TWI541304B - Conductive coating composition and laminate - Google Patents

Description

Conductive coating composition and laminate

The present invention relates to a conductive coating composition capable of forming a conductive film, an antistatic film, or the like, and a laminate using the composition.

When the surface of the optical film of a display such as a liquid crystal display is attached with dust due to static electricity, the visibility of the display is lowered. As a method for preventing this, it is known to provide an antistatic film on the surface of the optical film.

The conductive material formulated in such an antistatic film is previously made of an inorganic fine particle exhibiting conductivity such as tin antimony oxide (ATO) or indium tin oxide (ITO). Such inorganic fine particles have the advantage of being excellent in transparency or film strength.

However, the antistatic film containing inorganic fine particles is usually formed by sputtering or vacuum evaporation, and the like, which requires expensive equipment and a high temperature setting of, for example, 500 to 600 ° C in the formation process.

Further, when an antistatic film containing inorganic fine particles is formed on a glass substrate, the reflectance is increased, and as a result, the difference in refractive index from the glass is increased, and the visibility of the display is lowered. Further, since indium is a rare metal, the supply source is limited, and there is a variation in the amount of supply, etc., and therefore it is preferable to avoid use.

In place of the above-mentioned conductive material of the inorganic fine particles, a conductive organic polymer material such as polythiophene is used for an antistatic film of a liquid crystal display (see, for example, Patent Documents 1 and 2). In addition, in order to improve the adhesion to the substrate or the film hardness, for example, a conductive organic polymer material and various alkoxysilanes are used to form an antistatic film (see, for example, Patent Documents 3, 4, and 5).

When an organic conductive material is used, an antistatic film can be formed by a general coating method without sputtering or vacuum evaporation, and therefore, there is an advantage that a film can be formed by a simple and low-temperature process. Further, the obtained antistatic film has an advantage that the conductivity and the penetrability are high, and the adhesion to the substrate is also excellent.

However, the previously known organic antistatic film has a drawback that the film hardness is insufficient and the surface is easily damaged. Furthermore, there is also a problem of insufficient chemical resistance. For example, when used as an antistatic film in a liquid crystal display, after forming an antistatic film and before providing a polarizing plate on the surface thereof, it is necessary to perform cleaning with an organic solvent such as acetone or alkali cleaning, but the antistatic film is easily cleaned by the like. And the deterioration, so the industry requires improvement.

[Patent Document 1] Japanese Patent Laid-Open No. Hei 10-96953

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-246080

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2005-82768

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2006-294532

[Patent Document 5] Japanese Patent Publication No. 2010-528123

In view of the above circumstances, an object of the present invention is to provide an electroconductive coating which can form an antistatic film which is excellent in conductivity and permeability, is excellent in adhesion to a substrate, has high hardness, and is excellent in chemical resistance. Composition.

As a result of intensive studies, the present inventors have found that the above problem can be solved by forming a conductive polymer into particles having a small particle size and using it in combination with a specific hydrolyzable decane compound, thereby achieving the present invention. .

That is, the present invention relates to a conductive coating composition comprising conductive polymer particles having a particle diameter (D50) of 200 nm or less and a binder component containing an alkoxydecane oligomer represented by the following formula:

[Chemical 1]

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; and R ₃ and R _{4 are the} same or different and each represents an 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; and n represents an integer of from 2 to 20.

Furthermore, the present invention relates to a laminate comprising a substrate and a conductive film provided on the substrate, wherein the conductive film is formed of the conductive coating composition.

According to the conductive coating composition of the present invention, an antistatic film can be formed by applying it to a substrate at a low temperature by a general coating method, and the process from the coating to the film formation can be carried out simply and inexpensively.

The conductive film obtained from the conductive coating composition of the present invention has high conductivity (that is, a surface resistivity is low, being 1.0 E+10 Ω/□ or less), and has high penetrability and is in close contact with the substrate. Excellent also. Further, the film hardness is as high as the pencil hardness B or more.

When the conductive coating composition of the present invention is applied to a glass substrate, the film hardness is further increased to a pencil hardness of H or more, and excellent chemical resistance (organic solvent resistance and alkali resistance) can also be exhibited. ). Further, the formed conductive film has extremely high penetrability. Further, since the difference in refractive index from the glass is small, it is expected that the effect of the defects (holes or small pits) on the surface of the glass is hard to be observed.

Hereinafter, the details of the present invention will be described.

The conductive coating composition of the present invention contains conductive polymer particles and a binder component.

(conductive polymer particles)

The conductive polymer used in the present invention is a polymer material exhibiting conductivity. Specific examples thereof include a π-conjugated conductive polymer such as polythiophene, polyaniline, polypyrrole, polyparaphenylene, polyparaphenylene vinylene, or the like.

