JP2008222893A - Polyaniline complex solution and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyaniline composite solution good in viscosity stability of the solution employing a general purpose solvent. <P>SOLUTION: This polyaniline composite solution comprises an organic solvent, a protonated substituted or non-substituted polyaniline composite and a compound having a phenolic hydroxy group, in which moisture content is ≤3,000 ppm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyaniline complex solution and a cured product thereof. More specifically, the present invention relates to a polyaniline complex solution that has a small change in solution viscosity over time and is suitable as a raw material solution for spinning.

  Polyaniline is a conductive polymer excellent in environmental resistance and chemical stability, and its demand is increasing in recent years. In many cases, polyaniline fine particles are dispersed in various solvents and applied onto a polymer substrate to form a conductive film. In recent years, studies have been made on molding of polyaniline alone, for example, film formation, fiber formation, and the like, and if this becomes possible, it may become a more useful material.

Since polyaniline is difficult to be melted by heat due to its characteristics, it is essential to produce a stable solution for film formation and fiber formation.
For example, Patent Document 1 or 2 discloses spinning using polyaniline. In Patent Document 2, an example of spinning in the presence of residual water is also described. Although spinning is possible by these methods, it is necessary to use a special solvent such as dichloroacetic acid which is difficult to handle as a solvent.
The reason for using a special solvent is that it was industrially difficult to synthesize polyaniline soluble in a general-purpose solvent.

On the other hand, Patent Document 3 discloses polyaniline soluble in a general-purpose solvent such as toluene. However, in this technique, it is necessary to add a phenolic compound as a component of the polyaniline composition. In this case, however, there is a problem that the viscosity of the polyaniline solution increases with the passage of time.
JP 2006-511675 A JP-A-5-51451 International Publication No. 2005/052058 Pamphlet

  In view of the above problems, an object of the present invention is to provide a polyaniline complex solution using a general-purpose solvent and having good solution viscosity stability.

  In order to achieve the above object, as a result of intensive studies by the present inventors, it has been found that in the polyaniline composition described in Patent Document 3, the water content particularly has a great influence on the stability of the solution. . The inventors have found that a polyaniline complex solution having good storage stability can be obtained by reducing the water content in the composition to a predetermined value or less, and the present invention has been completed.

According to the present invention, the following polyaniline complex solution and the like are provided.
1. A polyaniline complex solution containing an organic solvent, a protonated substituted or unsubstituted polyaniline complex, and a compound having a phenolic hydroxyl group and having a water content of 3000 ppm or less.
2. The polyaniline complex solution according to 1, further comprising a resin component.
3. The polyaniline complex solution according to 1 or 2, which is used for fiber production.
4). Hardened | cured material manufactured using the solution in any one of said 1-3.
5. Hardened | cured material of 4 which is a fiber.
6). A fiber comprising a substituted or unsubstituted polyaniline complex that has been protonated and a compound having a phenolic hydroxyl group.
7). A fiber obtained by stretching the fiber according to 6 above.
8). A method for producing conductive fibers, woven fabrics or nonwoven fabrics, wherein fibers, woven fabrics or nonwoven fabrics are immersed in the solution according to any one of 1 to 3 above.

  ADVANTAGE OF THE INVENTION According to this invention, the polyaniline complex solution with the favorable storage stability of a viscosity can be provided. Thereby, since the molding conditions in the molding process such as spinning are stabilized, the production efficiency of the polyaniline molded product is improved.

  The polyaniline complex solution of the present invention is obtained by dissolving a protonated substituted or unsubstituted polyaniline complex and a compound having a phenolic hydroxyl group in an organic solvent, and the water content of the solution is 3000 ppm or less. It is characterized by.

  The organic solvent used in the solution of the present invention is only required to be substantially immiscible with water (water-immiscible organic solvent). For example, hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, tetralin; Halogen-containing agents such as methylene, chloroform, carbon tetrachloride, dichloroethane, and tetrachloroethane; and ester solvents such as ethyl acetate. Among these, toluene, xylene, chloroform, trichloroethane, and ethyl acetate are preferable from the viewpoint of excellent solubility of the polyaniline complex.

