TWI570477B - Organic conductive film - Google Patents

Description

Organic conductive film

The present invention relates to an organic conductive film excellent in durability, and an optical film, a packaging material, a transparent electrode film, and a liquid crystal display unit having such an organic conductive film.

As a transparent conductive film (such as a transparent electrode) used for display applications and the like, an inorganic conductive transparent material such as ITO is known.

However, the formation of a transparent conductive film using ITO is usually carried out by a method such as sputtering using a large-scale vacuum apparatus, and the manufacturing cost tends to be improved.

Further, ITO contains indium of a rare metal (so-called rare metal), and there is a shortage of resources.

Therefore, in recent years, an active attempt has been made to use a conductive polymer as a substitute for ITO.

The conductive polymer as the organic conductive material can be formed into a film by a simple method such as a roll coater or a wet process such as printing, and since the conductive polymer is organic, it is rich in resources. Inorganic conductive materials have advantages over.

In this field, it is known that a conductive polymer can be used in various applications, and when a conductive polymer is used for film formation, the film thickness is usually made uniform. On the other hand, an organic conductive film formed using a conductive polymer has a lower heat resistance and weather resistance than a conductive film made of an inorganic conductive material, and has a problem of poor durability. For example, polythiophene-based conductive poly A compound (for example, PEDOT/PSS) is known as a conductive polymer, but it is known that its conductivity is lowered with time, and its deterioration mechanism proposes an oxidation reaction due to oxygen in the air (for example, Non-Patent Document 1) .

Further, according to the findings of the present inventors, it is clear that when a polythiophene-based conductive polymer is used to form a uniform film, the conductivity is slowly lost and cannot be used for a long period of time.

[Non-Patent Document 1] edited by Kudo K., Electronic Journal Archives No. 118, Electronic Journal, 2011, 133 pages

An object of the present invention is to provide an organic conductive film having excellent durability, an optical film including the organic conductive film, a packaging material, a transparent electrode film, and a liquid crystal display unit.

In order to solve the above problems, the inventors of the present invention have found that the maximum height (Rz) of one surface of the organic conductive film can be made 35% or more with respect to the average film thickness, thereby making the organic conductive film The durability is particularly improved to complete the present invention.

In other words, the organic conductive film of the present invention is formed by using a conductive composition containing at least a conductive polymer, and the maximum height (Rz) of one surface thereof is 35% or more with respect to the average film thickness.

In the organic conductive film of the present invention, it is preferred that the conductive polymer is a polythiophene-based conductive polymer.

Further, the polythiophene-based conductive polymer is preferably a composite of poly(3,4-dialkoxythiophene) or poly(3,4-alkylenedioxythiophene) and a dopant, and the poly( 3,4-Dialkyloxythiophene) or poly(3,4-alkylenedioxythiophene) having the repeating structure of the following formula (I):

(wherein R ¹ and R ² independently of each other represent a hydrogen atom or an alkyl group of C _1-4 or an optionally substituted C _1-4 alkylene group).

The optical film of the present invention is characterized in that it has the organic conductive film of the present invention.

The packaging material of the present invention is characterized in that it has the organic conductive film of the present invention.

The transparent electrode film of the present invention is characterized in that it has the organic conductive film of the present invention.

The liquid crystal display unit of the present invention is characterized in that it has the organic conductive film of the present invention.

In the organic conductive film of the present invention, since the maximum height (Rz) of one surface thereof is 35% or more with respect to the average film thickness, the durability of the organic conductive film is extremely excellent.

Moreover, each of the optical film, the packaging material, the transparent electrode film, and the liquid crystal display unit including such an organic conductive film has excellent durability.

First, the organic conductive film of the present invention will be described.

The organic conductive film of the present invention is formed by using a conductive composition containing at least a conductive polymer. It is characterized in that the maximum height (Rz) of one side thereof is 35% or more with respect to the average film thickness.

Here, the maximum height (Rz) is a value measured in accordance with JIS B 0601-2001.

In addition, the average film thickness is an average value of the thickness when the organic conductive film is approximated to a film having a smooth surface, and when the conductive composition is uniformly applied and dried, the film thickness is calculated by calculating the film thickness. The value that comes out.

For example, when the conductive composition having a solid content of 1% is applied and dried at a film thickness of 9 μm, the average thickness of the organic conductive film is 90 nm.

In the organic conductive film, since the maximum height (Rz) of one surface thereof is 35% or more with respect to the average film thickness, the durability is extremely excellent.

