TW201224086A - Electroconductive coating composition and laminate - Google Patents

Abstract

The present invention provides an electroconductive coating composition capable of forming an antistatic film with high electroconductivity and transmittance, excellent tight adhesion with a substrate, higher hardness, and excellent chemical resistance. The electroconductive coating composition of th present invention comprises electroconductive polymer particles with a particle size (D50) less than 200 nm and an adhesive ingredient containing the alkoxysilane oligomer. The particle size of the electroconductive polymer particles is preferably less than 60 nm and more preferably less than 30 nm. The electroconductive polymer is preferably a complex of the poly (3,4-bisubstituted thiophene) and the polyanion.

Description

201224086 VI. Description of the Invention: 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. [Prior Art] When dust is attached to the surface of the optical film of a display such as a liquid crystal display 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 has previously been used as an inorganic fine particle exhibiting conductivity such as tin oxide (yttrium) or indium tin oxide (IT0). 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 true: vapor deposition or the like, and has disadvantages in that expensive equipment and, for example, 500 to 60 (the setting of the high temperature of rc) are required in the formation process thereof. When an antistatic film containing inorganic fine particles is formed on a glass substrate, the reflectance becomes high, and as a result, the difference in refractive index from the glass increases, and the visibility of the display also decreases. Further, 35 has a metal. The supply source is limited and there is a supply amount, '...to avoid use. The change is specific, so it is preferable to use the ku belt for another. For example, a polythiophene-specific conductive organic two-molecular material is used for a liquid crystal display. Patent Documents I and 2). Moreover, in the extraction/film (for example, or the film hardness, it is also disclosed that the oxyalkylene is closely attached to the substrate and used to report the rod Φ when the same knife material and various types of yoghurt y are used to form an antistatic 臈 ( For example, ...See document 3, 4 201224086 and 5). ^Using an organic conductive material, it is not necessary to form an antistatic film by a general coating method, and the film is formed by a process of low temperature and low temperature. It has the advantage of being electrically conductive and (4) ❹ and 'the antistatic film shoulder obtained. It is excellent in the adhesion to the substrate. The 'anti-static film of the organic system is known. Insufficient, the surface is easy to damage the shortcomings. _.., and, in turn, there is also a problem of insufficient chemical resistance. For example, when used as an antistatic film in the liquid crystal display After that, the surface of the surface is set to "& ^ pneumatic static, partial plate, and must be cleaned with an organic solvent such as acetone or alkaline cleaning, but the industry requires improvement. - 四 (4) cleaning and deterioration ' [Patent Document 1 ]Japanese Unexamined Japanese Patent No. 196953 [Patent Document] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-294. SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to provide an antistatic which is excellent in electrical conductivity and permeability, excellent in adhesion to a substrate, high in hardness, and excellent in chemical resistance. The inventors of the present invention conducted intensive studies and found that the conductive polymer is formed into particles having a small particle diameter and used in combination with a specific hydrolyzable decane compound. The present invention can be achieved by solving the above problems. That is, the present invention relates to a conductive coating composition comprising a conductive polymer which has a particle size of 4 〇Onm or less in 201224086 (D50). And a binder component containing the pyrochlore oxime oligomer represented by the following formula.

[Chemical 1]

I R4

RjO—Si— ο—r2 —η where 'RJ R2 is the same or not @, represents an alkyl group of carbon number 4; R3 and R4 are the same or different, and represent H (hydrogen atom), hydroxyl group, or carbon number i~4 The methoxy group, wherein at least one of the plurality of QR4s is a methoxy group; and n represents an integer of 2 to 20. Further, the present invention relates to a laminate comprising a substrate and a conductive film provided on the substrate, wherein the conductive lanthanum is formed of the conductive coating composition. According to the conductive coating composition of the present invention, it is possible to form an antistatic ruthenium 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 the penetrability is better than that of the substrate. Also excellent. Further, the film hardness is as high as the hardness of the ship pen. ° 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 Η or more, and the chemical resistance of the product is also improved. , and alkali resistance). also,

[Embodiment] Since the difference between the refractive index and the glass is small, the effect of defects (holes or small pits) can be obtained. 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. (Electroconductive polymer particles) The conductive polymer used in the present invention is a high molecular material which exhibits conductivity. Examples of the & conjugated conductive polymer such as polythiophene '% aniline, polypyrrole, polyparaphenylene, polyparaphenylene Vinylene, and derivatives thereof . 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 a poly(3,4-substituted sinus) and a dopant. The poly(3,4-disubstituted thiophene) constituting the polythiophene-based conductive polymer is preferably represented by the following formula (1):

