TWI512025B - Conductive composition - Google Patents

Description

Conductive composition

This invention relates to an electrically conductive composition.

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

As a method for producing polyaniline, a method of performing electrolytic oxidation polymerization of an aniline or an aniline derivative or a method of performing chemical oxidative polymerization is known.

In the electrolytic oxidation polymerization, Patent Document 1 or Patent Document 2 describes a method of polymerizing aniline on an electrode. A film excellent in electrical characteristics and the like can be obtained by electrolytic oxidation polymerization. However, in general, compared with chemical oxidative polymerization, it is expensive to manufacture, is not suitable for mass production, and it is also difficult to obtain a molded body of a complicated shape.

On the other hand, in order to obtain a conductive polymer of an aniline or an aniline derivative by chemical oxidative polymerization, it is usually necessary to add a doping to a polyaniline in a non-conductive basic state (so-called emeraldine base state). Protonation by doping agent.

However, since the polyaniline in a non-conductive basic state is hardly soluble in most of the organic solvent, it is not suitable for industrial production. Further, the conductive polyaniline (so-called emeraldine base state) formed after protonation is substantially insoluble and infusible, and it is difficult to easily produce a conductive composite material and a molded body thereof.

In such a case, several proposals have been made as a method of improving the doping of the polyaniline in a non-conductive alkali state and the affinity of the conductive polyaniline after doping to an organic solvent.

For example, Non-Patent Document 1 discloses that a protonic acid having an affinity for an organic solvent such as dodecylbenzenesulfonic acid or camphorsulfonic acid (CSA) is used as a dopant, thereby exhibiting excellent performance. Electrical characteristics.

Patent Document 3 describes a method in which a non-conductive alkali polyaniline is dissolved in m-cresol using, for example, adamantanesulfonic acid as a dopant.

Non-Patent Document 2 discloses, for example, a method in which 2-propenylamine-2-methyl-propanesulfonic acid is blended in a special solvent (halogen strong acid) such as 2,2-dichloroacetic acid. A dopant that is doped with a polyaniline in a non-conductive base state.

Patent Document 4 describes, for example, a method in which, in the same manner as in Patent Document 2, 2,2-dichloroacetic acid is used as a solvent, and bis(2-ethylhexyl) sulfosuccinate is used as a dopant. The polyaniline in a non-conductive basic state is doped.

On the other hand, Patent Document 5 discloses that in a two-phase polymerization system of a solvent and water which is not substantially mixed with water, by using an anionic surfactant as a dopant, it is easily obtained by doping. Polyaniline.

However, the electrical characteristics such as the electrical conductivity of the molded body containing the conductive polyaniline obtained by these methods are not necessarily excellent.

Advanced technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 62-230825

Patent Document 2: Japanese Patent Laid-Open No. 62-149724

Patent Document 3: Japanese Patent Laid-Open No. Hei 7-70312

Patent Document 4: Japanese Patent Laid-Open Publication No. 2003-183389

Patent Document 5: International Publication WO05/052058

Non-patent literature

Non-Patent Document 1: Synthetic metals, 48, 1992, pp. 91-97

Non-Patent Document 2: J. Phys.: Condens. Matter, 10, 1998, 8293-8303

In view of the above circumstances, an object of the present invention is to provide a conductive composition capable of forming a conductive molded body having a high electrical conductivity.

According to the invention, the following conductive composition and the like are provided.

1. A conductive composition comprising: a solvent; a π-conjugated conductive polymer doped with a dopant dissolved in the solvent; and an LD50 of 500 [mg/kg] or more and a phenolic compound represented by the formula (X):

[Chemical 1]

(wherein R ₁ is a group having a function of supplying an electron to the benzene ring in the formula (X)); a weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / The π-conjugated conductive polymer [kg]) is 0.01 to 10.0.

2. A conductive composition using at least the following (a) to (c) as raw materials:

(a) a solvent;

(b) a π-conjugated conductive polymer doped with a dopant dissolved in the solvent;

(c) A phenolic compound having an LD50 of 500 [mg/kg] or more and represented by the following formula (X):

[Chemical 2]

(wherein R ₁ is a group having a function of supplying an electron to the benzene ring in the formula (X)); a weight ratio of the phenolic compound (c) to the π-conjugated conductive polymer (b) (phenol) The compound [kg] / π conjugated conductive polymer [kg]) is 0.01 to 10.0.

A conductive composition comprising: a solvent; a π-conjugated conductive polymer doped with a dopant dissolved in the solvent; and a phenolic compound represented by the following formula (2):

[Chemical 3]

(wherein R ₂ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an aralkyl group); and the above phenolic compound and the above π-conjugated conductive polymer The weight ratio (phenolic compound [kg] / π conjugated conductive polymer [kg]) is 0.01 to 10.0.

