CN102473475B - Electrically conductive microparticle dispersion, photocurable composition containing electrically conductive microparticles, and article - Google Patents
Electrically conductive microparticle dispersion, photocurable composition containing electrically conductive microparticles, and article Download PDFInfo
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- CN102473475B CN102473475B CN201080036039.9A CN201080036039A CN102473475B CN 102473475 B CN102473475 B CN 102473475B CN 201080036039 A CN201080036039 A CN 201080036039A CN 102473475 B CN102473475 B CN 102473475B
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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Abstract
Disclosed are: an electrically conductive microparticle dispersion having excellent storage stability; a photocurable composition containing electrically conductive microparticles, which enables the formation of a cured film having excellent transparency and an antistatic function on the surface of a base material; and a cured film containing electrically conductive microparticles, which is produced by curing the photocurable composition. It becomes possible particularly to provide a dispersion useful for the formation of a high-refractive-index transparent electrically conductive film, a composition and a transparent electrically conductive film. Specifically disclosed are: an electrically conductive microparticle dispersion comprising electrically conductive microparticles, a metal complex and a dispersion medium, and optionally containing high-refractive-index microparticles having a refractive index of 1.8 or higher; a photocurable composition containing electrically conductive microparticles, which comprises electrically conductive microparticles, a metal complex, an activity energy ray-curable compound and a photopolymerization initiator and a dispersion medium, and optionally contains high-refractive-index microparticles having a refractive index of 1.8 or higher; and a cured film containing electrically conductive microparticles, which is produced by curing the photocurable composition containing electrically conductive microparticles.
Description
Technical field
The present invention relates to the electrically conductive microparticle dispersion liquid of bin stability excellence, the Photocurable composition that contains electrically conductive microparticle and the cured film that contains electrically conductive microparticle being obtained by said composition, more particularly, relating to can be at plastics, metal, timber, paper, glass, the surface of the various base materials such as slabstone forms transparency excellence and has the Photocurable composition of the cured film that contains electrically conductive microparticle of electrostatic-proof function, the transparency excellence being obtained by said composition and the cured film with electrostatic-proof function, and for the electrically conductive microparticle dispersion liquid of the bin stability excellence of the modulation of such Photocurable composition.
background technology
In recent years; as the binder material of the antisitic defect for various substrate surfaces (scratch) and antipollution protective finish material, printing-ink, require there is excellent painting work and can form hardness, marresistance, abrasion performance, low curling (カ ー Le on the surface of various base materials) solidification compound of the cured film that the outward appearance of property, adaptation, the transparency, chemical resistance, coated surface etc. is excellent.
In addition,, in the purposes for flat-panel monitor, touch pad, plastics optics parts etc., beyond above-mentioned requirements, also can to form the transparency excellent and have a solidification compound of the cured film such as nesa coating of electrostatic-proof function in requirement.
Further, in the image display devices such as liquid crystal display, cathode tube display unit and optical goods, use antireflection film (cured film).For this antireflection film, beyond the characteristic of high transparent and antiradar reflectivity, also require marresistance and prevent the function that the foreign matters such as dust and rubbish adhere to.For this reason, for the high refractive index layer of antireflection film, beyond high transparent and high index of refraction characteristic, also require excellent marresistance and antistatic characteristic.
So, as give the means of electrostatic-proof function for such cured film, known method of adding electrically conductive microparticle in solidification compound, described electrically conductive microparticle comprises surfactant, electric conductive polymer or as the metal oxide of main component, particularly in the situation that take that to make the film with permanent antistatic effect be object, the method for adding electrically conductive microparticle is general.As the method for such interpolation electrically conductive microparticle, there is in resin solution or solvent fusion chelating agent, make inorganic oxide be scattered in the method (referring to for example patent documentation 1 and 2) in this admixture.
Prior art document
Patent documentation
Patent documentation 1: JP 2001-139, No. 847 communiques
Patent documentation 2: JP 2001-139, No. 889 communiques
Summary of the invention
The problem that invention will solve
For electrically conductive microparticle dispersion liquid and the solidification compound thereof for such use, require that the particle diameter of electrically conductive microparticle is little and dispersion liquid bin stability excellent.Due to above-mentioned patent documentation 1 and 2 chelating agents of recording and metal formation chelate, there is the metal control equipment of use in dispersion treatment process and the problem of coating machine material corrosion.