6 201224086 The repeating structural unit shown in the cation (tetra) side cation form of polythiophene refers to the polythiophene which is taken into the ionic form by the self-polymerization of the p-anion. . Electron and a part of the positive type (1), the ruler 4 and r5 are independent of each other, and represent a hydrogen mat or a C 丨·4 burnt group, or a substitution or an unsubstituted C extension which forms a cyclic structure without R4R5 bonding. Hyunji. Examples of the thiol group of the above CN4 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=R5 is bonded to form a substituted or unsubstituted C" of the cyclic structure, and examples thereof include a methylene group, an α-ethyl propyl group, a 14-: butyl group, and an i-methyl ethyl group. 4 ethyl · hydrazine, ethyl, " base 4 extended propyl, 2 · methyl-hydrazine extended propyl and the like. The substituent which may have a stretching group of ^4 may be a group or a phenyl group. Preferably, the alkylene group of the c14 is an anthracenyl group, a 1,2-extended ethyl group, a 1,3_propyl group, and more preferably an anthracene 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 polyporous-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, polyacrylic 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. In 201224086, it is especially preferred to be polystyrene sulfonic acid. The polystyrene acid preferably has a weight average molecular weight of more than 2 Å and is 500,000 or less. More preferably 4〇〇〇〇~2〇〇〇〇〇. When polystyrenesulfonic acid having a molecular weight outside this range is used, there is a case where the dispersion stability of 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). The measurement was performed using uhrahydr〇gel 5〇〇(3)丨_ manufactured by Waters. The polythiophene-based conductive polymer can be obtained by oxidative polymerization in water using an oxidizing agent. Two kinds of oxidizing agents (a first oxidizing agent and a second oxidizing agent) are used in the oxidative polymerization. Preferred examples of the first oxidizing agent include: beroxodisulfuric acid peroxydisulfate, sodium peroxodisulfate, potassium peroxodisulfate, peroxodisulfate, hydrogen peroxide, potassium (potassium), potassium dichromate, and deletion. Acid salt: copper salt, etc. Among the first oxidizing agents, 'preferably sodium peroxodisulfate, potassium peroxodisulfate' ammonium peroxodisulfate, and peroxodisulfuric acid. The amount of the first oxidizing agent used is preferably 丨5 to 3.0 mol equivalents and further preferably 2 〇 2 to 6 mm 〇 1 equivalent based on the thiophene monomer to be used. Preferably, the second oxidizing agent is preferably added with a metal ion (e.g., 'iron' drill, 、, 目目' 鈒 ion) depending on the amount of the catalyst. Among them, iron ions are most effective. The amount of the metal ion to be added is preferably 〇 to 1.1 mol equivalent, more preferably 〇 〇1 to 〇 5 m〇i 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 propanol or a water-soluble solvent of acetone or acetonitrile may be added. 201224086 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 a waterjet body of a conductive polymer. The aqueous dispersion can be produced by the above-described oxidative polymerization, and can also be a conductive polymer particle contained in an organic solvent (especially an alcohol such as ethanol). The organic cold-knife dispersion of such a conductive polymer can be produced, for example, according to the method described in Japanese Patent No. 4 i 63. The particle size of the conductive polymer particles used in the process must be 2 〇〇 nm or less. Conductive by using particles with a small particle size of 200 nm or less! The compactness of the conductive film formed by the combination of the green polymer and the oxygen-burning oligomer is improved. Specifically, the dispersibility of the conductive polymer particles preferably enters the dense structure formed by the oxygen-depleted oxide oligomer, so that the film hardness is improved and the conductivity is high. Further, when the conductive coating composition of the present invention is applied to a glass substrate, the hardness of the film is further increased to a hardness of 错 or more, and/or chemical resistance. Sex (resistant to organic (four), resistant (four)) to get good. When using a particle having a particle diameter of more than 200 nm, it is difficult to achieve an amine, and the conductivity is low, and the quality is not improved. The smaller the particle size, the lower the effect. The particle size of the conductive polymer particles is preferably 60 nm, preferably 3 nm or more, more preferably 5 nm. In the present invention, the conductive poly character is more than m. Diameter measurement of conductive particles

The cumulative (cumulative) distribution of the number of bases of -S 9 201224086 is calculated as the particle size of 50% of the cumulative 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 the patent No. 3966252]. A dispersing mixer such as a homogenizer can be used (for example, refer to paragraph [〇〇19] of JP-A-2010-243 04). (Binder component) - The conductive coating composition of the present invention contains a binder component in addition to the conductive polymer particles. The binder component is a component necessary for the conductive coating group 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, the total amount of the adhesive component which is required to contain at least the alkoxysilane oligomer as the binder component is preferably from 150 to 10,000 parts by weight based on the weight of the conductive polymer particles. When the amount is more than 15 parts by weight, the use ratio 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 polymerization 16 is contained, so that a conductive film having high electrical conductivity and good chemical resistance can be obtained. More preferably, it is 300 to 7,000 parts by weight. (Alkoxydecane oligomer) The alkoxysilane oligomer is contained in the coating composition of the present invention. It is considered that since the alkoxydecane 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 has one or more oxygen bonds in the molecule (Si-0-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 500~1500 or so. Further, the weight average molecular weight of the above oligomer is a value measured by gel permeation chromatography (GPC). The measurement was carried out using ultrahydrogel manufactured by Waters Co., Ltd. 5〇〇 c〇iumil® The alkoxysilane 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 the alkoxy oxime compound modified by a polyether or a polyester. R1° - Si - 〇--r2 wherein 'Ri and I are the same or different' represent an alkyl group having 1 to 4 carbon atoms. R3 and R4 are the same or different and represent H (hydrogen atom), meridine, or carbon number 1 to 4