4. A conductive composition using at least the following (a) to (c) as raw materials:

(a) a solvent;

(b) a π-conjugated conductive polymer doped with a dopant dissolved in the solvent;

(c) a phenolic compound represented by the following formula (2):

[Chemical 4]

(wherein R ₂ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an aralkyl group); and the above phenolic compound (c) is electrically conductive with the above π-conjugated system The weight ratio of the polymer (b) (phenolic compound [kg] / π conjugated conductive polymer [kg]) is 0.01 to 10.0.

5. The conductive composition according to 3 or 4, wherein the phenolic compound (c) has an LD50 of 500 [mg/kg] or more.

6. The conductive composition according to any one of 1 to 5, wherein the doped π-conjugated conductive polymer is a protonated substituted or unsubstituted polyaniline, protonated Any of a substituted or unsubstituted polypyrrole or a protonated substituted or unsubstituted polythiophene.

7. The conductive composition according to any one of 1 to 6, wherein the dopant of the π-conjugated conductive polymer is an organic sulfonic acid.

8. The conductive composition according to any one of 1 to 7, wherein the dopant of the π-conjugated conductive polymer is succinic acid represented by the following (XX): M (O ₃ SCH(CH) ₂ COOR ¹² )COOR ¹³ ) _m (XX) (In the formula (XX), M is a hydrogen atom, an organic radical or an inorganic radical, m is a valence of M, and R ¹² and R ¹³ are each independently a hydrocarbon group or (R ¹⁴ O) a group represented by _{r -} R ¹⁵ , R ¹⁴ is a hydrocarbon group or a alkylene group, R ¹⁵ is a hydrogen atom, a hydrocarbon group or a group represented by R ¹⁶ ₃ Si-, R ¹⁶ is a hydrocarbon group, and 3 R ¹⁶ can be the same or different, r is an integer of 1 or more).

9. The conductive composition according to any one of 1 to 8, wherein the weight ratio of the phenolic compound to the solvent (phenolic compound [kg] / solvent [kg]) is 0.0004 or more and 0.75 or less.

A conductive laminate comprising: a substrate; and a conductive layer produced by the conductive composition according to any one of 1 to 9, which is laminated on the substrate.

11. The conductive laminate according to 10, wherein the substrate is a resin film.

A conductive article obtained by molding a conductive laminate such as 10 or 11.

A capacitor produced by using the conductive composition according to any one of 1 to 9.

A conductive film obtained by molding the conductive composition according to any one of 1 to 9.

A conductive film obtained by molding the conductive composition according to any one of 1 to 9.

A conductive article obtained by mixing the conductive composition according to any one of 1 to 9 with a substrate.

A conductive composition comprising: a π-conjugated conductive polymer; and a phenolic compound represented by the following formula (1):

[Chemical 5]

(wherein R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an aralkyl group); and the above phenolic compound and the above π-conjugated conductive polymer The weight ratio (phenolic compound / π conjugated conductive polymer) is 0.01 to 10.0; the π conjugated conductive polymer is a protonated substituted or unsubstituted polyaniline; the π conjugated system The conductive polymer is doped with an organic sulfonic acid.

According to the present invention, an electroconductive composition capable of forming a conductive molded body having a high electrical conductivity can be obtained.

The first conductive composition of the present invention comprises a solvent, a π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and an LD50 of 500 [mg/kg] or more and the following a phenolic compound represented by the formula (X).

The weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / π conjugated conductive polymer [kg]) is 0.01 to 10.0:

[Chemical 6]

(wherein R ₁ is a group having a function of supplying electrons to the benzene ring in the formula (X)).

In the present invention, the doped π-conjugated conductive polymer is dissolved in the composition in the solvent. Here, the term "dissolving" means that the π-conjugated conductive polymer is uniformly dissolved in a solvent in a molecular unit. Thereby, when the conductive composition is dried, a film having no grain boundary and a uniform π-conjugated conductive polymer can be obtained.

The so-called LD50, which is the half-lethal dose, is the case when half of the rats are killed during the test period when the chemical substance is administered to 50 rats (orally ingested). The amount of 50% of deaths in mice is expressed relative to the amount of body weight (mg/kg).

In fact, according to the data of animal experiments, a graph of dose-total mortality can be drawn to obtain a dose equivalent to 50% mortality (LD50).

The above refers to the LD50 disclosed in the Product Safety Data Sheet of Tokyo Chemical Industry Co., Ltd., and the substance not disclosed in the Product Safety Data Sheet of Tokyo Chemical Industry Co., Ltd. can be measured by the above measurement method.

The phenolic compound has an LD50 of 500 [mg/kg] or more. The LD50 is, for example, 30,000 [mg/kg] or less.