The present invention makes in view of the above problems, the Photocurable composition that provides (1) to contain electrically conductive microparticle is provided, said composition can be formed on the surface of base material the cured film that the transparency has electrostatic-proof function in excellent, and in dispersion treatment process, do not corrode metal control equipment and the coating machine material of use, (2) the various cured film such as nesa coating that the Photocurable composition that contains electrically conductive microparticle by this obtains, (3) display, this display has the cured film that the Photocurable composition that contains electrically conductive microparticle by this obtains, and (4) are for the electrically conductive microparticle dispersion liquid of the bin stability excellence of the modulation of such Photocurable composition that contains electrically conductive microparticle.
For the means of dealing with problems
As the result of attentively studying for reaching above-mentioned each object, the inventor finds, by electrically conductive microparticle and metal complex are scattered in decentralized medium, obtain the electrically conductive microparticle dispersion liquid of bin stability excellence, find in addition, by using such electrically conductive microparticle dispersion liquid, obtain in dispersion treatment process the not Photocurable composition that contains electrically conductive microparticle of corroding metal control equipment and coating machine material, thereby complete the present invention.
; electrically conductive microparticle dispersion liquid of the present invention is characterised in that and comprises electrically conductive microparticle, metal complex and decentralized medium; preferably; it is characterized in that the electrically conductive microparticle for every 100 mass parts; the content of metal complex is 2～45 mass parts, and the content of decentralized medium is 40～1000 mass parts.
In addition, in the present invention, the in the situation that of also requiring high index of refraction characteristic beyond electrically conducting transparent characteristic, this electrically conductive microparticle dispersion liquid is characterised in that comprising refractive index is more than 1.8 high-refractive index particulates, electrically conductive microparticle, the metal complex that does not comprise alkoxide, and decentralized medium, water content is below 3 quality %, preferably, it is characterized in that, high-refractive index particulate for every 100 mass parts, the content of electrically conductive microparticle is 30～900 mass parts, the content of metal complex is 3～450 mass parts, and the content of decentralized medium is 60～9000 mass parts.
And, the Photocurable composition that contains electrically conductive microparticle of the present invention is characterised in that and comprises electrically conductive microparticle, metal complex, active energy ray-curable compound, Photoepolymerizationinitiater initiater and decentralized medium, preferably, it is characterized in that, electrically conductive microparticle for every 100 mass parts, the content of metal complex is 2～45 mass parts, the content of decentralized medium is 40～1000 mass parts, the content of active energy ray-curable compound is 10～1000 mass parts, and the active energy ray-curable compound for every 100 mass parts, the content of Photoepolymerizationinitiater initiater is 0.1～20 mass parts.
In addition, in the present invention, be used to form the Photocurable composition that contains electrically conductive microparticle of the nesa coating that requires high index of refraction characteristic, the Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating with following feature: comprising refractive index is more than 1.8 high-refractive index particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide, active energy ray-curable compound, Photoepolymerizationinitiater initiater and decentralized media, and water content is below 3 quality %; Preferably, it is the Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating with following feature: for the high-refractive index particulate of every 100 mass parts, the content of electrically conductive microparticle is 30～900 mass parts, the content of metal complex is 3～450 mass parts, the content of decentralized medium is 60～70000 mass parts, and the content of active energy ray-curable compound is 14～10000 mass parts, and for this active energy ray-curable compound of every 100 mass parts, the content of Photoepolymerizationinitiater initiater is 0.1～20 mass parts.
Further, the cured film that contains electrically conductive microparticle of the present invention is characterised in that the coating of the above-mentioned Photocurable composition that contains electrically conductive microparticle or is printed on base material, solidifies and obtain, preferably, it is characterized in that refractive index is 1.45～1.90, light transmission rate is more than 75%, mist degree (ヘ イ ズ) is below 2.0%, and sheet resistance value is 10
12below Ω/.
In addition, in the present invention, the cured film that contains electrically conductive microparticle that is used to form the nesa coating that requires high index of refraction characteristic is the nesa coating with following feature: it is used to form the Photocurable composition that the contains electrically conductive microparticle coating of nesa coating or is printed on base material, solidifies and obtain above-mentioned, preferably, it is the nesa coating with following feature: refractive index is 1.55～1.90, light transmission rate is more than 85%, mist degree is below 1.5%, and sheet resistance value is 10
12below Ω/.