.S 11 201224086 Alkoxy. Wherein, a plurality of r + , at least i of the number of I and I are alkane η represents an integer of 2 to 20, and the main helmet is _. Hey. <The number of turns is more preferably an integer of 2 to 14. Examples of the alkyl group having a carbon number of 4 include methyl, „~ Ν芊Τ, ethyl, n-propyl' isopropyl, n-butyl isobutyl, tert-butyl, etc. Carbon number—τ anti-cracking 1 4 Examples of the alkoxy group include an oxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an iso-yl group, a third butoxy group, etc. The alkoxy decane used in the present invention. The oligomer; a compound consisting of only one compound represented by the following formula may be a mixture of the genus. In the present invention, 'by using a oxyalkylene oxide having a hydrazine bond in the molecule in advance. As the binder component, the oligomer is more likely to form a denser bell structure in the conductive film than the alkoxysilane monomer or epoxy decane having no oxime bond, and the result is estimated to be excellent in the invention. The effect is that the film formation temperature is as low as possible. Further, when an alkoxysilane polymer (the number of condensations η is larger than that of the oxysalisite oligomer) is used as the binder component, the stereoscopic repulsion becomes large. 'Therefore, the reactivity is deteriorated and it is difficult to form a dense structure, and it is estimated that the film hardness is weak. The larger the molecular weight, the more remarkable. The amount of the oxoxane oligomer is preferably 9 7 to 1 〇〇 by weight based on the total binder component contained in the conductive coating composition. Further, the denseness of the film obtained by blending the alkoxysilane oligomer can reach a sufficient level, and a conductive film exhibiting high film hardness and excellent chemical resistance can be formed, and more preferably 98.5% by weight or more. (Binder component other than alkoxysilane oligomer) As described above, the conductive coating composition of the present invention may further contain a binder component other than the alkoxysilane oligomer, as long as it contains the above alkoxydecane. 12 201224086 oligomers, there are no restrictions on other binder components, specifically, 3-glycidoxypropyltrimethoxydecane, polyether modified polydimethylsiloxane, polyether A decane coupling agent such as a modified decane is used as a binder component. Further, a resin binder may be used, and specific examples thereof include polystyrene, polyacrylic acid, polymethacrylate, polyurethane, and polyvinyl acetate. Ester, polyvinylidene chloride, a copolymer obtained by copolymerizing a homopolymer such as polyamine or polyimine, such as styrene, vinylidene chloride, ethylene ethylene, alkyl acrylate vinegar or alkyl methacrylate, etc. The binder may be used singly or in combination of two or more kinds. (> granule or dispersion medium) The conductive coating composition of the present invention may be composed only of conductive polymer particles and a hard emulsion oligomer. However, in order to facilitate the operation, it is generally preferred to contain a solvent and a dispersion medium. As a solvent or dispersion medium, it is necessary to dissolve or disperse the conductive polymer and the hospital oxygen oligomer: When the conductive coating composition is a water system, the mixed solvent of water and water and a solvent mixed in water and the solvent in water are not particularly limited, and examples thereof include ',, and: , 2-propanol, b-propanol and other alcohols; ethylene glycol monomethyl, diethylene glycol monoether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, etc. Purpose, - B. A, member, ethylene diether acetic acid ...: alcohol: = ... acetic acid sl, diethylene glycol Ding Wei and other Ethyl ether acetates; propylene glycol, propylene glycol and other propylene glycol; propylene glycol monomethyl, ;:, tripropanol monomethyl mystery, dipropylene glycol monoethyl bond, propylene glycol diethyl ether dimethyl ether, Propylene glycol diethyl ether, dipropane @ - alcohol - 0 propylene glycol ethers; C 13 201224086 monool monodecyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monoacetic acid 63⁄4, - ^. - propanol Propylene glycol ether acetate such as monoethyl ether acetate; monomethylacetamide, propyl acrylate, acetonitrile, and the like. When the conductive coating composition is an organic solvent system, the above-mentioned water-mixed solvent and hydrazine, diphenylbenzene, benzene, ethyl acetate, butyl acetate, methyl ethyl ketone may be used. , methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl first sing, 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 "solvent", and the case where some components are not dissolved and dispersed is referred to as "dispersion medium". - If the conductive coating composition is a uniform aqueous dispersion, the solid content concentration is not particularly limited, and is preferably @0. (Π~5〇% by weight is 卜(9)% by weight. In this range, the coating can be carried out relatively easily. However, in the case of sales of 忐 ,, 么 && ^ monthly sales of the coating composition can also be a higher concentration 'in this case, σ! y; fc is also required to be appropriately diluted by adding a solvent and/or a dispersion medium at the time of use. (Conductivity improving agent) To further improve conductivity, the conductive composition is further formulated in the coating composition of the present invention. The reinforcing agent is particularly limited as long as it is an electric isoelectric improving agent, and may be appropriately selected as needed. Specifically, dimethyl hydrazine, N-f pyrrolidone, and N•methyl AZQ may be mentioned. Indoleamide, N-di-f-carbamamine, isophorone, propylene carbonate, cyclohexyl 7-butyrolactone, diethylene glycol mono

