JP2018095728A - Conductive polymer dispersion liquid and production method thereof, and antistatic film and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a method for producing an antistatic film capable of suppressing a sharp increase in surface resistance value before stretching after stretching, an antistatic film having good antistatic property and water resistance, a conductive polymer dispersion liquid and its production. Provide a way. SOLUTION: (a) A conductive polymer dispersion liquid containing a conductive complex having a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol, and an aqueous dispersion medium in which the conductive complex is dispersed. . (B) The π-conjugated conductive polymer and the sulfonic acid group-containing polyvinyl alcohol are obtained by polymerizing a π-conjugated conductive polymer monomer in a solution containing a sulfonic acid group-containing polyvinyl alcohol and an aqueous dispersion medium. A method for producing a conductive polymer dispersion liquid, comprising: obtaining a conductive polymer dispersion liquid containing the conductive composite liquid having: and an aqueous dispersion medium in which the conductive composite liquid is dispersed. [Selection diagram] None

Description

  The present invention relates to a conductive polymer dispersion containing a π-conjugated conductive polymer and a method for producing the same, and an antistatic film and a method for producing the same.

As a film used for packaging electronic parts, an antistatic film for preventing the generation of static electricity that causes failure of the electronic parts is widely used.
As a conventional method for producing an antistatic film, a method has been proposed in which an antistatic layer containing a π-conjugated conductive polymer and a polyanion is provided on at least one surface of a film substrate and stretched as necessary ( For example, Patent Document 1).

Japanese Patent Laid-Open No. 2006-047501

  However, in the method for producing an antistatic film described in Patent Document 1, it has not been studied to suppress an increase in the surface resistance value of the conductive layer when stretched. Further, since the conductive layer contains water-soluble polyvinyl alcohol, the antistatic film tends to have low water resistance.

  The present invention relates to a method for producing an antistatic film capable of suppressing a rapid increase in surface resistance value before stretching after stretching, an antistatic film having good antistatic properties and water resistance, and a conductive polymer dispersion and its A manufacturing method is provided.

[1] A conductive polymer dispersion containing a conductive composite having a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol, and an aqueous dispersion medium in which the conductive composite is dispersed.
[2] The conductive polymer according to [1], wherein a content of water contained in the conductive polymer dispersion is 50% by mass or more based on a total mass of the conductive polymer dispersion. Dispersion.
[3] The conductive polymer dispersion according to [1] or [2], wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).
[4] The conductive polymer dispersion according to any one of [1] to [3], wherein the conductive polymer dispersion further includes a binder component.
[5] The conductive polymer dispersion according to [4], wherein the binder component is a water-dispersible emulsion.
[6] The conductive polymer dispersion according to [5], wherein the water-dispersible emulsion is a water-dispersible polyester emulsion.
[7] The conductive polymer dispersion according to any one of [1] to [6], wherein the conductive polymer dispersion further contains a highly conductive agent.
[8] The conductive polymer dispersion according to [7], wherein the highly conductive agent is propylene glycol.
[9] The π-conjugated conductive polymer and the sulfonic acid group-containing polyvinyl alcohol are obtained by polymerizing a π-conjugated conductive polymer monomer in a solution containing the sulfonic acid group-containing polyvinyl alcohol and an aqueous dispersion medium. A method for producing a conductive polymer dispersion, comprising: obtaining a conductive polymer dispersion containing a conductive composite having an aqueous dispersion and an aqueous dispersion medium in which the conductive composite is dispersed.
[10] The method for producing a conductive polymer dispersion according to [9], including a step of obtaining the sulfonic acid group-containing polyvinyl alcohol by bringing the sulfonate group-containing polyvinyl alcohol into contact with a cation exchange resin.
[11] A conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol in an aqueous dispersion medium is applied to at least one surface of the film substrate. A method for producing an antistatic film, comprising: a coating process for obtaining a coated film; and a stretching process for stretching the coated film to obtain a stretched film.
[12] A conductive polymer dispersion in which a conductive complex containing a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol is contained in an aqueous dispersion medium is used as at least one of the amorphous film substrate. A coating process for coating the surface to obtain a coating film; a stretching process for stretching the coating film to obtain a stretched film; and heating and cooling the stretched film to cool the amorphous film substrate. And a crystallization step of crystallizing to obtain a crystallized film.
[13] The method for producing an antistatic film according to [12], wherein a heating temperature of the stretched film in the crystallization step is 200 ° C. or higher.
[14] The method for producing an antistatic film according to any one of [11] to [13], wherein the amorphous film substrate is an amorphous polyethylene terephthalate film.
[15] An antistatic film having a film base and a conductive layer formed on at least one surface of the film base, wherein the conductive layer contains a π-conjugated conductive polymer and a sulfonic acid group An antistatic film containing polyvinyl alcohol.

According to the method for producing an antistatic film of the present invention, the coating film can be stretched, the surface resistance value before stretching is suppressed from rapidly increasing after stretching, and the antistatic film having good antistatic properties and water resistance. Can be manufactured.
The antistatic film of the present invention has good antistatic properties and water resistance. Moreover, also when the heat processing for crystallizing a film base material are performed, the raise of the surface resistance value is fully suppressed, and it also has favorable heat resistance.
The conductive polymer dispersion of the present invention is suitably used for the production of an antistatic film having a stretching process.
According to the method for producing a conductive polymer dispersion of the present invention, a target dispersion in which a conductive composite containing a sulfonic acid group-containing polyvinyl alcohol is dispersed can be easily obtained.

<< Conductive polymer dispersion >>
A first aspect of the present invention is a conductive polymer dispersion comprising a conductive composite having a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol, and an aqueous dispersion medium in which the conductive composite is dispersed. It is a liquid.
The conductive polymer dispersion may contain a high conductivity agent, a binder component, and other additives as necessary.

  The π-conjugated conductive polymer is not particularly limited as long as it has the effect of the present invention as long as the main chain is an organic polymer composed of π-conjugated system. For example, polypyrrole-based conductive polymer, polythiophene-based polymer Conductive polymer, polyacetylene conductive polymer, polyphenylene conductive polymer, polyphenylene vinylene conductive polymer, polyaniline conductive polymer, polyacene conductive polymer, polythiophene vinylene conductive polymer, and These copolymers are exemplified. From the viewpoint of stability in air, polypyrrole-based conductive polymers, polythiophenes, and polyaniline-based conductive polymers are preferable, and from the viewpoint of transparency, polythiophene-based conductive polymers are more preferable.

Examples of the polythiophene-based conductive polymer include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), and 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 ( -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 (3,4-dimethoxythiophene), poly (3,4-diethoxythiophene), poly ( 3,4-dipropoxythiophene), poly (3,4-dibutoxythiophene), poly (3,4-dihexyloxythiophene), poly (3,4-diheptyloxythiophene), poly (3,4-dioctyl) Oxythiophene), poly (3,4-didecyloxythiophene), poly (3, -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-carboxybutylthiophene) is mentioned.
Examples of the polypyrrole conductive polymer include polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), and poly (3-butyl Pyrrole), poly (3-octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3 -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-hexyl) Oxy pyrrole), poly (3-methyl-4-hexyloxy-pyrrole) and the like.
Examples of the polyaniline-based conductive polymer include polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-anilinesulfonic acid), and poly (3-anilinesulfonic acid).
Among the π-conjugated conductive polymers, poly (3,4-ethylenedioxythiophene) is particularly preferable from the viewpoint of conductivity, transparency, and heat resistance.
The π-conjugated conductive polymer may be one type alone or two or more types.