As the protonated substituted or unsubstituted polyaniline complex (hereinafter referred to as polyaniline complex), a substituted or unsubstituted polyaniline (hereinafter simply referred to as polyaniline) is an organic protonic acid represented by the following formula (I) or a salt thereof. Those obtained by protonation (hereinafter referred to as organic protonic acid (I) or a salt thereof) 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 solution 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 polyaniline complex solution 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, more preferably 1,000,000 or less.
The molecular weight of polyaniline was measured in N methylpyrrolidone (NMP) at 60 ° C. by gel permeation chromatography (GPC).

Examples of the substituent of the substituted polyaniline include a linear or branched hydrocarbon group 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, etc., 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 that may contain a substituent having 4 or more carbon atoms, a silyl group, an alkylsilyl group, a — (R ² O) x—R ³ group, or — (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.

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.

  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 1 to 10.

Specific examples in the case where R ¹² and R ¹³ are — (R ¹⁴ O) _r —R ¹⁵ groups are the same as those for — (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 present invention, two types of compounds function as dopants: an organic protonic acid or a salt thereof, and a compound having a phenolic hydroxyl group described later.
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 a phenolic hydroxyl group used in the present invention (hereinafter referred to as a phenolic compound) is not particularly limited, and is a compound represented by the general formula ArOH (wherein Ar is an aryl group or a substituted aryl group). Specifically, phenol, o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-propylphenol, o-, m- or p-butylphenol, o Substituted phenols such as-, m- or p-chlorophenol, salicylic acid, hydroxybenzoic acid and hydroxynaphthalene; polyhydric phenol compounds such as catechol and resorcinol; and polymer compounds such as phenolic resins, polyphenols and poly (hydroxystyrene) Etc. can be illustrated.

From the viewpoint of obtaining heat resistance and high conductivity, among phenolic compounds, it has two or more aromatic rings such as benzene ring, naphthalene ring, anthracene ring, pyridine ring, pyrrole ring, and 1 phenolic hydroxyl group. Those having at least two are preferred.
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) is particularly preferable. Since these have a high molecular weight, they have a high boiling point and are difficult to volatilize. Therefore, it is considered that a decrease in conductivity is suppressed even when used at high temperatures.
The phenolic compound used in the present invention functions as a dopant and contributes to the development of high conductivity.

The polyaniline complex solution of the present invention is obtained by adding (b) a phenolic compound to (a) a polyaniline complex in a state dissolved in a water-immiscible organic solvent, and adjusting the water content of the solution to 3000 ppm or less. Can be manufactured. The water content is preferably as low as possible, and it is not necessary to set a lower limit, but it is 10 ppm or more from the viewpoint of ease of dehydration.
The proportion of the (a) polyaniline complex in the water-immiscible organic solvent is usually 900 g / L or less, preferably 0.01 to 300 g / L, more preferably, depending on the type of the water-immiscible organic solvent. Is in the range of 10-100 g / L. 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, when there is too little content of a polyaniline complex, there exists a possibility that the viscosity of a solution may fall and it may become difficult to process.

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 complex solution 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 the present invention, the water content of the polyaniline complex solution is adjusted to 3000 ppm or less. The water content can be adjusted by, for example, adding a step of adding a desiccant into the system and dehydrating after preparing a polyaniline complex solution.
The desiccant is not particularly limited as long as it has the ability to remove water in the solution, and for example, sodium sulfate, magnesium sulfate, silica gel, molecular sieves, etc. are preferably used.