Among them, from the viewpoint of high conductivity and chemical stability, a polythiophene-based conductive polymer composed of a composite of polythiophene and a dopant can be preferably used. More specifically, the polythiophene-based conductive polymer is a composite of poly(3,4-disubstituted thiophene) and a dopant.

The poly(3,4-disubstituted thiophene) constituting the polythiophene-based conductive polymer is preferably represented by the following formula (1):

[Chemical 2]

The polymorphic form of the cationic form consisting of the repeating structural units shown. The polythiophene in the form of a cation refers to a polythiophene which partially forms a cationic form by taking away electrons from one part of the polythiophene in order to form a complex with a polyanion as a dopant.

Formula (1), R ₄ and R ₅ each independently represents a hydrogen atom or alkyl group of C _1-4, or R ₄ and R ₅ represents a bond to form a C _1-4 substituted or unsubstituted cyclic structure of The alkyl group. 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. R ₄ and R _{5 are} bonded to form a cyclic structure of a substituted or unsubstituted C _1-4 alkylene group, and examples thereof include a methylene group, a 1,2-extended ethyl group, and a 1,3-propanyl group. , 1,4-butylene, 1-methyl-1,2-extended ethyl, 1-ethyl-1,2-extended ethyl, 1-methyl-1,3-propanyl, 2- Methyl-1,3-propanyl and the like. The substituent which may have a C _1-4 alkylene group may, for example, be a halogen group or a phenyl group. Preferred examples of the alkylene group of C _1-4 include 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 an alkylene group as described above, poly(3,4-ethylenedioxythiophene) (poly(3,4-ethylenedioxythiophene)) is preferable.

The dopant constituting the polythiophene-based conductive polymer is preferably a polymer which forms a complex by ion pairing with the above polythiophene, and which can stably disperse polythiophene in water, that is, a polyanion. 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, polyvinylsulfonic acid). and many more. The carboxylic acid polymers and sulfonic acid polymers may also be copolymerized with vinyl carboxylic acids and vinyl sulfonic acids and other polymerizable monomers (for example, acrylates, styrene, etc.). Things. 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, it is 40,000 to 200,000. When polystyrenesulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene-based conductive polymer with respect to water may be lowered. Further, the weight average molecular weight of the above polymer is a value measured by gel permeation chromatography (GPC). The measurement was performed using an ultrahydrogel 500 column manufactured by Waters Corporation.

The polythiophene-based conductive polymer can be obtained by oxidative polymerization in water using 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 peroxodisulfuric acid, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, potassium permanganate, and potassium dichromate. Perboric acid alkali salt, copper salt, and the like. Among these first oxidizing agents, sodium peroxodisulfate, potassium peroxydisulfate, ammonium peroxodisulfate, and peroxodisulfuric acid are preferred. The amount of the first oxidizing agent 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.

A suitable second oxidant preferably adds metal ions (e.g., iron, cobalt, nickel, molybdenum, vanadium ions) depending on the amount of catalyst. Among them, iron ions are most effective. The amount of the metal ion to be added is preferably 0.005 to 0.1 mol equivalent, more preferably 0.01 to 0.05 mol equivalent, based on the thiophene monomer to be used.

Water is used as the reaction solvent in the present 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 can be obtained by the above oxidative polymerization.

The conductive coating composition of the present invention contains a particulate conductive polymer. Such a conductive polymer particle may be a conductive polymer particle contained in an aqueous dispersion of a conductive polymer. The aqueous dispersion can be produced by the above oxidative polymerization. Further, it may be a conductive polymer particle contained in a dispersion of an organic solvent (especially an alcohol such as ethanol). The organic solvent dispersion of such a conductive polymer can be produced, for example, according to the method described in Japanese Patent No. 4163867.

The conductive polymer particles used in the present invention must have a particle diameter of 200 nm or less. By using particles having a small particle diameter of 200 nm or less, the conductivity of the conductive film formed by combining the conductive polymer and the alkoxysilane oligomer is improved, and the film hardness is improved. Specifically, the dispersibility of the conductive polymer particles preferably enters the dense structure formed by the alkoxysilane oligomer, so that the film hardness is improved and the conductivity is high. Further, for the same reason, when the conductive coating composition of the present invention is applied to a glass substrate, the film hardness is further increased to a pencil hardness of H or more, and chemical resistance (organic solvent resistance) Sex, alkali resistance) improved. When a particle having a particle diameter of more than 200 nm is used, conductivity is low, and improvement in film hardness and chemical resistance cannot be achieved. The smaller the particle size, the greater the degree of improvement of the above effect. Therefore, the particle diameter of the conductive polymer particles is preferably 60 nm or less, more preferably 30 nm or less. The lower limit of the particle diameter is not particularly limited and is, for example, 1 nm or more, and preferably 3 nm or more. More preferably, it is 5 nm or more or 10 nm or more. In the present invention, the particle diameter of the conductive polymer particles is a cumulative (cumulative) distribution in which the number of conductive particles is measured, and is calculated as a particle diameter of 50% of the integrated value in the cumulative distribution.