The group having a function of supplying electrons has a function of supplying electrons to the benzene ring in the formula (X) and increasing the electron density in the benzene ring. For example, a hydrocarbon group such as an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or an aralkyl group; an alkoxy group such as a methoxy group, an ethoxy group or a propoxy group; and an aryloxy group such as a phenoxy group may, for example, be mentioned.

Here, the phenolic compound represented by the formula (X) has an LD50 of 500 [mg/kg] or more. For example, if the LD50 is a value of 500 [mg/kg] or more and its LD50 value, for example, the LD50 value of 3-methoxyphenol is 597, and the LD50 value of 4-methoxyphenol is 1600, the third pent. The LD50 value of the phenol is 1830, and the LD50 of 3-phenoxyphenol is 5,000.

The second conductive composition of the present invention is produced by using at least the following (a) to (c) as raw materials.

The weight ratio of the following phenolic compound (c) to the following π-conjugated conductive polymer (b) (phenolic compound [kg] / π conjugated conductive polymer [kg]) is 0.01 to 10.0:

(a) a solvent;

(b) a π-conjugated conductive polymer doped with a dopant dissolved in the solvent;

(c) a phenolic compound having an LD50 of 500 [mg/kg] or more and represented by the following formula (X):

[Chemistry 7]

(wherein R ₁ is a group having a function of providing an electron to the benzene ring in the formula (X)).

The third conductive composition of the present invention comprises a solvent, a π-conjugated conductive polymer doped with a dopant dissolved in the solvent, and a phenolic compound represented by the following formula (2).

The weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / π conjugated conductive polymer [kg]) is 0.01 to 10.0:

[化8]

(wherein R ₂ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an aralkyl group).

The fourth conductive composition of the present invention is produced by using at least the following (a) to (c) as raw materials.

The weight ratio of the following phenolic compound (c) to the following π-conjugated conductive polymer (b) (phenolic compound [kg] / π conjugated conductive polymer [kg]) is 0.01 to 10.0:

(a) a solvent;

(b) a π-conjugated conductive polymer doped with a dopant dissolved in the solvent;

(c) a phenolic compound represented by the following formula (2):

[Chemistry 9]

(wherein R ₂ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an aralkyl group).

The LD50 of the phenolic compound (c) in the third and fourth conductive compositions is preferably 500 [mg/kg] or more. The LD50 is, for example, 30,000 [mg/kg] or less.

The fifth conductive composition of the present invention is characterized by comprising a phenolic compound represented by the following formula (1) and a π-conjugated conductive polymer.

The weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound/π-conjugated conductive polymer) is 0.01 to 10.0, and the π-conjugated conductive polymer is protonated. The substituted or unsubstituted polyaniline, the above π-conjugated conductive polymer is doped with an organic sulfonic acid:

[化10]

(wherein R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an aralkyl group).

By using the above phenolic compound, a conductive composition having a higher conductivity can be obtained. Further, the above compounds are non-toxic and odorless. Therefore, unlike the m-cresol or the like, the above phenolic compound can be suitably used for industrial production of a conductive composition.

R R of the above formula (1) of, and (2) of _2, as the alkyl group of 1 to 20 carbon atoms, can include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Base, third butyl, etc.

The alkenyl group may be one having an unsaturated bond in the molecule of the above alkyl group.

Examples of the cycloalkyl group include cyclopentane and cyclohexane.

Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the alkylaryl group and the aralkyl group include a group obtained by combining the above alkyl group and an aryl group.

Among these groups, a methyl group or an ethyl group is preferred.

The substitution position of -R ₁ in the formula (X), -OR in the formula (1), and -OR _{2 in} the formula (2) is preferably a meta position or a para position with respect to the phenolic hydroxyl group. Thereby, the steric hindrance of the phenolic hydroxyl group can be lowered, and a composition having higher conductivity can be obtained.

The first to fifth conductive compositions are preferably a weight ratio of the phenolic compound to the solvent (phenolic compound [kg] / solvent [kg]) of 0.0004 or more and 0.75 or less. More preferably, it is 0.002 or more and 0.45 or less.

The π-conjugated conductive polymer contained in the first to fifth conductive compositions of the present invention preferably has a weight average molecular weight of 1,000 or more, more preferably 1,000 to 1,000,000.

Specific examples of the π-conjugated conductive polymer include substituted or unsubstituted polyaniline, polypyrrole, polythiophene, polyparaphenylene, polyparaphenylene acetylene, and the like. .

The π-conjugated conductive polymer is doped with a dopant as an electron-accepting substance such as Bronsted acid or Lewis acid.