<Sulphonic acid group-containing polyvinyl alcohol>
The sulfonic acid group of the sulfonic acid group-containing polyvinyl alcohol may be in a neutral state {-S (═O) ₂ —OH} in which a hydrogen atom is bonded, or a charged state in which the hydrogen atom is dissociated and has a negative charge. _{{-S (= O) 2 -O} -} may be. Since pKa of a sulfonic acid group is negative, it is considered to be in a charged state in a normal aqueous solvent.
In the conductive composite, from the viewpoint of increasing the binding force between the sulfonic acid group-containing polyvinyl alcohol and the π-conjugated conductive polymer, the sulfonic acid group of the sulfonic acid group-containing polyvinyl alcohol is in a charged state, and the sulfonic acid group contains It is preferred that the polyvinyl alcohol is in the form of a polyanion.
In the conductive complex, a cation such as sodium ion or potassium ion may be bonded as a counter cation to a part of the charged sulfonic acid group, and the sulfonate group may be partially present. .

The sulfonate group (or sulfonate group) -containing polyvinyl alcohol can be purchased from a reagent company. For example, a chemical reaction in which the hydroxyl group of the polyvinyl alcohol is replaced with a sulfonate group, or vinyl acetate and sodium allylsulfonate It can also be obtained by a known method such as a chemical reaction for copolymerizing such compounds.
Polyvinyl alcohol used as a raw material may be produced by saponifying acetyl groups of polyvinyl acetate, and in this case, some acetyl groups may remain unsaponified. Therefore, the sulfonic acid group-containing polyvinyl alcohol may contain vinyl acetate units. The saponification degree of polyvinyl alcohol used as a raw material is preferably 70% or more and 100% or less.
The mass average molecular weight of polyvinyl alcohol used as a raw material is preferably 1000 or more and 100,000 or less, and more preferably 1300 or more and 60000 or less. When the mass average molecular weight of polyvinyl alcohol is 1000 or more, the stretchability of the conductive layer can be sufficiently improved, and when it is 100,000 or less, the solubility in water can be improved.
The mass average molecular weight in the present specification is a value obtained by measuring with gel permeation chromatography and obtaining the standard substance as polystyrene.

The sulfonic acid group-containing polyvinyl alcohol may have one or both of a hydroxyl group and an acetyl group in addition to the sulfonic acid group as the oxygen-containing functional group. When the total of oxygen-containing functional groups of the sulfonic acid group-containing polyvinyl alcohol is 100 mol%, the sulfonic acid group content is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.5 mol% or more. 10 mol% or less is more preferable and 1 mol% or more and 5 mol% or less are still more preferable.
When the content ratio of the sulfonic acid group is 0.1 mol% or more, the binding force to the π-conjugated conductive polymer is increased, and the conductivity of the conductive composite can be further improved.
The adhesiveness with respect to the film base material of the conductive layer formed by apply | coating the conductive polymer dispersion liquid containing a conductive composite can be improved more as the said content rate of a sulfonic acid group is 20 mol% or less.

The mass average molecular weight of the sulfonic acid group-containing polyvinyl alcohol is preferably 1,000 or more and 1,000,000 or less, and more preferably 5,000 or more and 50,000 or less.
When the mass average molecular weight is 1,000 or more, the stretchability of the conductive layer can be further improved.
When the mass average molecular weight is 1,000,000 or less, the dispersibility with respect to the aqueous dispersion medium water can be further improved.

The content ratio of the sulfonic acid group-containing polyvinyl alcohol in the conductive composite is preferably in the range of 1 part by mass to 10,000 parts by mass with respect to 10 parts by mass of the π-conjugated conductive polymer, and 20 parts by mass or more. The range is preferably 1000 parts by mass or less, and more preferably 30 parts by mass or more and 500 parts by mass or less.
When the content ratio of the sulfonic acid group-containing polyvinyl alcohol is equal to or higher than the lower limit, the doping effect on the π-conjugated conductive polymer becomes strong, and the conductivity tends to increase. Further, the dispersibility of the conductive composite in the conductive polymer dispersion is further improved.
When the content ratio of the sulfonic acid group-containing polyvinyl alcohol is not more than the above upper limit value, the balance with the content of the π-conjugated conductive polymer becomes good, and sufficient conductivity is easily obtained.
The sulfonic acid group-containing polyvinyl alcohol contained in the conductive composite may be one type or two or more types.

  The content of the conductive complex with respect to the total mass of the conductive polymer dispersion is, for example, preferably 0.1% by mass to 20% by mass, more preferably 1.0% by mass to 15% by mass, 1.0 mass% or more and 10 mass% or less are more preferable.

The aqueous dispersion medium in this embodiment is a liquid in which the conductive composite is dispersed, and is water or a mixed liquid of water and an organic solvent.
The content ratio of water in the aqueous dispersion medium is preferably 60% by mass or more, more preferably 70% by mass or more, and more preferably 80% by mass or more with respect to the total mass (100% by mass) of the aqueous dispersion medium. More preferably. When the content ratio of water in the aqueous dispersion medium is not less than the lower limit, the dispersibility of the conductive composite in the conductive polymer dispersion is further improved.
Here, when the water-dispersible emulsion of the binder component mentioned later is contained in the conductive polymer dispersion, the water constituting the water-dispersible emulsion and the water that disperses the conductive polymer are not distinguished. That is, all the water contained in the conductive polymer dispersion constitutes an aqueous dispersion medium. The aqueous dispersion medium may form an emulsion of a binder component.

Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, and the like.
1 type may be sufficient as the said organic solvent, and 2 or more types may be sufficient as it.
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, t-butanol, and allyl alcohol.
Examples of ether solvents include propylene glycol monoalkyl ethers such as diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, and propylene glycol monomethyl ether, propylene glycol dialkyl ethers, and the like.
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, isopropylbenzene, and the like.

The conductive polymer dispersion of the present invention may contain a binder component as an optional component. The binder component has a polymer other than the π-conjugated conductive polymer and the sulfonic acid group-containing polyvinyl alcohol. By including a binder component, the strength of a coating film formed by applying a conductive polymer dispersion to a film substrate can be increased.
Specific examples of the polymer include acrylic resin, polyester resin, polyurethane resin, polyimide resin, polyether resin, melamine resin, and the like.
The binder component is preferably a water-dispersible resin that can be dispersed in a conductive polymer dispersion, and more preferably a water-dispersible emulsion that is made into an emulsion in a dispersion medium.

Specific examples of the water dispersible resin include acrylic resin, polyester resin, polyurethane resin, polyimide resin, melamine resin, and the like. The functional group possessed by these water-dispersible resins, for example, an acid group such as a carboxy group or a sulfo group, may form a salt bonded to a counter cation. The water dispersible resin may be water soluble. Here, water-soluble refers to a property of dissolving 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more with respect to distilled water (100% by mass) at 25 ° C.
Examples of the water-dispersible emulsion include those obtained by making the water-dispersible resin into an emulsion.
When the conductive polymer dispersion is applied to the polyester film substrate, the adhesiveness of the coating film is increased, so that the binder component is preferably a polyester emulsion.
The binder component may be used alone or in combination of two or more.