The particle diameter of the conductive polymer particles can be easily adjusted by appropriately selecting the dispersion conditions when the dispersion of the above conductive polymer is produced (for example, refer to paragraph [3962] of Patent No. 3966252). Specifically, a dispersing mixer such as a homogenizer can be used (for example, refer to paragraph [0019] of JP-A-2010-24304).

(adhesive composition)

The conductive coating composition of the present invention contains a binder component as well as the conductive polymer particles. The binder component is a component necessary for the conductive coating composition to form a film on the substrate. In the present invention, the binder component may be composed of only one type, or two or more types may be used in combination. However, in the present invention, it is necessary to contain at least an alkoxydecane oligomer as a binder component.

The total amount of the binder component is preferably 150 to 10,000 parts by weight based on 100 parts by weight of the conductive polymer particles. When it is 150 parts by weight or more, the ratio of use of the binder component becomes sufficient, and the formed conductive film can obtain good hardness and chemical resistance. When it is 10,000 parts by weight or less, a sufficient amount of the conductive polymer is contained, so that a conductive film having high conductivity and good chemical resistance can be formed. More preferably, it is 300 to 7000 parts by weight.

(alkoxy alkane oligomer)

The alkoxysilane oligomer is contained in the coating composition of the present invention. It is considered that since the alkoxysilane oligomer forms a dense structure in the coating film, the present invention can obtain a conductive film having a high hardness. Further, since the conductive polymer particles having a small particle diameter are excellent in dispersibility and enter the inside of the dense structure, a conductive film having excellent hardness and chemical resistance and having high conductivity can be obtained.

The alkoxysilane oligomer is a polymerized alkoxysilane formed by condensing monomers of alkoxysilanes, and means having one or more oxime bonds in one molecule (Si-O-Si). ) an oligomer. The weight average molecular weight is not particularly limited, but is preferably more than 152 and 4,000 or less. More preferably, it is about 500 to 1500. Further, the weight average molecular weight of the above oligomer is a value measured by gel permeation chromatography (GPC). The measurement was performed using an ultrahydrogel 500 column manufactured by Waters Corporation.

The alkoxynonane oligomer used in the present invention is represented by the following formula. As is clear from the formula, the alkoxysilane oligomer of the present invention is a monomer of the alkoxysilane previously used (a compound containing one atom per molecule) or an alkoxydecane having an epoxy group. A compound, a compound different from a modified alkoxysilane compound such as a polyether or a polyester.

[Chemical 3]

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 of 2 to 20, and more preferably represents an integer of 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, a 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 alkoxysilane oligomer used in the present invention may be one composed of only one compound represented by the following formula, or a mixture of plural kinds.

In the present invention, by using an alkoxysilane oligomer having a ruthenium oxygen bond in the molecule as a binder component, it is electrically conductive as compared with an alkoxysilane monomer or an epoxy decane having no oxime bond. It is easy to form a denser structure in the film, and it is speculated that the result can be excellent in the cost of the invention. This effect is more pronounced as the film formation temperature is lower. When alkoxysilane polymer (the number of condensation n is larger than the alkoxysilane oligomer) is used as the binder component, the steric repulsion becomes large, and the reactivity is deteriorated, so that it is difficult to form a dense structure. As a result, the film hardness is weak. This tendency is more pronounced as the molecular weight is larger.

The amount of the alkoxydecane oligomer is preferably from 97 to 100% by weight based on the total of the binder component contained in the conductive coating composition. When it is 97% by weight or more, the denseness of the film obtained by blending the alkoxysilane oligomer reaches a sufficient level, and a conductive film which exhibits high film hardness and excellent chemical resistance can be formed. More preferably, it is 98.5 wt% or more.

(Binder components other than alkoxysilane oligomers)

As described above, the conductive coating composition of the present invention may contain a binder component other than the alkoxysilane oligomer. As long as the alkoxydecane oligomer is contained, it is not limited to other binder components, specifically, 3-glycidoxypropyltrimethoxydecane, polyether modified polydimethyloxime A decane coupling agent such as an alkane or a polyether modified oxirane is used as a binder component. Further, a resin binder may be used, and specific examples thereof include polyester, polyacrylate, polymethacrylate, polyurethane, polyvinyl acetate, polyvinylidene chloride, polyamine, polyimine, and the like. A homopolymer; a copolymer obtained by copolymerizing a monomer such as styrene, vinylidene chloride, vinyl chloride, alkyl acrylate or alkyl methacrylate. These binders may be used singly or in combination of two or more.