Here, regarding the degree of doping, there is a doping ratio. The doping ratio is usually defined by (the number of moles of dopant molecules doped in the conductive polymer) / (monomer unit of the conductive polymer). When the doped π-conjugated conductive polymer is a polyaniline composite, the doping ratio a of the dopant is 0.5, which means that one molecule is doped with respect to two molecules of nitrogen. Preferably, the dopant has a conductivity which is highest near the value and the value.

Here, in the case where the π-conjugated conductive polymer contains a nitrogen atom and the dopant is a sulfonic acid, it is preferred that the composition of the present invention satisfies the formula (XXX):

0.2≦S ₁ /N ₁ ≦0.7...(XXX)

(S ₁ by the above-described dopant is contained in the composition and doping of the π-conjugated system of the number of moles of sulfur atoms in total conductive polymer, N ₁ is contained in the composition by the above-described The total number of moles of nitrogen atoms of the π-conjugated conductive polymer doped with a dopant.

Further, the molded body of the π-conjugated conductive polymer doped with a dopant preferably has a conductivity of 0.01 S/cm or more. The conductivity is measured by a four-terminal method. Here, the shaped body can be obtained in the following manner.

The "π-conjugated conductive polymer 500 mg doped with a dopant" was dissolved in 10 g of toluene to prepare a solution for measuring conductivity. As shown in FIG. 1, 1 ml of the conductivity measurement solution was applied by patterning the upper surface of the glass substrate 1 on which the indium tin oxide (ITO, Indium-Tin Oxide) electrode 2 was formed. Specifically, the coating is carried out by a spin coating method.

Here, the coating by the spin coating method was carried out under a nitrogen atmosphere. Further, the glass substrate rotation time after the solution for measuring conductivity was dropped onto the glass substrate by the spin coating method was 15 seconds. Further, the glass substrate rotation speed of the spin coating method was 500 rpm.

Thereafter, the glass substrate is dried to form a π-conjugated polymer film. Here, the drying is carried out under a nitrogen atmosphere. Also, the drying time was 5 minutes. Further, the drying temperature was 80 °C.

The molding system herein refers to a molded body of a π-conjugated conductive polymer formed on a glass substrate. Further, the electrical conductivity can be obtained, for example, in the following manner.

After drying the π-conjugated polymer film, as shown in FIG. 2, the portion of the π-conjugated polymer film 3 covering the terminals of the ITO electrode was cut in a nitrogen atmosphere, and the terminals of the ITO electrode were exposed to the surface. Conductivity was measured by a four-terminal method using a terminal of an ITO electrode exposed on the surface using a resistivity meter manufactured by Mitsubishi Chemical Corporation.

In the present invention, the doped π-conjugated conductive polymer is preferably a protonated substituted or unsubstituted polyaniline, a protonated substituted or unsubstituted polypyrrole, or a Particularly preferred of the protonated substituted or unsubstituted polythiophenes is a protonated substituted or unsubstituted polyaniline.

When the π-conjugated conductive polymer is polyaniline, the weight average molecular weight of the polyaniline is preferably 20,000 or more, more preferably 50,000 or more. If the weight average molecular weight of the polyaniline is less than 20,000, the strength or elongation of the conductive article obtained from the composition is lowered.

Further, the molecular weight distribution is, for example, 1.5 to 10.0 or less. From the viewpoint of electrical conductivity, it is preferred that the molecular weight distribution is small, but from the viewpoint of solubility and formability in a solvent, it is also preferable that the molecular weight distribution is wide.

The above molecular weight and molecular weight distribution can be measured by gel permeation chromatography (GPC, Gel Permeation Chromatography).

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 or an octyl group; an alkoxy group such as a methoxy group or a phenoxy group; an aryloxy group _; A halogen-containing hydrocarbon group or the like.

The dopant which is suitably used in the present invention is an organic sulfonic acid, and it can be used without particular limitation in chemical structure as long as it has sufficient acidity to cause a π-conjugated conductive polymer to generate a carrier. Examples thereof include alkylsulfonic acids such as methanesulfonic acid and ethanesulfonic acid, aromatic sulfonic acids such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid and isopropylnaphthalenesulfonic acid, and succinic acidsulfonic acids. It may also be a salt of such an acid (sodium salt, etc.).

It is known that these dopants control the conductivity of the π-conjugated conductive polymer or the solubility in a solvent by changing the structure thereof (Japanese Patent No. 3384566). In the present invention, the most suitable dopant can be selected according to the required characteristics of various uses.

It is preferred that the above π-conjugated conductive polymer is doped with succinic acid represented by the following (XX): M(O ₃ SCH(CH ₂ COOR ¹² )COOR ¹³ ) _m (XX) (formula In XX), M is a hydrogen atom, an organic radical or an inorganic radical, m is a valence of M, and R ¹² and R ¹³ are each independently a hydrocarbon group or a group represented by -(R ¹⁴ O) _r -R ¹⁵ , R ¹⁴ is a hydrocarbon group or a alkylene group, R ¹⁵ is a hydrogen atom, a hydrocarbon group or a group represented by R ¹⁶ ₃ Si-, and R ¹⁶ is a hydrocarbon group, and three R ^{16 's may} be the same or different, and r is an integer of 1 or more. ).