  A resin component can be further blended in the polyaniline complex solution of the present invention. These resins are added for the purpose of a binder base material, a plasticizer, a matrix base material, etc. according to the use. The resin component is not particularly limited as long as the intended purpose is achieved, and a thermoplastic resin, a thermosetting resin, a photocurable resin such as a UV curable resin, or the like is preferably used. When a curable resin is used, additives such as a curing agent and a photoinitiator may be used. Specific examples of these resin components include polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylic acid ester, polymethacrylic acid ester, polyvinyl alcohol, and polyurethane.

Moreover, you may add an inorganic material, a hardening | curing agent, a plasticizer, etc. to the polyaniline complex solution of this invention.
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 the purpose of, for example, 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 based on 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 removing the solvent from the polyaniline complex solution of the present invention by various means, a cured product having conductivity can be obtained. The cured product can have various shapes such as a fiber shape, a film shape, and a sheet shape. For example, in order to process into a fiber shape, a known technique such as wet spinning, dry spinning, or gel spinning may be employed. To process into a film or plate, a solution is applied on a substrate. Later, a method of removing the solvent can be used. Thus, various molded articles can be obtained from the polyaniline complex solution by a known molding method.

  The polyaniline complex solution of the present invention is particularly suitable as a solution for producing polyaniline fibers because the viscosity change with time is small and stable. In a spinning method using a raw material solution, generally, the raw material solution is passed through a nozzle (spinneret) having a small diameter to make a trickle, and then subjected to a curing treatment to be processed into a fiber. Specifically, in wet spinning, a trickle is put into a coagulation bath made of a coagulation liquid, and the resin component in the raw material solution is precipitated to form a fiber. In dry spinning, a trickle is passed in a hot atmosphere to evaporate the solvent and form a fiber.

  In any of the methods, since the raw material solution passes through the nozzle, it is important for spinning to keep the solution discharge amount constant. That is, when the discharge amount varies, the diameter of the resulting fiber varies, causing a problem in quality, and the yarn is broken during production, making continuous spinning difficult. Therefore, the raw material solution is pressurized by a metering / pressurizing device such as a gear pump and supplied to the nozzle. However, since the nozzle diameter is as thin as about 10 to 1000 μm, the viscosity of the raw material solution greatly affects the discharge amount. Conventionally, production conditions such as pressurization and temperature of the raw material solution have been adjusted in accordance with fluctuations in the viscosity of the raw material solution.

Since the polyaniline complex solution of the present invention is stable with little change in viscosity over time, fluctuations in the discharge rate due to an increase in the viscosity of the solution can be suppressed. Therefore, it is not necessary to adjust the manufacturing conditions in accordance with the fluctuation of the solution viscosity as in the conventional case, so that productivity is improved.
In the polyaniline complex solution of the present invention, a general-purpose solvent such as toluene can be used as described above. Since it is not necessary to use a solvent with poor handling properties such as dichloroacetic acid as in the past, the handling of the solution is easy.

  When wet spinning the polyaniline complex solution of the present invention, the coagulant must be a poor solvent for the polyaniline complex. Specifically, solvents other than aromatic solvents or halogen solvents can be used, for example, alcohol solvents such as isopropanol, ester solvents such as ethyl acetate, ketone solvents such as methyl ethyl ketone, and aliphatic solvents such as normal hexane. A solvent or the like is preferably used. These solvents can be appropriately selected from the viewpoints of easy handling and low environmental load.

The fiber of the present invention produced by the above method contains a protonated substituted or unsubstituted polyaniline complex and a compound having a phenolic hydroxyl group, and has high electrical conductivity.
The fiber of the present invention may be stretched. The electrical conductivity is further improved by stretching, and the mechanical properties of the resulting fiber can be improved.
Stretching can be performed by a conventionally known method. For example, there are a method of adjusting the amount of solution discharged from the take-up device and the nozzle in the fiber production process, and a method of providing a separate drawing process to apply tensile stress to the fiber after spinning. Usually, stretching is performed by adjusting the rotational speed ratio of two or more rolls and applying tensile stress to the fiber. Stretching can be performed at room temperature or under heating. The draw ratio may be appropriately adjusted according to the use of the fiber, but is preferably 3 times or less, and particularly preferably 1.2 to 2.5 times. Here, the draw ratio means a ratio of fiber lengths before and after drawing.
In addition, since not only a fiber but a film etc. extend | stretch, electrical conductivity improves, and it is preferable.