Among them, N amide and N-methylpyrrolidone are preferred. These can be used alone or in combination with two or more types of sweat. Conductive coating 14 201224086 The composition of the electric conductivity enhancer Moore is taken from A, ..., and is limited to 1 part by weight, preferably 0 to 13000 parts by weight relative to the poly-δ particles. Stone is better for 43 0~43 30 parts by weight. (Optional component): The conductive coating composition of the present invention may further contain an interface active surface modifier, an antifoaming agent, a rheology control agent, an adhesion imparting agent, an antioxidant, an oxidation catalyst, a particle, or the like. . The above-mentioned surfactant is only #, which is a high flatness, and is obtained by the coating of the film. Such a surfactant may be exemplified by a poly-modified polydimethyl sulphur-oxygen smoldering gas, a polyfluorinated sulphur-oxygen smoldering gas, and a hydroxy-containing polydimethyl methoxy oxane. Polyether modified polyacrylonitrile-containing polydidecyl fluorene oxide, polyester modified propylene-containing polydimethyl methoxy oxane, perfluoropolydimethyl oxa oxide, perfluoropolyether modified poly 2 a fluorinated organic compound such as a methyl fluorene oxide or a perfluoropolyester modified polydimethyl methoxy hydride; a fluorine-containing organic compound such as a perfluoroalkyl carboxylic acid or a fluoropropoxy ethoxylate; a polyether compound such as a phenylene oxide polymer 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, or an alkyl group. An ester compound such as an ether sulfate, a sorbitan fatty acid ester, a sulfonate, a sulphate or a succinate; an alkyl aryl sulfonate amine salt, a contiguous base acid dioctyl sodium, etc. Compound; acid-filling compound such as sodium dodecyl phosphate; brewing amine compound such as coconut oil fatty acid ethanol decylamine; and further acrylic copolymer . Among these, in view of leveling property, a naphthenic compound and a fluorine-containing compound are preferable, and a polyether-modified polydimethylsiloxane is particularly preferable. 15 201224086 In order to improve the viscosity, the # arginine derivative, Sanxian, and the second kind of tackifier may be listed as a water-soluble polymer such as a m-, an eclipse, a carrageenan or a cellulose such as cellulose. . The above-mentioned antioxidants and the winners 2|丨UP — _ , „ ^ u ..., particularly limited, may include a water-reducing antioxidant which is a reducing or non-reducing property, that is, a water-soluble antioxidant having a reducing property, for example, L- Ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, erythorbic acid, sodium erythorbate, sputum, blood, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium, potassium Sugar, cellobiose, xylose 'arabinose, glucose, fructose, galactose, mannose and other monosaccharides and two: class:: tea, fragrant bitter, Yangmei jaundice, quercetin, Shan Nai and so on Only bismuth, rosmarinic acid, oleic acid, phenylephrine, 34 5-tris-benzoic acid, etc. Compounds with more than 2 promising ketones; cysteine, cystein a compound having a thiol group such as a peptide or a neopentyl alcohol tetrakis(3 mercaptobutyric acid vinegar), etc. Examples of the non-reducing water-soluble antioxidant include benzene oxime acid, phenyl triazole sulfonic acid, and 2·. Hydroxypyrimidine, stearate of salicylic acid, 2·hydroxy-4-indolyl diphenyl ketone-5-supply acid Ultraviolet rays which are oxidatively inferior: Compounds. These may be used singly 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. Listed as inorganic particles, inorganic particles can be enumerated: Shi Xishi, oxygen reduction, zinc oxide, oxidative desorption, oxygen (four), oxidative oxidation record, tungsten oxide, oxidation town, titanium oxide, oxidation, oxidation, oxidation, iron oxide , cerium oxide, manganese oxide, tin oxide 'yttria, cerium oxide, cerium oxide, calcium carbonate, magnesium carbonate 'barium carbonate' calcium citrate, calcium titanate, calcium sulfate, barium sulfate and other metal oxides; or molybdenum sulfide, Cerium sulphide, tungsten sulphide, 16 201224086 nitriding rot, nickel and other complexes and their hydrates; clay, talc, mica, bentonite, hydrotalcite, zeolite, pyrophyllite, carbon black 'graphite, etc. Or synthetic mineral particles. (Manufacturing method of coating composition) The method for producing the conductive coating composition of the present invention is specifically modified by using a mixer such as a mechanical agitator or a magnetic stirrer. The composition: the surface is mixed and mixed, and (4) it is mixed for about no minutes. Specifically, the conductive particles are first prepared by electroconductive properties, and the conductive particles are mixed and mixed. The "dispersion" is then mixed with the respective components (layered body). The conductive coating composition of the present invention can be applied to the substrate to be coated by drying 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, and ethylene-acrylic acid copolymer. Polyolefin resin such as ionic polymer copolymer or cycloolefin resin; polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyoxyethylene, modified polyphenyl (P 〇lyphenylene), polyphenylene sulfide and other polyester resin; nylon 6, nylon 6,6, nylon 9, semi-aromatic polyamine 6 butyl 6, semi-aromatic polyamine 6 Τ 66, semi-aromatic polyamide 9 The polyamine resin; in addition to the above, acrylic resin, polystyrene, acrylonitrile styrene, acrylonitrile butadiene styrene, 1 vinyl resin and other organic materials; glass and other prosperous materials. 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 Η or more, 17 201224086 == excellent... academic properties (organic resistance) And the testability) is suitably selected by the coating method of a conductive coating composition. For example, it may be independently limited, and it may be known by a cloth method, a bar coating method, a dip coating method, a curtain coating method, a gravure printing coating, a fr--r m m / , a die coating method, and a spray coating method #. Screen printing, spray printing, etc. can also be applied. Also, printing methods such as plate printing and lithography. A dryer such as a wind dryer, a hot air dryer, or an infrared ray which is used for the coating of the above-mentioned conductive coating composition, such as a dryer (four), a dryer such as an external line dryer, and the like. In this case, a dryer (hot air dryer, infrared dryer, etc.) having a heating mechanism can be used to simultaneously perform dry heat. The heating means may be a heating 'pressure roller, a press machine or the like having a heating function in addition to the above drying. The drying conditions of the coating film are not particularly limited, and are, for example, 25 < t to 200. The squatting is carried out for 10 seconds to 2 hours, preferably at 8 (rc~15) for about 5 to 30 minutes. The dry film thickness of the coating film formed by the conductive coating composition of the present invention may be appropriately selected. However, in order to improve conductivity, hardness, and chemical resistance, it is preferably 25 to 380 nm, more preferably 30 to 350 nm, by applying a conductive coating composition to the surface of the substrate. Drying can produce a laminate including a conductive film formed on the surface of the substrate. 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 liquid crystal display. The layered body contained in the device. 201224086 Fig. 1 is a schematic diagram showing the laminated structure of the device which is not normally used. The symbol 1 system liquid crystal display device _ #衣夏T和和The color filter has an antistatic film (conductive film) 3 and a polarizing plate 4 laminated on the surface of the color filter 1 with a glass substrate 2 poles. The laminated body of the present invention may be a glass substrate only 2 With the antistatic film 3, ^ Α test is also the above liquid The layered structure of the crystal display device is also included in the laminated structure of the crystal display device, and the layered body composed of the color light-passing sheet 1, the glass substrate 2, and the doped retines and the electric film 3 before the liquid crystal display device of the 士士』马凡成Among the above-mentioned methods, the driving method of the liquid-day-day device is widely applied to three types of TN (Twisted Nematic) and VA (VerUcai, vertical, horizontal) driving methods. The laminated body can be applied to the liquid crystal display layer β of any one of them. In the transverse electric field driving method, in order to prevent dust adhesion and improve liquid crystal driving property, it is necessary to provide an antistatic film, and the laminated body of the present invention can also be preferably applied. In the liquid crystal display device of the horizontal electric field driving method, in this case, the antistatic film can achieve an effect of improving liquid crystal chaos caused by static electricity, and is also improved by high transparency or refractive index difference with glass. The effect of the visibility of the display. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. In the case of the weight distribution, the particle size (D5 0) is a cumulative (cumulative) knives of the number of the respective aqueous dispersions, and the particle diameter of 5 〇% as the integrated value in the cumulative distribution is calculated. Specifically, a sample of a solution of water 19 201224086 diluted with pure water and adjusted to 1.1% was used, and ZETASIZER Nano-ZS was used, (Example 1)