In the conductive composition of the present invention, the weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound/π-conjugated conductive polymer) is 0.01 to 10.0, that is, 0.01 or more and 10.0 or less. . When the ratio is less than 0.01, there is a case where the effect obtained by adding a phenolic compound is not sufficiently exhibited. Further, when it exceeds 10.0, the strength of the film obtained from the composition may be lowered. If it is within this range, the composition ratio can be arbitrarily set according to the characteristics required for various uses, and from the viewpoint of balance between conductivity and film strength, it is preferably from 0.05 to 5.0.

In the conductive composition of the present invention, the weight ratio of the phenolic compound to the π-conjugated conductive polymer is, for example, 2.5 or more and 5.0 or less, and 2.5 or more and 4.0 or less.

The composition of the present invention further contains a solvent in addition to the above phenolic compound and the π-conjugated conductive polymer. The solvent may be either an inorganic solvent or an organic solvent, and is preferably an organic solvent. By containing an organic solvent, for example, a coating material for forming a conductive film can be obtained.

The organic solvent may be an organic solvent (water-immiscible organic solvent) which is not substantially mixed with water, or a water-soluble organic solvent.

Examples of the water-immiscible organic solvent include hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and tetralin, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, and tetrachloroethane. A halogen-containing solvent, an ester solvent such as ethyl acetate, or the like. Among these solvents, toluene, xylene, chloroform, trichloroethane, and ethyl acetate are preferred in terms of excellent solubility of the doped polyaniline.

Examples of the water-soluble organic solvent include alcohols, ketones such as acetone and methyl ethyl ketone, tetrahydrofuran, and A polar ether such as an alkane or an aprotic polar solvent such as N-methylpyrrolidone.

In the organic solvent, a mixed organic solvent of a water-immiscible organic solvent and a water-soluble organic solvent is preferably used in a mass ratio of from 99 to 50:1 to 50. Thereby, when the composition of the present invention is stored, the generation of a gel or the like can be prevented.

As the water-immiscible organic solvent in which the organic solvent is mixed, a low polar organic solvent can be used. For example, toluene or chloroform is preferred. Further, as the water-soluble organic solvent in which the organic solvent is mixed, a highly polar organic solvent can be used. For example, methanol, ethanol, isopropanol, 2-methoxyethanol, 2-ethoxyethanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran or diethyl ether is preferred.

The proportion of the π-conjugated conductive polymer in the organic solvent depends on the kind of the organic solvent, and is usually 900 g/L or less, preferably 0.01 to 300 g/L or less. When the content of the π-conjugated conductive polymer is too large, the solution state cannot be maintained, and it is difficult to perform the operation for molding the molded body, thereby impairing the uniformity of the molded body, and further causing electrical properties, mechanical strength, and transparency of the molded body. Reduced sex. On the other hand, when the content of the π-conjugated conductive polymer is too small, it is possible to produce only a very thin film when the film is formed by the following method, and it is difficult to produce a uniform conductive film.

In the composition of the present invention, the π-conjugated conductive polymer, the phenolic compound, and the solvent may be contained, for example, in an amount of 1% by weight or more, 15% by weight or more, 45% by weight or more, or 100% by weight.

In addition to these components, other resins, inorganic materials, hardeners, plasticizers and the like may be contained in the composition of the present invention within a range not impairing the effects of the present invention.

The other resin is added, for example, in the form of a binder base material, a plasticizer, a matrix substrate, etc., and specific examples thereof include polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrene, and poly Ester, polyamine, polyacetal, polyethylene terephthalate, polycarbonate, polyethylene glycol, polyethylene oxide, polyacrylic acid, polyacrylate, polymethacrylate, polyvinyl alcohol, and the like. Preferred are chlorinated polyolefins.

Further, a thermosetting resin precursor such as an epoxy resin, a urethane resin or a phenol resin may be used instead of or in combination with a resin.

The inorganic material is added for the purpose of, for example, strength, surface hardness, dimensional stability, and other mechanical properties. Specific examples thereof include silica, titania, and alumina. )Wait.

The hardening agent is added for the purpose of, for example, strength, surface hardness, dimensional stability, and other mechanical properties. Specific examples thereof include a thermosetting agent such as a phenol resin, and an acryl-based monomer and photopolymerization. A light curing agent or the like formed by a sex initiator.