Furthermore, it can be twisted with other types of fibers to form a fiber bundle. The fiber twisted with the polyaniline fiber is not particularly limited. For example, electrical conductivity can be imparted to the fiber bundle by twisting with polyethylene fiber, polypropylene fiber, polyethylene terephthalate (PET) fiber or the like.
Moreover, electroconductivity can be provided by immersing another kind of fiber, a woven fabric, or a non-woven fabric in the polyaniline composite solution of the present invention, followed by drying. The types (materials) of fibers and the like that can be used in this case are not particularly limited as long as they are insoluble or hardly soluble in the polyaniline complex solution. Examples of the material include polyethylene, polypropylene, and polyethylene terephthalate.
In addition, as the fiber, a modified cross-section fiber is preferable because the polyaniline composite is easily attached.
Also in the above embodiment, it is preferable that there is no change in the viscosity of the polyaniline complex solution from the viewpoint of easy adhesion of the polyaniline complex.

The polyaniline complex solution of the present invention is applied to a substrate such as glass, a resin film, or a sheet having a desired shape, and then becomes an electroconductive film or film by removing the organic solvent.
In this case, as a method for applying the solution to the substrate, a known general method 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. Can be used.

  In order to remove the water-immiscible organic solvent, for example, 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. The heating temperature and the heating time are not particularly limited and may be appropriately selected according to the material 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 thermoplastic resin to the solution of the present invention.

  When the hardened | cured material of this invention is a film | membrane or a film, these thickness is 1 mm or less normally, Preferably it is the range of 10 nm-50 micrometers. A film having a thickness in this range is advantageous in that it does not easily crack during film formation and has uniform electrical characteristics.

Production Example 1
[Production of Protonated Polyaniline Complex]
144 L of aerosol OT (sodium diisooctylsulfosuccinate, purity 75% or more) manufactured by Wako Pure Chemical Industries, Ltd. was stirred and dissolved in 4 L of toluene, and a 30 L glass reactor (mechanical stirrer, jacket) , A thermometer with a 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 carried out 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 201 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: 61.3% by weight, hydrogen: 8.5% by weight, nitrogen: 3.6% by weight, sulfur: 5.6% 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 2.3. Moreover, the weight average molecular weight of the polyaniline skeleton in this polyaniline complex was 140,000 g / mol based on GPC measurement.

Example 1
The polyaniline complex obtained in Production Example 1 was again dissolved in toluene to prepare a toluene solution containing the polyaniline complex at a rate of 50 g / L. To this solution, 10 g of anhydrous magnesium sulfate per liter of toluene was added and stirred. Thereafter, the magnesium sulfate was filtered to obtain a toluene solution of the dehydrated polyaniline complex.
M Cresol was added to this solution to obtain a polyaniline complex solution. At this time, the amount of m cresol added was 0.9 mmol per 1 ml of the toluene solution.

Comparative Example 1
A polyaniline complex solution was obtained in the same manner as in Example 1 except that the dehydration treatment with anhydrous magnesium sulfate was not performed.

[Evaluation]
(1) Intrinsic conductivity of cured film Each of the polyaniline complex solutions prepared in Example 1 and Comparative Example 1 was developed on a glass substrate in a range of 14 mm × 52 mm and dried at 80 ° C. for 30 minutes in an air stream. A film having a thickness of 15 μm was produced. About these films | membranes, the intrinsic conductivity was measured using Lorester GP (Mitsubishi Chemical company_made; resistivity meter by the four-probe method). The measurement results are shown in Table 1.
(2) Water content of complex solution The water content of the polyaniline complex solution prepared in Example 1 and Comparative Example 1 was measured with a Karl Fischer moisture meter (CA-06 model + VA-06 model manufactured by Mitsubishi Kasei Co., Ltd.).
Specifically, each solution was put into a glass boat, placed in a glass heating rod, and heated to 150 ° C. under a nitrogen gas flow. The generated gas was blown into a Karl Fischer moisture meter, and the amount of moisture (weight ppm) was measured. The measurement results are shown in Table 1.

