JP7269816B2 - Conductive release film and manufacturing method thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a conductive polymer dispersion, a conductive film and its production method, and a conductive release film and its production method.

BACKGROUND ART Forming a conductive layer on the surface of a plastic substrate is required as a technique for manufacturing electronic devices. A π-conjugated conductive polymer is attracting attention as a material for forming a conductive layer because of its 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 complex containing a π-conjugated conductive polymer and a polyanion is dispersed in water is prepared. A method of coating a base material and drying it can be mentioned (Patent Document 1).

WO2015/108001

The present inventors have investigated the production of a laminate in which a release layer containing a silicone compound is further laminated on the surface of a conductive layer formed on the surface of a resin substrate. In this case, the conductive layer is required to have both high adhesion to the resin substrate and high adhesion to the laminated release layer.

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

［式中、Ｒ_１及びＲ_２はそれぞれ独立に水素原子又は任意の置換基を表す。］
［３］ 前記イソシアヌレート化合物が、トリアリルイソシアヌレート又は下記式（１－５）で表される化合物を含む、［１］又は［２］に記載の導電性高分子分散液。

［４］ 前記水分散性樹脂が水分散性ポリエステル樹脂である、［１］～［３］の何れか一項に記載の導電性高分子分散液。
［５］ 前記分散媒が一価アルコールを含有する、［１］～［４］の何れか一項に記載の導電性高分子分散液。
［６］ 前記一価アルコールがメタノールを含む、［５］に記載の導電性高分子分散液。
［７］ 高導電化剤をさらに含有する、［１］～［６］の何れか一項に記載の導電性高分子分散液。
［８］ 前記高導電化剤が二価アルコールを含む、［７］に記載の導電性高分子分散液。
［９］ 前記高導電化剤がプロピレングリコールを含む、［７］又は［８］に記載の導電性高分子分散液。
［１０］ 前記π共役系導電性高分子がポリ（３，４－エチレンジオキシチオフェン）である、［１］～［９］のいずれか一項に記載の導電性高分子分散液。
［１１］ 前記ポリアニオンがポリスチレンスルホン酸である、［１］～［１０］のいずれか一項に記載の導電性高分子分散液。
［１２］ フィルム基材と、前記フィルム基材の少なくとも一方の面に形成された、［１］～［１１］の何れか一項に記載の導電性高分子分散液の硬化層からなる導電層とを備える、導電性フィルム。
［１３］ フィルム基材と、前記フィルム基材の少なくとも一方の面に形成された、［１］～［１１］の何れか一項に記載の導電性高分子分散液の硬化層からなる導電層と、前記導電層の表面に積層された、シリコーン系化合物を含む離型層と、を備える、導電性離型フィルム。
［１４］ フィルム基材の少なくとも一方の面に、［１］～［１１］の何れか一項に記載の導電性高分子分散液を塗布し、形成した塗膜を乾燥し、導電層を形成することを含む、導電性フィルムの製造方法。
［１５］ フィルム基材の少なくとも一方の面に、［１］～［１１］の何れか一項に記載の導電性高分子分散液を塗布し、形成した塗膜を乾燥し、導電層を形成することと、前記導電層の表面に、シリコーン系化合物を含む離型剤組成物を塗布し、形成した塗膜を乾燥し、離型層を形成することと、を含む、導電性離型フィルムの製造方法。
［１６］ 前記シリコーン系化合物が付加硬化型シリコーン樹脂である、［１５］に記載の導電性離型フィルムの製造方法。 [1] A conductive polymer containing a conductive composite containing a π-conjugated conductive polymer and a polyanion, a water-dispersible resin, a dispersion medium, and an isocyanurate compound having one or more vinyl groups. dispersion.
[2] The conductive polymer dispersion according to [1], wherein the isocyanurate compound contains a compound represented by the following formula (1).

[In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an arbitrary substituent. ]
[3] The conductive polymer dispersion according to [1] or [2], wherein the isocyanurate compound comprises triallyl isocyanurate or a compound represented by the following formula (1-5).

[4] The conductive polymer dispersion according to any one of [1] to [3], wherein the water-dispersible resin is a water-dispersible polyester 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 conductive agent.
[8] The conductive polymer dispersion according to [7], wherein the conductive agent contains a dihydric alcohol.
[9] The conductive polymer dispersion according to [7] or [8], wherein the conductivity enhancer 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 polystyrenesulfonic acid.
[12] A conductive layer comprising a film substrate 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 substrate. A conductive film.
[13] A conductive layer comprising a film substrate 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 substrate. and a release layer containing a silicone compound laminated on the surface of the conductive layer.
[14] The conductive polymer dispersion according to any one of [1] to [11] is applied to at least one surface of a film substrate, and the formed coating is dried to form a conductive layer. A method of manufacturing a conductive film, comprising:
[15] The conductive polymer dispersion according to any one of [1] to [11] is applied to at least one surface of a film substrate, and the formed coating is dried to form a conductive layer. and applying a release agent composition containing a silicone compound to the surface of the conductive layer, drying the formed coating film, and forming a release layer. manufacturing method.
[16] The method for producing a conductive release film according to [15], wherein the silicone compound is an addition-curable silicone resin.