The plasticizer is added to improve mechanical properties such as tensile strength and bending strength, and specific examples thereof include phthalic acid esters and phosphate esters.

The compositions of the present invention can be prepared by known methods, for example, by the methods disclosed in WO 05/052058.

A conductive molded body can be obtained from the composition of the present invention.

For example, the composition of the present invention can be applied to a substrate having a desired shape of a glass or a resin film, a sheet, a nonwoven fabric or the like, and the solvent can be removed, whereby a conductive laminate having a conductive film can be produced (surface conductivity) article).

For example, the conductive laminate of the present invention can be processed into a desired shape by a known method such as vacuum molding or pressure forming to obtain a conductive article. From the viewpoint of molding, the substrate is preferably a resin film or sheet.

As a method of coating the composition on the substrate, a casting method, a spray method, a dip coating method, a doctor blade method, a bar coating method, a spin coating method, an electrospinning method, a screen printing method, a gravure printing method, or the like can be used. The general method.

When the coating film is dried, the coating film may be heated depending on the type of the solvent. For example, heating is carried out at a temperature of 250 ° C or lower, preferably 50 to 200 ° C under air flow, and heating is carried out under reduced pressure as necessary. The heating temperature and the heating time are not particularly limited, and may be appropriately selected depending on the materials to be used.

Further, for example, a conductive film can be produced by removing a solvent from the composition of the present invention. In the case where the formed body 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 an advantage that it is less likely to cause cracks during film formation and that electrical characteristics are uniform.

Further, the composition of the present invention may be mixed with a substrate to form a conductive article. Examples of the substrate include polyolefins such as polyethylene and polypropylene, chlorinated polyolefins, polystyrene, polyester, polyamine, polyacetal, polycarbonate, polyethylene glycol, and polyethylene oxide. A thermoplastic resin such as polyacrylic acid, polyacrylate, polymethacrylate or polyvinyl alcohol, or a thermosetting resin such as an epoxy resin, a phenol resin or a urethane resin.

Further, the composition of the present invention can also be formed into a self-supporting molded body free from a substrate. In the case of forming a self-supporting molded body, it is preferred that a molded body having a desired mechanical strength can be obtained if the composition contains the above other resin.

Example

Manufacturing example 1

[Manufacture of polyaniline composite 1]

1.8 g of AOT (sodium diisooctyl sulfosuccinate) was dissolved in 50 mL of toluene, and the solution was poured into a 500 mL separable flask placed under a nitrogen stream, and 1.8 mL of aniline was further added to the solution. Thereafter, 150 mL of 1 N hydrochloric acid was added to the solution, and the temperature of the solution was cooled to 5 °C.

When the internal temperature of the solution reached 5 ° C, a solution prepared by dissolving 3.6 g of ammonium persulfate in 50 mL of 1 N hydrochloric acid was added dropwise over 2 hours using a dropping funnel. 18 hours after the start of the dropwise addition, the reaction was carried out while maintaining the internal temperature of the solution at 5 °C. Thereafter, 125 mL of toluene was added, and the reaction temperature was raised to 25 ° C to maintain the reaction for 4 hours.

Thereafter, the liquid phase side separated into two phases by standing was separated, and the toluene phase side was washed twice with 50 mL of ion-exchanged water and once with 1 mL of hydrochloric acid 50 mL to obtain polyaniline. Complex (protonated polyaniline) toluene solution.

The insoluble matter contained in the composite solution was removed by #5C filter paper, and the toluene solution of the polyaniline composite was recovered. The solution was transferred to an evaporator, heated in a hot water bath at 60 ° C, and depressurized, whereby the volatile component was evaporated and evaporated to obtain a 1.25 g polyaniline complex.

Manufacturing Example 2

[Manufacture of polyaniline composite 2]

(1) Synthesis of sodium 3,4-bis[(2-ethylhexyl)oxycarbonyl]cyclohexanesulfonate

Under a stream of argon, 80 g of 4-cyclohexene-1,2-dicarboxylic acid di(2-ethylhexyl) ester (manufactured by Tokyo Chemical Industry Co., Ltd.) and 900 mL of isopropyl alcohol were added, and sodium hydrogen sulfite was added (and Manufactured by Pure Chemicals) 42.3 g of water 660 mL solution. The solution was heated to reflux temperature and stirred at 80-83 ° C for 16 hours. In the meantime, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) 1.66 was added every hour after 1 to 5 hours from the start of the reflux, and then after 9 hours and 10 hours. g. After cooling the reaction solution to room temperature, it was concentrated under reduced pressure. The concentrated residue was dissolved in 1 L of an ethyl acetate/hexane mixed solution, and 250 g of silica gel was added thereto for stirring, and the solution was separated by filtration.