(3) Stability Evaluation of Complex Solution The polyaniline complex solution prepared in Example 1 and Comparative Example 1 was left in a 30 ° C. water bath for 24 hours, and the viscosity of the solution was visually observed. As a result, the viscosity of the solution of Comparative Example 1 increased with time and finally lost its fluidity, whereas the solution of Example 1 showed a change in viscosity over 24 hours. I couldn't.

Example 2
The polyaniline complex solution of Example 1 was placed in a syringe, fibrillated by extruding into hexane through a 3 cm air layer, and spun from this solution. Thereafter, the fibers were taken out and dried for 1 minute with a dryer at 80 ° C. to obtain polyaniline fibers.

Example 3
50 g of polystyrene (GPPS HF77 manufactured by PS Japan Co., Ltd.) was added to 1 L of the polyaniline complex solution of Example 1. This was stirred at room temperature to obtain a solution. This solution was put into a syringe and slowly injected from the top of a vertical cylindrical drying furnace in which hot air at 80 ° C. was circulating. As a result, a fiber composed of polyaniline and polystyrene was obtained.

Example 4
200 denier atypical cross-section polypropylene fibers were immersed in the polyaniline composite solution prepared in Example 1. Thereafter, the fiber was taken out and dried for 1 minute with a dryer at 80 ° C. to obtain a polypropylene fiber to which polyaniline was adhered. When this fiber was washed with water and dried in the same manner as described above, it was confirmed that a conductive fiber was obtained from the point where the green color derived from polyaniline remained.

Example 5
A 10 cm × 10 cm sample was cut from a PP spunbonded nonwoven fabric (produced by Idemitsu Unitech Co., Ltd., Stratec PP) and immersed in the polyaniline composite solution of Example 1. Thereafter, the nonwoven fabric was taken out and dried for 10 minutes with a dryer at 80 ° C. to obtain a nonwoven fabric to which polyaniline was adhered. When this nonwoven fabric was washed with water and dried in the same manner as described above, it was confirmed that a conductive nonwoven fabric was obtained from the location where the green color derived from polyaniline remained.

The polyaniline complex solution of the present invention can be used as a raw material solution for a polyaniline molded article such as a film, sheet, or fiber.
The cured product obtained from the polyaniline complex solution of the present invention is, for example, in the field of power electronics and optoelectronics, an electrostatic / antistatic material, a transparent electrode, a conductive film material, an electroluminescent element material, a circuit material, and a capacitor. It can be used for dielectrics / electrolytes, electrode materials for solar cells and secondary batteries, fuel cell separator materials and the like.

Claims (8)

An organic solvent, a protonated substituted or unsubstituted polyaniline complex, and a compound having a phenolic hydroxyl group,
A polyaniline complex solution having a water content of 3000 ppm or less.   The polyaniline complex solution according to claim 1, further comprising a resin component.   The polyaniline complex solution according to claim 1 or 2, which is used for fiber production.   Hardened | cured material manufactured using the solution in any one of Claims 1-3.   The cured product according to claim 4, which is a fiber.   A fiber comprising a substituted or unsubstituted polyaniline complex that has been protonated and a compound having a phenolic hydroxyl group.   A fiber obtained by stretching the fiber according to claim 6. The manufacturing method of an electroconductive fiber, a woven fabric, or a nonwoven fabric which immerses a fiber, a woven fabric, or a nonwoven fabric in the solution in any one of Claims 1-3.