Invention effect
By the present invention, (1) provide the electrically conductive microparticle dispersion liquid of the bin stability excellence of dispersion liquid, (2) provide the Photocurable composition that contains electrically conductive microparticle, said composition can form on the surface of base material transparency excellence and have the cured film of electrostatic-proof function, and in dispersion treatment process, do not corrode metal control equipment and the coating machine material of use, and (3) transparency excellence being obtained by said composition and the cured film that contains electrically conductive microparticle with electrostatic-proof function are provided.
In addition, by the present invention, provide (1) to be used to form the composition of photo-curable nesa coating, said composition can form on the surface of base material transparency excellence and have high index of refraction, the nesa coating of electrostatic-proof function, and in dispersion treatment process, do not corrode metal control equipment and the coating machine material of use, (2) transparency that the composition that is used to form nesa coating by this obtains is excellent and have a nesa coating of high index of refraction and electrostatic-proof function, (3) there is the display of this nesa coating, and (4) are for the modulation of such composition that is used to form nesa coating, the dispersion liquid of bin stability excellence.
Embodiment
Specifically describe the specific embodiment of the present invention below.
Electrically conductive microparticle dispersion liquid of the present invention contains electrically conductive microparticle, metal complex and decentralized medium.The shape of the electrically conductive microparticle that the present invention uses is not particularly limited.As the conductivity of electrically conductive microparticle, specific insulation is 10
7below Ω cm, be preferably 10
3below Ω cm.In addition,, for the size of electrically conductive microparticle, can use primary particle size to be generally 1～500nm, preferred 10～100nm.
In addition, in the present invention, in the situation that the high index of refraction characteristic of special requirement nesa coating etc., it is more than 1.8 high-refractive index particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide and decentralized media that its electrically conductive microparticle dispersion liquid contains refractive index, and water content is below 3 quality %.The high-refractive index particulate using for the present invention and the shape of electrically conductive microparticle, be not particularly limited.In addition,, for the size of high-refractive index particulate and electrically conductive microparticle, can use primary particle size to be generally 1～500nm, preferred 10～100nm.
The kind of the electrically conductive microparticle using for the present invention, is not particularly limited if can achieve the goal, and can use commercially available product etc. known.For example, can use the metal oxides such as ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonates, antimony pentoxide and form the hydroxide of the metal of these metal oxides.For tin oxide, also can use the elements such as phosphorus that adulterated.For zinc oxide, also can use adulterated gallium and aluminium.In addition, metal particle and the organic conductive particulate of gold, silver, copper, platinum, aluminium etc. also can.These electrically conductive microparticles can only be used a kind, also can two or more also use.
In addition, in the present invention, fusion is in order to control the refractive index of nesa coating of formation and the particulate that adds in the high-refractive index particulate of electrically conductive microparticle dispersion liquid, preferably use the metal oxide that refractive index is 1.8～3.0, described electrically conductive microparticle dispersion liquid is for the purposes of the high index of refraction characteristic of special requirement nesa coating etc.In addition, the refractive index of various high-refractive index particulates is the intrinsic values of material, is recorded in various documents.In the situation that use the high-refractive index particulate of refractive index less than 1.8, can not get the film of high index of refraction, in addition, in the situation that use refractive index to surpass 3.0 high-refractive index particulate, there is the tendency of the transparency reduction of film.The kind of the high-refractive index particulate using for the present invention, is not particularly limited if can achieve the goal, and can use commercially available product etc. known.For example, can use zirconia (n=2.2), titanium oxide (n=2.76) and cerium oxide (n=2.2) etc.These high-refractive index particulates can only be used a kind, also can two or more also use.
In electrically conductive microparticle dispersion liquid of the present invention, in the purposes situation of above-mentioned electrically conductive microparticle and special requirement high index of refraction characteristic beyond the high-refractive index particulate of fusion, fusion metal complex in decentralized medium.This metal complex, owing to working as dispersant in dispersion liquid, can obtain the electrically conductive microparticle dispersion liquid of the bin stability excellence of dispersion liquid.In addition, metal complex does not substantially corrode metal control equipment and the coating machine material of use in dispersion process.