The solid content of the binder component is preferably 1 part by mass or more and 10000 parts by mass or less, and preferably 10 parts by mass or more and 1000 parts by mass or less with respect to 100 parts by mass of the solid content of the conductive composite. More preferably, it is 20 parts by mass or more and 100 parts by mass or less.
When the content ratio of the binder component is equal to or higher than the lower limit value, the film forming property and the film strength can be improved. When the content ratio of the binder component is less than or equal to the upper limit value, sufficient conductivity is easily obtained.

The conductive polymer dispersion may contain a highly conductive agent in order to further improve the conductivity. Here, the above-described π-conjugated conductive polymer, sulfonic acid group-containing polyvinyl alcohol, and binder component are not classified as high conductivity agents. However, the organic solvent may correspond to the highly conductive agent described here.
The highly conductive 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 groups, a compound having an amide group, It is preferably at least one compound selected from the group consisting of a compound having an imide group, a lactam compound, and a compound having a glycidyl group.
One high conductivity agent may be used alone, or two or more types may be used.

It is preferable that the conductive polymer dispersion contains a basic compound as a highly conductive agent because the conductivity is improved.
Here, the “basic compound” refers to a compound containing an atom (hetero atom) other than a carbon atom having a lone electron pair (lone pair) capable of binding a proton.
As the basic compound, a nitrogen-containing compound is preferable, and a nitrogen-containing aromatic cyclic compound is more preferable.

  Examples of nitrogen-containing aromatic cyclic compounds include pyridines and derivatives thereof containing one nitrogen atom, imidazoles and derivatives thereof containing two nitrogen atoms, pyrimidines and derivatives thereof, pyrazines and derivatives thereof And triazines containing three nitrogen atoms and derivatives thereof. From the viewpoint of solvent solubility and the like, pyridines and derivatives thereof, imidazoles and derivatives thereof, and pyrimidines and derivatives thereof are preferable.

  Specific examples of pyridines and derivatives thereof include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine, N-vinylpyridine, 2,4-dimethylpyridine, 2,4. , 6-trimethylpyridine, 3-cyano-5-methylpyridine, 2-pyridinecarboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 4-pyridinecarboxaldehyde, 4-aminopyridine, 2,3-diaminopyridine, 2 , 6-diaminopyridine, 2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 4-pyridinemethanol, 2,6-dihydroxypyridine, 2,6-pyridinedimethanol, methyl 6-hydroxynicotinate, 2 -Hydroxy-5-pyridinemethanol, ethyl 6-hydroxynicotinate, 4-pi Lysine methanol, 4-pyridineethanol, 2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol, 2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine, 1,2-di (4- Pyridyl) ethane, 1,2-di (4-pyridyl) propane, 2-pyridinecarboxaldehyde, 2-pyridinecarboxylic acid, 2-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, Examples include 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

  Specific examples of imidazoles and derivatives thereof include imidazole, 2-methylimidazole, 2-propylimidazole, 2-undecylimidazole, 2-phenylimidazole, N-methylimidazole, N-vinylimidazole, and N-allylimidazole. 1- (2-hydroxyethyl) imidazole (N-hydroxyethylimidazole), 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, 4,5-imidazoledicarbo Acid, dimethyl 4,5-imidazole dicarboxylate, benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonic acid, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, 2- ( 2-pyridyl) benzimidazole and the like.

  Specific examples of pyrimidines and derivatives thereof include 2-amino-4-chloro-6-methylpyrimidine, 2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine, 2-amino-4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine, 2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine, 2-amino-4-methylpyrimidine, 4,6 -Dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine, 2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, 2,4-pyrimidinediol, etc. Is mentioned.

  Specific examples of the pyrazines and derivatives thereof include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid, 2,3-pyrazinedicarboxylic acid, 5-methylpyrazinecarboxylic acid, pyrazineamide, 5 -Methylpyrazine amide, 2-cyanopyrazine, aminopyrazine, 3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, 2,3-diethylpyrazine and the like.

  Specific examples of triazines and derivatives thereof include 1,3,5-triazine, 2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine, and 2,4-diamino. -6-phenyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine, 2,4,6-tris (trifluoromethyl) -1,3,5-triazine, 2,4,6-tri-2-pyridine-1,3,5-triazine, 3- (2-pyridine) -5,6-bis (4-phenylsulfonic acid) -1,2,4-triazine disodium 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine, 3- (2-pyridine) -5,6-diphenyl-1,2,4-triazine-ρ, ρ′- Disodium disulphonate, 2-hydroxy-4,6-dichloro -1,3,5-triazine and the like.

  Examples of the compound having two or more hydroxy groups include propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, D-glucose, D-glucitol, isoprene glycol, dimethylolpropionic acid, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, thiodiethanol, glucose, tartaric acid, D-glucar Polyhydric aliphatic alcohols such as acid and glutaconic acid; polymer alcohols such as cellulose, polysaccharide and sugar alcohol; 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 2,3-dihydroxy-1-pentadecyl , 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,4-dihydroxybenzophenone, 2,6-dihydroxybenzophenone, 3,4-dihydroxybenzophenone, 3,5-dihydroxybenzophenone, 2,4'-dihydroxy Diphenyl sulfone, 2,2 ′, 5,5′-tetrahydroxydiphenyl sulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfone, hydroxyquinonecarboxylic acid and salts thereof, 2, 3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 1,4-hydroquinonesulfonic acid and salts thereof, 4 , 5-Hydroxybenzene 1,3-disulfonic acid and its salts, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxy Naphthalene-2,6-dicarboxylic acid, 1,6-dihydroxynaphthalene-2,5-dicarboxylic acid, 1,5-dihydroxynaphthoic acid, 1,4-dihydroxy-2-naphthoic acid phenyl ester, 4,5-dihydroxynaphthalene -2,7-disulfonic acid and its salts, 1,8-dihydroxy-3,6-naphthalenedisulfonic acid and its salts, 6,7-dihydroxy-2-naphthalenesulfonic acid and its salts, 1,2,3-tri Hydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene 5-methyl-1,2,3-trihydroxybenzene, 5-ethyl-1,2,3-trihydroxybenzene, 5-propyl-1,2,3-trihydroxybenzene, trihydroxybenzoic acid, trihydroxy Acetophenone, trihydroxybenzophenone, trihydroxybenzaldehyde, trihydroxyanthraquinone, 2,4,6-trihydroxybenzene, tetrahydroxy-p-benzoquinone, tetrahydroxyanthraquinone, methyl garlic acid (methyl gallate), ethyl garlic acid (gallic acid) Aromatic compounds such as ethyl acetate), potassium hydroquinone sulfonate and the like.

  Examples of the compound having one or more hydroxy groups and one or more carboxy groups include tartaric acid, glyceric acid, dimethylolbutanoic acid, dimethylolpropanoic acid, D-glucaric acid, and glutaconic acid.