The particle size distribution meter of Sysmex Co., Ltd. was used to measure the particle size of the electromotive force. Water dispersion 9^ (10) lH500 (HX.starek company made chest) using a conductive polymer (poly(ethylene dioxyn In the above, 98.9 parts of the above-mentioned conductive poly-amplifier and ion-exchanged water are contained. In the case where the conductive polymer is (10) parts, 'ion-exchanged water is a share, and the x-ray-oxygen oxide oligomer MS is a poisonous agent. -5U manufactured by Mitsubishi Chemical Corporation) 24# (2165 parts when the conductive polymer is HH), N_methylformamide (manufactured by Nacalai Tesque Co., Ltd.) 9 parts (in the case where the conductive polymer is H), part by weight, 514 parts of ethanol (manufactured by Shinwa Co., Ltd.) (when the conductive polymer is made of yam, 46727) Partially prepared, 48 parts of ion-exchanged water (4364 parts when the conductive polymer is (10) parts), and then prepared a uniform aqueous dispersion on the alkali-free glass plate, using an oven "(TC is added & 30 minutes to form a film, and a test piece with an antistatic film on the surface is obtained. The dry film thickness in the test piece was calculated and adjusted according to the coating amount of the aqueous dispersion. MS-51: In the above formula representing the alkoxydecane oligomer, R| = r: = methyl group, R3 = R_4 = decyloxy group, weight average molecular weight: 5 〇〇 7 7 〇〇 (given value), n = 4 to 7 (calculated based on weight average molecular weight) (Example 2) Using Baytron PH1000 (manufactured by HC Starck Co., Ltd., D50 was 52 20 201224086 nm' containing hi part of the above conductive polymer) Instead of the example PH500 (manufactured by HC Starck Co., Ltd.), a test piece was obtained in the same manner as in Example! (Example 3) Using Baytron P (HCStarck) A company manufactured by the company, having a 〇50 of 140 nm and containing 1.1 parts of the above-mentioned conductive polymer, was used in place of Baytron PH5 00 (manufactured by HC Starck Co., Ltd.) of Example 1, and a test piece was obtained in the same manner as in Example j. (Comparative Example 1) Using Baytron HC V4 (manufactured by HC Starck Co., Ltd., D50 was 570 nm, containing 1.1 parts of the above-mentioned conductive polymer) instead of Baytr〇n PH5 00 (manufactured by HC Starck Co., Ltd.) of Example 1 was obtained in the same manner as in Example 1. Test piece. (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-5 1 used as the binder was changed. (Examples 8 and 9) The components of Example 1 were excluded. Further, in the amount described in Table 3, Z-6〇43 (manufactured by Dow Corning Toray Co., Ltd.) as 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane was used in the same manner as in Example 1. The test piece was obtained in the same manner. (Example 10) In addition to the components of Example 1, in addition, in the amounts described in Table 4, μ 21 201224086 was used as z-glycidoxypropyltrimethoxy sulphide z-6040 (D〇) w Corning Toray Co., Ltd.) A test piece was obtained in the same manner as in Example 1. (Example 11) In addition to the components of Example 1, the BYK_3〇i (manufactured by BYK-Chemie Co., Ltd.) which is a polyether-modified polydimethyl oxime was used in the amount described in Table 4, and was carried out. A test piece was obtained in the same manner as in Example 1. (Example 12) The same procedure as in Example 1 except that 24 parts of MS-56 (manufactured by Mitsubishi Chemical Corporation) was used instead of 24 parts of the pyrithione oligomer MS-5 1 (manufactured by Mitsubishi Chemical Corporation) of Example 1. The way to get the test piece. MS-56: In the above formula representing alkoxydecane oligomer, R1=R2==methyl, r3=R4=methoxy, heavy! The average molecular weight is 1100~13〇〇 (given value), n = 1 〇 to 12 (calculated based on the weight average molecular weight) (Comparative Examples 2 to 4) In addition to the use of 24 parts of the following adhesives, respectively, instead of the oxyssite oligomer MS-5 1 of Example 1 (Mitsubishi Chemical) Test pieces were obtained in the same manner as in Example 1 except for 24 parts manufactured by the company. Comparative Example 2: Monomer (monomer of alkoxysilane (excluding oxime bond), thiol trimethyl ketone). Z-6366 (manufactured by Dow Corning Tor ay Co., Ltd.) Comparative Example 3. Polyacetate: pi As co at RZ-1 05 (manufactured by Mutual Chemical Co., Ltd.) Comparative Example 4: epoxy decane compound: z-6040 (manufactured by D〇w Corning Toray Co., Ltd.) 22 201224086 (Example 1 3) In addition to using N-fluorenyl n A test piece was obtained in the same manner as in Example 1 except that 19 parts of the flavonoid (manufactured by Nacalai Tesque Co., Ltd.) was used instead of 19 parts of N-methylformamide (manufactured by Nacaiai TeSqUe Co., Ltd.) of Example 1. (Examples 14 to 17) Test pieces were obtained in the same manner as in Example 除 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. (Example 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. The film was obtained by heating at 130 ° C for 30 minutes in an oven to obtain a surface. Test piece with antistatic film. (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. That is, according to the description of [〇〇51], an ethanol solution of 3,4_ethylidene dioxythiophene ig and 5 g of p-toluenesulfonate was applied to an alkali-free glass, and dried by an oven to form an organic conductive material. A test piece was prepared by film. (Comparative Example 6) In the present comparative example, the fifth embodiment of the patent document 日本 (Japanese Patent Laid-Open No. W96953) was verified. That is, according to the description of [〇〇7〇], 3,4_ethylidene dioxythiophene ig, 2 g of p-stanoic acid iron, and 5 g of polyvinyl acetate vinegar were dissolved in isopropanol on the alkali-free glass. Acetone (I: a solution obtained in a mixture) was heated and dried on a coated substrate. 23 201224086 Further, it was washed with a water stream, and (Comparative Example 7) was dried to prepare a test piece for verification in this comparative example. That is, by making a test piece, the previous antistatic film using inorganic ITO is formed by sputtering on the glass substrate by the sputtering method, and the above examples and comparative examples are obtained by the following methods. The physical properties of the film were evaluated. (1) Film strength TTQ The film strength (pencil hardness) of the antistatic film of each test piece was determined according to the test method of *Κ5600·5·4, using the scratch hardness of the pen manufactured by Yasuda Seiki Co., Ltd. (2) Adhesiveness The adhesion between the antistatic film and the substrate of each test piece was evaluated according to the JEV Κ5400's thumb peel test. The evaluation was carried out in the following three stages: ◎ : 10 minutes : 8 minutes : 6 points or less (3) Total light penetration Rate (%), haze (%) The total light transmittance and haze of each test piece were measured according to JIS Κ7150 using a haze meter HGM-2B (trade name) manufactured by SUGA Testing Machine Co., Ltd. (4) Surface resistivity / □) The surface resistivity of the antistatic film of each test piece is based on JIS K7194, using Hiresta UP (MCP-HT-450, trade name) manufactured by Mitsubishi Chemical Corporation, 24 201224086 using probe UA ( Probe UA) was measured at an applied voltage of 10V to 500V. (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 Co., Ltd. (6) Chemical resistance After the test pieces were immersed in a solvent (aqueous sodium hydroxide solution or acetone solution), the surface resistivity and the film strength were measured as described above, and evaluated in three stages according to the following criteria. the result. The impregnation conditions in the aqueous sodium hydroxide solution were set to be immersed for 2 minutes at room temperature. The impregnation conditions in acetone were set to impregnate for 1 hour at room temperature. 〇: 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.