By using the conductive polymer dispersion of the present invention, a conductive layer having excellent adhesion to a plastic substrate and a release layer can be formed. In the conductive layer, deterioration in conductivity over time in the atmosphere is suppressed.
In the conductive film of the present invention, the adhesion of the conductive layer to the film substrate is high, and the decrease in conductivity of the conductive layer over time in the atmosphere is suppressed.
In the conductive release film of the present invention, the adhesion of the conductive layer to the film substrate is high, and further, the deterioration of the conductivity of the conductive layer over time in the atmosphere is suppressed. Adhesion of the mold layer is also sufficient, and the surface of the release layer exhibits good releasability.
Each production method of the present invention can easily produce a conductive film and a conductive release film.

<Conductive polymer dispersion>
A first aspect of the present invention contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a water-dispersible resin, a dispersion medium, and an isocyanurate compound having one or more vinyl groups. , is a conductive polymer dispersion.

[Conductive composite]
The conductive composite contained in the conductive polymer dispersion of this embodiment contains a π-conjugated conductive polymer and a polyanion. The polyanion in the conductive composite forms a conductive composite having conductivity by doping the π-conjugated conductive polymer.
In the polyanion, only some of the anionic groups are doped into the π-conjugated conductive polymer, and there are surplus anionic groups that do not participate in the doping. Since the surplus anionic groups are hydrophilic groups, the conductive composite has water dispersibility.

(π-conjugated conductive polymer)
The π-conjugated conductive polymer may be any organic polymer having a π-conjugated main chain. molecules, polyphenylene-based conductive polymers, polyphenylene-vinylene-based conductive polymers, polyaniline-based conductive polymers, polyacene-based conductive polymers, polythiophene-vinylene-based conductive polymers, copolymers thereof, and the like. Polypyrrole-based conductive polymers, polythiophenes and polyaniline-based conductive polymers are preferable from the viewpoint of stability in air, and polythiophene-based conductive polymers are more preferable from the viewpoint of transparency.

Polythiophene-based conductive polymers 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(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 ,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-carboxy butylthiophene).
Polypyrrole-based conductive polymers include polypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole), poly(3-ethylpyrrole), poly(3-n-propylpyrrole), 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-hexyloxypyrrole), poly(3-methyl-4-hexyloxypyrrole).
Polyaniline-based conductive polymers include polyaniline, poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonic acid), and poly(3-anilinesulfonic acid).
Among these π-conjugated conductive polymers, poly(3,4-ethylenedioxythiophene) is particularly preferred from the viewpoint of conductivity, transparency and heat resistance.
The π-conjugated conductive polymer contained in the conductive composite may be of one type or two or more types.

(polyanion)
A polyanion is a polymer having two or more monomer units having an anionic group in its molecule. The anion group of this polyanion functions as a dopant for the π-conjugated conductive polymer and improves the conductivity of the π-conjugated conductive polymer.
The anionic group of the polyanion is preferably a sulfo group or a carboxy group.
Specific examples of such polyanions include polystyrenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyacrylic acid esters having a sulfo group, polymethacrylic acid esters having a sulfo group (e.g., poly(4-sulfobutyl methacrylate) , polysulfoethyl methacrylate, polymethacryloyloxybenzenesulfonic acid), poly(2-acrylamido-2-methylpropanesulfonic acid), polymers having a sulfo group such as polyisoprene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, Polymers having carboxy groups such as polyallylcarboxylic acid, polyacrylic acid, polymethacrylic acid, poly(2-acrylamido-2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, etc. A polyanion is a single monomer. may be a homopolymer obtained by polymerizing or a copolymer obtained by polymerizing two or more monomers.
Among these polyanions, a polymer having a sulfo group is preferable, and polystyrene sulfonic acid is more preferable, because the conductivity can be further increased.
One of the polyanions may be used alone, or two or more thereof may be used in combination.
The weight 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 determined by gel permeation chromatography and calculated in terms of polystyrene.

The content 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 with respect to 100 parts by mass of the π-conjugated conductive polymer, and is 10 parts by mass or more and 700 parts by mass or less. and more preferably in the range of 100 parts by mass or more and 500 parts by mass or less. If the polyanion content is at least the above lower limit, the doping effect on the π-conjugated conductive polymer tends to be stronger, resulting in higher conductivity. On the other hand, if the polyanion content is equal to or less than the above upper limit, the π-conjugated conductive polymer can be sufficiently contained, and 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, based on the total mass of the conductive polymer dispersion. 02% by mass or more and 0.5% by mass or less is preferable, and 0.03% by mass or more and 0.1% by mass or less is more preferable.
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 equal to or less than the upper limit of the above range, the dispersibility of the conductive composite in the conductive polymer dispersion can be enhanced, and a uniform conductive layer can be formed.

