticizer, etc. to the polyaniline composition of this invention according to the objective.
Other resin materials are added for the purpose of, for example, a binder substrate, a plasticizer, a matrix substrate, and specific examples thereof include, for example, polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, Examples thereof include polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, and polyvinyl alcohol. When the composition of the present invention contains other resin materials, the composition of the present invention becomes a conductive composite material.

  Inorganic materials are added for the purpose of, for example, improving strength, surface hardness, dimensional stability and other mechanical properties. Specific examples thereof include silica (silicon dioxide), titania (titanium oxide), alumina ( Aluminum oxide) and the like.

  The curing agent is added, for example, for the purpose of improving strength, surface hardness, dimensional stability and other mechanical properties, and specific examples thereof include, for example, thermosetting agents such as phenol resins, acrylate monomers and photopolymerization. Examples thereof include a photo-curing agent using a property initiator.

  The plasticizer is added for the purpose of improving mechanical properties such as tensile strength and bending strength, and specific examples thereof include phthalic acid esters and phosphoric acid esters.

By drying the polyaniline composition of the present invention and removing the organic solvent, a conductive molded body can be obtained.
For example, a conductive film can be manufactured by applying to a substrate such as glass, a resin film, or a sheet having a desired shape and removing the organic solvent.

  As a method for applying the composition of the present invention to a substrate, known general methods such as a casting method, a spray method, a dip coating method, a doctor blade method, a barcode method, a spin coating method, a screen printing, a gravure printing method, etc. The method can be used.

  In order to remove the water-immiscible organic solvent, the organic solvent may be volatilized by heating. As a method for volatilizing the water-immiscible organic solvent, for example, heating is performed at a temperature of 250 ° C. or less, preferably 50 to 200 ° C. under an air stream, and further, heating is performed under reduced pressure as necessary. Note that the heating temperature and the heating time are not particularly limited, and may be appropriately selected depending on the material to be used.

  Moreover, it can also be set as the self-supporting molded object which does not have a base material. In the case of forming a self-supporting molded article, a molded article having a desired mechanical strength can be obtained by adding the above-described other resin material to the composition of the present invention.

When the molded product of the present invention is a film or a film, the thickness is usually 1 mm or less, preferably 10 nm to 50 μm. A film having a thickness in this range has advantages such as being hard to crack during film formation and having uniform electrical characteristics.
[Example]

Production Example 1
Production of Protonated Polyaniline Complex 144 g of Aerosol OT ( sodium di-2-ethylhexylsulfosuccinate , purity 75% or more) manufactured by Wako Pure Chemical Industries, Ltd. was stirred and dissolved in 4 L of toluene and placed under a nitrogen stream. The solution was placed in a 30 L glass reactor (with a mechanical stirrer, jacket, thermometer, and dropping funnel), and 150 g of raw material aniline was further added to this solution and dissolved by stirring.
The flask was stirred and cooled with a refrigerant, and 12 L of 1N hydrochloric acid was added to the solution.
Next, in a state where the solution temperature was cooled to −3 ° C., a solution of 214 g of ammonium persulfate dissolved in 4 L of 1N hydrochloric acid was dropped with a dropping funnel, and the reaction was completed in 3 hours and 10 minutes. Stirring was performed for 18 hours and 30 minutes from the start of dropping while keeping the internal temperature of the solution at 0 ° C. ± 1 ° C. Thereafter, 8 L of toluene was added, the solution temperature was raised to 19 ° C., and the mixture was allowed to stand.
The aqueous phase (lower phase) separated into two phases by standing was withdrawn from the lower part of the reactor to obtain a crude polyaniline complex toluene solution.
Further, 4 L of ion exchange water was added to the complex solution and stirred, and then allowed to stand to separate the aqueous phase. After this operation was performed again, the complex solution was washed in the same manner with 4 L of 1N hydrochloric acid aqueous solution, allowed to stand, and then the acidic aqueous solution was separated to recover the toluene solution of the polyaniline complex.

Some insoluble matter contained in this complex solution was removed with # 5C filter paper, and a toluene solution of a polyaniline complex soluble in toluene was recovered. This solution was transferred to an evaporator, heated in a hot water bath at 60 ° C., and reduced in pressure to evaporate and remove volatile components to obtain 208 g of a polyaniline complex.
The results of elemental analysis of the polyaniline complex from which volatile components were substantially removed were as follows: carbon: 61.7% by weight, hydrogen: 8.2% by weight, nitrogen: 3.9% by weight, sulfur: 5.5% by weight %Met.