(solvent or dispersion medium)

The conductive coating composition of the present invention may be composed only of conductive polymer particles and alkoxysilane oligomers. However, in order to facilitate handling, it is usually preferred to further contain a solvent and/or a dispersion medium. The solvent or the dispersion medium is not particularly limited as long as it can dissolve or disperse the conductive polymer and the alkoxysilane oligomer. When the conductive coating composition is a water system, water, a mixed solvent of water and a solvent mixed in water can be used. The solvent to be mixed in water is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, 2-propanol, and 1-propanol; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and ethylene glycol; Glycol ethers such as alcohol diethyl ether and diethylene glycol dimethyl ether; ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Alcohol ether acetate; propylene glycol such as propylene glycol, dipropylene glycol, tripropylene glycol; 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 a propylene glycol ether such as diethyl ether or dipropylene glycol diethyl ether; a propylene glycol ether acetate such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate or dipropylene glycol monoethyl ether acetate; Methylacetamide, acetone, acetonitrile, and mixtures thereof. When the conductive coating composition is an organic solvent system, the above-mentioned water-mixed solvent and toluene, xylene, benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl group can be used. Isobutyl ketone, diethyl ether, diisopropyl ether, methyl tert-butyl ether, hexane, heptane, and the like. Among the above solvents or dispersion media, methanol, ethanol, and 2-propanol are particularly preferred. In addition, the case where the components of the conductive coating composition are completely dissolved is referred to as a "solvent", and the case where some components are not dissolved and dispersed is referred to as a "dispersion medium".

The concentration of the solid content component is not particularly limited as long as the conductive coating composition is a uniform aqueous dispersion, and is preferably about 0.01 to 50% by weight at the time of coating. More preferably, it is 1 to 20% by weight. If it is in this range, coating can be performed relatively easily. However, a higher concentration may be used in the case of selling or transporting the coating composition, and in this case, it may be appropriately diluted by adding a solvent and/or a dispersion medium at the time of use.

(Electrical conductivity improver)

In order to further improve the electrical conductivity, the conductivity improving agent may be further formulated in the coating composition of the present invention. The conductivity improving agent is not particularly limited, and may be appropriately selected as needed. Specific examples thereof include dimethyl hydrazine, N-methylpyrrolidone, N-methylformamide, N-dimethylformamide, isophorone, propylene carbonate, cyclohexanone, and γ. - Butyrolactone, diethylene glycol monoethyl ether, etc., among these, N-methylformamide and N-methylpyrrolidone are preferable. These may be used alone or in combination of two or more. The content of the conductivity improving agent in the conductive coating composition is not particularly limited, but is preferably about 430 to 13,000 parts by weight, more preferably about 430 to 4330 parts by weight, per 100 parts by weight of the conductive polymer particles.

(optional)

Further, a surfactant (surface conditioning agent), an antifoaming agent, a rheology controlling agent, an adhesion imparting agent, an antioxidant, an oxidation catalyst, particles, or the like can be appropriately added to the conductive coating composition of the present invention.

The surfactant is not particularly limited as long as it is a coating film which can improve uniformity and obtain a uniform coating film. Such a surfactant may be exemplified by a polyether modified polydimethyl siloxane, a polyether modified oxirane, a polyether ester modified with a hydroxyl group-containing polydimethyl siloxane, and a polyether modified product. Polypropylene oxyalkylene containing propylene group, polyester modified polydimethyl methoxy oxane containing propylene group, perfluoropolydimethyl siloxane, perfluoropolyether modified polydimethyl oxime Alkane, perfluoropolyester modified polyoxyalkylene compound such as polydimethyloxane; fluorine-containing organic compound such as perfluoroalkyl carboxylic acid, perfluoroalkyl polyoxyethylene ethanol; polyoxyethylene alkyl phenyl ether; a polyether compound such as a propylene oxide polymer or an ethylene oxide polymer; a carboxylic acid such as a coconut oil fatty acid amine salt or a gum rosin; a castor oil sulfate, a phosphate, an alkyl ether sulfate, and a sorbent An ester compound such as a sugar anhydride fatty acid ester, a sulfonate, a phosphate or a succinate; a sulfonate compound such as an alkylarylsulfonate amine salt or a dioctyl sodium sulfosuccinate; a dodecylphosphoric acid; a phosphate compound such as sodium; a guanamine compound such as coconut oil fatty acid ethanol decylamine; and an acrylic copolymer. Among these, from the viewpoint of leveling, a naphthenic compound and a fluorine-containing compound are preferable, and a polyether-modified polydimethylsiloxane is particularly preferable.

In order to increase the viscosity, a tackifier may also be added. Examples of such a tackifier include water-soluble polymers such as arginine derivatives, santillac derivatives, carbohydrates, and saccharides such as cellulose.