[Isocyanurate compound]
The isocyanurate compound contained in the conductive polymer dispersion of this embodiment includes one having one or more vinyl groups. Here, the vinyl group may be directly bonded to the nitrogen atom of the isocyanurate ring, or may be bonded to the nitrogen atom via a divalent linking group.

Examples of the divalent linking group include optionally substituted alkylene groups having 1 to 6 carbon atoms. Any methylene group of the alkylene group is one or more selected from -O-, -C(=O)-, -C(=O)-O-, and -OC(=O)- group may be substituted. However, the case where oxygen atoms are linked to each other is excluded. Any hydrogen atom of the alkylene group may be substituted with an alkyl group having 1 to 3 carbon atoms. The number of carbon atoms in the alkylene group is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1.

Preferred specific examples of the isocyanurate compound include compound (1) represented by the following general formula (1).

R ₁ and R ₂ in formula (1) are each independently a hydrogen atom or an arbitrary substituent.
The optional substituents include, for example, a vinyl group which may have a divalent linking group as described above, an epoxy group or an oxetane group which may have a divalent linking group as described above, and 1 to 1 carbon atoms. 14 alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, etc.), alkoxy groups having 1 to 14 carbon atoms (e.g., methoxy group, ethoxy group, propoxy group, butoxy group, etc.), hydroxyl group, amino group , a carboxy group, and the like. The hydrogen atoms of these substituents are further substituted by other substituents (e.g., (meth)acryloyloxy group, carboxyl group, hydroxyl group, epoxy group, amino group, trialkoxysilyl group, halogen (e.g., fluorine atom, chlorine atom). , bromine atom), etc.).
Among these, from the viewpoint that the effects of the present invention are further exhibited, the above-mentioned vinyl group that may have a divalent linking group interposed therebetween, and the epoxy group that may have the above-mentioned divalent linking group interposed therebetween Alternatively, an oxetane group is preferred.

Chemical formulas of preferred specific examples of the compound (1) are shown below. Among the following, the isocyanurate compounds represented by the chemical formulas (1-2), (1-5), and (1-6) are more preferable from the viewpoint that the effects of the present invention are further exhibited, and the chemical formula ( 1-2) and isocyanurate compounds represented by the chemical formula (1-5) are more preferred.

The isocyanurate compound contained in the conductive polymer dispersion of this embodiment may be one kind, or two or more kinds.

In the conductive polymer dispersion of this aspect, the content of the isocyanurate compound with respect to 100 parts by mass of the conductive composite is preferably 1 part by mass or more and 100 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less. It is preferably 20 parts by mass or more and 40 parts by mass or less. Within the above preferred range, the adhesion of the conductive layer to the film substrate and the release layer can be further enhanced, and the decrease in conductivity over time due to exposure to the atmosphere of the conductive layer can be further suppressed.

In the conductive polymer dispersion of this aspect, the content of the water-dispersible resin described later with respect to 100 parts by mass of the isocyanurate compound is preferably 100 parts by mass or more and 10000 parts by mass or less, and is preferably 1000 parts by mass or more and 8000 parts by mass or less. More preferably, it is 3000 parts by mass or more and 6000 parts by mass or less. Within the above preferred range, the adhesion of the conductive layer to the film substrate and the release layer can be further enhanced, and the decrease in conductivity over time due to exposure to the atmosphere of the conductive layer can be further suppressed.

[Water-dispersible resin]
The water-dispersible resin can function as a binder resin in the conductive layer formed from the coating film of the conductive polymer dispersion of this embodiment.
A water-dispersible resin is a resin that can be dispersed or dissolved in a dispersion medium containing water. In the conductive polymer dispersion of this embodiment, the state of the water-dispersible resin may be a dispersed state obtained by homogenization or the like, an emulsion state, or a dissolved state.
The water-dispersible resin is preferably a resin having a functional group that can be dissociated in water, such as an acid group such as a carboxy group or a sulfo group, or a salt thereof. Specifically, acrylic resins, polyester resins, polyurethane resins, polyimide resins, and melamine resins, preferably water-dispersible resins having an acid group such as a carboxy group or a sulfo group, or salts thereof.
Among the above water-dispersible resins, polyester resins, urethane resins, and acrylic resins are preferable because the adhesion of the conductive layer to the film substrate and the release layer is further improved. In particular, when the base film is a polyester resin, the water-dispersible resin is preferably a polyester resin.
The water-dispersible resin contained in the conductive polymer dispersion of this embodiment may be one kind, or two or more kinds.

