JP7382789B2 - conductive release film - Google Patents

Description

The present invention relates to a conductive polymer dispersion, a conductive film, and a method for manufacturing the same, and a conductive release film and a method for manufacturing the same.

BACKGROUND OF THE INVENTION As a technique for manufacturing electronic devices, it is required to form a conductive layer on the surface of a plastic base material. π-conjugated conductive polymers are attracting attention as materials for forming conductive layers because they have excellent conductivity and transparency.
As a method for forming a conductive layer containing a π-conjugated conductive polymer, for example, a conductive polymer dispersion in which a conductive composite containing a π-conjugated conductive polymer and a polyanion is dispersed in water is used. Examples include a method of coating on a base material and drying it (Patent Document 1).

International Publication No. 2015/108001

The surface of a plastic base material is usually hydrophobic unless it is subjected to a hydrophilic treatment. Therefore, a conductive layer formed by coating a plastic base material with an aqueous conductive polymer dispersion described in Patent Document 1 and the like tends to have low adhesion (adhesiveness) to the base material. When the plastic is a polyolefin resin, the adhesion is noticeably low.
Polyolefin resins have excellent processability, so if it is possible to form a conductive layer with excellent adhesion to the surface of polyolefin resins, it is expected that the applications of conductive plastics will further expand.
The present inventors investigated the production of a laminate in which a release layer containing a silicone compound was further laminated on the surface of a conductive layer formed on the surface of a resin base material. At this time, the conductive layer is required to have both high adhesion to the resin base material and high adhesion to the laminated release layer.

The present invention provides a conductive release film laminated in the order of film base material/conductive layer/release layer made of plastic, which has excellent adhesion to both the film base material and the release layer. Provided are a conductive polymer dispersion capable of forming a layer, a conductive film using the same, and a method for producing the same, and a conductive release film and a method for producing the same.

[1] A conductive polymer dispersion liquid containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a carboxy group-containing polyolefin resin, a polyester resin, and a dispersion medium.
[2] The conductive polymer dispersion according to [1], wherein the content of the polyester resin is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the carboxy group-containing polyolefin resin.
[3] The conductivity according to [1] or [2], wherein the dispersion medium includes an aqueous dispersion medium, and the carboxy group-containing polyolefin resin and the polyester resin are dispersed in the aqueous dispersion medium. Polymer dispersion.
[4] The conductive polymer dispersion according to any one of [1] to [3], further containing a glycidyl group-containing acrylic resin.
[5] The conductive polymer dispersion according to any one of [1] to [4], wherein the dispersion medium contains a monohydric alcohol.
[6] The conductive polymer dispersion according to [5], wherein the monohydric alcohol contains methanol.
[7] The conductive polymer dispersion according to any one of [1] to [6], further containing a highly conductive agent.
[8] The conductive polymer dispersion according to [7], wherein the high conductivity agent contains a dihydric alcohol.
[9] The conductive polymer dispersion according to [7] or [8], wherein the high conductivity agent contains propylene glycol.
[10] The conductive polymer dispersion according to any one of [1] to [9], wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene).
[11] The conductive polymer dispersion according to any one of [1] to [10], wherein the polyanion is polystyrene sulfonic acid.
[12] A conductive layer comprising a film base material and a cured layer of the conductive polymer dispersion according to any one of [1] to [11], formed on at least one surface of the film base material. A conductive film comprising:
[13] The conductive film according to [12], wherein the film base material is formed of a polyolefin resin.
[14] The conductive film according to [13], wherein the polyolefin resin is a polypropylene resin.
[15] A conductive layer comprising a film base material and a cured layer of the conductive polymer dispersion according to any one of [1] to [11], formed on at least one surface of the film base material. and a release layer containing a silicone compound, which is laminated on the surface of the conductive layer.
[16] Apply the conductive polymer dispersion according to any one of [1] to [11] to at least one surface of the film base material, dry the formed coating film, and form a conductive layer. A method for producing a conductive film, comprising:
[17] Apply the conductive polymer dispersion according to any one of [1] to [11] to at least one surface of the film base material, dry the formed coating film, and form a conductive layer. and applying a mold release agent composition containing a silicone-based compound to the surface of the conductive layer and drying the formed coating film to form a mold release layer. manufacturing method.
[18] The method for producing a conductive release film according to [17], wherein the silicone compound is an addition-curing silicone resin.

By using the conductive polymer dispersion of the present invention, a conductive layer with excellent adhesion to a plastic substrate and a release layer can be formed.
In the conductive film of the present invention, the conductive layer has high adhesion to the film base material.
In the conductive release film of the present invention, the adhesion of the conductive layer to the film base material is high, and the adhesion of the release layer to the conductive layer is also sufficient, and the surface of the release layer has good release properties. Demonstrate type.
Each manufacturing method of the present invention can easily manufacture a conductive film and a conductive release film.

<Conductive polymer dispersion>
A first aspect of the present invention is a conductive polymer dispersion containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a carboxy group-containing polyolefin resin, a polyester resin, and a dispersion medium. be.

[Conductive composite]
The conductive composite contained in the conductive polymer dispersion of this embodiment includes a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite is doped into a π-conjugated conductive polymer to form a conductive composite having conductivity.
In the polyanion, only some anion groups are doped into the π-conjugated conductive polymer, and there are surplus anion groups that do not participate in doping. Since the excess anion group is a hydrophilic group, the conductive composite has water dispersibility.

(π-conjugated conductive polymer)
The π-conjugated conductive polymer may be any organic polymer whose main chain is composed of a π-conjugated system, such as polypyrrole-based conductive polymers, polythiophene-based conductive polymers, and polyacetylene-based conductive polymers. Examples include polyphenylene conductive polymers, polyphenylene vinylene conductive polymers, polyaniline conductive polymers, polyacene conductive polymers, polythiophene vinylene conductive polymers, and copolymers thereof. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferred, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferred.

Polythiophene-based conductive polymers include polythiophene, poly(3-methylthiophene), poly(3-ethylthiophene), poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene). , poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene), poly(3-dodecylthiophene), poly(3-octadecylthiophene), poly(3-bromothiophene), poly (3-chlorothiophene), poly(3-iodothiophene), poly(3-cyanothiophene), poly(3-phenylthiophene), poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene) , poly(3-hydroxythiophene), poly(3-methoxythiophene), poly(3-ethoxythiophene), poly(3-butoxythiophene), poly(3-hexyloxythiophene), poly(3-heptyloxythiophene) , poly(3-octyloxythiophene), poly(3-decyloxythiophene), poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene), poly(3,4-dihydroxythiophene), poly(3-decyloxythiophene) ,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-dihexyloxythiophene) , poly(3,4-diheptyloxythiophene), poly(3,4-dioctyloxythiophene), poly(3,4-didecyloxythiophene), poly(3,4-didodecyloxythiophene), poly( 3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), poly(3,4-butylenedioxythiophene), poly(3-methyl-4-methoxythiophene), poly(3- methyl-4-ethoxythiophene), poly(3-carboxythiophene), poly(3-methyl-4-carboxythiophene), poly(3-methyl-4-carboxyethylthiophene), poly(3-methyl-4-carboxythiophene) butylthiophene).
Examples of polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), and poly(3-butylpyrrole). pyrrole), poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole), poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole), poly(3-dibutylpyrrole) -carboxypyrrole), poly(3-methyl-4-carboxypyrrole), poly(3-methyl-4-carboxyethylpyrrole), poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole) , poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole), poly(3-hexyloxypyrrole), and poly(3-methyl-4-hexyloxypyrrole).
Examples of polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-aniline sulfonic acid), and poly(3-aniline sulfonic acid).
Among these π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred in terms of conductivity, transparency, and heat resistance.
The number of types of π-conjugated conductive polymers contained in the conductive composite may be one or two or more types.

