JP2000186218A - Electrically conductive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrically conductive resin composition which cures at a low temperature. SOLUTION: An electrically conductive resin composition contains a water-soluble electrically conductive polymer (a), which is doped with an external dopant, and a modified hydrophilic group-containing polyester resin (b) which is modified by a polymer of an unsaturated bond-containing compound. The proportion of the polymer of the unsaturated bond-containing compound in the hydrophilic group-containing polyester resin modified product (b) is from 0.1 to 500 wt.%. The water-soluble electrically conductive polymer (a), which is doped with an external dopant, is at a state wherein the electrical conductance is 10-6 S/cm or larger and the water solubility (25 deg.C) is 0.5 wt.% or larger. Since this electrically conductive resin composition cures at a low temperature, it may be used as base materials softened at a low temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a conductive resin composition using a water-soluble conductive polymer and a modified polyester resin containing a specific hydrophilic group as a binder. The conductive resin composition of the present invention is cured at a low temperature and has excellent adhesiveness and water resistance. Therefore, the polymer composition can be easily formed by a simple method such as spin coating, dip coating and bar coating. It can be molded into resin molded products, can be used for substrates that melt at low temperatures, and exhibits an excellent antistatic effect.

[0002]

2. Description of the Related Art Polymer films, polymer fibers, polymer resin molded products, etc. are easily charged with static electricity because they are electrical insulators, and may damage electronic components, adsorb dust, and sometimes become a source of ignition. Even so, the measures are indispensable.

Conventionally, surfactants have been mainly used as these antistatic agents. However, surfactants exhibit ionic conduction utilizing moisture in the air, and therefore have a surface resistance of 1
It is difficult to reduce the resistance to less than 0 ⁹ Ω / □, and there is a problem that the antistatic effect is almost lost under low humidity conditions. On the other hand, there is an electron conduction type antistatic agent in which a fine metal particle such as carbon black, aluminum, copper, or silver and a fine semiconductor particle such as indium tin oxide or fluorine-doped tin oxide are dispersed in a general-purpose polymer as a filler. However, these fillers have to be added in a considerable amount, increasing the addition amount causes a sudden drop in electrical resistance at a certain point, so it is difficult to adjust the electrical resistance, and fillers appear on the coating film surface. Problems are that a smooth film is not obtained, transparency is not good, and strength of a coating film is low.

On the other hand, doped polyaniline or its derivative is stable as a conductive polymer and its raw material is inexpensive, so that it is applied to film electrodes, secondary batteries, capacitors, antistatic agents, electromagnetic wave shielding materials, and the like. Is being promoted. However, polyaniline is generally insoluble and infusible, and has a drawback that it is difficult to mold and process. Therefore, it is desirable to solubilize polyaniline and make it particularly water-soluble from the viewpoint of factory equipment. Here, the present inventors have disclosed a polyaniline which is water-soluble in a highly conductive state, that is, a doped state, and a simple method for producing the polyaniline, which is disclosed in Japanese Patent Application No. Hei.
No. 147476. In this publication, sulfonated polyaniline having a specific structure doped with an external dopant (hydrochloric acid) is obtained by reacting polyaniline with chlorosulfuric acid and then subjecting the polyaniline to hydrolysis, thereby achieving both high conductivity and high water solubility. It states that it can be done.

[0005] However, sulfonated polyaniline has excellent water-solubility and thus has poor water resistance due to its properties. Although the conductive resin composition is cured to impart water resistance, high-temperature treatment is often performed to shorten the curing time. For this reason, only a substrate having excellent heat resistance can be used as a substrate using the conductive resin composition. On the other hand,
Curing by low-temperature treatment necessarily results in poor workability. Further, such a conductive resin composition is desired to have improved adhesion to a substrate to be applied.

[0006] For this reason, attempts have been made to blend various binders to solve this problem. For example, a technique using sulfonated polyaniline as an antistatic agent is described in JP-A-10-279798. The antistatic agent is used by blending with a water-soluble polymer or a water-dispersed polymer in a sulfonated polyaniline in order to improve applicability, adhesion to a substrate, strength of a coating film, and water resistance. I can do it. However, even when a water-soluble polymer such as polyethylene glycol, polyvinyl alcohol, polyacrylamide or polyacrylic acid is used as a binder, when cured at a low temperature, the obtained coating film has a water resistance and Adhesion is not enough. Also,
The same applies to the case where an aqueous dispersion polymer is used. Although a method of insolubilizing the antistatic agent and improving the water resistance is also disclosed, the operation may be complicated and cost may be increased.

JP-A-9-279025 discloses a sulfonated polyaniline containing an alkoxy group-substituted aminobenzenesulfonic acid as a main component and a sulfonic acid group and / or
Alternatively, there is disclosed a conductive composition comprising a water-soluble or water-dispersible copolymerized polyester to which an alkali metal base is bonded, and a nonionic surfactant. However, only by using the water-dispersible copolymerized polyester described in the publication, even if the composition disclosed in the publication is prepared, the obtained coating film still has insufficient water resistance and adhesion to the substrate. .

Further, JP-A-10-119444 describes an antistatic coating film characterized by providing a protective layer or a layer having another function together with an antistatic layer containing an organic conductive material. I have. Since this technique mainly aims to obtain a useful antistatic coating film on a thermal transfer sheet, it is necessary to further form a heat-resistant lubricating layer after forming an antistatic layer on a substrate. Therefore, there have been problems such as complicated operation and increased cost.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a conductive resin composition which can be cured even at a low temperature, and which has excellent adhesion to a substrate and excellent water resistance. is there.

[0010]

The present inventors have conducted intensive studies on various water-soluble conductive polymers and binders, and have found that a water-soluble conductive polymer having a specific structure and a modified polyester resin containing a specific hydrophilic group are obtained. It has been found that a conductive resin composition containing as a binder, which is cured at a lower temperature than conventional, has excellent workability, and has excellent adhesion and water resistance, and can be applied to a substrate which melts at a low temperature. The present invention has been completed.

The above objects are achieved by the following (1) to (5).

(1) Contains a water-soluble conductive polymer (a) doped with an external dopant and a modified hydrophilic group-containing polyester resin (b) modified with a polymer of a compound having an unsaturated bond. Conductive resin composition characterized by performing.

(2) The ratio of the polymer of the compound having an unsaturated bond in the modified hydrophilic group-containing polyester resin (b) is 0.1 to 500% by weight. 3. The conductive resin composition according to item 1.