The compound having an amide group is a monomolecular compound having an amide bond represented by -CO-NH- (CO portion is a double bond) in the molecule. That is, as the amide compound, for example, a compound having functional groups at both ends of the bond, a compound in which a cyclic compound is bonded to one end of the bond, urea and urea derivatives in which the functional groups at both ends are hydrogen Etc.
Specific examples of amide compounds include acetamide, malonamide, succinamide, maleamide, fumaramide, benzamide, naphthamide, phthalamide, isophthalamide, terephthalamide, nicotinamide, isonicotinamide, 2-fluamide, formamide, N-methylformamide, propionamide , Propioluamide, butyramide, isobutylamide, palmitoamide, stearylamide, oleamide, oxamide, glutaramide, adipamide, cinnamamide, glycolamide, lactamide, glyceramide, tartaramide, citrulamide, glyoxylamide, pyruvamide, acetoacetamide, dimethylacetamide, benzyl Amide, anthranilamide, ethylenediaminetetraacetamide, Acetamide, triacetamide, dibenzamide, tribenzamide, rhodanine, urea, 1-acetyl-2-thiourea, biuret, butylurea, dibutylurea, 1,3-dimethylurea, 1,3-diethylurea and derivatives thereof Is mentioned.

Moreover, acrylamide can also be used as an amide compound. As acrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, Examples thereof include N-diethyl methacrylamide, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.
The molecular weight of the amide compound is preferably 46 or more and 10,000 or less, more preferably 46 or more and 5,000 or less, and particularly preferably 46 or more and 1,000 or less.

  As the amide compound, a monomolecular compound having an imide bond (hereinafter referred to as an imide compound) is preferable because of higher conductivity. Examples of the imide compound include phthalimide and phthalimide derivatives, succinimide and succinimide derivatives, benzimide and benzimide derivatives, maleimide and maleimide derivatives, naphthalimide and naphthalimide derivatives from the skeleton.

Moreover, although an imide compound is classified into an aliphatic imide, an aromatic imide, etc. by the kind of functional group of both terminal, an aliphatic imide is preferable from a soluble viewpoint.
Furthermore, the aliphatic imide compound is classified into a saturated aliphatic imide compound having no unsaturated bond between carbons in the molecule and an unsaturated aliphatic imide compound having an unsaturated bond between carbons in the molecule. .
The saturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and is a compound in which both R ¹ and R ² are saturated hydrocarbons. Specifically, cyclohexane-1,2-dicarboximide, allantoin, hydantoin, barbituric acid, alloxan, glutarimide, succinimide, 5-butylhydantoic acid, 5,5-dimethylhydantoin, 1-methylhydantoin, 1,5 , 5-trimethylhydantoin, 5-hydantoin acetic acid, N-hydroxy-5-norbornene-2,3-dicarboximide, semicarbazide, α, α-dimethyl-6-methylsuccinimide, bis [2- (succinimidooxycarbonyloxy) Ethyl] sulfone, α-methyl-α-propylsuccinimide, cyclohexylimide and the like.
The unsaturated aliphatic imide compound is a compound represented by R ¹ —CO—NH—CO—R ² , and one or both of R ¹ and R ² are one or more unsaturated bonds. Specific examples are 1,3-dipropylene urea, maleimide, N-methylmaleimide, N-ethylmaleimide, N-hydroxymaleimide, 1,4-bismaleimide butane, 1,6-bismaleimide hexane, 1,8-bis. Maleimide octane, N-carboxyheptylmaleimide and the like can be mentioned.
The molecular weight of the imide compound is preferably 60 or more and 5,000 or less, more preferably 70 or more and 1,000 or less, and particularly preferably 80 or more and 500 or less.

The lactam compound is an intramolecular cyclic amide of an aminocarboxylic acid, and a part of the ring is —CO—NR— (R is hydrogen or an arbitrary substituent). However, one or more carbon atoms in the ring may be replaced with an unsaturated or heteroatom.
Examples of the lactam compound include pentano-4-lactam, 4-pentanelactam-5-methyl-2-pyrrolidone, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexane lactam and the like.

  Examples of the compound having a glycidyl group include ethyl glycidyl ether, butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, benzyl glycidyl ether, glycidyl phenyl ether, bisphenol A, diglycidyl ether, glycidyl acrylate, methacrylic acid Examples thereof include glycidyl compounds such as glycidyl ether.

The content ratio of the highly conductive agent is preferably 1 part by mass or more and 10000 parts by mass or less, more preferably 10 parts by mass or more and 1000 parts by mass or less, based on 100 parts by mass of the conductive composite. More preferably, it is at least 500 parts by mass.
If the content ratio of the high conductive agent is equal to or higher than the lower limit value, the effect of improving the conductivity due to the addition of the high conductive agent is sufficiently exhibited. It is possible to prevent a decrease in conductivity due to the above.

  The total content of the highly conductive agent with respect to the total mass (100% by mass) of the conductive polymer dispersion is, for example, preferably 1% by mass to 50% by mass and more preferably 5% by mass to 20% by mass. preferable.

The conductive polymer dispersion may contain a known additive.
The additive is not particularly limited as long as the effect of the present invention is obtained, and for example, a surfactant, an inorganic conductive agent, an antifoaming agent, a coupling agent, an antioxidant, an ultraviolet absorber, and the like can be used. However, the additive comprises a compound other than the above-described π-conjugated conductive polymer, sulfonic acid group-containing polyvinyl alcohol, a binder component, and a highly conductive agent.
Examples of the surfactant include nonionic, anionic and cationic surfactants, and nonionic surfactants are preferred from the viewpoint of storage stability. Further, a polymer surfactant such as polyvinyl pyrrolidone may be added.
Examples of the inorganic conductive agent include metal ions and conductive carbon. The metal ion can be generated by dissolving a metal salt in water.
Examples of the antifoaming agent include silicone resin, polydimethylsiloxane, and silicone oil.
Examples of the coupling agent include silane coupling agents having a vinyl group, an amino group, an epoxy group, and the like.
Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, and saccharides.
Examples of UV absorbers include benzotriazole UV absorbers, benzophenone UV absorbers, salicylate UV absorbers, cyanoacrylate UV absorbers, oxanilide UV absorbers, hindered amine UV absorbers, and benzoate UV absorbers. Is mentioned.

  When the conductive polymer dispersion contains the additive, the content ratio is appropriately determined according to the type of the additive, but is generally 0. 10 parts by mass relative to 100 parts by mass of the solid content of the conductive composite. It is preferably within the range of 001 parts by mass to 5 parts by mass.

The dispersion medium excluding the conductive composite, the binder component, and the highly conductive agent with respect to the total mass (100% by mass) of the conductive polymer dispersion may contain other optional components. It is preferable that
The content of the aqueous dispersion medium excluding the solid content with respect to the total mass (100% by mass) of the conductive polymer dispersion is, for example, preferably 60% by mass to 99.9% by mass, and more preferably 80% by mass to 98%. The mass% or less is more preferable. When it is 60% by mass or more, the dispersibility of the conductive composite becomes better, and when it is 99.9% by mass or less, the coatability to the film substrate becomes better.

<< Method for Producing Conductive Polymer Dispersion >>
In a second aspect of the present invention, the π-conjugated conductive polymer and the sulfone are polymerized by polymerizing a π-conjugated conductive polymer monomer in a solution containing a sulfonic acid group-containing polyvinyl alcohol and an aqueous dispersion medium. This is a method for producing a conductive polymer dispersion, which obtains a conductive polymer dispersion containing a conductive composite having an acid group-containing polyvinyl alcohol and an aqueous dispersion medium in which the conductive composite is dispersed.
The conductive polymer dispersion obtained by the above production method is the same as the conductive polymer dispersion of the first aspect of the present invention.