  From the ratio of the nitrogen weight percent based on the aniline raw material and the sulfur weight percent based on the sulfosuccinic acid ester, the molar ratio of monomer unit / sulfosuccinic acid ester of polyaniline in the composite was 2.2. Moreover, the weight average molecular weight of the polyaniline skeleton in this polyaniline complex was 100,000 g / mol from GPC measurement.

Example 1
(1) Preparation of conductive polyaniline composition 1 g of the conductive polyaniline complex obtained in Production Example 1 was dissolved again in 20 ml of toluene to prepare a uniform conductive polyaniline complex solution. To this solution, 6.22 mmol of 3-phenoxyphenol was added to obtain a uniform conductive polyaniline composition having a 3-phenoxyphenol concentration of about 0.30 mol / L.
(2) Production of conductive polyaniline thin film About 1 ml of the conductive polyaniline composition obtained in (1) above was spread on a 30 mm × 30 mm square glass substrate and spin-coated at 2,000 rpm for 1 minute. This was dried at 160 ° C. for 30 minutes under an air stream to form a transparent and homogeneous thin film on the glass substrate. The resistance of the surface was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method), and the value was defined as an initial value (R ₀ ). The initial value (R ₀ ) was 410.6Ω / □.
(3) Heat Resistance Test of Conductive Polyaniline Molded Product The surface resistance was measured after heating the thin film of the conductive polyaniline composition obtained in (2) above at 160 ° C. under a nitrogen stream in a nitrogen stream for a predetermined time. The ratio (R / R ₀ ) between the surface resistance value (R) and the initial value after the lapse of a predetermined time was calculated to evaluate the heat resistance of the thin film. Table 1 shows the heating time and the surface resistance ratio (R / R ₀ ).

Example 2
(1) Preparation of conductive polyaniline composition 1 g of the conductive polyaniline complex obtained in Production Example 1 was dissolved again in 20 ml of toluene to prepare a uniform conductive polyaniline complex solution. To this solution, 8.03 mmol of β-naphthol was added to obtain a uniform conductive polyaniline composition having a β-naphthol concentration of about 0.39 mol / L.
(2) Production of conductive polyaniline thin film About 1 ml of the conductive polyaniline composition obtained in (1) above was spread on a 30 mm × 30 mm square glass substrate and spin-coated at 2,000 rpm for 1 minute. This was dried at 160 ° C. for 30 minutes under an air stream to form a transparent and homogeneous thin film on the glass substrate. The resistance of the surface was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method), and the value was defined as an initial value (R ₀ ). The initial value (R ₀ ) was 385.2Ω / □.
(3) Heat Resistance Test of Conductive Polyaniline Molded Product The surface resistance was measured after heating the thin film of the conductive polyaniline composition obtained in (2) above at 160 ° C. under a nitrogen stream in a nitrogen stream for a predetermined time. The ratio (R / R ₀ ) between the surface resistance value (R) and the initial value after the lapse of a predetermined time was calculated to evaluate the heat resistance of the thin film. Table 1 shows the heating time and the surface resistance ratio (R / R ₀ ).

Comparative Example 1
(1) Preparation of conductive polyaniline composition 1 g of the conductive polyaniline complex obtained in Production Example 1 was dissolved again in 20 ml of toluene to prepare a uniform conductive polyaniline complex solution. To this solution, 19 mmol of m-cresol was added to obtain a uniform conductive polyaniline composition having an m-cresol concentration of about 0.86 mol / L.
(2) Production of conductive polyaniline thin film About 1 ml of the conductive polyaniline composition obtained in (1) above was spread on a 30 mm × 30 mm square glass substrate and spin-coated at 2,000 rpm for 1 minute. This was dried at 80 ° C. for 1 minute in an air stream to form a transparent and homogeneous thin film on the glass substrate. The resistance of the surface was measured using a Lorester GP (manufactured by Mitsubishi Chemical Corporation; resistivity meter based on a four-probe method), and the value was defined as an initial value (R ₀ ). The initial value (R ₀ ) was 162.7Ω / □.
(3) Heat resistance test of conductive polyaniline molded body The thin film of the conductive polyaniline composition obtained in the above (2) was evaluated in the same manner as in Example 1. The results are shown in Table 1.