The metal complex using as the present invention, can enumerate the metal that contains selected among zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminium, zinc, indium, tin and platinum, preferably, from the few angle of the tone of dispersion liquid, the metal of selected among zirconium, titanium, aluminium, zinc, indium and tin, and contain the part that is selected from beta-diketon, preferably be selected from the metal complex of the part of pivaloyl trifluoroacetone, acetylacetone,2,4-pentanedione, trifluoroacetylacetone (TFA) and hexafluoroacetylacetone, more preferably do not comprise the metal complex of alkoxide.In the situation that the metal complex that use contains alkoxide, exist the contained moisture of alkoxide and solvent or airborne moisture along with the time reacts, make electrically conductive microparticle dispersion liquid and the bin stability of the Photocurable composition that contains electrically conductive microparticle and the tendency of membrane property reduction that are used to form nesa coating.
In the present invention, for the metal complex of fusion in the purposes situation of the high index of refraction characteristic at special requirement nesa coating etc., use the metal complex that does not comprise alkoxide.In the situation that the metal complex that use contains alkoxide, exist the contained moisture of alkoxide and solvent or airborne moisture along with the time reacts, make electrically conductive microparticle dispersion liquid and the bin stability of the Photocurable composition that contains electrically conductive microparticle and the situation of membrane property reduction that are used to form nesa coating.
In addition,, in order further to improve the object of the bin stability of dispersion liquid, also can further add other dispersant as dispersing aid.The kind of such dispersing aid is not particularly limited, and as such dispersing aid, preferably can enumerate the phosphate with polyxyethylated structure is non-ionic dispersing agent.
The decentralized medium using as the present invention, can enumerate the alcohols such as water, methyl alcohol, ethanol, isopropyl alcohol, n-butanol, 2-butanols, octanol; The ketones such as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; The ester classes such as ethyl acetate, butyl acetate, ethyl lactate, gamma-butyrolacton, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters; The ethers such as ethylene glycol monomethyl ether, diethylene glycol single-butyl ether; Benzene,toluene,xylene, ethylbenzene etc. are aromatic hydrocarbon based; Dimethyl formamide, N, the amide-types such as N-dimethyl aceto-acetamide, 1-METHYLPYRROLIDONE etc.In these, preferred alcohol, isopropyl alcohol, n-butanol, 2-butanols, methylethylketone, methyl iso-butyl ketone (MIBK), cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, ethyl acetate, butyl acetate, toluene, dimethylbenzene, ethylbenzene, more preferably methylethylketone, butanols, dimethylbenzene, ethylbenzene, toluene.In the present invention, as decentralized medium, can use separately a kind of, also can be two or more and use.
In the present invention, decentralized medium for fusion in the purposes situation of the high index of refraction characteristic at special requirement nesa coating etc., for the particle diameter that prevents electrically conductive microparticle dispersion liquid and be used to form the particulate containing in the Photocurable composition that contains electrically conductive microparticle of nesa coating is along with the time becomes large, making the contained water yield is below 3 quality %, being preferably below 1 quality %, is more preferably below 0.5 quality %.
In electrically conductive microparticle dispersion liquid of the present invention, the mix proportions of each composition can be set aptly according to the purposes of electrically conductive microparticle dispersion liquid, and for the electrically conductive microparticle of every 100 mass parts, the content of metal complex is preferably 2～45 mass parts, be more preferably 5～20 mass parts, the content of decentralized medium is preferably 40～1000 mass parts, is more preferably 60～600 mass parts.In the situation that the amount of metal complex is less than above-mentioned lower limit, electrically conductive microparticle disperses bad, and more than above-mentioned higher limit in the situation that, metal complex is not dissolved in decentralized medium, can produce precipitation.In addition, in the situation that the amount of decentralized medium is less than above-mentioned lower limit, the dissolving of metal complex, the dispersion of electrically conductive microparticle are insufficient, and more than above-mentioned higher limit in the situation that, the concentration of electrically conductive microparticle dispersion liquid is excessively rare, becomes impracticable.