In the conductive polymer dispersion of this aspect, the content of the water-dispersible resin with respect to 100 parts by mass of the conductive composite is preferably 100 parts by mass or more and 10000 parts by mass or less, and is preferably 500 parts by mass or more and 5000 parts by mass or less. It is more preferably 1000 parts by mass or more and 2000 parts by mass or less. Within the above preferred range, the adhesion of the conductive layer to the film substrate and the release layer can be enhanced, and good conductivity of the conductive layer can be ensured.

[Dispersion medium]
Examples of the dispersion medium contained in the conductive polymer dispersion of this embodiment include water, organic solvents, and mixtures of water and organic solvents.
Examples of organic solvents include alcohol-based solvents, ether-based solvents, ketone-based solvents, ester-based solvents, and aromatic hydrocarbon-based solvents.
Examples of alcohol 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 monohydric alcohols such as ethers and ethylene glycol monomethyl ether;
Examples of ether solvents include diethyl ether, dimethyl ether, ethylene glycol, propylene glycol, propylene glycol dialkyl ether and the like.
Ketone solvents include, for example, 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 ester-based solvents include ethyl acetate, propyl acetate, and butyl acetate.
Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene and the like.
An organic solvent may be used individually by 1 type, and may use 2 or more types together.
Among the organic solvents, monohydric alcohols are preferable, and methanol is more preferable, since the dispersibility of the conductive composite and the water-dispersible resin can be further enhanced.

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 of water in 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. A monohydric alcohol is preferable as a dispersion medium other than water. In addition, among the later-described high-conductivity agents, the mass of those corresponding to the above examples of the organic solvent shall be included in the mass of the total dispersion medium.

In the conductive polymer dispersion of this aspect, the water-dispersible resin is preferably dispersed in an aqueous dispersion medium. In such a dispersed state, the properties of the conductive layer obtained by applying the conductive polymer dispersion to the film substrate become uniform over the entire surface of the conductive layer, and the conductivity of the film substrate and the release layer becomes uniform. It is preferable because the adhesion of the layer is further improved.

[High conductivity agent]
The conductive polymer dispersion of this embodiment may contain a conductivity enhancer in order to further improve the conductivity. Here, the π-conjugated conductive polymer, the polyanion, the isocyanurate compound, the water-dispersible resin, and the binder component are not classified as high-conductivity agents.
Conductivity enhancing agents include sugars, nitrogen-containing aromatic cyclic compounds, compounds having two or more hydroxy groups, compounds having one or more hydroxy groups and one or more carboxy groups, compounds having an amide group, It is preferably at least one compound selected from the group consisting of compounds having an imide group, lactam compounds, and compounds having a glycidyl group.
As the conductivity enhancer, a compound having two or more hydroxy groups (dihydric alcohol) is preferable, and propylene glycol is more preferable.
The conductivity enhancing agent contained in the conductive polymer dispersion of this embodiment may be one type or two or more types.

The content ratio of the conductive agent in the conductive polymer dispersion of this embodiment 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 with respect to 100 parts by mass of the conductive composite. It is more preferably not more than 500 parts by mass and even more preferably 500 parts by mass or more and 9000 parts by mass or less. If the content of the high-conductivity agent is at least the above lower limit, the effect of improving conductivity by adding the high-conductivity agent is sufficiently exhibited, and if it is at or below the above upper limit, the concentration of the π-conjugated conductive polymer decreases. 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 water-dispersible resin.
Specific examples of the binder component include binder resins such as acrylic resins, epoxy resins, oxetane resins, polyurethane resins, polyimide resins, melamine resins, silicone resins, and vinyl acetate resins.
Also, the binder component may be a monomer or oligomer that forms the binder resin. A binder resin can be formed by polymerizing the monomer or the oligomer when forming the conductive layer.
One of the binder components may be used alone, or two or more of them may be used in combination.

[Other additives]
The conductive polymer dispersion of this embodiment may contain other additives.
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 and the like can be used. However, the additive consists of compounds other than the isocyanurate compound, the π-conjugated conductive polymer, the polyanion, the water-dispersible resin, the dispersion medium, the binder component, and the high-conductivity agent.
Examples of surfactants include nonionic, anionic, and cationic surfactants, with nonionic surfactants being preferred from the standpoint of storage stability. A polymeric surfactant such as polyvinylpyrrolidone may also be added.
Examples of inorganic conductive agents include metal ions and conductive carbon. Metal ions can be generated by dissolving a metal salt in water.
Antifoaming agents include silicone resins, polydimethylsiloxane, silicone oils and the like.
Examples of coupling agents include silane coupling agents having an epoxy group, a vinyl group, or an amino group.
Antioxidants include phenol antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants, sugars and the like.
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 above additive, the content ratio is appropriately determined according to the type of the additive. It can be in the 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 the isocyanurate compound, the water-dispersible resin, the dispersion medium, etc. to the aqueous dispersion of the conductive composite.
The aqueous dispersion of the conductive composite may be obtained by chemically oxidatively polymerizing a monomer forming a π-conjugated conductive polymer in an aqueous polyanion solution, or a commercially available one may be used.