The sulfonic acid group-containing polyvinyl alcohol can be obtained by removing the counter cation of the sulfonate group-containing polyvinyl alcohol.
The sulfonate group-containing polyvinyl alcohol can be purchased from a reagent company, but can also be obtained by, for example, the above-mentioned known synthesis.
The sulfonate group-containing polyvinyl alcohol is obtained by forming a salt with the sulfonate group of the sulfonate group-containing polyvinyl alcohol and the counter cation in the first embodiment of the present invention. Examples of the counter cation include monovalent cations such as lithium ion, sodium ion, and potassium ion. Further, as long as the salt is formed, it may be a divalent or higher cation such as magnesium or calcium.

  Examples of the method for removing the counter cation from the sulfonate group-containing polyvinyl alcohol include a method using a cation exchange resin. Specifically, a method of binding a counter cation to the cation exchange resin by bringing the sulfonate group-containing polyvinyl alcohol dispersed or dissolved in the aqueous dispersion medium into contact with the cation exchange resin can be mentioned. The cation exchange resin used here is not particularly limited, and commercially available products suitable for the purpose can be applied.

The conductive polymer dispersion intended by this embodiment is obtained by adding a monomer that forms a π-conjugated conductive polymer to a solution containing the sulfonic acid group-containing polyvinyl alcohol in the aqueous dispersion medium, and then adding the solution (reaction) In the liquid) by polymerizing the monomers.
The π-conjugated conductive polymer obtained by polymerization and the sulfonic acid group-containing polyvinyl alcohol are naturally bonded in the reaction solution to form a conductive composite.

  Examples of the aqueous dispersion medium constituting the reaction liquid include the same aqueous dispersion medium as in the first aspect. From the viewpoint of improving the dispersibility of the conductive composite formed, water is preferred.

The π-conjugated conductive polymer is the same as the π-conjugated conductive polymer of the first aspect. A known monomer can be applied as the monomer used for the polymerization.
A known catalyst may be applied to the polymerization. For example, an oxidizing agent such as ammonium persulfate or sodium persulfate can be used as a catalyst.

Examples of the charged amount of each material before the reaction with respect to the total mass (100% by mass) of the reaction solution include the following.
The charge amount of the sulfonic acid group-containing polyvinyl alcohol is, for example, preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, and more preferably 1% by mass to 10% by mass. Is more preferable.
The amount of the monomer charged is, for example, preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass, and further preferably 0.1% by mass to 0.8% by mass. preferable.
The amount of the catalyst charged is appropriately set according to the amount of the monomer charged in the same manner as the amount added to the conventional polymerization reaction, and is preferably 0.01% by mass or more and 1% by mass or less, for example, 0.05% by mass. The content is more preferably 1% by mass or less, and further preferably 0.1% by mass or more and 0.8% by mass or less.
The conditions for the polymerization reaction in the reaction solution can be the same as those for obtaining a conventional π-conjugated conductive polymer.

  The aqueous dispersion medium constituting the target conductive polymer dispersion liquid may be the same as the aqueous dispersion medium constituting the reaction liquid, or may be replaced with another aqueous dispersion medium.

<Method for producing antistatic film>
According to a third aspect of the present invention, there is provided a conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol in an aqueous dispersion medium. It is the manufacturing method of an antistatic film which has the coating process which coats on one surface, and obtains a coating film, and the extending process of extending | stretching the said coating film and obtaining a stretched film.

[Coating process]
By applying the conductive polymer dispersion of the first aspect to at least one surface of the film substrate, a coating film (conductive layer) is formed on the coated surface.

A plastic film is mentioned as a film base material used in a coating process.
Examples of the resin for the film base material constituting the plastic film include ethylene-methyl methacrylate copolymer resin, ethylene-vinyl acetate copolymer resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate. , Polyethylene naphthalate, Polyacrylate, Polycarbonate, Polyvinylidene fluoride, Polyarylate, Styrenic elastomer, Polyester elastomer, Polyethersulfone, Polyetherimide, Polyetheretherketone, Polyphenylene sulfide, Polyimide, Cellulose triacetate, Cellulose acetate propio And the like. Among these resins for film base materials, polyethylene terephthalate (PET) is preferable because it is inexpensive and has excellent mechanical strength.
The resin constituting the film base material may be amorphous or crystalline. Any of them can be a crystalline film substrate in any subsequent crystallization step, but an amorphous film is preferred from the viewpoint of good stretchability.
The film substrate may be unstretched or stretched, but when stretched in a subsequent stretching step, it is preferably unstretched in at least one direction.
Moreover, in order to improve the adhesiveness of the conductive layer formed by applying the conductive polymer dispersion on the film base material, the film base material is subjected to corona discharge treatment, plasma treatment, flame treatment, etc. A surface treatment may be applied.

The average thickness of the film substrate is preferably 10 μm or more and 1000 μm or less, and more preferably 20 μm or more and 500 μm or less. If the average thickness of the film substrate is equal to or greater than the lower limit value, it is difficult to break, and if it is equal to or less than the upper limit value, sufficient flexibility as a film can be ensured.
The thickness in the present specification is a value obtained by measuring the thickness at any 10 locations and averaging the measured values.

Examples of the method for applying the conductive polymer dispersion include a gravure coater, a roll coater, a curtain flow coater, a spin coater, a bar coater, a reverse coater, a kiss coater, a fountain coater, a rod coater, an air doctor coater, and a knife coater. A coating method using a coater such as a blade coater, cast coater or screen coater, a spraying method using a sprayer such as air spray, airless spray, or rotor dampening, a dipping method or the like can be applied.
Of these, a bar coater may be used because it can be applied easily. In the bar coater, the coating thickness varies depending on the type, and in the commercially available bar coater, a number is assigned to each type, and the larger the number, the thicker the coating can be made.
The amount of the conductive polymer dispersion applied to the film substrate is not particularly limited, but the solid content is preferably in the range of 0.1 g / m ² or more and 10.0 g / m ² or less.

  In the coating step, the conductive polymer dispersion may be applied only on one side of the film substrate to form a coating film only on one side, or the conductive polymer dispersion on both sides of the film substrate. May be applied to form a coating film on both sides. A film formed on a film substrate is referred to as a coating film.

  In order to improve the uniformity in the thickness direction after the coating process, the treatment for drying the coating film is preferably dried before being stretched or stretched in the stretching process and heated.

  The average thickness of the conductive layer after drying is preferably 10 nm or more and 5000 nm or less, more preferably 20 nm or more and 1000 nm or less, and further preferably 30 nm or more and 500 nm or less. If the average thickness of the conductive layer is equal to or higher than the lower limit, sufficiently high conductivity can be exhibited, and if the average thickness is equal to or lower than the upper limit, the conductive layer can be easily formed.

Examples of the method for drying the coated film include heat drying and vacuum drying. As heat drying, for example, a normal method such as hot air heating or infrared heating can be employed.
When heat drying is applied, the heating temperature is appropriately set according to the dispersion medium to be used, but is usually in the range of 50 ° C to 150 ° C. Here, the heating temperature is a set temperature of the drying apparatus.

[Stretching process]
The coated film obtained in the coating process is stretched to obtain a stretched film. By stretching the coating film, a large-area antistatic film can be obtained even if the coating area of the conductive polymer dispersion is reduced, and the productivity of the antistatic film is improved.