Hereinafter, the reason will be described with reference to the drawings.

Fig. 1(a) is a cross-sectional view schematically showing an example of the organic conductive film of the present invention, and (b) to (d) are schematic views showing changes over time of deterioration of the organic conductive film shown in (a).

Fig. 2(a) is a cross-sectional view schematically showing an example of a conventional organic conductive film, and (b) to (d) are schematic views showing temporal changes in deterioration of the organic conductive film shown in (a).

In general, it is known that an organic conductive film composed of a conductive composition containing a conductive polymer changes or changes a chemical structure of a conductive polymer by contact with oxygen in light or air, thereby conducting electricity. Sexual decline. For example, PEDOT/PSS, which is well known as a representative example of a conductive polymer, is proposed as one of its degradation mechanisms by oxygen in the air. Oxidation reaction caused (Non-Patent Document 1).

Therefore, it is predicted that the organic conductive film composed of the conductive composition containing the conductive polymer starts to deteriorate on the surface of the film which is in contact with the air and deteriorates inside the film.

It is considered that this deterioration is caused by the process of impregnation and diffusion of oxygen into the film, which is a cause of deterioration. However, since the deterioration reaction is a reaction in a solid, it is presumed that the reaction is a rate-limiting diffusion, and as a result, it is expected that the thicker the film, the longer the time until the film is completely deteriorated.

However, the organic conductive film formed using the conductive composition containing a conductive polymer is generally an organic conductive film 22a having a uniform thickness as shown in Fig. 2(a) (further, 21 in Fig. 2 is a substrate).

Further, since the deterioration of the organic conductive film 22a is performed by the above-described process, the deteriorated portion 22b is increased in uniform thickness (deterioration uniformly in the thickness direction) (see FIGS. 2(b) to 2(d)). Therefore, the time until the entire film deteriorates is accelerated.

On the other hand, in the organic conductive film of the present invention, the maximum height (Rz) of one surface thereof is 35% or more with respect to the average film thickness, and as shown in Fig. 1(a), the surface of the organic conductive film 12a has irregularities. . Therefore, in the organic conductive film 12a, the thin portion of the film is deteriorated earlier, but the thick portion of the film is present in a large amount, and the time required for the thick film portion to completely deteriorate and the coating of the same amount of the conductive composition are applied. The formed organic conductive film is longer.

In other words, the organic conductive film of the present invention is less likely to deteriorate (part of the undegraded portion) than the organic conductive film formed by applying the same amount of the conductive composition, and as a result, the deterioration rate of the entire film becomes slow. Furthermore, in Figure 1, 11 As the substrate, 12b is a deteriorated portion.

In the above organic conductive film, the maximum height (Rz) is 35% or more with respect to the average film thickness. The reason for this is that the durability (membrane durability) of the organic conductive film is remarkably deteriorated when the maximum height is less than 35%.

From the viewpoint of film durability, the maximum height (Rz) is preferably 50% or more, more preferably 100% or more, still more preferably 200% or more, and most preferably 250% or more with respect to the average film thickness.

Further, the maximum height (Rz) is preferably 600% or less with respect to the average film thickness.

The reason for this is that if the maximum height exceeds 600%, the diffuse reflection of light on the surface becomes remarkable and the optical characteristics are deteriorated. Further, from the viewpoint of optical characteristics, the maximum height (Rz) is more preferably 500% or less with respect to the average film thickness, and most preferably 450% or less.

Further, in the case where the above-described maximum height (Rz) is measured at a plurality of positions in the organic conductive film, it is particularly preferable that the maximum height (Rz) at at least one position is 250% or more. The reason for this is that excellent durability can be surely ensured.

The average thickness of the organic conductive film is preferably 60 nm or more, more preferably 60 to 400 nm, still more preferably 60 to 300 nm, and still more preferably 80 to 200 nm.

The reason for this is that when the average film thickness is less than 60 nm, the characteristics of the organic conductive film such as the hardness or chemical resistance of the film tend to be deteriorated, and on the other hand, if it exceeds 400 nm, the optical characteristics are deteriorated. The tendency.

The organic conductive film has conductivity because it contains a conductive polymer, and its surface resistivity (SR) is preferably from 10 ² to 10 ¹¹ Ω/□. The reason for this is that, if it is within this range, the characteristics required as, for example, an antistatic layer or a transparent electrode are sufficiently satisfied.

Such an organic conductive film is formed using a conductive composition.

Next, each component of the above conductive composition will be described in order.