The chemical oxidation polymerization can be performed using a known catalyst and oxidizing agent. Examples of catalysts 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 oxidation state.

(Effect)
Since the conductive polymer dispersion according to the present invention contains a specific isocyanurate compound, it is possible to form a conductive layer having excellent adhesion to a plastic substrate and a release layer. Furthermore, the conductive layer is prevented from decreasing in conductivity over time when exposed to the atmosphere. Although the details of this mechanism have not been elucidated, the vinyl group of the isocyanurate compound reacts with some of the acid groups of the polyanion constituting the conductive composite or some of the acid groups of the water-dispersible resin. It is thought that one of the factors is that

<Conductive film>
A second aspect of the present invention is a conductive film comprising a film substrate and a conductive layer formed on at least one surface of the film substrate and formed of a cured layer of the conductive polymer dispersion 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 substrate 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. is more preferred.
When the average thickness of the conductive layer is at least the lower limit value, sufficiently high conductivity can be exhibited, and when the average thickness is at most the upper limit value, the adhesion of the conductive layer is further improved.

The conductive layer of the conductive film of this aspect 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 more preferably has a surface resistance of ³ Ω/□ or more and 1×10 ⁸ Ω/□ or less, and more preferably 1×10 ⁴ Ω/□ or more and 1×10 ⁶ Ω/□ or less.

(Film substrate)
Examples of the film substrate include plastic films.
Examples of film substrate 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, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyimide, cellulose triacetate, cellulose acetate propio nate and the like.
From the viewpoint of enhancing the adhesion between the film substrate and the conductive layer, the resin for the film substrate is preferably the same type of resin as the water-dispersible resin, and among these, a polyester resin such as polyethylene terephthalate is preferable.

Resins for film substrates may be amorphous or crystalline.
The film substrate may be unstretched or stretched.
The film substrate 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 substrate is preferably 5 μm or more and 500 μm or less, more preferably 20 μm or more and 200 μm or less. When the average thickness of the film substrate is at least the lower limit, the film is less likely to break, and when it is at most the upper limit, sufficient flexibility as a film can be ensured.
The thickness of a member in this specification is a value obtained by measuring the thickness at arbitrary 10 points and averaging the measured values.

A known polarizing film can also be used as the film substrate.
As a polarizing film, for example, one having a pair of transparent films and a polarizing layer disposed therebetween is known.
Examples of the transparent resin that constitutes 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.
As the polarizing layer, for example, a hydrophilic film to which a dichroic substance is adhered is uniaxially stretched to orient the dichroic substance. Hydrophilic films include, for example, polyvinyl alcohol films and partially saponified ethylene/vinyl acetate copolymer films. Dichroic substances include, for example, iodine and dichroic dyes.
The thickness of the polarizing layer can be, for example, 10 μm or more and 500 μm or less.

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

<Method for producing conductive film>
A third aspect of the present invention comprises applying the conductive polymer dispersion of the first aspect to at least one surface of a film substrate, drying the formed coating film, and forming a conductive layer. It is a method for producing a flexible film. The conductive film of the second aspect can be produced by the production method of this aspect.

Examples of the method for applying (applying) the conductive polymer dispersion of the first embodiment to the film substrate 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. , methods using coaters such as rod coaters, air doctor coaters, knife coaters, blade coaters, cast coaters and screen coaters, methods using atomizers such as air spray, airless spray, and rotor dampening, immersion methods such as dipping, etc. can be applied.
Commercially available bar coaters are numbered according to coating thickness, and the larger the number, the thicker the coating.
The amount of the conductive polymer dispersion to be applied to the film substrate is not particularly limited, but in consideration of uniform and even coating, conductivity and film strength, the solid content is 0.01 g/m ^{2 .} It is preferably in the range of 10.0 g/m ² or more.

A conductive layer (conductive film) formed by curing the coating film by drying the coating film composed of the conductive polymer dispersion applied on the film substrate and removing the dispersion medium. You can get a sex film.
Heat drying, vacuum drying, etc. are mentioned as a method of drying a coating film. As heat drying, for example, a normal method such as hot air heating or infrared heating can be used.
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 or higher and 150°C or lower. Here, the heating temperature is the set temperature of the drying device.

When the coated conductive polymer dispersion contains a thermosetting monomer or oligomer as a binder component, the coating film is heated to cure the binder component, thereby forming a conductive polymer having a conductive layer. you can get the film.
When the coated conductive polymer dispersion contains a photocurable monomer or oligomer as a binder component, the coating film is irradiated with ultraviolet rays or electron beams to cure the binder component, thereby forming the conductive layer. A formed conductive film can be obtained.