X: The surface resistivity is 10 or more, and the film strength is pencil hardness B or less. The results obtained above are shown in Tables 1 to 8 below. [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Conductive polymer particle size (nm) Particle size 20 Particle size 52 Particle size 140 Particle size 570 Conductive polymer (parts) 100 100 100 100 Alkane oxygen Decane oligomer (parts) 2165 2165 2165 2165 Conductivity improver (parts) 1730 1730 1730 1730 Ethanol (parts) 46727 46727 46727 46727 25 201224086 Ion exchange water (parts) 13355 13355 13355 13355 Film thickness (nm) 224 224 224 224 Substrate glass glass glass film strength (sand hardness) 3H Η Η F Adhesiveness ◎ ◎ ◎ ◎ Total light transmittance 92.6 92.5 92.5 93.0 Haze 0.1 0.1 0.0 0.2 Surface resistivity 4.0E + 04 3.7Ε + 04 3.3 Ε + 05 3.4Ε+12 Refractive index 1.45 1.45 1.46 1.45 Chemical resistance (test) 〇〇〇Δ Chemical resistance (acetone) 〇〇〇Δ 26 201224086 [Table 2] Example 4 Example 5 Example 1 Example 6 Example 7 Conductive polymer (parts) 100 100 100 100 100 Alkoxysilane oligomer (parts) 9090 4550 2165 430 220 Conductivity improver (parts) 1730 1730 .1730 1730 1730 Adhesive / conductive Polymer ratio 90.9 45.5 21.7 4.3 2.2 Ethanol (parts) 46727 46727 46727 46727 46727 Ion exchange water (parts) 13355 13355 13355 13355 13355 Film thickness (nm) 224 224 224 224 224 Substrate glass glass glass glass film strength (wrong pen hardness) 2H 4H 3H HB密 Adhesiveness ◎ ◎ ◎ ◎ ◎ Total light transmittance 92.2 91.7 92.6 90.1 90.0 Haze 0.0 0.1 0.1 0.0 0.0 Surface resistivity 5.9E + 07 1.6E + 07 4.0E + 04 1.1 E + 04 9.5Ε + 03 Refractive index 1.50 1.47 1.45 1.43 1.39 and t chemical properties (test) △ 〇〇〇 Δ chemical resistance (acetone) 〇〇〇〇〇 [Table 3] Example 1 Example 8 Example 9 Conductive polymer (parts) 100 100 100 alkoxydecane oligomer (parts) 2165 2143 2122 Conductivity improver (parts) 1730 1730 1730 Other components (parts) 0 22 43 Oligomer ratio in the adhesive 100.0 99.0 98.0 Ethanol (parts) 46727 46727 46727 Ion exchange water (parts) 13355 13355 13355 Film thickness (nm) 224 224 224 Substrate glass glass film strength (pencil hardness) 3H BB Adhesion ◎ ◎ ◎ Total light transmittance 92.6 90.9 81.0 Haze 0.1 0.1 0.1 Surface resistivity 4.0E + 04 8.1 E + 04 5.6E + 05 Refractive index 1.45 1.47 1.49 Chemical properties (test) 〇〇△ Chemical resistance (acetone) 〇〇〇27 201224086 [Table 4] Implementation Example 1 Example 10 Example 11 Conductive polymer (parts) 100 100 100 Alkoxy oxane oligomer (parts) 2165 2165 2165 Conductivity improver (parts) 1730 1730 1730 decane coupling agent (parts) 0 22 22 decane The type of coupling agent is not 3-glycidoxypropyltrimethoxy decane polyether modified polydimethyl methoxy oxane ethanol (parts) 46727 46727 46727 ion exchange water (parts) 13355 13355 13355 film thickness (nm ) 224 226 226 Substrate glass glass film strength (tank hardness) 3H 3H 4H Adhesion ◎ ◎ ◎ Total light transmittance 92.6 92.5 92.6 Haze 0.1 0.0 0.1 Surface resistivity 4.0E + 04 6.4E + 05 1, 1 E + 05 Refractive index 1.45 1.46 1.46 Chemical resistance (base) 〇〇〇 Chemical resistance (acetone) 〇〇〇28 201224086 [Table 5] Example 1 Example 12 Comparative Example 2 Comparative Example 3 Comparative Example 4 Conductive polymer (parts) 100 100 100 100 100 alkane Decane oligomer (parts) 2165 2165 0 0 0 Alkoxysilane oligomer type MS-51 MS-56 - - - Conductivity improver (parts) 1730 1730 1730 1730 1730 Other components (parts) 0 0 2165 2165 2165 Types of other ingredients (except alkoxydecane oligomer) No monomer-free polystyrene resin 3-glycidoxypropyltrimethoxyoxyethanol (part) 46727 46727 46727 46727 46727 Ion exchange water ( Parts) 13355 13355 13355 13355 13355 Film thickness (nm) 224 224 224 224 225 Substrate glass glass glass glass film strength (pencil hardness) 3Η Η F Β The following Β the following adhesion ◎ ◎ ◎ ◎ ◎ Total light transmittance 92.6 91.4 90.5 89.8 90.0 Haze 0.1 0.1 0.1 0.1 0.0 Surface resistivity 4.0Ε + 04 1.2Ε + 07 2.2Ε + 04 1.4Ε + 04 9.4Ε + 03 Refractive index 1.45 1.5 1.45 1.54 1.47 and chemical (test) 〇 〇XX Δ Chemical resistance (acetone) 〇〇Δ X Δ [Table 6] Example 1 Example 13 Conductive polymer (parts) 100 100 Alkoxy oxane oligomer (part) 2165 2165 Conductivity improver ( Parts) 1730 1730 Conductivity improver Type NMFA NMP Ethanol (parts) 46727 46727 Ion exchange water (parts) 13355 13355 Film thickness (nm) 224 224 Substrate glass film strength (tank hardness) 3H 2H Adhesion ◎ ◎ Total light transmittance 92.6 90.7 Fog Degree 0.1 0.1 Surface resistivity 4.0E + 04 1.3 E + 09 Refractive index 1.45 1.47 Chemical resistance (alkali) 〇〇 Chemical resistance (acetone) 〇〇29 201224086