(Polyanion)
A polyanion is a polymer having two or more monomer units having anionic groups in its molecule. The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer to improve the conductivity of the π-conjugated conductive polymer.
The anion group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallylsulfonic acid, polyacrylic ester having a sulfo group, polymethacrylic ester having a sulfo group (for example, poly(4-sulfobutyl methacrylate) , polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polyisoprene sulfonic acid, and other polymers with sulfo groups, polyvinylcarboxylic acid, polystyrenecarboxylic acid, Polymers having carboxyl groups such as polyarylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), and polyisoprenecarboxylic acid are mentioned. may be a homopolymer obtained by polymerizing two or more types of monomers, or a copolymer obtained by polymerizing two or more types of monomers.
Among these polyanions, polymers having sulfo groups are preferred, and polystyrene sulfonic acid is more preferred, since it can further increase the conductivity.
The polyanions may be used alone or in combination of two or more.
The mass average molecular weight of the polyanion is preferably 20,000 or more and 1,000,000 or less, more preferably 100,000 or more and 500,000 or less. The mass average molecular weight is a mass-based average molecular weight measured using gel permeation chromatography and calculated in terms of polystyrene.

The content ratio of the polyanion in the conductive composite is preferably in the range of 1 part by mass or more and 1000 parts by mass or less, and 10 parts by mass or more and 700 parts by mass or less, based on 100 parts by mass of the π-conjugated conductive polymer. It is more preferable that it is, and it is even more preferable that it is in the range of 100 parts by mass or more and 500 parts by mass or less. If the content ratio of the polyanion is equal to or higher than the lower limit value, the doping effect on the π-conjugated conductive polymer tends to become stronger, and the conductivity becomes higher. On the other hand, if the content of the polyanion is below the upper limit value, the π-conjugated conductive polymer can be sufficiently contained, so that sufficient conductivity can be ensured.

The content of the conductive composite contained in the conductive polymer dispersion of this embodiment is preferably 0.01% by mass or more and 1% by mass or less, and 0.01% by mass or more and 1% by mass or less, based on the total mass of the conductive polymer dispersion. 02% by mass or more and 0.5% by mass or less, more preferably 0.03% by mass or more and 0.1% by mass or less.
When it is at least the lower limit of the above range, the conductivity of the conductive layer formed by applying the conductive polymer dispersion can be further improved.
When it is below the upper limit of the above range, the dispersibility of the conductive composite in the conductive polymer dispersion can be improved and a uniform conductive layer can be formed.

[Carboxy group-containing polyolefin resin]
The carboxyl group-containing polyolefin resin contained in the conductive polymer dispersion of this embodiment is a polyolefin resin having one or more carboxyl groups, and the polyolefin resin constituting the main chain contains an unsaturated carboxylic acid monomer having a carboxyl group. It is a copolymerized product. The number of carboxyl groups that the carboxyl group-containing polyolefin has is preferably two or more because the adhesion of the conductive layer to the plastic base material and the release layer becomes higher.
Specifically, the carboxy group-containing polyolefin resin may be a graft copolymer obtained by graft polymerizing an unsaturated carboxylic acid monomer to a polyolefin resin, or a random copolymer or block copolymer of an olefin monomer and an unsaturated carboxylic acid monomer. May be combined.
One type of carboxyl group-containing polyolefin resin may be used alone, or two or more types may be used in combination.

Examples of the olefin monomer constituting the polyolefin resin include unsaturated hydrocarbons having 2 or more and 6 or less carbon atoms. Examples of unsaturated hydrocarbons having 2 to 6 carbon atoms include ethylene, propylene, 1-butene, isobutene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, Examples include butadiene and isoprene. The unsaturated hydrocarbons may be used alone or in combination of two or more.
The olefin monomer constituting the polyolefin resin is preferably selected depending on the plastic substrate to be coated with the conductive polymer dispersion of this embodiment. For example, when using a polypropylene base material as a plastic base material, it is preferable to use propylene as the olefin monomer that makes up the polyolefin resin, and when using a polyethylene base material as the plastic base material, it is preferable to use propylene as the olefin monomer that makes up the polyolefin resin. It is preferable to use ethylene as the solvent.

The content of olefin monomer units in the carboxy group-containing polyolefin resin is preferably 60% by mass or more and 99.5% by mass or less, more preferably 80% by mass or more and 99.5% by mass or less, and 90% by mass. More preferably, the content is 99.5% by mass or less. If the content of olefin monomer units in the carboxy group-containing polyolefin resin is within the above range, the adhesion of the conductive layer to the plastic base material and the release layer will be higher.

The unsaturated carboxylic acid monomer used in this embodiment is preferably a compound having one or more vinyl groups and one or more carboxy groups, and an acid anhydride thereof. Specific examples of unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, fumaric acid, crotonic acid, citraconic acid, and mesaconic acid. acid, allylsuccinic acid, etc. The unsaturated carboxylic acid monomers may be used alone or in combination of two or more.
Among the unsaturated carboxylic acid monomers, maleic anhydride, acrylic acid, and methacrylic acid are preferred, and maleic anhydride is more preferred, since they can be easily introduced into the polyolefin resin.

The content of unsaturated carboxylic acid monomer units in the carboxy group-containing polyolefin resin is preferably 0.5% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, More preferably, the content is 1% by mass or more and 10% by mass or less. If the content of unsaturated carboxylic acid monomer units in the carboxy group-containing polyolefin resin is at least the above-mentioned lower limit, the adhesion of the conductive layer to the plastic base material and the release layer will be higher, and if it is below the above-mentioned upper limit, Carboxy group-containing polyolefin resin can be easily produced.
The carboxylic acid value in the carboxy group-containing polyolefin resin preferably ranges from 5 mgKOH/g to 500 mgKOH/g, more preferably from 10 mgKOH/g to 100 mgKOH/g. If the carboxylic acid value of the carboxy group-containing polyolefin resin is at least the above lower limit, the adhesion of the conductive layer to the plastic base material and the release layer will be higher; if it is below the above upper limit, the carboxy group-containing polyolefin resin Easy to manufacture.