<Conductive release film>
A fourth aspect of the present invention is a film substrate, a conductive layer formed on at least one surface of the film substrate and formed of a cured layer of the conductive polymer dispersion of the first aspect, and the conductive layer. A conductive release film comprising a release layer containing a silicone compound laminated on a surface thereof.
The conductive release film of this aspect can have the same configuration as the conductive film of the second aspect except that the release layer is provided. Therefore, the explanation overlapping with the explanation of the second aspect is 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-based compound contained in the release layer contributes to release properties (easy peelability).

As the silicone-based compound, a silicone-based compound known as a release agent is applied. Here, silicone is a polymer generally referred to as organopolysiloxane, having a main chain (silicone skeleton) in which organic groups (eg, alkyl groups, phenyl groups, etc.) are bonded to siloxane bonds. As the organopolysiloxane, polydimethylsiloxane (PDMS) is preferable, and polydimethylsiloxane partially having a reactive functional group or a non-reactive functional group is also preferable. Acrylic resins and alkyd resins having organopolysiloxane in side chains can also be used as the silicone compound.

As the silicone-based 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 curable silicone or a condensation curable silicone. The curable silicone forms a three-dimensional crosslinked structure upon reaction and cures.
Examples of addition-curable silicones include linear polymers having siloxane bonds and having polydimethylsiloxane having vinyl groups at both ends of the linear chain and hydrogensilane. A platinum-based curing catalyst may be used to accelerate curing.
Specific examples of addition-curable 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-curable silicone dissolved or dispersed in an organic solvent is preferably used.

The content of the silicone-based compound contained in the release layer of this embodiment can be, for example, 20% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass or less, relative to the total mass of the release layer. is preferred.
In the release layer of this embodiment, a binder component other than a silicone-based compound, or a binder component other than a silicone-based compound, as long as the adhesion of the conductive layer to the release layer is not impaired and the releasability of the release layer is not impaired. known additives such as agents and antistatic agents.

The average thickness of the release layer is, for example, preferably 10 nm or more and 50 μm or less, more preferably 20 nm or more and 20 μm or less.
When the average thickness of the release layer is at least the lower limit value, higher releasability can be exhibited, and when the average thickness is at most the upper limit value, adhesion 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 and expose the rest of the conductive layer to the surface.

(Effect)
Since the conductive layer of the conductive release film according to the present invention contains a specific cyanurate compound and a water-dispersible resin, it can exhibit sufficient adhesion (adhesiveness) even to a release layer containing silicone. As a result, the release layer included in the conductive release film of the present invention can exhibit excellent releasability for objects attached to the release layer without being separated from the main 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 the release layer covering 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 to the outside from the exposed part. be. In addition, the presence of the conductive layer inside the conductive release film can prevent charging of the conductive release film itself without any special treatment.
It is generally known that the gas permeability of silicone rubber is higher than that of other rubbers, and simply laminating a release layer containing silicone on a conductive layer cannot sufficiently shield the conductive layer from the atmosphere. . Therefore, the conductive layer itself is required to have resistance to atmospheric exposure. Since the conductive layer according to the present invention contains the isocyanurate compound and the water-dispersible resin, it has improved resistance to atmospheric exposure.

<Method for producing 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 substrate, dry the formed coating film, and form a conductive layer (conductive layer formation step), and applying a release agent composition containing a silicone compound to the surface of the conductive layer, drying the formed coating film, and forming a release layer (release layer forming step). A method for producing a conductive release film, comprising:

(Conductive layer forming step)
This step can be performed in the same manner as in the method for producing a conductive film of the third aspect. Therefore, the description is omitted here.

(Release layer forming step)
The release agent composition used in this step contains a silicone compound. The description of the silicone-based compound is the same as the description of the fourth aspect, so the description is omitted here.
In addition to the silicone-based compound, the release agent composition may optionally contain additives such as organic solvents, curing catalysts, binder components other than silicone-based compounds, adhesion improvers, and antistatic agents. good too. When addition-curable silicone is used as the silicone-based compound, it is preferable to blend at least one of toluene and methyl ethyl ketone as the organic solvent. Conventional methods are applied to the mixing ratio and mixing method of each material contained in the release agent composition.
The method of applying the 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 coating method and drying/curing method for forming the conductive layer.
By the above method, the conductive release film according to the present invention can be produced.

(Production Example 1) Synthesis of Polyanion Dissolve 206 g of sodium styrenesulfonate in 1000 ml of ion-exchanged water, and while stirring at 80° C., add 1.14 g of ammonium persulfate oxidant solution previously dissolved in 10 ml of water for 20 minutes. was added dropwise and the solution was stirred for 12 hours.
1000 ml of sulfuric acid diluted to 10% by mass was added to the resulting sodium polystyrenesulfonate-containing solution, and about 1000 ml of the solvent in the obtained polystyrenesulfonic 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 washing operation was repeated three times.
Water in the obtained solution was removed under reduced pressure to obtain a colorless solid polystyrene sulfonic acid.