  When the heat resistance test data of the thin film to which m-cresol was added and the thin film to which phenoxyphenol or naphthol was added were compared, it was confirmed that the increase in the surface resistance value was suppressed in the thin film to which phenoxyphenol or naphthol was added.

  The polyaniline composition of the present invention is particularly useful in the field of power electronics and optoelectronics. Electrostatic / antistatic materials, transparent electrodes, conductive film materials, electroluminescent element materials, circuit materials, capacitor dielectrics / electrolytes, solar cells And can be used as an electrode material for a secondary battery, a fuel cell separator material, and the like.

Claims (6)

A substituted or unsubstituted polyaniline complex that is protonated with an organic protonic acid represented by the formula (I) or a salt thereof dissolved in a hydrocarbon solvent, a halogen-containing solvent, or an ester solvent;
A conductive polyaniline composition comprising a compound having two or more aromatic rings and a phenolic hydroxyl group.
M (YARn) m (I)
(In Formula (I), M is a hydrogen atom or an organic or inorganic free radical. Y is an acidic group. A is a hydrocarbon group that may contain a substituent. R is independently selected. -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ , -CO (COR ¹ ), and -CO (COOR ¹ ), where R ¹ may contain a substituent having 4 or more carbon atoms. hydrogen group, a silyl group, an alkylsilyl group, or ^{- (R 2 O) x-} R 3 _{^{group, - (OSiR 3 2) x}} -oR 3 (R 2 represents an alkylene group, also ^{R 3} is different from each identical Tei It is a good hydrocarbon group, x is an integer of 1 or more), n is an integer of 2 or more, and m is the valence of M.) The conductive polyaniline composition according to claim 1, wherein the compound having a phenolic hydroxyl group is a compound represented by the following formula (1 ) .
Ar-X-Ar '(1)
[Wherein, X is a single bond, a group containing an oxygen atom, a nitrogen atom, or a group containing a carbon atom . A r and Ar 'is an aromatic ring group, it may be the same or different. Ar and / or Ar ′ has at least one hydroxyl group. Ar and Ar ′ may have one or more substituents selected from the group consisting of a halogen atom, a nitro group, a nitrile group, an amino group, and a carbonyl group. ]   The conductive polyaniline composition according to claim 1, wherein the compound having a phenolic hydroxyl group is a compound in which a hydroxyl group is bonded to a polycyclic aromatic ring. An aromatic ring is attached to a substituted or unsubstituted polyaniline complex that is protonated with an organic protonic acid represented by the formula (I) or a salt thereof dissolved in a hydrocarbon solvent, a halogen-containing solvent, or an ester solvent. A method for producing a conductive polyaniline composition comprising adding a compound having two or more and having a phenolic hydroxyl group.
M (YARn) m (I)
(In Formula (I), M is a hydrogen atom or an organic or inorganic free radical. Y is an acidic group. A is a hydrocarbon group that may contain a substituent. R is independently selected. -R ¹ , -OR ¹ , -COR ¹ , -COOR ¹ , -CO (COR ¹ ), and -CO (COOR ¹ ), where R ¹ may contain a substituent having 4 or more carbon atoms. hydrogen group, a silyl group, an alkylsilyl group, or ^{- (R 2 O) x-} R 3 _{^{group, - (OSiR 3 2) x}} -oR 3 (R 2 represents an alkylene group, also ^{R 3} is different from each identical Tei It is a good hydrocarbon group, x is an integer of 1 or more), n is an integer of 2 or more, and m is the valence of M.) The method for producing a conductive polyaniline composition according to claim 4, wherein the compound having a phenolic hydroxyl group is a compound represented by the following formula (1 ) or a compound in which a hydroxyl group is bonded to a polycyclic aromatic ring.
Ar-X-Ar '(1)
[Wherein, X is a single bond, a group containing an oxygen atom, a nitrogen atom, or a group containing a carbon atom . A r and Ar 'is an aromatic ring group, it may be the same or different. Ar and / or Ar ′ has at least one hydroxyl group. Ar and Ar ′ may have one or more substituents selected from the group consisting of a halogen atom, a nitro group, a nitrile group, an amino group, and a carbonyl group. ]   The electroconductive molded object obtained by drying the electroconductive polyaniline composition in any one of Claims 1-3.