The antioxidant is not particularly limited, and examples thereof include a reducing or non-reducing water-soluble antioxidant. Examples of the water-soluble antioxidant having a reducing property include a compound having a lactone ring substituted with two hydroxyl groups, such as L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, erythorbic acid, sodium erythorbate or potassium erythorbate; Monosaccharides and disaccharides such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose; flavonoids such as catechin, rutin, myricetin, quercetin and kaempferol; Curcumin, rosmarinic acid, bleaching acid, hydroquinone, 3,4,5-trihydroxybenzoic acid and other compounds having two or more phenolic hydroxyl groups; cysteine, glutathione, neopentyl A compound having a thiol group such as tetraol tetrakis(3-mercaptobutyrate). Examples of the non-reducing water-soluble antioxidant include benzzimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, and 2-hydroxy-4-methoxydiphenylketone-5- A compound which absorbs ultraviolet rays which is a cause of oxidative degradation, such as sodium sulfonate. These may be used alone or in combination of two or more.

Further, the conductive coating composition of the present invention may contain particles which impart abrasion resistance or slidability. Examples of the particles include inorganic particles, and examples of the inorganic particles include vermiculite, alumina, zinc oxide, potassium oxide, calcium oxide, chromium oxide, cerium oxide, tungsten oxide, magnesium oxide, titanium oxide, cerium oxide, cerium oxide, and cobalt oxide. Metal oxides such as iron oxide, cerium oxide, manganese oxide, tin oxide, cerium oxide, zirconium oxide, cerium oxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium citrate, calcium titanate, calcium sulfate, barium sulfate; or vulcanization One or a plurality of compositions of molybdenum, strontium sulfide, tungsten sulfide, boron nitride, nickel iodide, and the like thereof; or kaolin, clay, talc, mica, bentonite, hydrotalcite, zeolite, pyrophyllite, carbon Natural or synthetic mineral particles such as black and graphite.

(Manufacturing method of coating composition)

The method for producing the conductive coating composition of the present invention is not particularly limited, and the respective components may be mixed while stirring with a stirrer such as a mechanical stirrer or a magnetic stirrer, and stirred and mixed for about 1 to 60 minutes. Specifically, the dispersion of the conductive polymer is first produced so that the conductive polymer particles have a specific particle diameter, and then the components are mixed and stirred.

(layered body)

The conductive coating composition of the present invention can be applied to a substrate to be coated and then dried to form a conductive coating film. The material constituting the substrate to be coated to which the conductive coating composition is applied is not particularly limited, and examples thereof include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, and ionic polymer. Polyolefin resin such as copolymer or cycloolefin resin; polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyoxyethylene, modified polyphenylene, polyphenylene Polyester resin such as thioether; nylon 6, nylon 6,6, nylon 9, semi-aromatic polyamide 6T6, semi-aromatic polyamide 6T66, semi-aromatic polyamide 9T, etc.; Examples thereof include organic materials such as acrylic resin, polystyrene, acrylonitrile styrene, acrylonitrile butadiene styrene, and vinyl chloride resin; and inorganic materials such as glass. In particular, the conductive coating composition of the present invention is applied to a glass substrate, and the film hardness is extremely high, and the pencil hardness is H or more, and excellent chemical resistance (organic solvent resistance) can be exhibited. It is alkali resistant, so it is especially preferred.

The coating method of the conductive coating composition is not particularly limited, and can be appropriately selected from known methods. For example, a spin coating method, a gravure coating method, a bar coating method, a dip coating method, a curtain coating method, a die coating method, a spray coating method, and the like can be mentioned. Further, a printing method such as screen printing, spray printing, inkjet printing, letterpress printing, gravure printing, or lithography may be applied.

The drying of the coating film of the above-mentioned conductive coating composition is a dryer such as a general air dryer, a hot air dryer, or an infrared dryer. When such a dryer (hot air dryer, infrared dryer, etc.) having a heating mechanism is used in these, drying and heating can be simultaneously performed. The heating means may be a heating, a pressure roller, a press machine or the like having a heating function in addition to the above-described dryer.

The drying conditions of the coating film are not particularly limited, and are, for example, about 25 seconds to 2 hours at 25 to 200 ° C, preferably about 8 to 30 minutes at 80 to 150 ° C.

The dry film thickness of the coating film formed from the conductive coating composition of the present invention can be appropriately selected as needed. However, in order to improve conductivity, hardness, and chemical resistance, it is preferably 25 to 380 nm. More preferably, it is 30 to 350 nm.

By coating the conductive coating composition on the surface of the substrate and drying it, a laminate including the conductive film formed on the surface of the substrate can be produced. The laminate can be applied to various applications as described below, and particularly when the substrate is a glass substrate, it can be preferably used as a laminate contained in a liquid crystal display device.

Fig. 1 is a schematic view showing a laminated structure of a general liquid crystal display device. The symbol 1 is a color filter in a liquid crystal display device, and the glass substrate 2 is provided on the surface layer of the color filter 1. Further, an antistatic film (conductive film) 3 and a polarizing plate 4 are laminated in this order. The laminate of the present invention may be composed only of the glass substrate 2 and the antistatic film 3, or may be included in the laminated structure of the liquid crystal display device. Further, it may be included in the laminate including the color filter 1, the glass substrate 2, and the antistatic film 3 before the liquid crystal display device is completed.