(3) The modified polyester resin contains a hydrophilic component such as polyethylene glycol, a hydroxyl group, a carboxyl group, a carboxylic acid group, a sulfonic acid group, a sulfate ester salt, a phosphate ester salt, etc. in the molecule. The conductive resin composition according to the above (1), which is characterized in that:

(4) The water-soluble conductive polymer (a)
Has an average of 0.1 to 4 SO ₃ M per aromatic ring in the polyaniline skeleton (where M is a hydrogen atom,
It is at least one selected from the group consisting of an alkali metal atom, an alkaline earth metal atom and an ammonium group. ) And on average from 0 to 3.9 R
(Where R is a hydrogen atom, a halogen atom, a carbon atom 1
An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, a carboxyl group, and an ester residue having 1 to 1 carbon atoms. It is at least one member selected from the group consisting of 20 carboxylic acid ester groups, nitro groups and cyano groups. However, the sum of SO ₃ M and R is 4. (1) to (3), wherein the water-soluble conductive polyaniline is substituted with 0.025 to 1 of nitrogen atoms in the main skeleton and doped with an external dopant. The conductive resin composition according to any one of the above.

(5) The water-soluble conductive polymer (a)
^Has a solubility in water (25 ° C.) of 0.5% by weight or more in a state where the electric conductivity is 10 ⁻⁶ S / cm or more;
The conductive resin composition according to any one of (1) to (3), wherein the conductive resin composition is a water-soluble conductive polymer that is doped with an external dopant.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The conductive resin composition of the present invention comprises a water-soluble conductive polymer (a) doped with an external dopant and a hydrophilic group modified by a polymer of a compound having an unsaturated bond. Containing modified polyester resin (b)
And a conductive resin composition comprising: By blending a modified hydrophilic polyester resin (b) modified with a polymer of a compound having an unsaturated bond as a binder, the resulting conductive resin composition is compatible with the water-soluble conductive polymer (a). Mix well with solubility
In addition, it cures at a low temperature and has excellent adhesion to the base, and additionally has excellent water resistance of the coating film. In particular, since the curing action is quickly performed even at a low temperature, the conductive resin composition can be applied to a member that could not be used as a base material because of its inferior heat resistance. It is possible to provide prevention. The conductive resin composition of the present invention is insoluble after curing and has excellent water resistance while maintaining good operability due to the conductive resin being aqueous. Moreover, if other crosslinking agents are blended, the range of types and blending amounts is limited in terms of compatibility with the water-soluble conductive polymer (a) and the like, but according to the present invention,
By blending the modified polyester resin containing a specific hydrophilic group (b), a conductive resin composition having excellent low-temperature curability and excellent in water resistance, mechanical strength and antistatic property can be obtained. is there. Hereinafter, the present invention will be described in detail.

(1) Water-soluble conductive polymer (a) The water-soluble conductive polymer (a) used in the present invention has a solubility in water of at least 0.01%, preferably 0.5%.
It is the above.

The water-soluble conductive polymer (a) used in the conductive resin composition of the present invention includes water-soluble conductive polyaniline, water-soluble conductive polypyrrole, water-soluble conductive polythiophene, and water-soluble conductive polyparaphenylene. And water-soluble conductive polyparaphenylene vinylene. In the conductive resin composition of the present invention, one kind of these water-soluble conductive polymers may be used alone, or two or more kinds may be used in combination.

The water-soluble conductive polymer (a) used in the present invention includes the above-mentioned water-soluble conductive polymer (a).
The external doping type is preferable to the self-doping type. This is because the water solubility is improved. Among them, the externally doped water-soluble conductive polyaniline is most preferably used from the viewpoint of stability in air.

As the externally doped water-soluble conductive polyaniline, the polyaniline skeleton has an average of 0.1 to 4 SO ₃ M per aromatic ring and an average of 0 to 3 SO ₃ M. It is substituted with 9 Rs (provided that the total of SO ₃ M and R is 4), and the nitrogen atom in the main skeleton (excluding the nitrogen atom in the substituent) is 0.025 to
One is doped with an external dopant.

In the water-soluble conductive polyaniline, M in SO ₃ M represents a hydrogen atom, an alkali metal (eg, sodium, potassium, rubidium, etc.), or an alkaline earth metal (eg, calcium, magnesium, etc.). And an ammonium group, preferably a hydrogen atom.

R is a hydrogen atom, a halogen atom, preferably a chlorine atom, a fluorine atom and a bromine atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, and 1 to 20 carbon atoms, preferably An alkoxy group having 1 to 8, an alkylthio group having 1 to 20, preferably 1 to 8 carbon atoms,
The alkylamino group, carboxyl group, or ester residue having 1 to 20, preferably 1 to 8 carbon atoms has 1 carbon atom.
And at least one selected from the group consisting of carboxylic acid ester groups, nitro groups and cyano groups of from 1 to 20, preferably 1 to 8. Of these, electron-donating groups such as a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, and an alkylamino group are preferred.

Also, SO ₃ M is preferably 0.5 to 1.5 on average, and R is preferably 2.5 to 3.5 on average. However, the sum of SO ₃ M and R is 4.

Furthermore, 0.025 to 1, preferably 0.1 to 1, per nitrogen atom in the main skeleton of the polyaniline.
0.5 are doped with external dopants. This is because if doped in this range, the conductivity is excellent.

When the water-soluble conductive polyaniline used in the conductive resin composition of the present invention is represented by a structural formula, it has a repeating unit represented by the general formula (1) as an essential repeating unit, and further, if necessary, a compound represented by the formula It has a repeating unit represented by (2) and / or the formula (3) or another repeating unit.

[0027]

Embedded image

Wherein M and R are as described above, p is 0.1 to 4, and q is 0 to 3.9 (provided that
p + q = 4), X is an anion of a protonic acid as a dopant, and n is a valency of the anion, usually 1 to
Trivalent, preferably 1-2. ]

[0029]

Embedded image

[0030]

Embedded image

Here, as the anion of the protonic acid,
Chloride ion, bromide ion, iodine ion, nitrate ion, sulfate ion, phosphate ion, borofluoride ion, perchlorate ion, thiocyanate ion, acetate ion, propionate ion, p-toluenesulfonic acid ion, trifluoroacetate ion And a trivalent anion such as trifluoromethanesulfonic acid ion, and preferably a monovalent anion.

The degree of polymerization of the water-soluble conductive polyaniline used in the conductive resin composition of the present invention is 2 to 10,000.
It is preferably 0, particularly preferably 20 to 1,000. If the degree of polymerization is 2 or less, conductivity cannot be obtained, and if it exceeds 10,000, solubility may not be obtained.

According to the results of elemental analysis, the water-soluble conductive polyaniline obtained as a typical example has a nitrogen / sulfur ratio of 4/4 to 4/3 and a sulfonic acid group of 3 to 4 aromatic rings. ４4 are introduced. Also, 50-1
This is an externally doped polyaniline which is doped with chloride ions at a doping rate of 00% and is different from the self-doped polyaniline as disclosed in WO 91-06887.