In addition, in the present invention, electrically conductive microparticle dispersion liquid in the purposes of the high index of refraction characteristic for special requirement nesa coating etc., high-refractive index particulate for every 100 mass parts, the content of electrically conductive microparticle is preferably 30～900 mass parts, be more preferably 40～500 mass parts, the content of metal complex is preferably 3～450 mass parts, be more preferably 7～200 mass parts, the content of decentralized medium is preferably 60～9000 mass parts, is more preferably 100～5000 mass parts.In the situation that the amount of electrically conductive microparticle is less than above-mentioned lower limit, although the refractive index of the film forming is high, conductivity reduces.On the contrary, in the situation that the amount of electrically conductive microparticle is higher than above-mentioned higher limit, although the conductivity of the film forming is high, refractive index reduces.In addition, in the situation that the amount of metal complex is less than above-mentioned lower limit, the dispersion of high-refractive index particulate and electrically conductive microparticle becomes bad, and more than above-mentioned higher limit in the situation that, metal complex is not dissolved in decentralized medium, can produce precipitation.In addition, in the situation that the amount of decentralized medium is less than above-mentioned lower limit, the dispersion of the dissolving of metal complex, high-refractive index particulate and electrically conductive microparticle is insufficient, more than above-mentioned higher limit in the situation that, the concentration of high-refractive index particulate and electrically conductive microparticle is excessively rare, becomes impracticable.
Electrically conductive microparticle dispersion liquid of the present invention, by by electrically conductive microparticle, metal complex and decentralized medium and further in the purposes situation of special requirement high index of refraction characteristic the high-refractive index particulate of fusion with random order, add, be fully obtained by mixing.Conventionally, electrically conductive microparticle and high-refractive index particulate be scattered in the decentralized medium that has dissolved metal complex and manufacture.Before carrying out scatter operation, also can carry out pre-dispersed operation.Pre-dispersed operation can be carried out as follows: in having dissolved the decentralized medium of metal complex; in with stirrings such as dispersion machines; conductive particle and high-refractive index particulate are slowly added, fully stir until by the visual piece that can not recognize these electrically conductive microparticles and high-refractive index particulate.In addition, the in the situation that of fusion high-refractive index particulate, also the dispersion liquid that can modulate in advance the dispersion liquid that comprises high-refractive index particulate, metal complex and decentralized medium and comprise electrically conductive microparticle, metal complex and decentralized medium, then mixes these dispersion liquids and manufactures.
The scatter operation of electrically conductive microparticle and high-refractive index particulate can be used coating rocker (ペ イ Application ト シ エ mono-カ mono-), ball mill, sand mill, centrifugal vortex dispersion machine etc. to carry out.When scatter operation, preferably use the dispersions such as bead, zirconium oxide bead to use pearl.Bead footpath is not particularly limited, and is generally approximately 0.05～1mm, is preferably 0.05～0.65mm.The in the situation that of fusion high-refractive index particulate, more preferably 0.08～0.65mm, is particularly preferably 0.08～0.5mm.
In electrically conductive microparticle dispersion liquid of the present invention, the particle diameter of electrically conductive microparticle and high-refractive index particulate is preferably below 120nm as median diameter (メ ジ ア Application footpath), more preferably below 80nm.If the tendency that median diameter more than it, exists the mist degree of the cured film that contains electrically conductive microparticle being obtained by the Photocurable composition that contains electrically conductive microparticle to uprise.
Electrically conductive microparticle dispersion liquid of the present invention, stably disperses in electrically conductive microparticle and high-refractive index particulate are long-term, in addition, owing to not comprising the acetylacetone,2,4-pentanedione etc. that makes corrosion of metals, can in metal container, preserve.
Electrically conductive microparticle dispersion liquid of the present invention can be included in to be used to form in the composition of diaphragm, the composition that is used to form antireflection film, adhesive, encapsulant, adhesive material etc. and use, and particularly can be used to form suitably the composition of the antireflection film with electrostatic-proof function.
The Photocurable composition that contains electrically conductive microparticle of the present invention contains electrically conductive microparticle, metal complex, active energy ray-curable compound, Photoepolymerizationinitiater initiater and decentralized medium, and electrically conductive microparticle, metal complex and decentralized medium are as previously discussed.
In addition, it is more than 1.8 high-refractive index particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide, active energy ray-curable compound, Photoepolymerizationinitiater initiater and decentralized media that the Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating of the present invention contains refractive index, water content is that below 3 quality %, high-refractive index particulate, electrically conductive microparticle and decentralized medium are as previously discussed.