In the driving method of the liquid crystal display device, three types of TN (Twisted Nematic), VA (Vertical Alignment), and Horizontal Electric Field are widely used. The laminate of the present invention can be applied to a liquid crystal display layer of any of the modes. Among them, in the horizontal electric field driving method, in order to prevent dust from adhering and to improve liquid crystal driving properties, it is necessary to provide an antistatic film, and the laminated body of the present invention can be preferably applied to the liquid crystal display device of the horizontal electric field driving method. In this case, the antistatic film can achieve an effect of improving the liquid crystal disorder caused by static electricity, and also has an effect of improving the visibility of the display due to high transparency or a difference in refractive index from the glass.

[Examples]

The invention is illustrated in more detail below by way of examples, but the invention is not limited to the examples. Hereinafter, "parts" means "parts by weight" unless otherwise specified.

The particle diameter (D50) is a cumulative (cumulative) distribution of the number basis of each aqueous dispersion, and the particle diameter which is 50% of the integrated value in the cumulative distribution is calculated. Specifically, a sample having an electrohydraulic particle size was measured using a particle size distribution meter ZETASIZER Nano-ZS manufactured by Sysmex Corporation using a sample in which each aqueous dispersion was diluted with pure water and adjusted to 0.1%.

(Example 1)

100 parts of an aqueous dispersion of Baytron PH500 (manufactured by HC Starck Co., Ltd.) containing a conductive polymer (poly(3,4-extended ethylenedioxythiophene/polystyrenesulfonic acid) having a particle diameter (D50) of 20 nm (including the above) 1.1 parts of a conductive polymer and 98.9 parts of ion-exchanged water. When the conductive polymer is 100 parts, the ion-exchanged water is 8991 parts), and the alkoxysilane oligomer MS-51 which is a binder (Mitsubishi Chemical) 24 parts (manufactured by the company, 2165 parts when the conductive polymer is 100 parts), N-methylformamide (manufactured by Nacalai Tesque Co., Ltd.), which is a conductivity improver, 19 parts When the amount of the conductive polymer was 100 parts, it was 1,730 parts), 514 parts of ethanol (manufactured by Nacalai Tesque Co., Ltd.) (46,627 parts when the conductive polymer was 100 parts), and 48 parts of ion-exchanged water ( A uniform aqueous dispersion was prepared by using 4364 parts of the conductive polymer as 100 parts.

Then, the dispersion liquid was applied onto an alkali-free glass plate, and the film was formed by heating at 130 ° C for 30 minutes in an oven to obtain a test piece having an antistatic film on its surface. Further, the dry film thickness in the test piece was calculated and adjusted according to the amount of the aqueous dispersion applied.

MS-51: In the above formula representing alkoxydecane oligomer, R ₁ = R ₂ = methyl group, R ₃ = R ₄ = methoxy group, and the weight average molecular weight is 500 to 700 (given value), n=4 to 7 (calculated based on weight average molecular weight)

(Example 2)

A test piece was obtained in the same manner as in Example 1 except that Baytron PH1000 (manufactured by H. C. Starck Co., Ltd., D50 was 52 nm, containing 1.1 parts of the above-mentioned conductive polymer) was used instead of Baytron PH500 (manufactured by H. C. Starck Co., Ltd.) of Example 1.

(Example 3)

A test piece was obtained in the same manner as in Example 1 except that Baytron P (manufactured by H. C. Starck Co., Ltd., D50 was 140 nm, containing 1.1 parts of the above-mentioned conductive polymer) was used instead of Baytron PH500 (manufactured by H. C. Starck Co., Ltd.) of Example 1.

(Comparative Example 1)

A test piece was obtained in the same manner as in Example 1 except that Baytron HC V4 (manufactured by H. C. Starck Co., Ltd., D50 was 570 nm, containing 1.1 parts of the above-mentioned conductive polymer) was used instead of Baytron PH500 (manufactured by H. C. Starck Co., Ltd.) of Example 1.

(Examples 4 to 7)

A test piece was obtained in the same manner as in Example 1 except that the amount of the alkoxydecane oligomer MS-51 used as the binder was changed as described in Table 2.

(Examples 8 and 9)

In addition to the components of Example 1, Z-6043 (manufactured by Dow Corning Toray Co., Ltd.) as 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane was used in the amounts described in Table 3, A test piece was obtained in the same manner as in Example 1.

(Embodiment 10)

In the amount described in Table 4, Z-6040 (manufactured by Dow Corning Toray Co., Ltd.) as 3-glycidoxypropyltrimethoxydecane was used in the same manner as in Example 1, except that the components of Example 1 were used. The way to get the test piece.