In the conductive resin composition of the present invention, the water-soluble
The preferred use of conductive polyaniline is conductive,
In other words, it shows high water solubility when doped.
You. That is, -SO introduced into the polyaniline chain_ThreeH group
Proton is not used for self-doping and is free
Because it can be dissociated in water because it exists in water. this thing
Is proved by the following facts. First of all
In the IR spectrum, a self-doped sulfone
Absorption that polyaniline bromide does not have, namely -SO _ThreeH group
2500 to 3700 cm based on -OH stretching vibration^-1Attached
A close broad absorption is observed. Second, with alkali
Following changes in the visible absorption spectrum while neutralizing
And visible absorption spectrum as long as alkali is not added
No change is seen, change starts from a certain point,
The end is a constant spectrum. This is initially-
SO_ThreeOnly neutralization of the H group occurs, followed by undoping.
It indicates that you are sick. Third, the neutralization titration curve is
-SO_ThreeH-group neutralization and undoping
Indicate the end point and then estimate -SO_ThreeNumber of H groups and
And doping rates are within the range of theoretical expectations.

(2) Method for producing water-soluble conductive polymer (a) As the water-soluble conductive polymer (a) used in the present invention,
The method for producing the water-soluble conductive polyaniline will be described.

First, polyaniline is stirred and dispersed in an organic solvent, and chlorosulfuric acid is added thereto while heating, whereby the aromatic ring in the polyaniline skeleton is chlorosulfated, and the obtained chlorosulfonylpolyaniline is hydrolyzed in water. As a result, a water-soluble and conductive sulfonated polyaniline can be obtained.

As the raw material polyaniline, any of a doped state (emeraldine salt) and a undoped state (emeraldine base) may be used, and the dopant of the emeraldine salt may be any as long as it is a protonic acid.
Hydrochloric acid, sulfuric acid, nitric acid, borofluoric acid, perchloric acid, amidosulfuric acid, p-toluenesulfonic acid, acetic acid, propionic acid and the like can be used. However, it is preferable to use a doped state (emeraldine salt) because a dedoping step is not required. In each of the above cases, most of the external dopant is hydrochloric acid generated by hydrolysis of chlorosulfonyl group, but part of the external dopant contains sulfuric acid generated by hydrolysis of raw material polyaniline dopant or excess chlorosulfuric acid. There is also. This is thought to be due to the fact that ion exchange occurs because hydrochloric acid is the strongest acid and has a high proton supply capacity. On the other hand, self-doping does not occur because benzenesulfonic acid is a weak acid compared to hydrochloric acid.

As the raw material polyaniline and its derivative, aniline and o- or m-substituted aniline can be used by electrochemically or chemically oxidatively polymerizing it. Since the conductivity of the sulfonated polyaniline is also affected, it is preferable to use a highly conductive polyaniline as much as possible, and an unsubstituted polyaniline of the emeraldine salt type is particularly preferable. The emeraldine salt type polyaniline has, for example, a basic skeleton in which a reduced unit (phenylenediamine skeleton) and an oxidized unit (quinone imine skeleton) represented by the general formula (4) are present in a ratio of 1: 1 as a repeating unit. A material obtained by doping the emeraldine-type polyaniline characterized by the above with a protonic acid is preferable.

[0039]

Embedded image

In general, there are two methods for producing emeraldine salt type polyaniline, an electrochemical oxidative polymerization method and a chemical oxidative polymerization method using an oxidizing agent. Chemical oxidative polymerization using is preferred. The chemical oxidative polymerization of polyaniline is carried out by adding an oxidizing agent to an acidic or basic solution of aniline and its derivative and stirring the solution.

As the oxidizing agent, any oxidizing agent capable of oxidizing aniline may be used.
Persulfuric acids such as persulfuric acid, sodium persulfate and potassium persulfate; hydrogen peroxide; ferric chloride; and the like are particularly preferred. Persulfuric acids represented by ammonium persulfate are preferred, and 0.1 to 1 mol of monomer. ~ 5 mol is good, especially 0.5
~ 1 mol is preferred.

Examples of the polymerization solvent include water, methanol, ethanol, isopropanol, acetonitrile, dimethylformamide, acetone, 2-butanone, dimethylacetamide, etc., and water and methanol are particularly preferred.

The reaction temperature of the polymerization is preferably between -15 and 70 ° C, particularly preferably between -10 and 20 ° C. If the temperature is outside the above temperature range, the conductivity tends to decrease.

The amount of chlorosulfuric acid charged to the sulfonation reaction of the polyaniline in the step of producing the water-soluble conductive polyaniline used in the conductive resin composition of the present invention is 0.5 to 10 times the amount of the aromatic ring of the polyaniline. Is good,
Preferably, it is 0.5 to 3 times. For example, when the reaction is performed at less than 0.5 times, only one or less sulfone group is introduced into two aromatic rings, and the solubility in water is reduced. When the reaction is performed more than three times, the sulfone group is excessively introduced, and the solubility is improved, but the conductivity tends to decrease.

The solvent used for the reaction may be any solvent that does not react with chlorosulfuric acid, such as carbon disulfide, carbon tetrachloride, 1,1,2,2-tetrachloroethane, 1,2- Examples thereof include dichloroethane, chloroform, and dichloromethane. In particular, 1,2-dichloroethane and 1,1,2,2-tetrachloroethane are preferable because of good compatibility with chlorosulfuric acid. The charged amount of the solvent and the polyaniline is preferably 1 to 30% by weight, particularly preferably 2 to 10% by weight. If the amount is outside the above range, the reaction efficiency tends to decrease. The reaction temperature for sulfonation is from -20 to 20.
0 ° C. is good, preferably 20 to 150 ° C., particularly 4 ° C.
The temperature is preferably from 0 to 140 ° C., and if it is outside the above range, the conductivity tends to decrease.

The amount of chlorosulfonated polyaniline charged to the aqueous solvent in the hydrolysis reaction is 0.1 to 10% by weight.
And more preferably 0.5 to 5% by weight. Outside the above range, the reaction efficiency tends to decrease. The reaction temperature at this time is preferably from 20 to 120C, more preferably from 60 to 120C. That is, when the temperature is lower than 20 ° C., the reaction efficiency tends to decrease.

The water-soluble conductive polymer (a) used in the conductive resin composition of the present invention has an electric conductivity of 10 ^-6.
Under the condition of S / cm or more, preferably 10 ^-4 S / cm or more, the solubility in water (25 ° C.) is 0.5% by weight or more, preferably 3% by weight or more.