Further, for the Photocurable composition that contains electrically conductive microparticle of the present invention, in order to give marresistance, abrasion performance, low crimpiness, adaptation, the transparency, refractive index, chemical resistance, the static electricity resistance of cured film, can use above-mentioned electrically conductive microparticle particulate in addition.For the kind of particulate, if can achieve the goal, be not particularly limited, can use commercially available product etc. known.Can use inorganic particles such as zirconia, titanium oxide, aluminium oxide and silica and organic fine particles etc.These particulates can only be used a kind, also can two or more also use.
The active energy ray-curable compound using as the present invention, can enumerate free radical polymerization monomer, radical polymerization oligomers etc.
Instantiation as free radical polymerization monomer, can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) isopropyl acrylate, (methyl) 2-EHA, (methyl) butyl acrylate, (methyl) acrylic acid cyclohexyl ester, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, polyethyleneglycol (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, polypropylene glycol list (methyl) acrylate, polyethylene glycol polypropylene glycol list (methyl) acrylate, polyethylene glycol polytetramethylene glycol list (methyl) acrylate, simple function (methyl) acrylate such as (methyl) glycidyl acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, diethylene glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, pi-allyl two (methyl) acrylate, bisphenol-A two (methyl) acrylate, oxirane modified bisphenol A two (methyl) acrylate, poly(ethylene oxide) modified bisphenol A two (methyl) acrylate, oxirane modified bisphenol S bis-(methyl) acrylate, bisphenol S two (methyl) acrylate, 1, 4-butanediol two (methyl) acrylate, 1, two senses (methyl) acrylate such as 3-butanediol two (methyl) acrylate, (methyl) acrylate more than trifunctional such as trimethylolpropane tris (methyl) acrylate, glycerine three (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, ethene modification trimethylolpropane tris (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, the free radical polymerization monomers such as styrene, vinyltoluene, vinylacetate, NVP, acrylonitrile, propenyl.
In addition; as the instantiation of radical polymerization oligomers, can enumerate the prepolymer that polyester (methyl) acrylate, polyurethane (methyl) acrylate, epoxy resin (methyl) acrylate, polyethers (methyl) acrylate, oligomeric (methyl) acrylate, alkyd (methyl) acrylate, polyalcohol (methyl) acrylate, organosilicon (methyl) acrylate etc. have at least 1 (methyl) acryloyl group.Particularly preferred radical polymerization oligomers is each (methyl) acrylate of polyester, epoxy resin, polyurethane.In the present invention, active energy ray-curable compound can be used separately a kind of, also can two or more and use.
In the Photocurable composition that contains electrically conductive microparticle of the present invention, owing to containing Photoepolymerizationinitiater initiater (photosensitizer), can make by the irradiation of a small amount of active energy beam the Photocurable composition that contains electrically conductive microparticle solidify.
The Photoepolymerizationinitiater initiater (photosensitizer) using as the present invention, can enumerate for example 1-hydroxycyclohexylphenylketone, benzophenone, benzyl dimethyl ketal, styrax methyl ether, styrax ethylether, p-chlorobenzophenone, 4-benzoyl-4-methyldiphenyl base sulfide, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino-1-acetone.Photoepolymerizationinitiater initiater can be used separately a kind of, also can two or more and use.
In the Photocurable composition that contains electrically conductive microparticle of the present invention, the mix proportions of each composition can be set aptly according to the purposes of the Photocurable composition that contains electrically conductive microparticle, and for the electrically conductive microparticle of every 100 mass parts, the content of metal complex is preferably 2～45 mass parts, be more preferably 5～20 mass parts, the content of decentralized medium is preferably 40～1000 mass parts, be more preferably 60～600 mass parts, the content of active energy ray-curable compound is preferably 10～1000 mass parts, be more preferably 25～150 mass parts, and the active energy ray-curable compound for every 100 mass parts, the content of Photoepolymerizationinitiater initiater is preferably 0.1～20 mass parts, it is more preferably 1～15 mass parts.