Example 14 Example 15 Example 1 Example 16 Example 17 Conductive polymer (part) 100 100 100 100 100 Alkoxydecane oligomer (part) 2165 2165 2165 2165 2165 Conductivity improver (part) 1730 1730 1730 1730 1730 Ethanol (parts) 46727 46727 46727 46727 46727 Ion exchange water (parts) 13355 13355 13355 13355 13355 Film thickness (nm) 28 34 224 336 370 Substrate glass glass glass glass film strength (pencil hardness) 4H 4H 3H F HB Adhesiveness ◎ ◎ ◎ ◎ ◎ Total light transmittance 90.5 90.5 92.6 92.7 92.2 Haze 0.1 0.0 0.1 0.0 0.1 Surface resistivity 6.4E + 09 8.0E + 05 4.0E + 04 1.9E + 04 1.7E + 04 1.45 1.45 1.45 1.45 1.45 Chemical resistance (base) Δ 〇〇〇 Δ Chemical resistance (acetone) 〇〇〇〇〇 [Table 8] Example 1 Example 18 Comparative Example 5 Comparative Example 6 Comparative Example 7 Conductivity Polymer (parts) 100 100 alkoxydecane oligomer (parts) 2165 2165 Conductivity improver (parts) 1730 1730 Ethanol (parts) 46727 46727 Ion-exchanged water (parts) 13355 13355 Film thickness (nm) 224 224 Material glass PET glass glass film strength (pen hardness) 3H HB B below B 6H adhesion ◎ ◎ ◎ ◎ total light transmittance 92.6 90.7 86.3 91.4 80% or more haze 0.1 2.8 0.5 0.2 3~4% surface resistance Rate 4.0E + 04 4.8E + 04 1.2E + 08 5.8E+12 1~2 Refractive index 1.5 1.5 Unable to measure Unable to measure 2.1 Chemical properties (test) 〇Δ XX 〇 Chemical resistance (acetone) 〇〇XX 〇30 201224086 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 2 〇〇 nm or less, and when the particle diameter exceeds 2 〇〇 nm, the surface resistivity increases (that is, the conductivity is higher. Low), poor chemical resistance. According to the examples 1 and 12 and the comparative examples 2 to 4 of Table 5, when the oligomer of the smoldering oxygen is used as the binder component, the chemical resistance is excellent and the film hardness is high, but if alkoxy decane is used, In the case of the monomer, the chemical resistance is greatly lowered, and the right-hand use of the vinegar-based compound or the epoxy-based compound is reduced in chemical hardness in addition to chemical resistance. According to the examples 1 and 4 to 7 of Table 2, it is understood that 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. effect. According to the embodiment 1, 8, and 9 of Table 3 and the embodiment 1 of Table 4 ! It can be seen that even in the case where the composition of the present invention contains a component other than the alkoxysilane oligomer, the proportion of the alkoxysilane oligomer in the binder component is 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, when the antistatic and dry film thickness is in the range of 25 to 380 nm, the excellent effects of the invention can be obtained. According to the embodiment 18 of Table 8, it is understood that the excellent effects of the present invention can be achieved even if it is applied to a PET substrate other than the alkali-free glass. [Industrial Applicability] 31 201224086 The conductive coating composition of the present invention can be used in a liquid crystal display (Lcd) 'electroluminescence display, plasma display, electronic color display, solar cell, battery' capacitor, chemical sense In a detector, a display element, a semiconductor material, an electromagnetic wave mask, or the like, a conductive film or an antistatic film is formed on the substrate by coating a substrate. Further, it can also be used as a conductive paint or a rust preventive paint applied to glass such as glasses or automobiles. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a laminated structure of a general liquid crystal display device. [Main component symbol description] 1 Color filter 2 Glass substrate 3 Antistatic layer 4 Polarizer 32