The coating film (conductive layer) of the coating film may be dried or may not be dried.
However, from the viewpoint of enhancing the followability of the conductive layer in stretching and reliably preventing cracking and peeling of the conductive layer, the coating film that has not been dried is heated to dry and stretch the conductive layer. It is preferable to obtain a stretched film.

In the stretching step, the coated film may be stretched simultaneously with heating, or may be stretched immediately after the coated film is heated. If the film is stretched at the same time as the heating, or is stretched immediately after the heating, the coated film is softened to facilitate the stretching. If the heating for stretching is also used for drying, energy efficiency can be further increased.
In addition, since part of the sulfonic acid group-containing polyvinyl alcohol may be decomposed and disappeared by heating, all of the sulfonic acid group-containing polyvinyl alcohol contained in the conductive polymer dispersion is included in the conductive layer. Not necessarily.

  Although the temperature at the time of heating a coating film in an extending | stretching process is suitably set according to the kind of film base material to be used, it can be 50 degreeC or more and 150 degrees C or less, for example. The heating temperature in the stretching step is preferably lower than the temperature for heating for the purpose of crystallizing the film substrate in the subsequent crystallization step. Here, the heating temperature is a set temperature of the heating device.

The stretching may be uniaxial stretching or biaxial stretching, but when a uniaxially stretched film is used as the film substrate, it is preferably stretched in a direction perpendicular to the already stretched direction. For example, when a uniaxially stretched film stretched along the longitudinal direction is used as a film substrate, it is preferably stretched along the width direction (short direction).
The stretch ratio of the coated film is preferably 2 to 20 times. If the draw ratio is set to the above lower limit value or higher, the productivity of the antistatic film can be further increased, and if the draw ratio is lower than the upper limit value, the film can be prevented from being broken.

[Crystalling process]
The crystallization process is an optional process. The resin constituting the film substrate can be crystallized by heating and then cooling the stretched film obtained in the stretching step. Usually, a crystallized film has higher mechanical strength than an amorphous film (amorphous film).

  The temperature at which the stretched film is heated depends on the type of film substrate, but is preferably 200 ° C. or higher. When heated to 200 ° C. or higher, at least a part of the resin constituting the film substrate starts to melt. After the melting, when cooled to a temperature lower than the crystallization temperature of the resin, the molten resin crystallizes and solidifies. Thereby, a film base material can be made into the crystalline film base material which consists of crystalline resin.

The temperature lowering temperature to be cooled after heating depends on the type of film substrate, but is preferably 1 ° C./min to 200 ° C./min, and more preferably 10 ° C./min to 100 ° C./min.
Within the above range, the mechanical strength of the film substrate can be easily improved.

As the resin constituting the film substrate, polyethylene terephthalate (PET) is preferable. A film substrate made of a crystalline PET film is excellent in mechanical properties such as tensile strength.
By the crystallization process described above, an antistatic film having a conductive layer on one side or both sides of a crystalline film substrate can be obtained.

<Antistatic film>
According to a fourth aspect of the present invention, there is provided an antistatic film comprising a film substrate and a conductive layer formed on at least one surface of the film substrate, wherein the conductive layer has a π-conjugated conductive polymer. And a sulfonic acid group-containing polyvinyl alcohol.
The antistatic film of the fourth aspect may be obtained by the production method of the third aspect, or may be obtained by another production method.

The content of the π-conjugated conductive polymer with respect to the total mass (100% by mass) of the conductive layer in the antistatic film of this embodiment is, for example, preferably 0.1% by mass or more and 10% by mass or less. 2 mass% or more and 6 mass% or less are more preferable, and 0.3 mass% or more and 3 mass% or less are further more preferable. Within the above range, good antistatic properties are easily exhibited.
As content of the said sulfonic acid group containing polyvinyl alcohol with respect to the total mass (100 mass%) of the said electroconductive layer in the antistatic film of this aspect, 0.01 mass% or more and 99.9 mass% or less are preferable, for example, 0 More preferably, the content is 1% by mass or more and 99.9% by mass or less. Within the above range, superior water resistance, heat resistance, stretchability and antistatic properties are easily exhibited.

<Effect>
A conventional conductive composite is a conductive composite in which a polyanion is doped into a π-conjugated conductive polymer. For example, PEDOT-PSS is a conductive composite obtained by doping poly (3,4-ethylenedioxythiophene) with polystyrene sulfonic acid. Polyvinyl alcohol used in Patent Document 1 is not electronically bonded to this conductive composite (not ionically bonded to the positive charge of PEDOT), and mainly van der Waals force or It is thought that they are in contact by hydrogen bonding. For this reason, when the conductive layer of Patent Document 1 comes into contact with water or is stretched, the polyvinyl alcohol in the conductive layer is easily dissociated from the conductive composite, and the water resistance of the conductive layer is reduced. In some cases, the surface resistance value varies (is different) for each portion of the conductive layer.

On the other hand, the conductive composite used in each aspect of the present invention is a conductive composite in which a π-conjugated conductive polymer is doped with a sulfonic acid group-containing polyvinyl alcohol that has not been conventionally used as a dopant. The bonding form of the π-conjugated conductive polymer and the sulfonic acid group-containing polyvinyl alcohol in this conductive composite is not particularly limited, and the bonding form of the π-conjugated conductive polymer and the polyanion in the conventional conductive composite It may be the same or different.
Although the details of the bonding form between the π-conjugated conductive polymer and the sulfonic acid group-containing polyvinyl alcohol are not yet elucidated, the sulfonic acid group-containing polyvinyl alcohol has a large number of sulfonic acid groups. It is presumed that it is electronically bonded to the conjugated conductive polymer. It is thought that the solubility with respect to the water of the sulfonic acid group containing polyvinyl alcohol which comprises the said electroconductive composite_body | complex is reduced with this coupling | bonding form. Further, even when the conductive layer formed by the conductive composite is in contact with water, the sulfonic acid group-containing polyvinyl alcohol is hardly dissociated from the conductive composite, and the water resistance of the conductive layer is improved. it is conceivable that.
The sulfonic acid group-containing polyvinyl alcohol can increase the conductivity of the π-conjugated conductive polymer and function as a dispersant for the conductive composite. For this reason, the conductive layer formed of the conductive polymer dispersion according to the first aspect of the present invention can easily follow the stretching of the film, hardly cause cracking or peeling, and the surface resistance value varies from site to site. There are few things to put on.
By the above mechanism, it is considered that the antistatic film of the fourth aspect of the present invention exhibits excellent antistatic properties and water resistance.

In the method for producing an antistatic film according to the third aspect of the present invention, since a conductive layer (antistatic layer) containing a sulfonic acid group-containing polyvinyl alcohol is formed, defects such as cracking and peeling are observed despite stretching. Can be prevented. The manufactured antistatic film has sufficient conductivity to perform an antistatic function.
Moreover, since the said conductive layer has sulfonic acid group containing polyvinyl alcohol, it can suppress that the surface resistance of a conductive layer raises rapidly by extending | stretching. Although the detailed mechanism is not yet elucidated, the flexibility of the conductive layer formed by the conductive composite (followability to stretching) by incorporating the sulfonic acid group-containing polyvinyl alcohol as a polyanion into the conductive composite. Is estimated to have improved.
Furthermore, since the said conductive layer has sulfonic acid group containing polyvinyl alcohol, it can suppress that the surface resistance of a conductive layer raises by the heat processing for the purpose of crystallization. Although the detailed mechanism is not yet elucidated, it is presumed that the thermal stability of the conductive composite is improved by incorporating the sulfonic acid group-containing polyvinyl alcohol as a polyanion in the conductive composite. .