(Example 11)

In the same manner as in Example 1, except that each component of Example 1 was used, BYK-301 (manufactured by BYK-Chemie Co., Ltd.) which is a polyether-modified polydimethyl siloxane was used in the amount shown in Table 4 in the same manner as in Example 1. Get the test piece.

(Embodiment 12)

A test piece was obtained in the same manner as in Example 1 except that 24 parts of MS-56 (manufactured by Mitsubishi Chemical Corporation) was used instead of 24 parts of the alkoxydecane oligomer MS-51 (manufactured by Mitsubishi Chemical Corporation) of Example 1. MS-56: In the above formula representing alkoxydecane oligomer, R ₁ = R ₂ = methyl group, R ₃ = R ₄ = methoxy group, and the weight average molecular weight is from 1100 to 1300 (given value), n=10~12 (calculated based on weight average molecular weight)

(Comparative examples 2 to 4)

A test piece was obtained in the same manner as in Example 1 except that 24 parts of the following adhesive were used instead of 24 parts of the alkoxydecane oligomer MS-51 (manufactured by Mitsubishi Chemical Corporation) of Example 1.

Comparative Example 2: Monomer (alkoxysilane monomer (excluding oxime bond), methyltrimethoxy decane): Z-6366 (manufactured by Dow Corning Toray Co., Ltd.)

Comparative Example 3: Polyester resin: Plascoat RZ-105 (manufactured by Mutual Chemical Co., Ltd.)

Comparative Example 4: epoxy decane compound: Z-6040 (manufactured by Dow Corning Toray Co., Ltd.)

(Example 13)

It was obtained in the same manner as in Example 1 except that 19 parts of N-methylpyrrolidone (available from Nacalai Tesque Co., Ltd.) was used instead of 19 parts of N-methylformamide (manufactured by Nacalai Tesque Co., Ltd.) of Example 1. Audition.

(Examples 14 to 17)

A test piece was obtained in the same manner as in Example 1 except that the dry film thickness was changed as described in Table 7 by adjusting the coating amount of the aqueous dispersion of Example 1.

(Embodiment 18)

The aqueous dispersion of Example 1 was applied onto a PET film (Lumirror T-60, manufactured by Toray Co., Ltd.) instead of a glass plate, and heated at 130 ° C for 30 minutes in an oven to form a film to obtain an antistatic film on the surface. sheet.

(Comparative Example 5)

In the present comparative example, the first embodiment of Patent Document 1 (Japanese Patent Laid-Open No. Hei 10-96953) was verified. Specifically, according to the description of [0051], an ethanol solution of 1 g of 3-, 4-ethylenedioxythiophene and 5 g of iron p-toluenesulfonate was applied to an alkali-free glass, and dried by an oven to form an organic conductive film. Audition.

(Comparative Example 6)

In the present comparative example, the fifth embodiment of Patent Document 1 (Japanese Patent Laid-Open No. Hei 10-96953) was verified. That is, according to the description of [0070], 1 g of 3,4-extended ethyldioxythiophene, 2 g of iron p-toluenesulfonate, and 5 g of polyvinyl acetate were dissolved in isopropanol-acetone (1) on the alkali-free glass. :1) After the solution obtained in the mixture, the coated substrate is dried by heating. Further, it was washed with a water stream and dried to prepare a test piece.

(Comparative Example 7)

In the present comparative example, the previous antistatic film using the inorganic ITO was verified. That is, a test piece was produced by forming an ITO film on a glass substrate by a sputtering method.

The physical properties of the test pieces obtained by the above Examples and Comparative Examples were evaluated by the following methods.

(1) Film strength

The film strength (pencil hardness) of the antistatic film of each test piece was measured by a pencil scratch hardness tester manufactured by Yasuda Seiki Co., Ltd. according to the test method of JIS-K5600-5-4.

(2) Adhesion

The adhesion between the antistatic film of each test piece and the substrate was evaluated in accordance with the grid peeling test of JIS K5400. The evaluation was carried out in the following three stages.

◎: 10 points

○: 8 points

×: 6 points or less

(3) Total light transmittance (%), haze (%)

The total light transmittance and haze of each test piece were measured in accordance with JIS K7150 using a haze meter HGM-2B (trade name) manufactured by Suga Test Instruments Co., Ltd.

(4) Surface resistivity (Ω/□)

The surface resistivity of the antistatic film of each test piece was based on JIS K7194, using Hiresta UP (MCP-HT-450, trade name) manufactured by Mitsubishi Chemical Corporation, and applying voltage of 10 V to 500 V using probe UA (Probe UA). The measurement was carried out.

(5) Refractive index

The refractive index of each test piece was measured at a wavelength of 632.8 nm using an Ellipsometer DHA-XA2/S6 (trade name) manufactured by Ikebukuro Optical Industry Co., Ltd.