Conductive polymer

The conductive composition contains a conductive polymer as an essential component.

The conductive polymer is a blend for imparting conductivity (for example, surface resistivity, hereinafter referred to as SR) to the formed organic conductive film.

Examples of the conductive polymer include polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylacetylene, polynaphthalene, derivatives thereof, and the like, and a composite thereof.

Among these, a polythiophene-based conductive polymer composed of a composite of polythiophene and a dopant is preferable, and a polythiophene-based conductive polymer is more preferably a poly(3,4-dialkoxy group). A complex of thiophene) or poly(3,4-alkylenedioxythiophene) with a dopant.

As the poly(3,4-dialkoxythiophene) or poly(3,4-alkylenedioxythiophene), a cationic form of a repeating structural unit represented by the following formula (I) is preferred. Thiophene,

Here, R ¹ and R ² each independently represent a hydrogen atom or a C _1-4 alkyl group, or a C _1-4 alkylene group which may be substituted together.

Examples of the alkyl group of the above C _1-4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, and a third butyl group.

Further, as the C _1-4 alkylene group which may be substituted by R ¹ and R ² together, for example, a methylene group, a 1,2-extended ethyl group, a 1,3-propanyl group, and 1 may be mentioned. , 4-tert-butyl, 1-methyl-1,2-extended ethyl, 1-ethyl-1,2-extended ethyl, 1-methyl-1,3-propanyl, 2-methyl -1,3-propyl group and the like. It is preferably a methylene group, a 1,2-extended ethyl group, a 1,3-propanyl group, and more preferably a 1,2-extended ethyl group. As the polythiophene having the above alkylene group, poly(3,4-ethylenedioxythiophene) is particularly preferable.

The composite composed of poly(3,4-ethylenedioxythiophene) and a dopant is excellent in chemical stability in addition to conductivity or transparency, and is organically formed using the composite as a conductive polymer. The conductive film has extremely stable conductivity independent of humidity and extremely high transparency. Further, since the conductive composition containing the composite as the conductive polymer can form a film at a low temperature for a short period of time, it is also highly suitable for the production of an organic conductive film which requires mass production.

The dopant constituting the polythiophene-based conductive polymer is a polymer having an anionic form in which a complex is formed by forming an ion pair with the polythiophene, whereby the polythiophene can be stably dispersed in water.

Examples of such a dopant include carboxylic acid polymers (for example, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), and sulfonic acid polymers (for example, polystyrenesulfonic acid, polyvinylsulfonate). Acid, polyisoprene sulfonic acid, etc.). Further, the carboxylic acid polymers and sulfonic acid polymers may be ethylene carboxylic acids and vinyl sulfonic acids and other polymerizable monomers such as acrylates, styrene A copolymer of an aromatic vinyl compound such as an alkene or a vinylnaphthalene. Among them, polystyrenesulfonic acid is particularly preferred.

The above polystyrenesulfonic acid preferably has a weight average molecular weight of more than 20,000 and 500,000 or less. More preferably 40,000 to 200,000. When polystyrenesulfonic acid having a molecular weight outside this range is used, the dispersion stability of water by the polythiophene-based conductive polymer is lowered. Further, the weight average molecular weight of the above polymer is a value measured by gel permeation chromatography (GPC). An ultrahydroge 1500 column manufactured by Waters Corporation was used for the measurement.

The above polythiophene-based conductive polymer can be obtained by oxidative polymerization using water having an oxidizing agent. Two kinds of oxidizing agents (first oxidizing agent and second oxidizing agent) are used in the oxidative polymerization.

Preferred examples of the first oxidizing agent include peroxodisulfate, sodium peroxodisulfate, potassium peroxydisulfate, ammonium peroxodisulfate, hydrogen peroxide, potassium permanganate, potassium dichromate, and alkali metal perborate. Salt, copper salt, etc. Among these first oxidizing agents, sodium peroxodisulfate, potassium peroxydisulfate, ammonium peroxodisulfate and peroxodisulfuric acid are preferred.

The amount of the first oxidizing agent to be used is preferably 1.5 to 3.0 mol equivalents, more preferably 2.0 to 2.6 mol equivalents, based on the thiophene monomer to be used.

Preferably, the second oxidizing agent is added with a metal ion (for example, ions of iron, cobalt, nickel, molybdenum or vanadium) in a catalytic amount. Among them, iron ions are most effective.

The amount of the metal ion added is preferably 0.005 to 0.1 mol equivalent, and more preferably 0.01 to 0.05 mol, based on the thiophene monomer to be used. the amount.