(3) Modified polyester resin containing hydrophilic group (b) The modified polyester resin containing hydrophilic group (b) which can be contained in the conductive resin composition of the present invention is a compound having an unsaturated bond. There is no particular limitation so long as it is a modified hydrophilic group-containing polyester resin modified by the above polymer. The reason for containing a hydrophilic group is that the water-soluble conductive polymer (a) is excellent in compatibility since it is water-soluble. Here, hydrophilicity means that the solubility in water is 0.01% or more, preferably 0.5% or more. The reason why the polyester-based resin is used as the object to be modified is that the polyester-based resin has excellent compatibility with the above-mentioned water-soluble conductive polymer and also has excellent adhesion to the base material. That is, the modified hydrophilic group-containing polyester resin used in the present invention is modified by a polymer of a compound having an unsaturated bond, and the compound having a hydrophilic group-containing polyester portion and an unsaturated bond in the component. And a polymer portion of It is unclear why the modified hydrophilic resin containing a hydrophilic group-containing polyester (b) has excellent electrical conductivity, cures at a low temperature, and provides excellent adhesion and water resistance. However, the hydrophilic group-containing polyester portion is excellent in compatibility with the modified hydrophilic group-containing polyester resin (b) and excellent in adhesion to the substrate, and a compound having an unsaturated bond existing in the same composition. It is considered that the polymer portion imparts excellent water resistance, and this, combined with the improvement in the adhesion of the hydrophilic group-containing polyester portion, is considered to exert a further excellent effect.

The molecular weight of the modified hydrophilic group-containing polyester resin (b) is preferably from 2,000 to 10,000, more preferably from 3,000 to 8,000, and particularly preferably from 4,000 to 7000. If the molecular weight exceeds 10,000, the compatibility with the modified hydrophilic group-containing polyester resin (b) is poor, while if it is less than 2,000, the water resistance may be poor.

(4) Method for producing modified polyester resin containing hydrophilic group (b) The modified polyester resin containing hydrophilic group of the present invention is obtained by modifying the polyester containing hydrophilic group with a polymer of a compound having an unsaturated bond. It was done. The production method is not particularly limited, but can be prepared by the following method.

(I) Hydrophilic Group-Containing Polyester The hydrophilic group-containing polyester includes a sulfone group, a glycol, a polyethylene glycol, a hydroxyl group, a carboxyl group, a carboxylate, a sulfonate, a sulfate, and a phosphate in the molecule. There is a polyester resin containing a hydrophilic group such as a salt. The requirement that a hydrophilic group be an essential requirement
This is because the water-soluble conductive polymer (a) is water-soluble and thus has excellent compatibility in an aqueous solution state.

The polyester containing a hydrophilic group is specifically a polyester containing a hydrophilic group in a dicarboxylic acid component and / or a glycol component, and more preferably a sulfonic acid in a part of the dicarboxylic acid component and / or the glycol component. There are polyesters with attached groups and their alkali metal bases. This is because they are excellent in water solubility or water dispersibility, and also excellent in miscibility with the water-soluble conductive polymer (a). In particular, the aromatic dicarboxylic acid component containing a sulfonic acid group and its alkali metal base is used in an amount of 10 to 40 mol%, more preferably 12 to 20 mol%, based on the total acid component.
Copolymerized polyesters prepared at a molar ratio of 12 to 18 mol% are preferred. When the compounding amount of the aromatic dicarboxylic acid component containing a sulfonic acid group or the like is within this range, the compound is excellent in water solubility or water dispersibility, and excellent in compatibility with the water-soluble conductive polymer (a). This is because the modified polyester resin having a hydrophilic group is uniformly mixed in the composition. As an example of such a dicarboxylic acid, 5-sodium sulfoisophthalic acid is preferred.

Other dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, p-β-oxyethoxybenzoic acid, 2,6-naphthalenedicarboxylic acid,
4'-dicarboxydiphenyl, 4,4'-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, sebacic acid, cyclohexane-1,
4-dicarboxylic acid and the like. Terephthalic acid and isophthalic acid are preferred from the viewpoint of improving the adhesion and surface hardness of a coating film obtained by applying the conductive composition of the present invention to a substrate.

As the glycol component for preparing the copolymerized polyester, ethylene glycol is mainly used, and in addition, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, and ethylene oxide adduct of bisphenol A are also used. , Polyethylene glycol,
Polypropylene glycol, polytetramethylene glycol and the like can be used.

In addition, the copolymer component may contain a small amount of a dicarboxylic acid component or a glycol component containing an amide bond, a urethane bond, an ether bond, a carbonate bond or the like. Further, in order to improve the surface hardness of the coating film obtained by applying the obtained conductive resin composition of the present invention to a substrate, trimellitic acid, trimesic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride It is also possible to use a polycarboxy group-containing monomer such as an acid at a ratio of 5 mol% or less as a copolymerization component of the polyester. If it exceeds 5 mol%, the resulting polyester becomes thermally unstable and easily gelates, which is not preferable as a component of the conductive composition of the present invention.

The above-mentioned hydrophilic group-containing polyester can be prepared by, for example, a transesterification reaction or a polycondensation reaction using the above-mentioned dicarboxylic acid component, the above-mentioned glycol component and, if necessary, the above-mentioned polycarboxyl group-containing monomer. Is obtained. The obtained hydrophilic group-containing polyester can be used as an aqueous solution or aqueous dispersion, for example, by heating and stirring together with water.

(Ii) Compound Having an Unsaturated Bond Examples of the compound having an unsaturated bond that can be used for modifying the above-mentioned polyester containing a hydrophilic group include unsaturated carboxylic acids or their esters, vinyl esters, and compounds containing an epoxy group. , Unsaturated allyl carboxylate compounds, nitrogen-containing compounds, hydrocarbons and vinyl silane compounds.

As unsaturated carboxylic acids or esters thereof, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
Methacrylic acid, methyl methacrylate, butyl methacrylate, maleic acid, butyl maleate, octyl maleate, fumaric acid, butyl fumarate, octyl fumarate, hydroxy methacrylic acid, hydroxyethyl methacrylate, hydroxyethyl methacrylate, hydroxy acrylate There are ethyl, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, polyethylene glycol dimethacrylate, and polyethylene glycol diacrylate.

Examples of the epoxy group-containing compound include glycidyl methacrylate, glycidyl acrylate, 1-butene oxide and 2-butene oxide.

The vinyl ester includes vinyl propionate, vinyl stearate, and tertiary vinyl ester.

The unsaturated carboxylic acid amides include acrylamide, methacrylamide, methylolacrylamide, and butoxymethylolacrylamide. As unsaturated nitrile, acrylonitrile, as an allyl compound, butyl acetate, allyl glycidyl ether,
Allyl methacrylate, allyl acrylate, diallyl itaconate, nitrogen-containing compounds include vinylpyridine and vinylimidazole, and hydrocarbons include ethylene, propylene, hexene, octene, styrene, vinyltoluene, and butadiene. Further, examples of the vinylsilane compound include dimethylvinylmethoxysilane, dimethylethylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropylmethyldimethoxysilane.

In order for the modified polyester resin containing a hydrophilic group (b) of the present invention to have excellent adhesion to a substrate and water resistance, a compound having an epoxy group as a compound having an unsaturated bond is contained. Is preferred. The compounds having an unsaturated bond may be used alone or in combination of two or more.