(6) Chemical resistance

After immersing each test piece in a solvent (aqueous sodium hydroxide solution or acetone solution), the surface resistivity and the film strength were measured as described above, and the results were evaluated in three stages according to the following criteria. The immersion conditions in the aqueous sodium hydroxide solution were set to be immersed at room temperature for 2 minutes. The immersion conditions in acetone were set to be immersed at room temperature for 1 hour.

○: The surface resistivity is 10 or less, and the film strength is pencil hardness B or more.

△: The surface resistivity is 10 or less, or the film strength is pencil hardness B or more.

×: The surface resistivity is 10 or more, and the film strength is equal to or less than the pencil hardness B.

The results obtained above are shown in Tables 1 to 8 below.

Further, in Comparative Examples 5 and 6 in Table 8, the surface of the film formed by the antistatic film formed was rough, and thus the refractive index could not be measured.

According to Examples 1 to 3 and Comparative Example 1 of Table 1, the particle diameter of the conductive polymer particles must be 200 nm or less. When the particle diameter exceeds 200 nm, the surface resistivity increases (that is, the conductivity is low). Poor chemical properties.

According to Examples 1 and 12 and Comparative Examples 2 to 4 of Table 5, when an oligomer of alkoxysilane is used as a binder component, chemical resistance is excellent and film hardness is high, but if alkoxysilane is used, When the monomer is used, the chemical resistance is greatly lowered. When a polyester decane compound or an epoxy decane compound is used, the film hardness is lowered in addition to the chemical resistance.

According to the examples 1 and 4 to 7 of Table 2, when the amount of the alkoxysilane oligomer used is in the range of 150 to 10,000 parts by weight based on 100 parts by weight of the conductive polymer particles, the invention can be excellent. The effect.

According to Examples 10, 8 and 9 of Table 3 and Examples 10 and 11 of Table 4, it is understood that as long as the composition of the present invention contains a binder component other than the alkoxysilane oligomer, as long as the binder component The ratio of the alkoxysilane oligomer in the range of 97 to 100% by weight can achieve the excellent effect of the invention.

According to Example 1 and Examples 14 to 17 of Table 7, it is understood that if the dried film thickness of the antistatic film is in the range of 25 to 380 nm, the excellent effect of the invention can be obtained.

According to Example 18 of Table 8, it is understood that the excellent effects of the present invention can be achieved even when applied to a PET substrate other than alkali-free glass.

[Industrial availability]

The conductive coating composition of the present invention can be used in liquid crystal displays (LCDs), electroluminescent displays, plasma displays, electronic color display, solar cells, batteries, capacitors, chemical sensors, display elements, semiconductor materials, electromagnetic waves. In a mask or the like, a conductive film or an antistatic film is formed on the substrate by coating a substrate. Moreover, it can also be used as a conductive coating or rust-proof coating applied to the glass of glasses, an automobile, etc..

1. . . Color filter

2. . . glass substrate

3. . . Antistatic layer

4. . . Polarizer

Fig. 1 is a view showing a laminated structure of a general liquid crystal display device.

Claims (11)

A conductive coating composition comprising conductive polymer particles having a particle diameter (D50) of 200 nm or less and a binder component containing an alkoxynonane oligomer represented by the following formula; The blending amount is 150 to 10000 parts by weight based on 100 parts by weight of the conductive polymer particles; and the alkoxydecane oligomer in the binder component is formulated in an amount of 97 to 100% by weight: Formula, R ₁ is and R ₂ are the same or different and each represents an alkyl group having 1 to 4 carbon atoms, the; same or different, R ₃ and R _4, represents H (a hydrogen atom), a hydroxyl group, or an alkoxy having 1 to 4 carbon atoms of the group Wherein at least one of the plurality of R ₃ and R ₄ is an alkoxy group; and n represents an integer of from 2 to 20. The conductive coating composition according to claim 1, wherein the conductive polymer particles have a particle diameter of 60 nm or less. The conductive coating composition according to claim 1, wherein the conductive polymer particles have a particle diameter of 30 nm or less. The conductive coating composition according to any one of claims 1 to 3, wherein the conductive polymer is a composite of poly(3,4-disubstituted thiophene) and a polyanion. The conductive coating composition according to any one of claims 1 to 3, further comprising a conductivity improving agent. The conductive coating composition according to claim 5, wherein the conductivity improving agent is at least one selected from the group consisting of N-methylformamide and N-methylpyrrolidone. The conductive coating composition according to any one of claims 1 to 3 is for forming an antistatic layer contained in a liquid crystal display device. A laminated body comprising a substrate and a conductive film provided on the substrate, wherein the conductive film is formed by the conductive coating composition according to any one of claims 1 to 7. . The laminate of claim 8 wherein the conductive film has a dry film thickness of 25 to 380 nm. The laminate of claim 8 or 9, wherein the substrate is a glass substrate. The laminate according to claim 10 of the patent application is included in a liquid crystal display device.