Water is used as the reaction solvent in the above oxidative polymerization. In addition to water, an alcohol such as methanol, ethanol, 2-propanol or 1-propanol or a water-soluble solvent such as acetone or acetonitrile may be added.

An aqueous dispersion of a conductive polymer is obtained by such oxidative polymerization.

The content of the conductive polymer is not limited, and is preferably 1 to 10% by weight based on the solid content of the solid content of the conductive composition. More preferably, it is 3 to 6% by weight. If it is less than 1% by weight, it is difficult to exhibit conductivity, and if it is more than 10% by weight, precipitation may occur due to mixing with other components, and the pot life of the conductive composition may be shortened.

In addition to the above conductive polymer, the conductive composition may contain the following components as needed.

2. Adhesive composition

The conductive composition of the present invention may also contain a binder component.

The binder component contributes to the formation of a film on the substrate using the above-described conductive composition.

Examples of the binder component include a decane coupling agent such as 3-glycidoxypropyltrimethoxydecane, a polyether modified polydimethyl siloxane, or a polyether modified oxirane, and an alkoxy decane. a homopolymer of a polyester, a polyester, a polyacrylate, a polymethacrylate, a polyurethane, a polyvinyl acetate, a polyvinylidene chloride, a polyamide, a polyimide, or the like; A resin binder such as a copolymer obtained by copolymerizing a monomer such as vinylidene chloride, vinyl chloride, an alkyl acrylate or an alkyl methacrylate. These may be used alone or in combination of two or more.

Further, when the conductive composition of the present invention is applied to a glass substrate, it is preferred to contain at least an alkoxydecane oligomer as the binder component. In the case of containing an alkoxydecane oligomer, since the conductive polymer is well dispersed in the dense structure, it is excellent in hardness and chemical resistance, and has high conductivity. Conductive film.

Examples of the alkoxydecane oligomer include those represented by the following formula (II).

In the formula, R ¹ and R ^{2 are the} same or different and each represents an alkyl group having 1 to 4 carbon atoms. R ³ and R ^{4 are the} same or different and each represents H (hydrogen atom), a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms. Wherein at least one of the plurality of R ³ and R ⁴ is an alkoxy group.

n represents an integer from 2 to 20, and more preferably represents an integer from 2 to 14.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third butoxy group.

The alkoxydecane oligomer used in the present invention may be one composed of only one of the compounds represented by the above formula (II), or a mixture of plural kinds.

Further, by using an alkoxydecane oligomer having a decane bond in the molecule as the binder component, and an alkane-free alkane Compared with an oxoxane monomer or an epoxy decane, it is easy to form a denser structure in a conductive film.

This effect is remarkable as the film formation temperature is lower.

Further, when alkoxysilane polymer (the number of condensation n is larger than that of the alkoxydecane oligomer) is used as the binder component, the steric repulsion becomes large, so that the reactivity is deteriorated and the dense structure is not easily formed. This can be inferred that the result is a decrease in film hardness. This tendency is more pronounced as the molecular weight is larger.

The alkoxydecane oligomer is a polymerized alkoxydecane formed by condensing monomers of alkoxydecane to each other, and means having one or more decane bonds in one molecule (Si). -O-Si) oligomer.

The weight average molecular weight of the above oligomer is not particularly limited, but is preferably more than 152 and 4,000 or less. More preferably around 500~1500.

Further, the weight average molecular weight of the above oligomer is a value measured by gel permeation chromatography (GPC). An ultrahydroge 1500 column manufactured by Waters Corporation was used for the measurement.

The alkoxydecane oligomer is preferably added in an amount of from 97 to 100% by weight based on the total amount of the binder component contained in the conductive composition. When the amount is 97% by weight or more, the alkoxysilane oligomer is blended to achieve a sufficient density of the film, and a conductive film exhibiting high film hardness and excellent chemical resistance can be formed. More preferably, it is 98.5 wt% or more.

The total blending amount of the binder component is preferably from 150 to 10,000 parts by weight based on 100 parts by weight of the conductive polymer. When the amount is 150 parts by weight or more, the binder component is used in a sufficient ratio to impart good hardness to the formed organic conductive film. If it is 10,000 parts by weight or less, it contains A sufficient amount of the conductive polymer can form an organic conductive film having high conductivity. More preferably, it is 300 to 7,000 parts by weight.

3. Conductivity enhancer

The conductive composition of the present invention may also contain a conductivity enhancer.