The carboxy group-containing polyolefin resin may have monomer units other than the unsaturated hydrocarbon unit and the unsaturated carboxylic acid monomer unit.
Other monomers include acrylic acid alkyl esters (e.g., methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), methacrylic acid alkyl esters (e.g., methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc.), acrylic acid hydroxy Alkyl esters (e.g., 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, etc.), hydroxyalkyl methacrylate esters (e.g., 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, etc.), unsaturated hydrocarbons having 7 or more carbon atoms (eg, 1-octene, etc.), vinyl esters (eg, vinyl acetate, etc.), vinyl cyanide (eg, acrylonitrile, etc.), aromatic vinyls (eg, styrene, etc.), and the like. The other monomers may be used alone or in combination of two or more.
However, the content of the other monomer units in the carboxy group-containing polyolefin resin is preferably 20% by mass or less.

The method for producing the carboxy group-containing polyolefin resin is not particularly limited, and known polymerization methods can be applied.
For example, if the carboxy group-containing polyolefin resin is a graft copolymer obtained by graft polymerizing an unsaturated carboxylic acid monomer onto a polyolefin resin, the unsaturated carboxylic acid monomer is reacted with the polyolefin resin in the presence of a radical polymerization initiator. One example is how to do it. In the reaction, the polyolefin resin may be dissolved or dispersed in an organic solvent, or the polyolefin resin may be heated and melted without using an organic solvent.
Examples of the radical polymerization initiator include di-tert-butyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, tert-butyl cumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene hydroperoxide, Examples include organic peroxides such as tert-butyl peroxybenzoate, ethyl ethyl ketone peroxide, and di-tert-butyl diperphthalate; and azo compounds such as azobisisobutyronitrile.

The mass average molecular weight of the carboxy group-containing polyolefin resin is preferably 20,000 to 150,000, more preferably 30,000 to 120,000, even more preferably 30,000 to 100,000, and 3 It is particularly preferable that it is 90,000 or more and 90,000 or less. The mass average molecular weight of the carboxy group-containing polyolefin resin was determined by measuring the elution time using gel permeation chromatography (GPC) and based on a calibration curve of elution time versus molecular weight obtained in advance from a polystyrene standard material with known molecular weight. It is the molecular weight based on mass.
If the mass average molecular weight of the carboxy group-containing polyolefin resin is at least the lower limit of the above range, the adhesion of the conductive layer to the plastic base material and the release layer can be further improved, and if it is below the upper limit of the above range. , the dispersibility of the carboxy group-containing polyolefin resin in the conductive polymer dispersion can be improved.

The carboxylic acid contained in the carboxy group-containing polyolefin resin may be neutralized. If the carboxyl group-containing polyolefin resin is neutralized, the dispersibility of the carboxyl group-containing polyolefin resin in the conductive polymer dispersion can be improved.
Carboxy group-containing polyolefin resins can be neutralized by adding an alkali compound.
The alkali compound may be either an inorganic alkali or an organic alkali.
Examples of the inorganic alkali compound include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, and the like.
Examples of the organic alkali include primary amines, secondary amines, tertiary amines, quaternary ammonium salts, and nitrogen-containing aromatic cyclic compounds.
Examples of primary amines include aniline, toluidine, benzylamine, and ethanolamine.
Examples of the secondary amine include diethanolamine, dimethylamine, diethylamine, dipropylamine, diphenylamine, dibenzylamine, and dinaphthylamine.
Examples of the tertiary amine include triethanolamine, trimethylamine, triethylamine, tripropylamine, triphenylamine, tribenzylamine, and trinaphthylamine.
Examples of the quaternary ammonium salt include tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetraphenylammonium salt, tetrabenzylammonium salt, and tetranaphthylammonium salt. A hydroxide ion can be mentioned as an anion that serves as a pair with ammonium.
Examples of nitrogen-containing aromatic cyclic compounds include aniline, benzylamine, pyrrole, imidazole, 2-methylimidazole, 2-propylimidazole, N-methylimidazole, 1-(2-hydroxyethyl)imidazole, 2-ethyl -4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 1-acetylimidazole, 2-aminobenzimidazole, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2-(2-pyridyl)benzimidazole, pyridine, etc. Can be mentioned.
One type of alkali compound may be used alone, or two or more types may be used in combination.

The amount of the alkali compound added is preferably 0.3 times equivalent or more and 3 times equivalent or less, more preferably 0.5 times equivalent or more and 2 times equivalent or less, relative to the carboxyl group of the carboxy group-containing polyolefin resin. , more preferably 0.6 times equivalent or more and 1.5 times equivalent or less. If the amount of the alkaline compound added is at least the above lower limit, the dispersibility of the carboxy group-containing polyolefin resin can be further improved, and if it is below the above upper limit, the conductive polymer dispersion becomes excessively alkaline. This can prevent conductivity from decreasing.

The content of the carboxy group-containing polyolefin resin in the conductive polymer dispersion is preferably 100 parts by mass or more and 10,000 parts by mass or less, and 100 parts by mass or more and 5,000 parts by mass or less, based on 100 parts by mass of the conductive composite. It is more preferable that the amount is 100 parts by mass or more and 1000 parts by mass or less. If the content of the carboxy group-containing polyolefin resin is at least the above lower limit, the adhesion of the conductive layer to the plastic base material and the release layer can be further improved, and if it is below the above upper limit, the conductive composite It is possible to prevent a decrease in conductivity due to a decrease in the content of .

[Polyester resin]
The polyester resin contained in the conductive polymer dispersion of this embodiment is a resin having an ester bond formed by polycondensation of a polyhydric carboxylic acid and a polyalcohol. The polyester resin used in this embodiment preferably has acid groups from the viewpoint of improving water dispersibility. The acid group may form a salt. Furthermore, the polyester resin used in this embodiment is preferably a saturated polyester resin that does not contain reactive double bonds, from the viewpoint of improving the weather resistance of the conductive layer.

Examples of polyester resins having acid groups include polyester resins that are polycondensates of dicarboxylic acid components and diglycol components and have alkali metal salts of acid groups (sulfonic acid groups, carboxylic acid groups, phosphoric acid groups, etc.). (hereinafter referred to as "polyester resin (1)").
Since this polyester resin (1) has high polarity, it has excellent water dispersibility and can be stably dispersed in water without using an emulsifier or stabilizer.

Dicarboxylic acid components include aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, orthophthalic acid, etc. Examples thereof include succinic acid, adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
One type of dicarboxylic acid may be used alone, or two or more types may be used in combination.
The dicarboxylic acid component may include a dicarboxylic acid having a sulfonic acid alkali metal salt type substituent (-SO ₃ -X ⁺ , (X ⁺ is an alkali metal ion)) in which the sulfonic acid group is neutralized with an alkali metal. preferable.

A dicarboxylic acid having a sulfonic acid alkali metal salt type substituent is a compound in which the sulfonic acid group in a dicarboxylic acid having a sulfonic acid group is converted into an alkali metal salt.
Examples of the dicarboxylic acid having a sulfonic acid group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalic acid-2,7-dicarboxylic acid, and derivatives thereof. Examples of alkali metals include sodium and potassium.
As the dicarboxylic acid having an alkali metal sulfonic acid salt type substituent, sodium salts of 5-sulfoisophthalic acid and derivatives thereof are preferred.