The proportion of the polymer of the compound having an unsaturated bond in the modified hydrophilic group-containing polyester resin (b) is 0.1 to 500% by weight, preferably 1 to 20% by weight.
It is preferably 0% by weight, particularly preferably 10 to 100% by weight. This is because a conductive resin composition having excellent conductivity in the above range, excellent adhesion to a substrate, and excellent water resistance can be obtained.

(Iii) Modification Method In order to modify the hydrophilic group-containing polyester with a polymer of a compound having an unsaturated bond, a radical polymerization initiator is added to the aqueous dispersion of the hydrophilic group-containing polyester, and
The vinyl monomer is added and reacted at a temperature of ９５95 ° C. or less, more preferably 60-85 ° C. As a polymerization initiator, ammonium persulfate, potassium persulfate, or azobis-2-
When an azo compound such as methylpropionamidine hydrochloride or azoisobutyronitrile is used, the modification of the hydrophilic group-containing polyester is difficult, and a homopolymer of a vinyl compound is generated. Therefore, the reaction with an organic peroxide is preferable.

Examples of the organic peroxide include ketone peroxides such as benzoyl peroxide and methyl ethyl ketone peroxide; hydroperoxides such as t-butyl hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide. Class; t-
Peroxyesters such as butylperoxyacetate, peroxyketals such as n-butyl-4,4-bis (t-butylperoxy) valate; diacyl peroxides such as acetyl peroxide; di-isopropylperoxy Examples include peroxydicarbonates such as dicarbonate; and other organic peroxides such as acetylcyclohexylsulfonyl peroxide. One or more of these may be used in combination.

An emulsifier may be used in the polymerization reaction.
When a nonionic surfactant is used as an emulsifier, a nonionic surfactant is more effective than a nonionic surfactant.

Examples of such nonionic surfactants include:
For example, polyoxyethylene alkyl ether; polyoxyethylene alkyl aryl ether; sorbitan aliphatic ester; polyoxyethylene sorbitan aliphatic ester; aliphatic monoglyceride such as glycerol monolaurate; polyoxyethylene oxypropylene copolymer; Examples include condensation products of oxides with aliphatic amines, amides or acids.

Further, in such a polymerization reaction, known compounds such as a chain transfer agent chelating agent which can be used in emulsion polymerization can be used.

(5) Conductive Resin Composition The conductive resin composition of the present invention may contain the water-soluble conductive polymer (a) and the modified hydrophilic group-containing polyester resin (b). The compounding amount thereof is 10 to 2000 parts by weight, more preferably 50 to 1000 parts by weight, based on 100 parts by weight of the water-soluble conductive polymer (a). is there.
When the amount of the modified hydrophilic polyester resin (b) is 20
When the amount is more than 00 parts by weight, the conductivity of the water-soluble conductive polymer does not appear and the original antistatic function is not exhibited, which is not preferable.

The conductive resin composition of the present invention is usually dissolved or dispersed in a solvent and applied to a desired substrate surface.
As the solvent used here, any organic solvent can be used as long as it does not dissolve or swell the substrate (eg, a polyester film or the like). By using water, or a mixed solvent of water and an organic solvent, not only is preferable in terms of use environment, but also the antistatic property of the obtained conductive resin composition of the present invention and the base material of this conductive resin composition In some cases, the applicability of the resin is improved.

Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and isopropanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; cellosolves such as methyl cellosolve and ethyl cellosolve; methyl propylene glycol; Propylene glycols such as glycol; amides such as dimethylformamide and dimethylacetamide; N-methylpyrrolidone;
Pyrrolidones such as ethylpyrrolidone are preferably used. These organic solvents can be used by being mixed with water at an arbitrary ratio. Examples of mixing include water / methanol, water / ethanol, water / propanol, water / isopropanol, water / methyl propylene glycol, water / ethyl propylene glycol, and the like. The mixing ratio is preferably water / organic solvent = 1/10 to 10/1.

The proportion of the solvent to be used is not particularly limited, but when the water-soluble conductive polyaniline is usually used as the water-soluble conductive polymer (a), the solvent is preferably added to 100 parts by weight of the water-soluble conductive polyaniline. 1000-20,000
Parts by weight. When the amount of the solvent used is extremely large, the obtained conductive resin composition of the present invention may have poor long-term storage stability and poor wettability and coatability on the substrate surface. Therefore, pinholes are likely to occur in the coating film on the surface, and the conductivity of the coating film may be significantly reduced, that is, the antistatic property may be reduced. When the amount of the solvent used is extremely small, the solubility or dispersibility of the water-soluble conductive polyaniline in the solvent may be insufficient, and the surface of the obtained coating film may not be easily flattened.

The conductive resin composition of the present invention is excellent in coatability and spreadability, and has good surface hardness of the coating film obtained by using only the above-mentioned components. May be further used in combination. This is because application to a substrate having poor wettability becomes possible.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether and polyoxyethylene sorbitan fatty acid ester, and fluoroalkyl carboxylic acids, perfluoroalkyl carboxylic acids, and the like. Fluorinated surfactants such as perfluoroalkylbenzenesulfonic acid, perfluoroalkylquaternary ammonium, and perfluoroalkylpolyoxyethyleneethanol are used. When the water-soluble conductive polyaniline is used as the water-soluble conductive polymer (a), the amount of the surfactant is 0.001 to 1000 parts by weight based on 100 parts by weight of the water-soluble conductive polyaniline. Part or less. If the amount of the surfactant exceeds 1,000 parts by weight, the surfactant in the coat layer may be set off on the non-coated surface, which may cause a problem in secondary processing or the like.

Since the conductive resin composition of the present invention exhibits high solubility in water, it can be directly applied to a substrate from an aqueous solution of the composition alone. In order to improve the strength, water resistance, etc. of the polymer, it can be used by blending with a water-soluble polymer or an aqueous polymer emulsion (a water-dispersible polymer) as necessary. The mixing ratio is a ratio to the total amount of the water-soluble conductive polymer (a),
0.01 to 0.99, preferably 0.1 to 0.9.

Examples of the water-soluble polymer include polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, sodium polyacrylate, polyacrylic acid and poly-2-acrylamide-2.
-Homopolymers such as methylpropanesulfonic acid, sodium polystyrenesulfonic acid, polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylamine, and polyethyleneimine, and copolymers containing these components, and the like. Examples of the aqueous polymer emulsion include styrene, acrylic acid, methacrylic acid,
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, acrylic acid Aqueous polymer emulsions obtained by (co) polymerizing hydroxyl, hydroxyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, and the like are included.