The above conductivity improving agent can further improve the conductivity of the formed organic conductive film.

Examples of the conductive enhancer include decylamine compounds such as N-methylformamide, N,N-dimethylformamide, γ-butyrolactone, and N-methylpyrrolidone; and ethylene glycol; Diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexane a compound containing a hydroxyl group such as an alcohol, cyclohexane dimethanol, glycerin, diethylene glycol monoethyl ether or propylene glycol monomethyl ether; isophorone, propylene carbonate, cyclohexanone, ethyl acetonide, ethyl acetate, ethyl hydrazine A compound containing a carbonyl group such as ethyl acetate, methyl orthoacetate or ethyl orthoformate; a compound having a sulfo group such as dimethyl hydrazine or the like. These may be used alone or in combination of two or more.

Among these, a guanamine compound is preferred from the viewpoints of the pot life of the coating liquid, the volatility at a low temperature, the conductivity of the formed organic conductive film, the adhesion to the substrate, and the like. More preferably, it is N-methylpyrrolidone and N-methylformamide.

Further, the content of the conductive enhancer is not particularly limited, but is preferably 0.1 to 60% by weight in the conductive composition.

4. Solvent or dispersion medium

The solvent or the dispersion medium is not particularly limited as long as it dissolves or disperses each component contained in the conductive composition, and for example, it can be listed. Lift: water, organic solvents, mixtures of these, etc.

In the present invention, the case where the components other than the solvent or the dispersion medium contained in the conductive composition are dissolved is referred to as a solvent, and at least one component constituting the conductive composition is uniformly dispersed. It is called a dispersion medium.

In the case where the conductive composition contains the alkoxydecane oligomer, the alkoxydecane oligomer is not dissolved in water, and thus water and an organic solvent can be used. The mixture acts as a solvent or dispersion medium. Further, when a mixture of water and an organic solvent is used, the organic solvent preferably contains at least one organic solvent mixed with water, and if it contains an organic solvent mixed with water, it may further contain no water mixed. (hydrophobic) organic solvent. There is a case where the volatility is improved by using a mixture of an alcohol-based organic solvent having a relatively low boiling point and water as a solvent or a dispersion medium, which is advantageous in drying and heat curing. Further, in the case of using a resin substrate, the alcohol-based organic solvent also contributes to an improvement in leveling property.

4-1. Organic solvents

Examples of the organic solvent include those in which a component such as an alkoxysilane oligomer which is hardly soluble in water is uniformly dissolved or dispersed.

Examples of the organic solvent to be mixed with water include alcohols such as methanol, ethanol, 2-propanol and 1-propanol; and ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. Alcohols; glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol Glycol ether acetates such as monoethyl ether acetate and diethylene glycol monobutyl ether acetate; propylene glycol, dipropylene glycol, tripropylene glycol, etc. Glycols; propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether and other propylene glycol ethers; a propylene glycol ether acetate such as methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; tetrahydrofuran, acetone, acetonitrile; and mixtures thereof.

Further, examples of the hydrophobic organic solvent include esters such as ethyl acetate, butyl acetate, and ethyl lactate; ethers such as diisopropyl ether and diisobutyl ether; and methyl ethyl ketone and methyl Ketones such as butyl ketone; aliphatic hydrocarbons such as hexane, octane and petroleum ether; aromatic hydrocarbons such as toluene and xylene; and mixtures thereof.

These organic solvents may be used singly or in combination of two or more.

In the case where the conductive composition is a water-based composition, the content of the organic solvent is preferably 20 parts by weight or more based on 100 parts by weight of water. When it is less than 20 parts by weight, the hydrophobic component such as the alkoxysilane oligomer may not be uniformly dissolved or dispersed, and the properties such as the appearance of the film, the adhesion to the substrate, and the peeling force may not be exhibited. In the case where the conductive composition is a solvent-based composition, the content of the solvent is not limited.

Further, in the present invention, when the conductive composition contains water, the composition is referred to as a water-based composition, and when the conductive composition does not contain water, the composition is referred to as a solvent-based composition. .

4-2. Water

Examples of the water used for the water-based conductive composition include distilled water, ion-exchanged water, and ion-exchange distilled water. Again, the above Water also contains water dispersions of conductive polymers and water contained in other components.

The content of the water is preferably 1% by weight or more in the conductive composition.