In the dicarboxylic acid component, the dicarboxylic acid component other than the dicarboxylic acid having an alkali metal sulfonic acid salt type substituent is preferably an aromatic dicarboxylic acid, and more preferably terephthalic acid or isophthalic acid. The aromatic nucleus of aromatic dicarboxylic acid has a high affinity with hydrophobic plastics and also has excellent hydrolysis resistance.

The content of the dicarboxylic acid having a sulfonic acid alkali metal salt type substituent is preferably 6 mol% or more and 20 mol% or less, and preferably 10 mol% or more and 18 mol% or less in the total dicarboxylic acid component. More preferred. If the content ratio of the dicarboxylic acid having an alkali metal sulfonic acid salt type substituent is equal to or higher than the lower limit value, it is possible to suppress the deterioration of the solvent resistance of the conductive layer. Higher water resistance.

Examples of the diglycol component forming the polyester resin (1) include diethylene glycol, aliphatic glycols having 2 to 8 carbon atoms, or alicyclic glycols having 6 to 12 carbon atoms. Specific examples of aliphatic glycols having 2 to 8 carbon atoms or alicyclic glycols having 6 to 12 carbon atoms include ethylene glycol, 1,3-propanediol, 1,2-propylene glycol, neopentyl glycol, 1, Examples include 4-butanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,6-hexanediol, p-xylylene glycol, triethylene glycol, and the like. One type of diglycol component may be used alone, or two or more types may be used in combination.
The diglycol component preferably contains diethylene glycol because it further improves water resistance and solvent resistance.

The number average molecular weight of the polyester resin (1) is preferably 2,000 or more and 30,000 or less, more preferably 10,000 or more and 27,000 or less. The number average molecular weight of the polyester resin (1) was determined by measuring the elution time using gel permeation chromatography (GPC) and based on a calibration curve of elution time versus molecular weight obtained in advance from a polystyrene standard material with a known molecular weight. It refers to molecular weight based on numbers.
If the number average molecular weight of the polyester resin (1) is at least the lower limit, the adhesion of the conductive layer will be higher, and if it is lower than the upper limit, the water dispersibility of the polyester resin (1) will be higher.

The method for producing the polyester resin (1) is not particularly limited, and for example, a dicarboxylic acid component and a diglycol component are esterified or transesterified at 130°C or higher and 200°C or lower, and then 200°C or higher under reduced pressure conditions. A method of carrying out a polycondensation reaction at 250° C. or lower is exemplified. Examples of the reaction catalyst used in the method for producing the polyester resin (1) include metal acetates such as zinc acetate and manganese acetate, metal oxides such as antimony oxide and germanium oxide, and titanium compounds.
The obtained polyester resin (1) may be added to water to form an aqueous dispersion. In the aqueous dispersion of polyester resin (1), if the solid content (nonvolatile components) concentration becomes high, it becomes difficult to obtain a uniform dispersion, so the solid content concentration is preferably 30% by mass or less.

The content of the polyester resin in the conductive polymer dispersion is preferably 100 parts by mass or more and 50,000 parts by mass or less, and preferably 100 parts by mass or more and 10,000 parts by mass or less, based on 100 parts by mass of the conductive composite. More preferably, the amount is 200 parts by mass or more and 10,000 parts by mass or less. If the content of the binder component is equal to or higher than the lower limit value, the adhesion of the conductive layer can be improved, and if it is lower than the upper limit value, the conductivity decreases due to a decrease in the content of the conductive composite. can be prevented.

In the conductive polymer dispersion, the content of the polyester resin based on 100 parts by mass of the carboxyl group-containing polyolefin resin is preferably 20 parts by mass or more and 150 parts by mass or less, more preferably 25 parts by mass or more and 125 parts by mass or less, and 30 parts by mass or more. It is more preferably 35 parts by mass or more and 90 parts by mass or less, more preferably 35 parts by mass or more and 90 parts by mass or less.
Within the above preferred range, the adhesion of the conductive layer to the film base material and the release layer is further enhanced.

[Dispersion medium]
Examples of the dispersion medium contained in the conductive polymer dispersion of this embodiment include water, an organic solvent, and a mixture of water and an organic solvent.
Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, and aromatic hydrocarbon solvents.
Examples of alcoholic solvents include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, allyl alcohol, propylene glycol monomethyl Examples include monohydric alcohols such as ether and ethylene glycol monomethyl ether.
Examples of the ether solvent include diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, and propylene glycol dialkyl ether.
Examples of the ketone solvent include diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisopropyl ketone, methyl ethyl ketone, acetone, diacetone alcohol, and the like.
Examples of the ester solvent include ethyl acetate, propyl acetate, butyl acetate, and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, propylbenzene, and isopropylbenzene.
One type of organic solvent may be used alone, or two or more types may be used in combination.
Among the organic solvents, monohydric alcohol is preferable, and methanol is more preferable because it can further improve the dispersibility of the conductive composite, the carboxy group-containing polyolefin resin, and the polyester resin.

Since the conductive composite has high dispersibility in water, the dispersion medium of the conductive polymer dispersion of this embodiment is preferably an aqueous dispersion medium containing water.
The content ratio of water to the total dispersion medium contained in the conductive polymer dispersion of this embodiment can be, for example, 5% by mass or more and 100% by mass or less, preferably 10% by mass or more and 50% by mass or less, and 20% by mass. % or more and 40% by mass or less is more preferable. As the dispersion medium other than water, monohydric alcohol is preferred. Note that among the high conductivity agents described below, the mass of those that fall under the examples of the organic solvents mentioned above shall be included in the mass of the total dispersion medium.

In the conductive polymer dispersion of this embodiment, the carboxy group-containing polyolefin resin and the polyester resin are preferably dispersed in an aqueous dispersion medium. In such a dispersion state, the characteristics of the conductive layer obtained by applying the conductive polymer dispersion to the film base material will be uniform over the entire surface of the conductive layer, and the conductivity to the film base material and release layer will be uniform. This is preferred because the adhesion of the layer is further improved.

[High conductivity agent]
The conductive polymer dispersion of this embodiment may contain a high conductivity agent in order to further improve conductivity. Here, the π-conjugated conductive polymer, the polyanion, the above-mentioned carboxy group-containing polyolefin resin, the above-mentioned polyester resin, and the binder component are not classified as high-conductivity agents.
The high conductivity agent is a saccharide, a nitrogen-containing aromatic cyclic compound, a compound having two or more hydroxy groups, a compound having one or more hydroxy groups and one or more carboxy group, a compound having an amide group, Preferably, it is at least one compound selected from the group consisting of imide group-containing compounds, lactam compounds, and glycidyl group-containing compounds.
The number of highly conductive agents contained in the conductive polymer dispersion of this embodiment may be one type, or two or more types.
The content ratio of the high conductivity agent in the conductive polymer dispersion is preferably 1 part by mass or more and 100,000 parts by mass or less, and 10 parts by mass or more and 10,000 parts by mass or less, based on 100 parts by mass of the conductive composite. More preferably, it is 500 parts by mass or more and 9000 parts by mass or less. If the content ratio of the high conductivity agent is above the lower limit value, the conductivity improvement effect by adding the high conductivity agent will be fully exhibited, and if it is below the upper limit value, the concentration of π-conjugated conductive polymer will be reduced. It is possible to prevent a decrease in conductivity caused by

[Other binder components]
The conductive polymer dispersion of this embodiment may contain a binder component other than the carboxy group-containing polyolefin resin and the polyester resin.
Specific examples of the binder component include binder resins such as acrylic resin, epoxy resin, oxetane resin, polyurethane resin, polyimide resin, melamine resin, silicone resin, and vinyl acetate resin.
Examples of the acrylic resin include glycidyl group-containing acrylic resins. The glycidyl group-containing acrylic resin is an acrylic resin having a glycidyl group. Specifically, for example, a homopolymer of a monomer having a glycidyl group and an acryloyloxy group or a methacryloyloxy group, a copolymer of the monomer and a monomer having another radically polymerizable unsaturated group that can be copolymerized therewith. One example is merging.
Further, the binder component may be a monomer or oligomer forming the binder resin. At the time of forming the conductive layer, a binder resin can be formed by polymerizing the monomer or the oligomer.
The binder components may be used alone or in combination of two or more.