(Production Example 2) Synthesis of conductive composite 14.2 g of 3,4-ethylenedioxythiophene and 36.7 g of polystyrene sulfonic acid obtained in Production Example 1 were dissolved in 2000 ml of deionized water. Mixed at 20°C. The resulting mixed solution was kept at 20° C., and with 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, 2,000 ml of ion-exchanged water was added to the reaction solution, and about 2,000 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 2000 ml of ion-exchanged water are added to the obtained solution, about 2000 ml of the solvent is removed by ultrafiltration, and 2000 ml of ion-exchanged water is added to the residual liquid. , about 2000 ml of solvent was removed by ultrafiltration. This operation was repeated three times.
Furthermore, 2000 ml of ion-exchanged water was added to the resulting solution, and about 2000 ml of the solvent was removed by ultrafiltration. This operation was repeated five times to obtain an aqueous dispersion of polystyrenesulfonic acid-doped poly(3,4-ethylenedioxythiophene) (PEDOT-PSS) with a solid content concentration of 1.2% by mass.

(Example 1)
To 15 g of the PEDOT-PSS aqueous dispersion obtained in Production Example 2 (solid content: 0.18 g), 65 g of water, 10 g of propylene glycol, and a water-dispersible polyester resin, Plascoat RZ-105 (manufactured by Goo Chemical Co., Ltd., solid content 25% by mass), 300 g of methanol, and 0.05 g of triallyl isocyanurate represented by the formula (1-2) were added to obtain a paint.
The obtained paint was applied onto a PET film (Lumirror T60 manufactured by Toray Industries, Inc.) using a #4 bar coater and dried at 120°C for 1 minute to obtain a conductive film having a conductive layer on the PET film. .
Table 1 shows the results of measuring the surface resistance of the obtained conductive film.

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

(Example 2)
A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that 0.05 g of triallyl isocyanurate in Example 1 was changed to 0.1 g, and the surface resistance and the like were measured. bottom. Table 1 shows the results.

(Example 3)
A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that 0.05 g of triallyl isocyanurate in Example 1 was changed to 0.15 g, and the surface resistance and the like were measured. bottom. Table 1 shows the results.

(Example 4)
A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that 0.05 g of triallyl isocyanurate in Example 1 was changed to 0.2 g, and the surface resistance and the like were measured. bottom. Table 1 shows the results.

(Example 5)
A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that 0.05 g of triallyl isocyanurate in Example 1 was changed to 0.25 g, and the surface resistance and the like were measured. bottom. Table 1 shows the results.

(Example 6)
A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that 0.05 g of triallyl isocyanurate in Example 1 was changed to 0.3 g, and the surface resistance and the like were measured. bottom. Table 1 shows the results.

(Example 7)
A conductive film and a conductive A release film was obtained, and its surface resistance value and the like were measured. Table 1 shows the results.

(Example 8)
A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that 0.05 g of triallyl isocyanurate in Example 1 was changed to 0.15 g of diallyl monoglycidyl isocyanurate. etc. were measured. Table 1 shows the results.

(Example 9)
A conductive film and a conductive release film were obtained in the same manner as in Example 1, except that 0.05 g of triallyl isocyanurate in Example 1 was changed to 0.2 g of diallyl monoglycidyl isocyanurate. etc. were measured. Table 1 shows the results.

(Example 10)
A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that 0.05 g of triallyl isocyanurate in Example 1 was changed to 0.25 g of diallyl monoglycidyl isocyanurate. etc. were measured. Table 1 shows the results.

(Comparative example 1)
A conductive film and a conductive release film were obtained in the same manner as in Example 1 except that 0.05 g of triallyl isocyanurate was not added, and the surface resistance and the like were measured. Table 1 shows the results.

<Evaluation>
[Surface resistance value]
For the conductive film of each example, the surface resistance value of the conductive layer was measured using a resistivity meter (Hiresta, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) under the condition of an applied voltage of 10V. Table 1 shows the measurement results of the surface resistance value.
For the conductive release film of each example, a probe is placed on the release layer, and the surface resistance value of the conductive layer is measured with a resistivity meter (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Hiresta) was used, and the measurement was performed under the condition of an applied voltage of 10V. The surface resistance value was measured both immediately after the production of the conductive release film (R ₀ ) and after exposure to the atmosphere for 24 hours (R ₁ ). Each measurement result is shown in Table 1. "Ω/□" in the table means ohms per square. Also, "5.0E+08" represents "5.0×10 ⁸ ".