When the conductive composition is a water-based composition, the pH of the conductive composition is preferably in the range of 1 to 14, and more preferably 1 to 7 in consideration of hardenability at low temperature or conductivity of the film. , especially good for 1.5~4. The pH of the conductive composition can be adjusted by a pH adjuster such as a base.

Examples of the pH adjuster include alkanolamines such as ammonia, ethanolamine, and isopropanolamine.

Here, since the base forms a salt with an acid, the hardening catalyst has a function of curing the catalyst to reduce the hardening promoting effect of the curing catalyst on the alkoxysilane oligomer, and the higher the pH of the conductive composition is The lower the hardenability at low temperature, the more the self-crosslinking of the alkoxydecane oligomer in the solution is inhibited, so the stability of the solution or the pot life of the conductive composition is improved, taking into account the above, as long as appropriate It is only necessary to determine the amount of the pH adjusting agent to be added. Further, the pH adjusting agent is an optional component in the conductive composition of the present invention.

5. Other additives

The conductive composition of the present invention may further contain other additives.

Examples of other additives include a leveling agent, a fine particle dispersion, a decane coupling agent, and a tackifier.

5-1. Leveling agent

The above leveling agent is used to uniformly apply the conductive composition to the substrate In the above, the leveling agent can improve the wettability of the conductive composition to the substrate to uniformly form the organic conductive film.

Examples of the leveling agent include a fluorine-containing compound, a polyfluorene oxide compound, and an acrylic compound.

Examples of the leveling agent containing a fluorine compound include a perfluoroalkane, a perfluoroalkylcarboxylic acid, and a perfluoroalkylethylene oxide adduct.

Examples of the leveling agent for the polyoxymethane compound include polyether modified polydimethyl siloxane, polyether ester modified polydimethyl siloxane, and hydroxyl group-containing polyether modified polydimethyl. a siloxane, a polyether modified polydimethyl siloxane containing an acrylate group, a polyester modified polydimethyl siloxane containing an acryl group, a perfluoropolyether modified polydimethyl siloxane, Perfluoropolyester modified polydimethyloxane, polyfluorene modified acrylic compound, and the like.

Further, examples of the leveling agent for the acrylic compound include a homopolymer or a copolymer.

These may be used alone or in combination of two or more.

The content of the leveling agent is not particularly limited, and the upper limit thereof is preferably 5 to 25% by weight, and more preferably 7 to 15% by weight based on the solid content of the solid content of the conductive composition.

When the content exceeds 25% by weight, the crosslinking density of the organic conductive film may decrease, and as a result, the adhesion to the substrate or the peeling force may be lowered. On the other hand, if the content of the leveling agent is less than 5% by weight, the appearance of the film may not be improved.

The organic conductive film of the present invention formed using the conductive composition composed of such a structure is as described above, and the maximum height (Rz) is relative to The average film thickness is 35% or more, and the surface state (maximum height (Rz)) of the organic conductive film can be controlled by various methods, for example, by a composition of a conductive composition or a method of forming an organic conductive film described below. Take control.

More specifically, for example, when the organic conductive film is formed by a spray coating method, the organic conductive film can be controlled by controlling the spray amount, the hydraulic pressure, the average coating amount per unit area, the moving speed of the spray, and the like. Surface state (maximum height (Rz)).

Next, a method of producing the organic conductive film of the present invention will be described.

The organic conductive film is formed by using the conductive composition described above, and is formed by applying the conductive composition to a substrate, drying it, and thermally curing the film.

The coating method of the above-mentioned conductive composition is not particularly limited, and a known method can be used. For example, a spin coating method, a gravure coating method, a bar coating method, a dip coating method, or a shower curtain type can be used. Coating method, die coating method, spray coating method, and the like. Further, a printing method such as screen printing, spray printing, inkjet printing, letterpress printing, gravure printing, or lithography may be used. In this case, the coating conditions may be appropriately set so that the surface state (maximum height (Rz)) of the formed organic conductive film is within the above range.

As a coating method of the above-mentioned conductive composition, a spraying method is preferred.

The above-mentioned spraying method can be carried out, for example, by using a device such as a Badger Air Brush manufactured by TAMIYA Co., Ltd. or a PRO-SPRAY MK-2 manufactured by GSI CREOS Co., Ltd., and can be sprayed on a substrate such as a glass plate by the above device. At this time, it is appropriately set based on technical knowledge in the field. The organic conductive film having a desired surface state (maximum height (Rz)) and film thickness can be formed by uniformly dispersing liquid concentration, ejection amount, hydraulic pressure and the like, and adjusting the coating amount.