[Other additives]
The conductive polymer dispersion of this embodiment may contain other additives.
The additives are not particularly limited as long as the effects of the present invention can be obtained, and for example, surfactants, inorganic conductive agents, antifoaming agents, coupling agents, antioxidants, ultraviolet absorbers, etc. can be used. However, the additives are made of compounds other than the aforementioned π-conjugated conductive polymer, polyanion, carboxyl group-containing polyolefin resin, polyester resin, dispersion medium, binder component, and high conductivity agent.
Examples of the surfactant include nonionic, anionic, and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Additionally, a polymeric surfactant such as polyvinylpyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions, conductive carbon, and the like. Note that metal ions can be generated by dissolving metal salts in water.
Examples of antifoaming agents include silicone resins, polydimethylsiloxanes, silicone oils, and the like.
Examples of the coupling agent include silane coupling agents having an epoxy group, a vinyl group, or an amino group.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, sugars, and the like.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, benzoate UV absorbers, etc. can be mentioned.
When the conductive polymer dispersion liquid contains the above-mentioned additive, the content ratio is appropriately determined depending on the type of additive, but for example, 0.001 parts by mass per 100 parts by mass of the conductive composite. The content may be in a range of 5 parts by mass or less.

<Method for producing conductive polymer dispersion>
Examples of the method for producing the conductive polymer dispersion of this embodiment include a method of adding a carboxyl group-containing polyolefin resin, a polyester resin, a dispersion medium, etc. to an aqueous dispersion of a conductive composite.
The aqueous dispersion of the conductive composite may be obtained by chemical oxidative polymerization of a monomer that forms a π-conjugated conductive polymer in an aqueous solution of a polyanion, or a commercially available dispersion may be used.

The chemical oxidative polymerization can be performed using a known catalyst and oxidizing agent. Examples of the catalyst include transition metal compounds such as ferric chloride, ferric sulfate, ferric nitrate, and cupric chloride. Examples of the oxidizing agent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate. The oxidizing agent can return the reduced catalyst to its original oxidized state.

(effect)
Conductive polymer dispersions containing π-conjugated conductive polymers are often aqueous dispersions due to their manufacturing method, and have low wettability to plastic substrates. Therefore, there has been a problem in that the adhesion of a conductive layer formed from a conventional conductive polymer dispersion to a plastic substrate is low.
Since the conductive polymer dispersion according to the present invention contains a carboxy group-containing polyolefin resin and a polyester resin, it is possible to form a conductive layer with excellent adhesion to a plastic substrate. The details of this mechanism are unknown, but since adhesion does not improve if either one of the carboxy group-containing polyolefin resin and polyester resin is missing, the physical phenomenon that occurs when the carboxy group-containing polyolefin resin and polyester resin coexist. It is thought that chemical interaction contributes to improving the adhesion of the conductive layer (see Comparative Example below).
Further, the adhesion of the conductive layer formed from the conductive polymer dispersion according to the present invention is excellent not only to the film base material but also to another layer formed on the conductive layer. Therefore, for example, a release layer containing silicone may be formed on the conductive layer.

<Conductive film>
A second aspect of the present invention provides a conductive material comprising a film base material and a conductive layer formed on at least one surface of the film base material and comprising a hardened layer of the conductive polymer dispersion liquid of the first aspect. It's a film.

(conductive layer)
The average thickness of the conductive layer provided on at least one surface of the film base material is, for example, preferably 10 nm or more and 5000 nm or less, more preferably 20 nm or more and 1000 nm or less, and 30 nm or more and 500 nm or less. It is even more preferable.
If the average thickness of the conductive layer is equal to or greater than the lower limit, sufficiently high conductivity can be exhibited, and if the average thickness is equal to or less than the upper limit, the adhesion of the conductive layer is further improved.

The conductive layer of the conductive film of this embodiment preferably has a surface resistance value of, for example, 1×10 ² Ω/□ or more and 1×10 ¹⁰ Ω/□ or less, as a measure of good conductivity. It is more preferable to have a surface resistance value of ⁵ Ω/□ or more and 1×10 ⁹ Ω/□ or less, and more preferably a surface resistance value of 1×10 ⁶ Ω/□ or more and 1×10 ⁸ Ω/□ or less.

(Film base material)
Examples of the film base material include plastic films.
Examples of film base resins constituting plastic films include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, and polybutylene terephthalate. , polyethylene naphthalate, polyacrylate, polycarbonate, polyvinylidene fluoride, polyarylate, styrene elastomer, polyester elastomer, polyether sulfone, polyetherimide, polyether ether ketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio Examples include Nate. Among these film base resins, polyethylene terephthalate is preferred because it is inexpensive and has excellent mechanical strength.
In addition, since the conductive polymer dispersion of the first embodiment has good wettability when applied and the formed conductive layer has good adhesion, a film made of polyolefin resin can be used as a film base material. It is also preferable to use
The type of the polyolefin resin is not particularly limited, and any known polyolefin resin can be used. Among these, it is preferable that the film base material contains a polypropylene resin since the above-mentioned wettability is good.

The resin for the film base material may be amorphous or crystalline.
The film base material may be unstretched or stretched.
The film base material may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, etc. in order to further improve the adhesion of the conductive layer formed from the conductive polymer dispersion.

The average thickness of the film base material is preferably 5 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less. If the average thickness of the film base material is greater than or equal to the lower limit, it will be difficult to break, and if it is less than or equal to the upper limit, sufficient flexibility can be ensured as a film.
The thickness of a member in this specification is a value obtained by measuring the thickness at arbitrary 10 locations and averaging the measured values.

A known polarizing film can also be used as the film base material.
As a polarizing film, for example, one including a pair of transparent films and a polarizing layer disposed between them is known.
Examples of the transparent resin constituting the transparent film include triacetyl cellulose, polyethylene terephthalate, polycarbonate, polycycloolefin, polystyrene, polyvinyl alcohol, and acrylic resin.
The thickness of the transparent film can be, for example, 10 μm or more and 500 μm or less, and preferably 20 μm or more and 300 μm or less in terms of achieving both thinness and strength.
Examples of the polarizing layer include those in which a dichroic substance is attached to a hydrophilic film and uniaxially stretched to orient the dichroic substance. Examples of the hydrophilic film include a polyvinyl alcohol film and a partially saponified film of ethylene/vinyl acetate copolymer. Examples of dichroic substances include iodine and dichroic dyes.
The thickness of the polarizing layer can be, for example, 10 μm or more and 500 μm or less, and preferably 20 μm or more and 300 μm or less in terms of achieving both thinness and polarization.