[Peeling force]
The release force of the conductive release film of each example was measured by the following method to evaluate the releasability of the release layer.
A 25 mm wide polyester adhesive tape (manufactured by Nitto Denko, No. 31B) is attached to the surface of the release layer of the conductive release film, and a load of 1976 Pa is applied from above the adhesive tape and pressure is applied at 25 ° C. for 20 hours. processed. Next, according to JIS Z0237, using a tensile tester, the adhesive tape attached to the release layer was peeled at an angle of 180 ° (peeling speed 0.3 m / min), and the peel force (unit: N) was measured. It was measured. Table 1 shows the measurement results. The smaller the peel force, the higher the releasability of the release layer.

[Adhesion]
For 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 according to the following criteria. Table 1 shows the results.
(Evaluation 1): The release layer was completely removed by the fifth finger rubbing, and the easy peelability was lost. That is, the adhesiveness between the release layer and the conductive layer is poor.
(Evaluation 2): The release layer remained until the 5th rubbing with the finger, but the release layer was completely removed by the 10th rubbing with the finger, and the easy releasability was lost. That is, the adhesion between the release layer and the conductive layer is poor.
(Evaluation 3): The release layer did not come off by the 10th finger rubbing, a large change in the color of the release layer was observed, and the easy releasability was reduced. That is, the adhesion between the release layer and the conductive layer is normal.
(Evaluation 4): The release layer did not come off by the 10th finger rubbing, and a small change in the color of the release layer was observed, but the easy releasability was hardly degraded. That is, the adhesion between the release layer and the conductive layer is excellent.
(Evaluation 5): The release layer did not come off until the 10th rubbing with a finger, no change in the color of the release layer was observed, and the easy releasability was not lowered. That is, the adhesion between the release layer and the conductive layer is particularly excellent.
In the five-level evaluation criteria described above, easy peelability (mold releasability) is based on the results of testing the ease of peeling off an adhesive tape attached to the surface rubbed with a finger. The color change 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 is lifted when the pressure-sensitive adhesive tape attached to the surface of the release layer is peeled off, resulting in reduced peelability.

From the results in Table 1, it can be seen that in the conductive films of Examples 1 to 10 according to the present invention, the adhesion of the conductive layer to the PET film and release layer is generally good. Good adhesion is exhibited by containing a specific isocyanurate compound and a water-dispersible resin in the conductive layer. On the other hand, the conductive layer of Comparative Example 1, which does not contain a specific isocyanurate compound, has poor adhesion and is not suitable for practical use.

Claims (13)

a film substrate;
a conductive layer formed of a cured layer of a conductive polymer dispersion formed on at least one surface of the film substrate;
A release layer containing a silicone-based compound, laminated on the surface of the conductive layer;
A conductive release film comprising
The conductive polymer dispersion contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a water-dispersible resin, a dispersion medium, and an isocyanurate compound having one or more vinyl groups. and the conductive release film, wherein the content of the isocyanurate compound is 1 part by mass or more with respect to 100 parts by mass of the conductive composite contained in the conductive polymer dispersion. The conductive release film according to claim 1, wherein the isocyanurate compound contains a compound represented by the following formula (1).

[In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an arbitrary substituent. ] The conductive release film according to claim 1 or 2, wherein the isocyanurate compound comprises triallyl isocyanurate or a compound represented by the following formula (1-5).

The conductive release film according to any one of claims 1 to 3, wherein the water-dispersible resin is a water-dispersible polyester resin. The conductive release film according to any one of claims 1 to 4, wherein the dispersion medium contains a monohydric alcohol. 6. The conductive release film of claim 5, wherein said monohydric alcohol comprises methanol. The conductive release film according to any one of claims 1 to 6, further comprising a conductive agent. 8. The conductive release film according to claim 7, wherein the conductivity enhancer comprises a dihydric alcohol. The conductive release film according to claim 7 or 8, wherein the conductivity enhancer contains propylene glycol. The conductive release film according to any one of claims 1 to 9, wherein the π-conjugated conductive polymer is poly(3,4-ethylenedioxythiophene). The conductive release film according to any one of claims 1 to 10, wherein the polyanion is polystyrenesulfonic acid. Applying a conductive polymer dispersion to at least one surface of a film substrate and drying the formed coating film to form a conductive layer;
applying a release agent composition containing a silicone-based compound to the surface of the conductive layer and drying the formed coating film to form a release layer;
A method for producing a conductive release film, comprising
The conductive polymer dispersion contains a conductive composite containing a π-conjugated conductive polymer and a polyanion, a water-dispersible resin, a dispersion medium, and an isocyanurate compound having one or more vinyl groups. and the content of the isocyanurate compound with respect to 100 parts by mass of the conductive composite contained in the conductive polymer dispersion is 1 part by mass or more. 13. The method for producing a conductive release film according to claim 12 , wherein the silicone compound is an addition-curable silicone resin.