Further, extraction was carried out twice with a solution of 1 L of ethyl acetate/hexane, and the filtrate was combined and concentrated under reduced pressure. The concentrate was purified by column chromatography (1500 g of silica gel, solvent: ethyl acetate/hexane), and the purified product was dried over anhydrous sodium sulfate. Sodium 3,4-bis[(2-ethylhexyl)oxycarbonyl]cyclohexanesulfonate (Na salt of Compound A shown by the following formula) 52.4 g:

[11]

(2) Manufacture of polyaniline composites

Using 2.0 g of sodium 3,4-bis[(2-ethylhexyl)oxycarbonyl]cyclohexanesulfonate synthesized in the above (1) in place of 1.8 g of AOT in Production Example 1, in addition to In the same operation and procedure as in Production Example 1, 1.32 g of a polyaniline composite was obtained.

Example 1

0.1 g of the polyaniline composite 1 obtained in Production Example 1 was redissolved in toluene to prepare a 5% by weight solution. 0.02 g of 4-methoxyphenol (LD50 = 1600 mg/kg) was added thereto, and the mixture was stirred and stirred at room temperature for 30 minutes. This solution was formed into a film by a spin coating method, formed on a ITO (Indium Tin Oxide) substrate by spin coating, and the intrinsic conductivity was measured by a four-terminal method.

Specifically, about 1 mL of this solution was applied to the upper surface of the glass substrate 1 on which the ITO electrode 2 was formed by patterning as shown in FIG. Here, the coating by a spin coating method was carried out under a nitrogen atmosphere. Further, the glass substrate rotation time after the solution was dropped onto the glass substrate by the spin coating method was set to 15 seconds. Further, the glass substrate rotation speed of the spin coating method was set to 500 rpm. Thereafter, the glass substrate is dried to form a conductive polyaniline film. Here, the drying is carried out under a nitrogen atmosphere. Further, the drying time was set to 5 minutes. Further, the drying temperature was set to 80 °C.

After drying the conductive polyaniline film, as shown in FIG. 3, the portion of the conductive polyaniline film 4 covering the terminals of the ITO electrode was cut in a nitrogen atmosphere, and the terminals of the ITO electrode were exposed to the surface. The intrinsic conductivity was measured using a terminal of the ITO electrode on the exposed surface using Loresta-GP (manufactured by Mitsubishi Chemical Corporation; a resistivity meter using a four-terminal method).

Example 2

A film was formed in the same manner as in Example 1 except that the amount of the 4-methoxyphenol added was changed to 0.4 g, and the intrinsic conductivity was measured.

Example 3

A film was formed in the same manner as in Example 1 except that the amount of the 4-methoxyphenol added was changed to 0.001 g, and the intrinsic conductivity was measured.

Example 4

A film was formed in the same manner as in Example 1 except that the amount of the 4-methoxyphenol added was changed to 1.0 g, and the intrinsic conductivity was measured.

Example 5

A film was formed in the same manner as in Example 1 except that 0.02 g of 3-methoxyphenol (LD50 = 597 mg/kg) was used instead of 4-methoxyphenol, and the intrinsic conductivity was measured.

Example 6

A film was formed in the same manner as in Example 3 except that 0.4 g of 3-methoxyphenol was used, and the intrinsic conductivity was measured.

Example 7

A film was formed in the same manner as in Example 1 except that 0.02 g of 3-phenoxyphenol (LD50 = 5000 mg/kg) was used instead of 4-methoxyphenol, and the intrinsic conductivity was measured.

Example 8

A film was formed in the same manner as in Example 5 except that 0.4 g of 3-phenoxyphenol was used, and the intrinsic conductivity was measured.

Example 9

0.1 g of the polyaniline composite 2 obtained in Production Example 2 was redissolved in toluene to prepare a 5% by weight solution. 0.02 g of 4-methoxyphenol was added thereto, and the mixture was stirred and stirred at room temperature for 30 minutes. This solution was formed into a film by a spin coating method, formed on a ITO (Indium Tin Oxide) substrate by spin coating, and the intrinsic conductivity was measured by a four-terminal method.

Comparative example 1

A film was formed in the same manner as in Example 1 except that 4-methoxyphenol was not added, and the intrinsic conductivity was measured.

Comparative example 2

A film was formed in the same manner as in Example 1 except that the amount of the 4-methoxyphenol added was changed to 0.0005 g, and the intrinsic conductivity was measured.

Comparative example 3

The film was formed in the same manner as in Example 1 except that the amount of the 4-methoxyphenol added was 2.0 g. However, the film itself was significantly brittle and the conductivity could not be measured.

Comparative example 4

A film was formed in the same manner as in Example 1 except that 0.4 g of m-cresol (LD50 = 242 mg/kg) was added instead of 4-methoxyphenol, and the intrinsic conductivity was measured.