When the conductive film is used for optical purposes, it is preferable that the film base material is transparent. Specifically, the total light transmittance of the film base material is preferably 65% or more, more preferably 70% or more, and even more preferably 80% or more. The total light transmittance is a value measured according to JIS K7136.

<Method for manufacturing conductive film>
A third aspect of the present invention includes applying the conductive polymer dispersion of the first aspect to at least one surface of a film base material, drying the formed coating film, and forming a conductive layer. This is a method for producing a sex film. By the manufacturing method of this aspect, the conductive film of the second aspect can be manufactured.

Examples of the method for coating (coating) the conductive polymer dispersion of the first embodiment on a film base material include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, and a fountain coater. , a method using a coater such as a rod coater, an air doctor coater, a knife coater, a blade coater, a cast coater, a screen coater, a method using a sprayer such as air spray, airless spray, rotor dampening, an immersion method such as dipping, etc. can be applied.
Commercially available bar coaters are numbered according to the coating thickness, and the higher the number, the thicker the coating can be applied.
The amount of the conductive polymer dispersion applied to the film base material is not particularly limited, but in consideration of uniform and even coating, conductivity and film strength, the solid content should be 0.01 g/m ² It is preferably in the range of 10.0 g/m ² or less.

A conductive film in which a conductive layer (conductive film) is formed by curing the coating film by drying a coating film made of a conductive polymer dispersion coated on a film base material and removing the dispersion medium. A transparent film can be obtained.
Examples of methods for drying the coating film include heating drying, vacuum drying, and the like. For heating and drying, for example, a conventional method such as hot air heating or infrared heating can be used.
When heat drying is applied, the heating temperature is appropriately set depending on the dispersion medium used, but is usually within the range of 50°C or higher and 150°C or lower. Here, the heating temperature is the set temperature of the drying device.

When the applied conductive polymer dispersion contains a thermosetting monomer or oligomer as a binder component, the conductive layer is formed by heating the coating film and curing the binder component. You can get the film.
When the applied conductive polymer dispersion contains a photocurable monomer or oligomer as a binder component, the conductive layer can be cured by irradiating the coating film with ultraviolet rays or electron beams to harden the binder component. A formed conductive film can be obtained.

<Conductive release film>
A fourth aspect of the present invention includes a film base material, a conductive layer formed on at least one surface of the film base material, and comprising a hardened layer of the conductive polymer dispersion according to the first aspect; This is an electrically conductive release film that includes a release layer containing a silicone compound and laminated on the surface.
The conductive release film of this embodiment can have the same structure as the conductive film of the second embodiment except that it includes the release layer. Therefore, the explanation that overlaps with the explanation of the second aspect will be omitted.

(Release layer)
The release layer included in the conductive release film of this embodiment can have the same configuration as the release layer included in known release films. The silicone compound contained in the release layer contributes to exhibiting release properties (easy peelability).

As the silicone compound, a silicone compound known as a mold release agent is applied. Here, silicone is a polymer collectively referred to as organopolysiloxane, which has a main chain (silicone skeleton) in which an organic group (eg, an alkyl group or a phenyl group) is bonded to a siloxane bond. As the organopolysiloxane, polydimethylsiloxane (PDMS) is preferable, and polydimethylsiloxane having a reactive functional group or a non-reactive functional group in a part of the polydimethylsiloxane is also preferable. Furthermore, acrylic resins and alkyd resins having organopolysiloxane in their side chains can also be used as the silicone compound.

As the silicone compound contained in the release layer of this embodiment, a cured product of curable silicone is preferable because it exhibits stable release properties and excellent film forming properties during production.
The curable silicone may be either an addition-curing silicone or a condensation-curing silicone. When curable silicone reacts, it forms a three-dimensional crosslinked structure and cures.
Examples of addition-curable silicones include linear polymers having siloxane bonds, including polydimethylsiloxane having vinyl groups at both ends of the linear chain, and hydrogen silane. A platinum-based curing catalyst may be used to accelerate curing.
Specific examples of addition-curing silicones include KS-3703T, KS-847T, KM-3951, X-52-151, X-52-6068, and X-52-6069 (manufactured by Shin-Etsu Chemical Co., Ltd.). .
Addition-curing silicones that are dissolved or dispersed in organic solvents are preferably used.

The content of the silicone compound contained in the release layer of this embodiment can be, for example, 20% by mass or more and 100% by mass, and 80% by mass or more and 100% by mass or less, based on the total mass of the release layer. A range of is preferred.
The release layer of this embodiment may contain a binder component other than a silicone compound or a binder component for improving adhesion, as long as the adhesion of the conductive layer to the release layer is not impaired and the release properties of the release layer are not impaired. It may also contain known additives such as antistatic agents and antistatic agents.

The average thickness of the release layer is, for example, preferably 10 nm or more and 5000 nm or less, more preferably 20 nm or more and 1000 nm or less, and even more preferably 30 nm or more and 500 nm or less.
If the average thickness of the release layer is equal to or greater than the lower limit value, higher mold release properties can be exhibited, and if it is equal to or less than the upper limit value, the adhesiveness to the conductive layer is further improved.

The release layer of the conductive release film of this embodiment may cover the entire surface of the conductive layer, or may cover only a portion of the conductive layer, with the remainder of the conductive layer exposed on the surface.

(effect)
The conductive layer of the conductive release film according to the present invention contains a carboxy group-containing polyolefin resin and a polyester resin derived from the applied conductive polymer dispersion, so the conductive layer is a release layer containing silicone. It can also exhibit sufficient adhesion (adhesiveness) to. As a result, the release layer included in the conductive release film of the present invention can exhibit excellent release properties for objects attached to the release layer without peeling off from the main body of the conductive film. .
The release layer included in the conductive release film according to the present invention is basically an insulating layer. Therefore, the surface where the conductive layer is not exposed due to being covered by the release layer does not exhibit conductivity. However, even if the conductive layer is not exposed on the surface, if the conductive layer is exposed on the side (cross section) of the conductive release film, it is possible to electrically connect the exposed part to the outside. be. Further, even without taking any special measures, the presence of the conductive layer inside the conductive release film makes it possible to prevent the conductive release film itself from being charged.

<Method for manufacturing conductive release film>
A fifth aspect of the present invention is to apply the conductive polymer dispersion of the first aspect to at least one surface of a film base material, dry the formed coating film, and form a conductive layer (conductive layer formation). step), and applying a mold release agent composition containing a silicone compound to the surface of the conductive layer, drying the formed coating film, and forming a mold release layer (mold release layer forming step). A method for producing a conductive release film, including:

(Conductive layer formation process)
This step can be performed in the same manner as the method for manufacturing a conductive film according to the third embodiment. Therefore, the explanation will be omitted here.