At this, in the situation that the amount of metal complex is less than above-mentioned lower limit, exists electrically conductive microparticle to become and disperse bad tendency, more than above-mentioned higher limit in the situation that, metal complex is not dissolved in decentralized medium, can produce precipitation.In the situation that the amount of decentralized medium is less than above-mentioned lower limit, the inadequate tendency that has the dissolving of metal complex, the dispersion of electrically conductive microparticle becomes, more than above-mentioned higher limit in the situation that, exist the concentration of electrically conductive microparticle dispersion liquid to cross additive effect rare and electrically conductive microparticle the inadequate tendency that becomes.In the situation that the amount of active energy ray-curable compound is less than above-mentioned lower limit, exist the refractive index of cured film to uprise and the tendency of transparency reduction, more than above-mentioned higher limit in the situation that, the refractive index of cured film can not the high degree to expectation.In addition,, in the situation that the amount of Photoepolymerizationinitiater initiater is less than above-mentioned lower limit, there is the tendency of the curing rate reduction of Photocurable composition, and conventionally also can not get the effect of its balance more than above-mentioned higher limit.
In addition, in being used to form the Photocurable composition that contains electrically conductive microparticle of nesa coating, high-refractive index particulate for every 100 mass parts, the content of electrically conductive microparticle is preferably 30～900 mass parts, be more preferably 40～500 mass parts, the content of metal complex is preferably 3～450 mass parts, be more preferably 7～200 mass parts, the content of decentralized medium is preferably 60～70000 mass parts, be more preferably 100～50000 mass parts, the content of active energy ray-curable compound is preferably 14～10000 mass parts, be more preferably 35～2000 mass parts, and the active energy ray-curable compound for every 100 mass parts, the content of Photoepolymerizationinitiater initiater is preferably 0.1～20 mass parts, it is more preferably 1～15 mass parts.
At this, be used to form in the Photocurable composition that contains electrically conductive microparticle of nesa coating, in the situation that the amount of electrically conductive microparticle is less than above-mentioned lower limit, although the refractive index of the film forming is high, conductivity reduces.On the contrary, in the situation that the amount of electrically conductive microparticle is higher than above-mentioned higher limit, although the conductivity of the film forming is high, refractive index reduces.In the situation that the amount of metal complex is less than above-mentioned lower limit, the tendency that exists the dispersion of high-refractive index particulate and electrically conductive microparticle to become bad, more than above-mentioned higher limit in the situation that, metal complex is not dissolved in decentralized medium, can produce precipitation.In the situation that the amount of decentralized medium is less than above-mentioned lower limit, there is the dispersion of dissolving, high-refractive index particulate and the electrically conductive microparticle of the metal complex inadequate tendency that becomes, more than above-mentioned higher limit in the situation that, the concentration of Photocurable composition is excessively rare, becomes impracticable.In the situation that the amount of active energy ray-curable compound is less than above-mentioned lower limit, exist the refractive index of nesa coating to uprise and the tendency of transparency reduction, more than above-mentioned higher limit in the situation that, the refractive index of nesa coating can not the high degree to expectation, and it is insufficient that electrostatic-proof function also becomes.In addition,, in the situation that the amount of Photoepolymerizationinitiater initiater is less than above-mentioned lower limit, there is the tendency of the curing rate reduction of Photocurable composition, and conventionally also can not get the effect of its balance more than above-mentioned higher limit.
Further, in the Photocurable composition that contains electrically conductive microparticle of the present invention, in not damaging the scope of its object, also can the above-mentioned habitual various additives in addition of fusion.As such additive, can enumerate polymerization inhibitor, curing catalysts, antioxidant, levelling agent, coupling agent etc.
The Photocurable composition that contains electrically conductive microparticle of the present invention can be coated with or be printed in plastics (Merlon, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melmac, triacetyl cellulose resin, PETG, ABS resin, AS resin, norbornene resin etc.), metal, timber, paper, glass, the surface of the various base materials such as slabstone, be solidified to form film, for example can be for plastics optics parts, touch pad, film-type liquid crystal cell, plastic containers, flooring material as building built-in material, wall material, artificial marble etc. for antisitic defect (scratch) and antipollution protective finish material, the antireflection film of film-type liquid crystal cell, touch pad, plastics optics parts etc., the adhesive of various base materials, encapsulant, the adhesive materials of printing-ink etc., particularly can be used to form the composition of the antireflection film with electrostatic-proof function suitably.In addition, in the situation that fusion the Photocurable composition that contains electrically conductive microparticle of high-refractive index particulate, particularly can be suitably for the formation of the nesa coating of high index of refraction.