Further, when the conductive composition is applied, the conductive composition may be diluted with an alcohol or the like to prepare a coating liquid, and the coating liquid may be applied.

When the coating film of the above-mentioned conductive composition is dried or thermally cured, a dryer such as a general air dryer, a hot air dryer, or an infrared dryer is used. When such a dryer (hot air dryer, infrared dryer, etc.) having a heating means is used, drying and heating can be simultaneously performed. As the heating means, in addition to the above-described dryer, a heating/pressurizing roller having a heating function, a press, or the like can be used.

Here, the conditions of drying and thermosetting are preferably carried out at a temperature of 150 ° C or lower (60 to 130 ° C) for 30 minutes or less, and more preferably at a temperature of 120 ° C or lower (80 to 100 ° C) for 15 minutes or less. The conductive composition can sufficiently form an organic conductive film under the above conditions, and the above conditions are conditions in the technical field which are relatively low temperature for a short period of time. Therefore, when the above-mentioned organic conductive film is formed using the above-mentioned conductive composition, productivity is also excellent.

In addition, when the curing is insufficient under such conditions, it may be cured in a dryer or a storage in a state of 25 ° C to 60 ° C in a roll film state after roller coating for 1 hour to several weeks.

The method for preparing the above-mentioned conductive composition is not particularly limited, and each component can be prepared by mixing with a stirrer such as a mechanical stirrer or a magnetic stirrer while stirring. Here, the agitation is preferably continued for about 1 to 60 minutes.

The organic conductive film of the present invention can be preferably used as a constituent member of an optical film, a packaging material, a transparent electrode film, a liquid crystal display unit, etc., and an optical film, a packaging material, a transparent electrode film, and a liquid crystal display having the organic conductive film of the present invention. The unit has excellent durability.

Examples of the optical film include those in which the organic conductive film is formed on a transparent resin film. In this case, a transparent resin film is used as the substrate 11 shown in Fig. 1(a), and the organic conductive film 12a is laminated on the single-layer layer.

Examples of the packaging material include those in which the organic conductive film is formed on one surface of the film.

Examples of the transparent electrode film include those in which the organic conductive film is formed in an arbitrary pattern on a transparent substrate.

The liquid crystal display unit may be, for example, one surface or both surfaces of a glass substrate in which liquid crystal is sealed, or the organic conductive film formed on one surface or both surfaces of a glass substrate before liquid crystal sealing.

The optical film, the packaging material, the transparent electrode film, and the liquid crystal display unit are also one of the inventions.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples.

(Example 1)

100 parts of an aqueous dispersion containing a conductive polymer, Clevios PH500 (manufactured by Heraeus Co., Ltd.) (containing 1.1 parts of a conductive polymer), and alkoxydecane oligomer MS-51 (manufactured by Mitsubishi Chemical Corporation), 24 parts, N -Methylformamide (manufactured by Nacalai Tesque Co., Ltd.) 19 A solution, 514 parts of ethanol (manufactured by Nacalai Tesque Co., Ltd.), and 48 parts of ion-exchanged water were prepared to prepare a uniform dispersion.

Then, the dispersion liquid was applied onto a glass plate by the following method, and heated in an oven at 130 ° C for 30 minutes to form 13 100 × 100 mm organic conductive films (Examples 1-1 to 1 - 13) for evaluation. Further, the coating amount is 80 nm (Example 1-1, 2, 4, 5, 7 to 13), 120 nm (Example 1-3) or 60 nm in accordance with the relationship with the concentration of the uniform dispersion. The adjustment was carried out in the manner of (Example 1-6).

(coating method)

The amount of coating was adjusted so that the average film thickness was 80 nm, 120 nm or 60 nm by adjusting the uniform dispersion concentration, the ejection amount, and the hydraulic pressure using a Badger Air Brush manufactured by Tamiya.

(Evaluation of shape of organic conductive film)

The maximum value (MAX), the minimum value (MIN), and the average value of the maximum height (Rz) are calculated for each of the ten positions of each of the organic conductive films by the following method, and the maximum value and the minimum value are calculated. The ratio (%) of the average film thickness (80 nm, 120 nm or 60 nm). The results are shown in Table 1.

The maximum height (Rz) was measured using a stylus type surface shape measuring device DEKTAK 6M (manufactured by Veeco Co., Ltd.) under the conditions of a measurement mode of 3000 μm, 30 seconds, and 10 mg.