Claims (1)

201224086 VII. Patent application scope: 1. A conductive coating composition comprising conductive polymer particles having a particle diameter (D50) of 2 〇〇 nm or less, and a oxynase represented by the following formula Adhesive component of oligomer: r3 f IIR*i〇--Si-〇--Rz where 'Ri and R2 are the same or different, meaning the number of carbons 1~4; R3 and R4 are the same or different' H (hydrogen atom), a hydroxyl group, or an alkoxy group having a carbon number of 1 to 4 wherein at least one of the plurality of scales 3 and I is an alkoxy group; and η represents an integer of 2 to 20. 2. The conductive coating composition according to the above aspect of the invention, wherein the s-conductive polymer particles have a particle diameter of 6 Å or less. 3. The conductive coating composition according to the first aspect of the invention, wherein the particle size of the 5 metaconductive polymer particles is 3 〇 nm or less. 4. The conductive coating composition according to any one of claims 1 to 3, wherein the total amount of the binder component is 15 parts by weight based on 1 part by weight of the conductive polymer particles. 〇~1〇〇〇〇 by weight. 5. The conductive coating according to any one of the first to fourth aspects of the patent application, wherein the amount of the pyrooxane oligomer in the binder component is 97 to 1 〇 〇% by weight. 6. The conductive coating 33 201224086 cloth composition according to any one of the preceding claims, wherein the conductive polyanion complex. ^ The mouthpiece is a conductive coating of any of the poly(3,4-disubstituted thiophene) and the item 7. The composition of the scope of the invention is added to the composition of the sixth to sixth, and further comprises a conductivity improving agent. The conductive coating composition of the seventh aspect of the invention, wherein the β-thin conductivity improving agent is at least one selected from the group consisting of N-methylamine and N-methylpyrrolidone. 9. The conductive coating composition according to any one of claims 1 to 8 is for forming an antistatic layer contained in a liquid crystal display device. 10. A laminate comprising a substrate and a conductive film disposed on the substrate, wherein the conductive film is composed of a conductive coating according to any one of claims 1 to 9. The object is formed. 11. The laminate according to claim 1, wherein the conductive film has a dry film thickness of 25 to 380 nm. 12. The laminated body according to the first or the eleventh aspect of the patent application, wherein the substrate is a glass substrate. 13. The laminated body of the item 12 of the patent application is incorporated in a liquid crystal display device. 34