[0077] The conductive resin composition of the present invention contains
May include various additives. As such an additive
The TiO_Two, SiO_Two, Kaolin, CaCO_Three, A
l_TwoO_Three, BaSO_Four, ZnO, talc, mica, composite grains
Inorganic particles such as particles; polystyrene, polyacrylate,
Or organic particles composed of cross-linked products thereof, etc.
Can be In order to further improve conductivity, oxide oxide
Powder of tin oxide, fluorine-doped tin oxide, it
Coated with inorganic particles (TiO 2_Two, BaSO _FourSuch),
Carbon such as carbon black, graphite and carbon fiber
It is also possible to add a system conductive filler or the like. Up
The content of the additive is 100% water-soluble conductive polyaniline.
Not more than 4000 parts by weight based on parts by weight
Is preferred. If it exceeds 4000, the conductive composition
May cause uneven coating due to increased viscosity.
You.

(6) Substrate As the substrate on which the conductive resin composition of the present invention is applied,
Examples include polymer films, polymer fibers, polymer resin molded products, rubber, paper, glass, and metals. A polymer film made of polyester, nylon, polypropylene, polyethylene or the like is preferable. Particularly, as the polymer film, for example, a polyester film such as polyethylene terephthalate can be used. Note that polyester films are widely used as bases for overhead projector sheets, video tapes, audio tapes, computer tapes, floppy disks, and the like. The conductive resin composition of the present invention immediately starts curing even at a low temperature. For this reason, it is characterized in that it can also be used for polyesters, polyethylenes and polypropylenes having a low softening point, which could not be used as a base material conventionally.

(7) Coating Method In order to apply the conductive resin composition of the present invention to a substrate, a method such as spin coating, bar coating, gravure coating, kiss coating, blade coating, roll coating, and dip coating is used. Can be.

Examples of the method of applying the water-soluble conductive composition of the present invention on the surface of the substrate include a gravure roll coating method, a reverse roll coating method, a knife coater method, a dip coating method, and a spin coating method.
The coating method suitable for the conductive resin composition is not particularly limited.
There are an in-line coating method in which application to a film is performed simultaneously in a film-forming process and an offline coating method in which coating is independently performed after the production of a film-forming roll. However, a preferable method can be selected according to the application, and there is no particular limitation.

The conductive resin composition of the present invention is cured at a temperature of 80 ° C. or more by using the above specific binder, and does not affect the conductivity. For this reason, although it depends on the kind of other additives to be compounded, it is usually 80 to 200 hours in a short time.
° C, more preferably 90-150 ° C, especially 9 ° C
0-120 ° C. Therefore, it can be particularly preferably used for a substrate having a low melting point, and is excellent in workability because it is cured in a short time.

(8) Use The conductive resin composition of the present invention can be used for antistatic, conductive material, semiconductor material and the like.

For antistatic purposes, a PET film (O
HP sheet, magnetic tape, floppy disk substrate, packaging, etc., semiconductor related (wafer storage box, IC magazine, carrier tape, cover tape, resist removal tape, packaging plastic bag, air cap, policy, protective gloves) , Dust-proof clothing, etc., printer related (transfer film, ink-jet image receiving paper, transport belt, charging roller, paper feed roller, transport roller, transfer roller, developing roller, supply roller, cleaning roller, fixing roller, pressure roller, discharging Rollers, etc.), abrasives, conductive paper, adhesive films (clean mats), sandblasting materials, toner binder compositions, glass packing materials, pressure-sensitive adhesives, fiber treatment agents, floppy disk bodies, displays Top coat / protective film, partition board for clean room, printing Screen mesh, shrink film, cables, glass non-woven fabric, plate making material, anti-fog heater, thermal transfer recording (image receiving) sheet, pressure-sensitive recording sheet, silver halide photographic light-sensitive material and substrate, patrone for photographic film, camera pressing plate Rubbing cloth for liquid crystal alignment film, cover lens for endoscope, protective layer for optical recording medium, carrier tape / cover tape for packaging electronic components, liquid wax, recording (image receiving) sheet for electrophotography, AV cassette housing, AV Magnetic tape back coat layer, floppy disk case, magnetic tape base material (white polyester), lithography mask, vending machine front plate, mouse trackball, footwear, heat-sensitive stencil master, CRT top coat,
Optical transmission lines, communication equipment housings, insulating rubber top coats for wires and cables, transmissive screens such as LCDs (color filters, optical compensation sheets, etc.), refrigerator housings,
Heat seal connector, artificial grass, light diffusion plate, transfer foil,
There are conductive fibers, non-woven fabrics, original plates for direct plate making, boxes for transporting glass substrates, electrostatic shoes, underground socks, fuel hoses, conductive trays, electronic component storage cases, finger cots, automobile tires, and the like.

For conductive and semiconductor materials,
Electrodes for solid electrolytic capacitors, electrodes for secondary batteries, EL elements, electrochromic elements, transparent electrodes, paints for floor walls for clean rooms, PTC thermistors, EMI applications, etc.

Further, it can be used for other rust inhibitors, corrosion inhibitors (electronic parts, dry batteries, etc.), and non-linear optical materials.

[0086]

EXAMPLES Examples and comparative examples of the present invention will be described below, but the present invention is not limited to these examples. The evaluation method used in the present invention is shown below.

(1) Electric Conductivity The electric conductivity of the water-soluble conductive polymer used in the conductive resin composition of the present invention can be determined, for example, by preparing a compressed pellet using a tablet of a sulfonated polyaniline powder. Then, it was measured by a DC four-terminal method. At this time, a constant current of 1 μA was applied to the outer two terminals from a constant current source (Kesley 220), and the potential difference between the inner two terminals was measured with a digital multimeter (Kesley 2001).

(2) Surface Resistance The surface resistance of the antistatic agent thin film of the present invention can be measured by a two-terminal method by evaporating a comb-shaped gold electrode on the thin film using a vacuum evaporation apparatus (VPC-410 manufactured by Vacuum Kiko Co., Ltd.). And measured with an insulation resistance meter (type 6517 manufactured by Kesley). The thickness of the thin film was measured using a tapping mode atomic force microscope of a scanning probe microscope (Nanoscope IIIa manufactured by Digital Instruments). The unit of the surface resistance in Table 1 is Ω / □.

(3) Evaluation of applicability The conductive resin composition of the present invention was applied to a 50 μm-thick polyester (PET) film at a predetermined thickness using a bar coater, and the presence or absence of repelling of the coated surface was evaluated. Was evaluated as follows.

A sample having no repelling and being uniformly applied was rated as ○, a portion having very small repelling was rated as Δ, and a coating solution repelled was rated as ×.