Table 1 shows the measurement results of the compositions and intrinsic conductivity of the conductive compositions of the above Examples and Comparative Examples.

Industrial availability

The conductive composition of the present invention can be used in the fields of power electronics and optoelectronics for electrostatic and antistatic materials, transparent electrodes and conductive thin film materials, materials for electroluminescent elements, circuit materials, electromagnetic wave shielding materials, dielectrics of capacitors. Body and electrolyte, polar materials for solar cells and secondary batteries, fuel cell separator materials, etc., or electroplated primers, rust inhibitors, etc.

The embodiments and/or the embodiments of the present invention have been described in detail above, but the embodiments and/or embodiments of the present invention are susceptible to being practiced without departing from the spirit and scope of the invention. More changes. Accordingly, many such modifications are intended to be included within the scope of the present invention.

The contents of the documents described in this specification are hereby incorporated by reference in their entirety.

1. . . glass substrate

2. . . ITO electrode

3. . . Π-conjugated polymer film

4. . . Conductive polyaniline film

1 is a view showing an upper surface of a glass substrate on which an indium tin oxide (ITO) electrode is formed;

2 is a view showing an upper surface of a glass substrate on which a π-conjugated polymer film is removed and a terminal of the ITO electrode is exposed on the surface; and

Fig. 3 is a view showing the upper surface of the glass substrate on which the conductive polyaniline film is peeled off and the terminal of the ITO electrode is exposed on the surface.

Claims (14)

An electroconductive composition comprising: a solvent; a π-conjugated conductive polymer doped with a dopant dissolved in the solvent; and a phenolic compound represented by the following formula (2), wherein the LD50 is 500 [mg/kg] or more: (wherein R ₂ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group or a cycloalkyl group); and the dopant of the above π conjugated conductive polymer is selected from the group consisting of succinic sulfonic acid and alkyl sulfonic acid In the above, the weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound [kg] / π conjugated conductive polymer [kg]) is 0.01 to 10.0. The conductive composition of claim 1, wherein the doped π-conjugated conductive polymer is a protonated substituted or unsubstituted polyaniline, protonated substituted or unsubstituted Polypyrrole, or any of the protonated substituted or unsubstituted polythiophenes. The conductive composition according to claim 1 or 2, wherein the dopant of the π-conjugated conductive polymer is succinic acid represented by the following (XX): M (O ₃ SCH(CH ₂ COOR ¹² ) COOR ¹³ ) _m (XX) (In the formula (XX), M is a hydrogen atom, an organic radical or an inorganic radical, m is a valence of M, and R ¹² and R ¹³ are each independently a hydrocarbon group or a -(R ¹⁴ O a group represented by _{r -} R ¹⁵ , R ¹⁴ is a hydrocarbon group or a alkylene group, R ¹⁵ is a hydrogen atom, a hydrocarbon group or a group represented by R ¹⁶ ₃ Si-, and R ¹⁶ is a hydrocarbon group, and three R ^{16 may} be the same Alternatively, r is an integer of 1 or more). The conductive composition according to claim 1 or 2, wherein the dopant is one or more selected from the group consisting of a sodium salt of a succinic acid salt and a sodium salt of an alkylsulfonic acid. The conductive composition according to claim 1 or 2, wherein the dopant of the π-conjugated conductive polymer is sodium diisooctyl sulfosuccinate. The conductive composition according to claim 1 or 2, wherein the weight ratio of the phenolic compound to the solvent (phenolic compound [kg] / solvent [kg]) is 0.0004 or more and 0.75 or less. A conductive laminate comprising: a substrate; and a conductive layer produced by the conductive composition according to any one of claims 1 to 6, which is laminated on the substrate. The conductive laminate according to claim 7, wherein the substrate is a resin film. A conductive article obtained by molding the conductive laminate of claim 7 or 8. A capacitor manufactured by using the conductive composition according to any one of claims 1 to 6. A conductive film which is electrically conductive as claimed in any one of claims 1 to 6. The composition is formed into a composition. A conductive film obtained by molding the conductive composition according to any one of claims 1 to 6. A conductive article obtained by mixing the conductive composition according to any one of claims 1 to 6 with a substrate. A conductive composition comprising: a π-conjugated conductive polymer; and a phenolic compound represented by the following formula (1): (wherein R is an alkyl group having 1 to 20 carbon atoms, an alkenyl group or a cycloalkyl group); a weight ratio of the phenolic compound to the π-conjugated conductive polymer (phenolic compound/π-conjugated conductive) The π-conjugated conductive polymer is a protonated substituted or unsubstituted polyaniline; and the π conjugated conductive polymer is selected from the group consisting of succinic sulfonic acid And one or more dopings of alkyl sulfonic acids.