(Production Example 1)
10 g of ASF-05 (Nihon Vinegar Bipoval, sodium sulfonate-modified polyvinyl alcohol) is dissolved in 90 g of water, 10 g of Duolite C255LFH (manufactured by Sumika Chemtex, cation exchange resin) is added, and the mixture is stirred at room temperature for 16 hours. did. Next, Duolite C255LFH was removed using a 100-mesh filter, and a solution in which sodium sulfonate modification of ASF-05 was modified with sulfonic acid was produced. (Hereinafter referred to as ASF-05 sulfonic acid solution.) The pH of this ASF-05 sulfonic acid solution (solid content 10 mass%) was 2.20.
The sulfonic acid-modified polyvinyl alcohol is a sulfonic acid group-containing polyvinyl alcohol.

(Production Example 2)
10 g of Gohsenol CKS-50 (manufactured by Nippon Synthetic Chemical Co., Ltd., sodium sulfonate-modified polyvinyl alcohol) was dissolved in 90 g of water, 10 g of Duolite C255LFH was added, and the mixture was stirred at room temperature for 16 hours. Next, Duolite C255LFH was removed using a 100-mesh filter, and a solution in which sodium sulfonate modification of Gohsenol CKS-50 was modified with sulfonic acid was produced. (Hereinafter referred to as GOHSENOL CKS-50 sulfonic acid solution.) The pH of this GOHSENOL CKS-50 sulfonic acid solution (solid content 10 mass%) was 1.52.

(Production Example 3)
10 g of Gohsenol L-3266 (manufactured by Nippon Synthetic Chemical Co., Ltd., sodium sulfonate-modified polyvinyl alcohol) was dissolved in 90 g of water, 10 g of Duolite C255LFH was added, and the mixture was stirred at room temperature for 16 hours. Next, Duolite C255LFH was removed using a 100-mesh filter, and a solution in which sodium sulfonate modification of Gohsenol L-3266 was modified with sulfonic acid was produced. (Hereinafter, it is referred to as GOHSENOL L-3266 sulfonic acid solution.) The pH of this GOHSENOL L-3266 sulfonic acid solution (solid content 10% by mass) was 1.37.

Example 1
ASF-05 sulfonic acid solution 75 g, water 75 g and 3,4-ethylenedioxythiophene 0.5 g were mixed and stirred at 25 ° C. for 10 minutes. Next, a solution in which 0.3 g of ferric sulfate was mixed with 4.7 g of water was added, and further a solution in which 1.1 g of ammonium persulfate was mixed with 8.9 g of water was added, followed by stirring at 25 ° C. for 8 hours. . Next, 13.2 g of Duolite C255LFH and 13.2 g of Duolite A368S (manufactured by Sumika Chemtex Co., Ltd., an anion exchange resin) were added and allowed to stand for 16 hours. A368S was removed, and the resulting solution was dispersed using a high-pressure homogenizer to obtain a conductive polymer dispersion.
The obtained solution was applied onto an amorphous polyethylene terephthalate film (A-PET film) using a # 12 bar coater and dried at 100 ° C. for 1 minute to obtain a coated film. The surface resistance value of the obtained coated film was measured under the condition of an applied voltage of 10 V using a resistivity meter (Hiresta manufactured by Mitsubishi Chemical Analytic Co.). The results are shown in Table 1.
Furthermore, the water resistance test was performed as follows. That is, using a non-woven fabric moistened with water, the coating film after drying of the coated film was rubbed 10 times at a pressure of 10 g / cm ² to confirm the change in appearance. The results are shown in Table 1.
Next, using a biaxial stretching apparatus (11A9, manufactured by Imoto Seisakusho Co., Ltd.), the coated film was stretched twice to obtain a stretched film. Table 1 shows the results of measuring the surface resistance of the stretched film in the same manner as described above.

(Example 2)
A coated film and a stretched film were obtained in the same manner as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to 150 g of ASF-05 sulfonic acid solution. The surface resistance value was measured. The measurement results of each film are shown in Table 1.

(Example 3)
A coated film and a stretched film were obtained in the same manner as in Example 1 except that 75 g of the ASF-05 sulfonic acid solution in Example 1 was changed to 75 g of Gohsenol CKS-50 sulfonic acid solution. It was measured. The measurement results of each film are shown in Table 1.

Example 4
A coating film and a stretched film were obtained in the same manner as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to Gohsenol CKS-50 sulfonic acid solution 150 g. The surface resistance value of was measured. The measurement results of each film are shown in Table 1.

(Example 5)
Coating was carried out in the same manner as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to (Gocenol L-3266 sulfonic acid solution 18.75 g and water 131.25 g). Films and stretched films were obtained and their surface resistance values were measured. The measurement results of each film are shown in Table 1.

(Example 6)
Coating was carried out in the same manner as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to (Gosenol L-3266 sulfonic acid solution 37.5 g and water 112.5 g). Films and stretched films were obtained and their surface resistance values were measured. The measurement results of each film are shown in Table 1.

(Example 7)
The coated film and the stretched film were the same as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to (Gosenol L-3266 sulfonic acid solution 75 g and water 75 g). And their surface resistance values were measured. The measurement results of each film are shown in Table 1.

(Example 8)
A coated film and a stretched film were obtained in the same manner as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to Gohsenol L-3266 sulfonic acid solution 150 g. The surface resistance value of was measured. The measurement results of each film are shown in Table 1.

Example 9
30 g of the conductive polymer dispersion obtained in Example 4, 55 g of water, 10 g of propylene glycol, and 5 g of Pluscoat Z-690 (Kyoto Chemical Co., Ltd., water-dispersible polyester emulsion, solid content 25%) were mixed.
The obtained mixed solution was applied onto an A-PET film using a # 12 bar coater and dried at 100 ° C. for 1 minute to obtain a coated film. The surface resistance value of the obtained coated film was measured in the same manner as described above. The results are shown in Table 2.
Next, using a biaxial stretching apparatus (11A9, manufactured by Imoto Seisakusho Co., Ltd.), the coated film was stretched twice to obtain a stretched film. The surface resistance value of the obtained stretched film was measured in the same manner as described above. The results are shown in Table 2.
Subsequently, after the stretched film is heated at 240 ° C. for 30 seconds, it is slowly cooled so that the cooling rate is 80 ° C. to 100 ° C./min, and the A-PET film constituting the stretched film substrate is crystallized. Thus, a crystalline PET film was obtained. The surface resistance value of the obtained crystallized film was measured in the same manner as described above. The results are shown in Table 2.

(Example 10)
A coated film, a stretched film, and a crystallized film were obtained in the same manner as in Example 9 except that the stretched film was stretched 4 times, and the surface resistance values thereof were measured. Table 2 shows the measurement results for each film.

(Example 11)
A coated film in the same manner as in Example 9, except that (conductive polymer dispersion obtained in Example 4) in Example 9 was changed to (conductive polymer dispersion obtained in Example 8). A stretched film and a crystallized film were obtained and their surface resistance values were measured. Table 2 shows the measurement results for each film.