(Release layer formation process)
The mold release agent composition used in this step contains a silicone compound. Since the explanation of the silicone compound is the same as that of the fourth embodiment, the explanation will be omitted here.
In addition to the silicone compound, the mold release agent composition may contain additives such as an organic solvent, a curing catalyst, a binder component other than the silicone compound, an adhesion improver, and an antistatic agent, if necessary. Good too. When addition-curing silicone is used as the silicone compound, it is preferable to mix at least one of toluene and methyl ethyl ketone as the organic solvent. Conventional methods are applied to the blending ratio and blending method of each material contained in the mold release agent composition.
The method of applying the mold release agent composition to the conductive layer and the method of drying and curing the applied coating film can be performed in the same manner as the application method and drying/curing method when forming the conductive layer.
The conductive release film according to the present invention can be manufactured by the above method.

(Production Example 1) Synthesis of polyanion Dissolve 206 g of sodium styrene sulfonate in 1000 ml of ion-exchanged water, and while stirring at 80°C, add 1.14 g of ammonium persulfate oxidizing agent solution previously dissolved in 10 ml of water for 20 minutes. was added dropwise and the solution was stirred for 12 hours.
1,000 ml of sulfuric acid diluted to 10% by mass was added to the obtained sodium polystyrene sulfonate-containing solution, and about 1,000 ml of the solvent in the obtained polystyrene sulfonic acid-containing solution was removed by ultrafiltration. Next, 2000 ml of ion-exchanged water was added to the residual liquid, about 2000 ml of the solvent was removed by ultrafiltration, and the polystyrene sulfonic acid was washed with water. This water washing operation was repeated three times.
Water in the resulting solution was removed under reduced pressure to obtain colorless solid polystyrene sulfonic acid.

(Production Example 2) Synthesis of conductive composite A solution of 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 dissolved in 2000 ml of ion-exchanged water was prepared. Mixed at 20°C. While keeping the resulting mixed solution at 20°C and stirring, 29.64 g of ammonium persulfate and 8.0 g of ferric sulfate oxidation catalyst solution dissolved in 200 ml of ion-exchanged water were slowly added, and the mixture was stirred for 3 hours. The mixture was stirred and reacted.
After the reaction, 2000 ml of ion-exchanged water was added to the reaction solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated three times.
Next, 200 ml of sulfuric acid diluted to 10% by mass and 2,000 ml of ion-exchanged water were added to the obtained solution, approximately 2,000 ml of the solvent was removed by ultrafiltration, and 2,000 ml of ion-exchanged water was added to the remaining solution. About 2000 ml of solvent was removed by ultrafiltration. This operation was repeated three times.
Further, 2000 ml of ion-exchanged water was added to the obtained solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated five times to obtain an aqueous dispersion of polystyrene sulfonic acid-doped poly(3,4-ethylenedioxythiophene) (PEDOT-PSS) with a solid content concentration of 1.2% by mass.

(Example 1)
15 g of the PEDOT-PSS water dispersion obtained in Production Example 2 (solid content 0.18 g), 65 g of water, 10 g of propylene glycol, and Arrowbase DB-4010J2 (manufactured by Unitika Co., Ltd., which is a water-dispersed polypropylene resin containing a carboxyl group) were added. Carboxylic acid value: unmeasurable, solid content concentration 25% by mass) 6.75g, and 0.75g of Pluscoat RZ-570 (manufactured by Gooh Kagaku Co., Ltd., solid content 25% by mass, Tg 60°C), which is a water-dispersed polyester resin. 300 g of methanol was added to obtain a paint.
The obtained paint was applied onto a polypropylene film (manufactured by Shin-Etsu Polymer Co., Ltd.) using a #4 bar coater and dried at 120° C. for 1 minute to obtain a conductive film having a conductive layer on the polypropylene film.
Table 1 shows the results of measuring the surface resistance value of the obtained conductive film.

Next, 1.5 g of addition-curing silicone KS-3703T (manufactured by Shin-Etsu Chemical Co., Ltd., solid content 30% by mass, toluene solution), 25.5 g of toluene, 63 g of methyl ethyl ketone, and CAT-PL, a platinum catalyst. -50T (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.03 g was mixed to obtain a paint.
The resulting paint was applied to the surface of the conductive layer of the conductive film obtained above using a #8 bar coater, and dried at 150°C for 2 minutes to form a release layer on top of the conductive layer. A conductive release film was obtained.
Table 1 shows the results of measuring the surface resistance value of the obtained conductive release film.

(Example 2)
A conductive film and a conductive release mold were prepared in the same manner as in Example 1, except that the blend of Arrowbase DB-4010J2 was changed to 6.0 g and the blend of Pluscoat RZ-570 was changed to 1.5 g. A film was obtained and its surface resistance value was measured.

(Example 3)
A conductive film and a conductive release mold were prepared in the same manner as in Example 1, except that the blend of Arrowbase DB-4010J2 was changed to 5.25 g and the blend of Pluscoat RZ-570 was changed to 2.25 g. A film was obtained and its surface resistance value was measured.

(Example 4)
A conductive film and a conductive release mold were prepared in the same manner as in Example 1, except that the blend of Arrowbase DB-4010J2 was changed to 4.5 g and the blend of Pluscoat RZ-570 was changed to 3.0 g. A film was obtained and its surface resistance value was measured.

(Example 5)
A conductive film and a conductive release mold were prepared in the same manner as in Example 1, except that the blend of Arrowbase DB-4010J2 was changed to 3.75 g and the blend of Pluscoat RZ-570 was changed to 3.75 g. A film was obtained and its surface resistance value was measured.

(Example 6)
A conductive film and a conductive release mold were prepared in the same manner as in Example 1, except that the blend of Arrowbase DB-4010J2 was changed to 3.0 g and the blend of Pluscoat RZ-570 was changed to 4.5 g. A film was obtained and its surface resistance value was measured.

(Example 7)
A conductive film and a conductive release mold were prepared in the same manner as in Example 1, except that the blend of Arrowbase DB-4010J2 was changed to 2.25 g and the blend of Pluscoat RZ-570 was changed to 5.25 g. A film was obtained and its surface resistance value was measured.

(Example 8)
The same procedure as in Example 3 was carried out, except that Pluscoat RZ-570 in Example 3 was changed to Pluscoat RZ-105 (manufactured by Gooh Kagaku Co., Ltd., solid content 25% by mass, Tg 52°C), which is a water-dispersed polyester resin. A conductive film and a conductive release film were obtained, and their surface resistance values were measured.

(Example 9)
The same procedure as in Example 3 was carried out except that in Example 3, Pluscoat RZ-570 was changed to Pluscoat Z-561 (manufactured by Gooh Kagaku Co., Ltd., solid content 25% by mass, Tg 64°C), which is a water-dispersed polyester resin. A conductive film and a conductive release film were obtained, and their surface resistance values were measured.

(Example 10)
The same procedure as in Example 3 was carried out except that in Example 3, Pluscoat RZ-570 was changed to Pluscoat Z-565 (manufactured by Gooh Kagaku Co., Ltd., solid content 25% by mass, Tg 64°C), which is a water-dispersed polyester resin. A conductive film and a conductive release film were obtained, and their surface resistance values were measured.