(4) Evaluation of Adhesion A cellophane tape was stuck, and it was judged whether or not it was peeled off when peeled off. ：: did not peel at all △: partially peeled ×: completely peeled (5) Evaluation of strength Judgment was made based on whether or not it was rubbed off with a nail. ：: did not peel off at all △: partially peeled off: completely peeled off (6) Evaluation of water resistance Judgment was made based on whether or not the water flowed out. ：: did not flow out at all x: even partly flowed out

(Synthesis Example 1) 28 g of aniline was added dropwise to 300 ml of a 1.2 mol / l aqueous hydrochloric acid solution with stirring.
This was cooled to 0 ° C. 30 g of ammonium persulfate was dissolved in 60 ml of ion-exchanged water and added dropwise to the above solution over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at 0 ° C. for 5 hours. The deposited green precipitate was filtered and washed with ion-exchanged water until the color of the filtrate disappeared. Further, the filtrate was washed with methanol until the color of the filtrate disappeared.

The dry weight was 12.5 g. The obtained polyaniline was molded into pellets, and the electric conductivity measured by a four-terminal method was 2.02 S / cm.

1 g of the obtained polyaniline was added to 1,1,2,2
It was dispersed in 50 ml of 2-tetrachloroethane (hereinafter, TCE) and heated to 85 ° C. 2.4 g (about 2 times mol) of chlorosulfuric acid was dissolved in 6 ml of TCE and added dropwise. After completion of the dropwise addition, the mixture was further heated and stirred at 85 ° C. for 5 hours. After cooling to room temperature, the reaction product was filtered out and washed with chloroform. After air drying, disperse in 50 ml
Heated to reflux for an hour. The resulting green solution was filtered to remove insolubles, the filtrate was concentrated with a rotary evaporator, and acetone was added to precipitate a green precipitate. The deposited precipitate was filtered and washed with acetone. Dry weight is
1.4 g.

The results of elemental analysis were as follows: H: 4.11% C: 32.86% N: 7.02%
S: 14.46% Cl: 4.57% Composition: C ₂₄ H ₃₅ N _4.4 O ₂₀ S ₄ C
l _1.1 and the S / N ratio was 0.91. If all the sulfur atoms are based on the introduced sulfone groups, it means that 9 or more sulfone groups are introduced for 10 aromatic rings of polyaniline. Assuming that all the counter ions are Cl ⁻ , the doping rate is 0.25 (50%).

The solubility in water at 25 ° C. was 8.1% by weight.

The resulting sulfonated polyaniline was formed into pellets, and the electric conductivity measured by a four-terminal method was 1.99 × 10 ⁻³ S / cm.

(Synthesis Example 2) 9 g of the sulfonated polyaniline obtained in Synthesis Example 1 was mixed with 1,2-dichloroethane (hereinafter referred to as D
CE) Dispersed in 270 ml and heated to 85 ° C. 21.8 g (about 2 moles) of chlorosulfuric acid was dissolved in 15 ml of DCE and added dropwise. 85 ° C for another 5 hours after the completion of dropping
And stirred. After cooling to room temperature, the reaction product was filtered out and washed with chloroform. 400m after air drying
The mixture was dispersed in 1 l of ion-exchanged water and heated under reflux for 4 hours. The resulting green solution was filtered to remove insolubles, the filtrate was concentrated with a rotary evaporator, and acetone was added to precipitate a green precipitate. The deposited precipitate was filtered and washed with acetone. The dry weight was 12.0 g.

The results of elemental analysis were as follows: H: 3.52% C:
39.24% N: 8.28% S: 13.78% C
l: 2.99% Composition formula: C ₂₄ H ₃₀ N _4.3 O ₁₅ S _3.2 Cl _0.7 , and S / N ratio was 0.74. Assuming that all the sulfur atoms are from the introduced sulfone groups, it means that less than three sulfone groups are introduced for every four aromatic rings of polyaniline. Assuming that all the counter ions are Cl ⁻ , the doping rate is 0.175 (35%).

The solubility in water measured at 25 ° C. was 5.0% by weight.

The obtained water-soluble conductive polymer (sulfonated polyaniline) was formed into pellets, and the electric conductivity was measured by a four-terminal method. As a result, it was 5.7 × 10 ⁻³ S / cm.

(Synthesis Example 3: Synthesis of modified polyester resin containing hydrophilic group (b)) In a four-necked flask, an aqueous dispersion of a sulfonic acid group-containing polyester resin (Pesthresin 841) was added.
5, 935 parts by weight of Takamatsu Yushi Co., Ltd.), 2 parts by weight of benzoyl peroxide, 3.5 parts by weight of polyoxyethylene alkyl ether phosphate (Plysurf A-217E, manufactured by Daiichi Kogyo Co., Ltd.) and methacrylic acid Methyl 15
After weight parts were charged and nitrogen gas was blown in for 20 minutes while stirring to perform deoxygenation, the temperature was raised to 70 ° C. Next, a vinyl monomer liquid of 39 parts by weight of methyl methacrylate and 6 parts by weight of glycidyl methacrylate was added at 75 to 80 ° C.
It was added dropwise over 50 minutes. After completion of the dropwise addition, the temperature was raised to 80 to 85 ° C., and the reaction was performed for 90 minutes. 20.5 wt% solids, p
A stable modified polyester resin (b) having an H of 4.8 (hereinafter, simply referred to as an aqueous resin dispersion) was obtained.

(Synthesis Example 4: Synthesis of modified polyester resin containing hydrophilic group (b)) In a four-necked flask, an aqueous dispersion of polyester resin containing a sulfonic acid group (Pesthresin 841) was added.
5, 905 parts by weight of Takamatsu Yushi Co., Ltd.), 2 parts by weight of benzoyl peroxide, 3.5 parts by weight of polyoxyethylene alkyl ether phosphate (Plysurf A-217E, manufactured by Dai-ichi Kogyo Co., Ltd.) and methacrylic acid Methyl 15
After weight parts were charged and nitrogen gas was blown in for 20 minutes while stirring to perform deoxygenation, the temperature was raised to 70 ° C. Next, a vinyl monomer liquid of 81 parts by weight of methyl methacrylate and 9 parts by weight of glycidyl methacrylate was added at 75 to 80 ° C and 40 to 80 ° C.
It was added dropwise over 50 minutes. After completion of the dropwise addition, the temperature was raised to 80 to 85 ° C., and the reaction was performed for 90 minutes. 23.1% by weight solids, p
A stable aqueous resin dispersion of H5.2 was obtained.

(Synthesis Example 5: Synthesis of modified polyester resin containing hydrophilic group (b)) In a four-necked flask, an aqueous dispersion of a sulfonic acid group-containing polyester resin (Pesthresin 841) was added.
5, 922 parts by weight of Takamatsu Yushi Co., Ltd.), 2 parts by weight of benzoyl peroxide, 3.5 parts by weight of polyoxyethylene alkyl ether phosphate (Plysurf A-217E, manufactured by Daiichi Kogyo Co., Ltd.) and methacrylic acid Methyl 15
After weight parts were charged and nitrogen gas was blown in for 20 minutes while stirring to perform deoxygenation, the temperature was raised to 70 ° C. Next, a vinyl monomer liquid of 50.7 parts by weight of methyl methacrylate and 7.3 parts by weight of glycidyl methacrylate was added to 75 to 80 parts by weight.
C., dropwise over 40-50 minutes. 80- after dropping
The temperature was raised to 85 ° C., and the reaction was performed for 90 minutes. 21.7 solids
A stable aqueous resin dispersion having a weight percentage of pH 4.4 was obtained.