(Comparative Example 1)

A uniform dispersion liquid prepared in the same manner as in Example 1 was applied to a glass plate by the following method, and heated at 130 ° C for 30 minutes by a hot air dryer to form six 100 × 100 mm organic conductive films (Comparative) Example 1-1 to Comparative Example 1-6) were used for evaluation. Further, the coating amount was adjusted so that the average film thickness became 80 nm in accordance with the relationship with the concentration of the uniform dispersion.

(coating method)

The wire rod of No. 4 (wet film thickness: 9 μm) was uniformly applied and applied at a uniform speed.

(Evaluation of shape of organic conductive film)

The maximum value (MAX), the minimum value (MIN), and the average value of the maximum height (Rz) are calculated for each of the ten positions of each of the organic conductive films by the following method, and the maximum value and the minimum value are calculated relative to the average value. The ratio (%) of the film thickness (80 nm). The results are shown in Table 2.

The measurement method of the above maximum height (Rz) is the same as that of the first embodiment.

(durability test)

The organic conductive film (Examples 1-1 to 1-6, 1-11 to 1-13) produced in Example 1 and the organic conductive film produced in Comparative Example 1 (Comparative Example 1-1 to Comparative Example 1) 6) Perform any of the following durability tests (1) and (2).

Durability test (1): maintained at 85 ° C for 1100 hours

Durability test (2): 850 hours at 65 ° C, 90% humidity

Specifically, the durability of the organic conductive film produced in each of Examples 1-1 to 1-3, 1-11 and 1-12, and Comparative Examples 1-1 to 1-3 was performed. In the test (1), the surface resistivity /SR (Ω / □) was measured by the following method before and after the test, and the surface resistivity / SR (Ω / □) increase magnification before and after the durability test was calculated. The results are shown in Table 3.

Further, the organic conductive films produced in each of Examples 1-4 to 1-6 and 1-13 and Comparative Examples 1-4 to 1-6 were subjected to a durability test (2), and the surface resistance was measured by the following method before and after the test. Rate / SR (Ω / □), and the surface resistivity / SR (Ω / □) increase magnification before and after the durability test was calculated. The results are shown in Table 4.

The surface resistivity / SR (Ω / □) was measured at an applied voltage of 10 V using a UA probe of Hiresta UP (MCP-HT450 type, trade name) manufactured by Mitsubishi Chemical Corporation according to JIS K 7194.

From the results of Tables 3 and 4, it was confirmed that the organic conductive film of the present invention is excellent in durability.

Further, the durability test (1) was also carried out for Examples 1-7 to 1-10, and as a result, it was confirmed that the durability was also excellent.

[Industrial availability]

The organic conductive film of the present invention is preferably an antistatic film or a transparent electrode, and is preferably used for an optical film, a packaging material, a transparent electrode film, a liquid crystal display unit, or the like.

11, 21‧‧‧ substrate

12a, 22a‧‧‧Organic conductive film

12b, 22b‧‧‧Degraded part

Fig. 1(a) is a cross-sectional view schematically showing an example of the organic conductive film of the present invention, and (b) to (d) are schematic views showing changes over time of deterioration of the organic conductive film shown in (a).

Fig. 2(a) is a cross-sectional view schematically showing an example of a conventional organic conductive film, and (b) to (d) are schematic views showing temporal changes in deterioration of the organic conductive film shown in (a).

11‧‧‧Substrate

12a‧‧‧Organic conductive film

12b‧‧‧Degraded part

Claims (7)

An organic conductive film formed by using a conductive composition containing at least a conductive polymer, wherein a maximum height (Rz) of one surface thereof is 50% or more with respect to an average film thickness, and an average film thickness is 60~400nm. The organic conductive film of claim 1, wherein the conductive polymer is a polythiophene-based conductive polymer. The organic conductive film of claim 2, wherein the polythiophene-based conductive polymer is poly(3,4-dialkoxythiophene) or poly(3,4-alkylenedioxythiophene) A composite of dopants, the poly(3,4-dialkoxythiophene) or poly(3,4-alkylenedioxythiophene) having a repeating structure of the following formula (I): (wherein R ¹ and R ² independently of each other represent a hydrogen atom or an alkyl group of C _1-4 or an optionally substituted C _1-4 alkylene group). An optical film having the organic conductive film according to any one of claims 1 to 3. A packaging material having the organic conductive film according to any one of claims 1 to 3. A transparent electrode film having the organic conductive film according to any one of claims 1 to 3. A liquid crystal display unit having patent claims 1 to 3 An organic conductive film of any one of them.