(Example 11)
Same as Example 3, except that Pluscoat RZ-570 in Example 3 was changed to Pluscoat Z-3310, a water-dispersed polyester resin, manufactured by Goo Kagaku Co., Ltd., solid content 25% by mass, Tg -20°C) A conductive film and a conductive release film were obtained, and their surface resistance values were measured.

(Example 12)
Except for changing Arrowbase DB-4010J2 in Example 3 to Arrowbase TC-4010 (manufactured by Unitika, carboxylic acid value: 40 mgKOH/g, solid content concentration 25% by mass), which is a water-dispersed polypropylene resin containing a carboxyl group. obtained a conductive film and a conductive release film in the same manner as in Example 3, and measured their surface resistance values.

(Example 13)
Except that Pluscoat RZ-570 in Example 3 was changed to Pesresin A-124GP (manufactured by Takamatsu Yushi Co., Ltd., solid content 25% by mass, Tg 55°C), which is a mixture of water-dispersed polyester resin and glycidyl group-containing acrylic resin. A conductive film and a conductive release film were obtained in the same manner as in Example 3, and their surface resistance values were measured.
Note that Example 13 is a reference example.

(Comparative example 1)
A conductive film and a conductive release film were prepared in the same manner as in Example 1, except that the blend of Arrowbase DB-4010J2 was changed to 7.5 g and Pluscoat RZ-570 was not blended. The surface resistance value was measured.

(Comparative example 2)
A conductive film and a conductive release film were obtained in the same manner as in Example 1, except that Arrowbase DB-4010J2 was not blended and the blend of Pluscoat RZ-570 was changed to 7.5 g. Then, the surface resistance value was measured.

(Comparative example 3)
A conductive film and a conductive release film were prepared in the same manner as in Example 12, except that the blend of Arrowbase TC-4010 was changed to 7.5 g and Pluscoat RZ-570 was not blended. The surface resistance value was measured.

<Evaluation>
[Surface resistance value]
Regarding the conductive film of each example, the surface resistance value of the conductive layer was measured using a resistivity meter (manufactured by Mitsubishi Chemical Analytic Corporation, Hiresta) under the condition of an applied voltage of 10 V. Table 1 shows the measurement results of surface resistance values.
For the conductive release film of each example, a probe was placed on the release layer, and the surface resistance value of the conductive layer was measured with a resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) with the release layer interposed. The measurement was carried out under the condition of an applied voltage of 10 V using a HIRESTA). Table 1 shows the measurement results of surface resistance values. In addition, "Ω/□" in the table means ohm per square. Moreover, "1.0E+08" represents "1.0×10 ⁸ ".

[Peeling force]
Regarding the conductive release film of each example, the peel force was measured by the method described below to evaluate the release properties of the release layer.
A 25 mm wide polyester adhesive tape (manufactured by Nitto Denko Corporation, No. 31B) was pasted on the surface of the release layer of the conductive release film, and a load of 1976 Pa was applied from above the adhesive tape and pressure was applied at 25°C for 20 hours. Processed. Next, in accordance with JIS Z0237, the adhesive tape attached to the release layer was peeled off at an angle of 180° (peel speed 0.3 m/min) using a tensile tester to determine the peel force (unit: N). It was measured. The measurement results are shown in Table 1. It means that the smaller the peeling force is, the higher the mold release property of the mold release layer is.

[Adhesion]
Regarding the conductive release film of each example, the surface of the release layer was rubbed 10 times with a finger, and the degree of damage to the release layer was evaluated using the following criteria. The results are shown in Table 1.
(Evaluation 1): The release layer completely falls off by the fifth finger rubbing, and easy peelability is lost. In other words, the adhesion between the release layer and the conductive layer is poor.
(Evaluation 2): The release layer remains until the 5th finger rub, but after that, the release layer completely falls off by the 10th finger rub, and easy peelability is lost. In other words, the adhesion between the release layer and the conductive layer is poor.
(Evaluation 3): The release layer did not fall off by finger rubbing 10 times, a large change in the color of the release layer was observed, and the easy peelability decreased. In other words, the adhesion between the release layer and the conductive layer is normal.
(Evaluation 4): The release layer did not fall off by finger rubbing 10 times, and a small change in the color of the release layer was observed, but the easy peelability hardly decreased. In other words, the adhesion between the release layer and the conductive layer is excellent.
(Evaluation 5): The release layer did not fall off by finger rubbing 10 times, no change was observed in the color of the release layer, and easy peelability did not decrease. In other words, the adhesion between the release layer and the conductive layer is particularly excellent.
In the above five-level evaluation criteria, easy peelability (mold releasability) is based on the results of testing the ease of peeling off an adhesive tape after it has been applied to a finger-rubbed surface. The change in color of the release layer indicates the degree of peeling at the interface between the release layer and the conductive layer. If this interface is partially peeled off, the interface will be lifted up when the adhesive tape attached to the surface of the release layer is peeled off, and the peelability will be reduced.

From the results in Table 1, it can be seen that in the conductive films of Examples 1 to 13 according to the present invention, the adhesion of the conductive layer to the film made of polyolefin resin and the release layer is generally good. Good adhesion is achieved by containing both the carboxyl group-containing polyolefin resin and the polyester resin in the conductive layer. The conductive layers of Comparative Examples 1 to 3, which did not contain any resin, had poor adhesion and were not suitable for practical use.

Claims (10)

A film base material formed of polyolefin resin ,
A conductive layer made of a cured layer of a conductive polymer dispersion formed on at least one surface of the film base material, and a release layer containing a silicone compound laminated on the surface of the conductive layer. Prepare ,
The conductive polymer dispersion includes a conductive composite containing a π-conjugated conductive polymer and a polyanion, a carboxy group-containing polyolefin resin, a polyester resin, and a dispersion medium. However, conductive release films (excluding those containing glycidyl group-containing acrylic resins) . The conductive polymer according to claim 1, wherein in the conductive polymer dispersion , the content of the polyester resin is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the carboxy group-containing polyolefin resin. Release film . In the conductive polymer dispersion, the dispersion medium includes an aqueous dispersion medium, and the carboxy group-containing polyolefin resin and the polyester resin are dispersed in the aqueous dispersion medium. The conductive release film described above. The conductive release film according to any one of claims 1 to 3, wherein in the conductive polymer dispersion , the dispersion medium contains a monohydric alcohol. The conductive release film according to claim 4, wherein in the conductive polymer dispersion, the monohydric alcohol contains methanol . The conductive release film according to any one of claims 1 to 5, wherein the conductive polymer dispersion further contains a highly conductive agent. The conductive release film according to claim 6, wherein in the conductive polymer dispersion, the high conductivity agent contains a dihydric alcohol . The conductive release film according to claim 6 or 7, wherein in the conductive polymer dispersion, the high conductivity agent contains propylene glycol. The conductive release film according to any one of claims 1 to 8, wherein in the conductive polymer dispersion, the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). . The conductive release film according to any one of claims 1 to 9, wherein the polyanion in the conductive polymer dispersion is polystyrene sulfonic acid .