(Example 1) The water-soluble conductive polyaniline obtained in Synthesis Example 1 and the aqueous resin dispersion obtained in Synthesis Example 3 were mixed at a weight ratio of 3:17, and a solid content of 10% was obtained. An aqueous solution was prepared. These aqueous solutions were spin-coated on a polyethylene terephthalate (PET) film to form a thin film, and the measurement items shown in Table 1 were measured. The results are shown in Table 1.

Example 2 The drying temperature in Example 1 was set to 80 ° C.
The procedure was performed in the same manner as in Example 1 except that the temperature was changed to 100 ° C.

(Example 3) The water-soluble conductive polyaniline obtained in Synthesis Example 1 and the aqueous resin dispersion obtained in Synthesis Example 4 were mixed at a weight ratio of 3:17, and a solid content of 5% was obtained. An aqueous solution was prepared. From these aqueous solutions, a thin film was formed by spin coating on a polyethylene terephthalate (PET) film, and the measurement items shown in Table 1 were measured. The results are shown in Table 1.

(Example 4) The water-soluble conductive polyaniline obtained in Synthesis Example 2 and the aqueous resin dispersion obtained in Synthesis Example 5 were mixed at a weight ratio of 3:17 to obtain a solid content of 5%. An aqueous solution was prepared. From these aqueous solutions, a thin film was formed by spin coating on a polyethylene terephthalate (PET) film, and the measurement items shown in Table 1 were measured. The results are shown in Table 1.

(Example 5) The water-soluble conductive polyaniline obtained in Synthesis Example 2 and the aqueous resin dispersion obtained in Synthesis Example 4 were mixed at a weight ratio of 3:17 to obtain a solid content of 5%. An aqueous solution was prepared. From these aqueous solutions, a thin film was formed by spin coating on a polyethylene terephthalate (PET) film, and the measurement items shown in Table 1 were measured. The results are shown in Table 1.

Comparative Example 1 The sulfonated polyaniline obtained in Synthesis Example 2 was replaced with polyacrylic acid (Aqualic HL-
580, average molecular weight 800,000, manufactured by Nippon Shokubai Co., Ltd.) so that the weight ratio of the solid content is 3:17.
An aqueous solution having a solid content of 10% by weight was prepared. The aqueous solution was spin-coated on a polyethylene terephthalate (PET) film to form a thin film. Table 1 shows the results of evaluating the performance of the same items as in Example 1.

Comparative Example 2 The weight ratio of the sulfonated polyaniline obtained in Synthesis Example 2 to the aqueous dispersion of a sulfone group-containing polyester resin (Pes resin 8415, manufactured by Takamatsu Oil & Fats Co., Ltd.) was 3:17. And solids 1
A 0% by weight aqueous solution was prepared. The aqueous solution was spin-coated on a polyethylene terephthalate (PET) film to form a thin film. Table 1 shows the results of evaluating the performance of the same items as in Example 1.

Comparative Example 3 An attempt was made to spin-coat a 5% by weight aqueous solution of the sulfonated polyaniline obtained in Synthesis Example 2 on a polyethylene terephthalate (PET) film and apply it. .

[0113]

[Table 1]

[0114]

The conductive resin composition of the present invention is a conductive resin composition using a sulfonated polyaniline which is water-soluble in a state having high conductivity, that is, a doped state, which has not been achieved conventionally. . By blending with a specific binder, it has self-crosslinking properties and can be cured in a short time even at a low temperature.

For this reason, spin coating,
A thin film can be formed on a polymer film, polymer fiber, polymer resin molded product, or the like by dip coating or bar coating, and can be cured in a short time, so that workability is excellent.

The surface resistance of this thin film is 10 ⁶ Ω / □ to 1
It can be adjusted to any value within the range of 0 ¹¹ Ω / □, and exhibits an excellent antistatic effect even under low humidity.

Since the conductive resin composition of the present invention cures at a low temperature, it can be used also for a low-temperature softening base material which could not be used conventionally.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masato Ito 1-25-25 Kannondai, Tsukuba City, Ibaraki Prefecture Inside Nippon Shokubai Co., Ltd. (72) Yoshinobu Asako 1-25-25 Kannondai, Tsukuba City, Ibaraki Prefecture 12 Nippon Shokubai Co., Ltd. XB11 XB34 YB05 YB13 YB38 ZA22 ZA44 ZB44 ZB49

Claims (5)

[Claims] 1. A water-soluble conductive polymer (a) doped with an external dopant, and a modified hydrophilic group-containing polyester resin (b) modified by a polymer of a compound having an unsaturated bond. A conductive resin composition comprising: 2. The modified polyester resin having a hydrophilic group (b), wherein the proportion of the polymer of the compound having an unsaturated bond is 0.1 to 500% by weight. Conductive resin composition. 3. The modified polyester resin containing a hydrophilic group (b) has a hydrophilicity such as polyethylene glycol, a hydroxyl group, a carboxyl group, a carboxylic acid group, a sulfonic acid group, a sulfate ester salt and a phosphate ester salt in the molecule. The conductive resin composition according to claim 1, further comprising a component. 4. The method according to claim 1, wherein the water-soluble conductive polymer (a) has a polyaniline skeleton having an aromatic ring having an average of 0.2 per aromatic ring.
Substituted with 1 to 4 SO ₃ M (where M is at least one selected from the group consisting of a hydrogen atom, an alkali metal atom, an alkaline earth metal atom and an ammonium group), and averaged From 0 to 3.9 R (where R is a hydrogen atom, a halogen atom,
An alkyl group of 0, an alkoxy group having 1 to 20 carbon atoms,
An alkylthio group having 1 to 20 carbon atoms,
It is at least one selected from the group consisting of 20 alkylamino groups, carboxyl groups, and carboxylic acid ester groups having 1 to 20 carbon atoms in ester residues, nitro groups, and cyano groups. However, the sum of SO ₃ M and R is 4. ) And a nitrogen atom 1 in the main skeleton
The conductive resin composition according to any one of claims 1 to 3, wherein 0.025 to 1 is a water-soluble conductive polyaniline doped with an external dopant. 5. The water-soluble conductive polymer (a) has a solubility in water (25 ° C.) of 0.5% by weight or more in a state where the electric conductivity is 10 ⁻⁶ S / cm or more, The conductive resin composition according to any one of claims 1 to 3, wherein the conductive resin composition is a water-soluble conductive polymer that is doped with an external dopant.