(Example 12)
A coated film, a stretched film, and a crystallized film were obtained in the same manner as in Example 11 except that the stretched film was stretched 4 times, and their surface resistance values were measured. Table 2 shows the measurement results for each film.

(Comparative Example 1)
Coating was carried out in the same manner as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to {polystyrenesulfonic acid (10% aqueous solution) 18.75 g and water 131.25 g}. A processed film and a stretched film were obtained, and their surface resistance values were measured. The measurement results of each film are shown in Table 1.
The conductive polymer dispersion obtained in Comparative Example 1 contains PEDOT-PSS.

(Comparative Example 2)
A coating film and a stretched film are the same as Comparative Example 1 except that 2.5 g of Kuraray Poval PVA210 (manufactured by polyvinyl alcohol Kuraray Co., Ltd.) is further added to the solution of the material for synthesizing PEDOT-PSS in Comparative Example 1. And their surface resistance values were measured. The coated film was subjected to a water resistance test. The results of each film are shown in Table 1.

(Comparative Example 3)
Coating was carried out in the same manner as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to {polystyrenesulfonic acid (10% aqueous solution) 37.5 g and water 112.5 g}. A processed film and a stretched film were obtained, and their surface resistance values were measured. The measurement results of each film are shown in Table 1.
The conductive polymer dispersion obtained in Comparative Example 3 contains PEDOT-PSS.

(Comparative Example 4)
The water resistance of the coating film was the same as in Comparative Example 3 except that 2.5 g of Kuraray Poval PVA210 (manufactured by Polyvinyl Alcohol Kuraray Co., Ltd.) was further added to the solution of the material for synthesizing PEDOT-PSS in Comparative Example 3. And a coated film and a stretched film were obtained, and their surface resistance values were measured. The coated film was subjected to a water resistance test. The measurement results of each film are shown in Table 1.

(Comparative Example 5)
Conductive polymer dispersion in the same manner as in Example 1 except that (ASF-05 sulfonic acid solution 75 g and water 75 g) in Example 1 was changed to {polystyrenesulfonic acid (10% aqueous solution) 75 g and water 75 g}. The reaction was performed for the purpose of obtaining a liquid. However, since the solution gelled during the reaction, the conductive polymer dispersion could not be obtained, and the production of the coated film was stopped.

(Comparative Example 6)
A coated film in the same manner as in Example 9, except that (conductive polymer dispersion obtained in Example 4) in Example 9 was changed to (conductive polymer dispersion obtained in Comparative Example 1). A stretched film and a crystallized film were obtained and their surface resistance values were measured. Table 2 shows the measurement results for each film.

(Comparative Example 7)
A coated film in the same manner as in Example 9, except that (conductive polymer dispersion obtained in Example 4) in Example 9 was changed to (conductive polymer dispersion obtained in Comparative Example 3). A stretched film and a crystallized film were obtained and their surface resistance values were measured. Table 2 shows the measurement results for each film.

<Discussion>
In the above results, the antistatic film of each Example contains the sulfonic acid group-containing polyvinyl alcohol in the conductive layer, so that the increase in the surface resistance value after stretching is suppressed within 1 to 35 times before stretching. . This means that the conductive layer constituting the antistatic film of the example is excellent in followability to the base film.
Moreover, the antistatic film of each Example did not change in appearance even when rubbed with a non-woven fabric containing water by including a sulfonic acid group-containing polyvinyl alcohol in the conductive layer. This means that the conductive layer constituting the antistatic film of the example is excellent in water resistance.
Furthermore, the antistatic film of each Example contains a sulfonic acid group-containing polyvinyl alcohol in the conductive layer, so that the increase in surface resistance value after heat treatment at a relatively high temperature for crystallization is 1 before stretching. It is suppressed to about 2.5 times. This means that the conductive layer constituting the antistatic film of the example is excellent in heat resistance.

On the other hand, since the antistatic film of each comparative example (excluding Comparative Examples 2 and 4) does not contain sulfonic acid-modified polyvinyl alcohol in the conductive layer, the increase in the surface resistance value of the conductive layer after stretching is far 10,000 times. It will exceed.
Since the antistatic films of Comparative Examples 2 and 4 contain polyvinyl alcohol in the conductive layer, the increase in the surface resistance value after stretching is moderated as compared with other Comparative Examples, but still exceeds 100 times. Yes. Further, the water resistance is clearly lowered due to the influence including polyvinyl alcohol.
From the above, the antistatic film of the present invention has an excellent performance that the increase in the surface resistance value can be kept low even when stretched or heated in addition to stretching.

Claims (15)

  A conductive polymer dispersion containing a conductive composite having a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol, and an aqueous dispersion medium in which the conductive composite is dispersed.   2. The conductive polymer dispersion according to claim 1, wherein the content of water contained in the conductive polymer dispersion is 50% by mass or more based on the total mass of the conductive polymer dispersion.   3. The conductive polymer dispersion according to claim 1, wherein the π-conjugated conductive polymer is poly (3,4-ethylenedioxythiophene).   4. The conductive polymer dispersion according to any one of claims 1 to 3, wherein the conductive polymer dispersion further contains a binder component.   5. The conductive polymer dispersion according to claim 4, wherein the binder component is a water-dispersible emulsion.   6. The conductive polymer dispersion according to claim 5, wherein the water-dispersible emulsion is a water-dispersible polyester emulsion.   7. The conductive polymer dispersion according to any one of claims 1 to 6, wherein the conductive polymer dispersion further contains a highly conductive agent.   8. The conductive polymer dispersion according to claim 7, wherein the highly conductive agent is propylene glycol. By polymerizing a monomer of a π-conjugated conductive polymer in a solution containing a sulfonic acid group-containing polyvinyl alcohol and an aqueous dispersion medium,
A conductive polymer dispersion containing the conductive composite having the π-conjugated conductive polymer and the sulfonic acid group-containing polyvinyl alcohol, and an aqueous dispersion medium in which the conductive composite is dispersed is obtained. A method for producing a polymer dispersion.   10. The method for producing a conductive polymer dispersion according to claim 9, wherein the sulfonate group-containing polyvinyl alcohol is obtained by bringing the sulfonate group-containing polyvinyl alcohol into contact with a cation exchange resin. Apply a conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol in an aqueous dispersion medium to at least one surface of the amorphous film substrate. A coating process to obtain a coated film,
And a stretching step of stretching the coated film to obtain a stretched film. Apply a conductive polymer dispersion containing a conductive complex containing a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol in an aqueous dispersion medium to at least one surface of the amorphous film substrate. A coating process to obtain a coated film,
A stretching step of stretching the coating film to obtain a stretched film;
A method for producing an antistatic film, comprising: heating the stretched film and then cooling to crystallize the amorphous film substrate to obtain a crystallized film.   13. The method for producing an antistatic film according to claim 12, wherein the heating temperature of the stretched film in the crystallization step is 200 ° C. or higher.   The method for producing an antistatic film according to any one of claims 11 to 13, wherein the amorphous film substrate is an amorphous polyethylene terephthalate film. An antistatic film having a film base and a conductive layer formed on at least one surface of the film base,
An antistatic film, wherein the conductive layer includes a π-conjugated conductive polymer and a sulfonic acid group-containing polyvinyl alcohol.