The Photocurable composition that contains electrically conductive microparticle can carry out according to means such as conventional method such as roller coat, spin coating, silk screen printings to coating or the printing of base material.Heat as required and make decentralized medium (solvent) evaporation, making dried coating film, then irradiating active energy beam (ultraviolet ray or electron ray).As active energy beam source, can use ultraviolet source and the electron ray accelerators such as Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, metal halide lamp, xenon lamp, excimer laser, pigment laser.For the exposure of active energy beam, 50～3000mJ/cm in ultraviolet situation
2in scope, be suitable, 0.2～1000 μ C/cm in electron ray situation
2in scope, be suitable.By the irradiation of this active energy beam, above-mentioned active energy ray-curable compound generation polymerization, forms electrically conductive microparticle by the film of resin-bonded.The thickness of this film is generally preferably within the scope of 0.1～10.0 μ m.
The cured film that contains electrically conductive microparticle of the present invention that the Photocurable composition that contains electrically conductive microparticle with electrically conductive microparticle dispersion liquid of the present invention modulation is solidified and obtain, electrically conductive microparticle is dispersed in cured film, refractive index can be controlled, the transparency is high, mist degree is low, and specifically refractive index is 1.45～1.90, and light transmission rate is more than 75%, mist degree is below 2.0%, and sheet resistance value is 10
12below Ω/.
In addition, in the present invention, the composition that contains electrically conductive microparticle that makes to be used to form the nesa coating that requires high index of refraction characteristic solidifies and the nesa coating of the present invention that obtains, and high-refractive index particulate and electrically conductive microparticle are dispersed in nesa coating, refractive index can control and refractive index high, the transparency is high, mist degree is low, and specifically refractive index is 1.55～1.90, and light transmission rate is more than 85%, mist degree is below 1.5%, and sheet resistance value is 10
12below Ω/.In order to control refractive index, can adjust the ratio of the amount of high-refractive index particulate and electrically conductive microparticle and the amount of active energy ray-curable compound.Nesa coating can be for display surface of conductivity anti-reflection material and display etc.
Embodiment
Below by embodiment and comparative example, illustrate the present invention.It is pointed out that in embodiment and comparative example, " part " is all " mass parts ".
[embodiment 1～5 and comparative example 1～2]
The composition that embodiment 1～5 and comparative example 1～2 are used is the following stated.
< electrically conductive microparticle >
ATO (refractive index 2.0, specific insulation 10 Ω cm, primary particle size 0.05 μ m)
ITO (refractive index 2.0, specific insulation 0.02 Ω cm, primary particle size 0.04 μ m)
Tin oxide (refractive index 2.0, specific insulation 100 Ω cm, primary particle size 0.06 μ m)
Zinc oxide (refractive index 1.95, specific insulation 100 Ω cm, primary particle size 0.06 μ m)
< inorganic particles >
Aluminium oxide (refractive index 1.76, primary particle size 0.04 μ m)
< metal complex >
Acetylacetone,2,4-pentanedione zirconium [Zr (C
5h
7o
2)
4]
Titanium acetylacetone [Ti (C
5h
7o
2)
4]
Zinc acetylacetonate [Zn (C
5h
7o
2)
2]
Dibutyl tin diacetyl acetonate [(C
4h
9)
2sn (C
5h
7o
2)
2]
< dispersing aid >
PVC Star Network ケ ミ mono-ジ ヤ パ Application (strain) system, BYK-142
< active energy ray-curable compound >
Japan's chemical drug (strain) system, KAYARAD DPHA
< Photoepolymerizationinitiater initiater >
チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) system, IRGACURE 184
< chelating agent >
ダ イ セ Le chemical industry (strain) system, acetylacetone,2,4-pentanedione
[embodiment 1]
With respect to 100 parts of tin oxide, 20 parts of acetylacetone,2,4-pentanedione zirconiums, 250 parts of methylethylketone and 400 parts of beades are all added in container, use coating rocker mix 3 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of methylethylketone and obtain Photocurable composition.The PET film ((strain) A4100 processed spins in Japan) of this Photocurable composition being coated to thickness 100 μ m with scraping strip coating machine is upper, makes after organic solvent evaporation, uses high-pressure mercury light irradiation 300mJ/cm under air
2light, making thickness is the nesa coating of 3 μ m.The Photocurable composition that is produced on of film has just been made and has carried out after 6 months.
[embodiment 2]
With respect to 100 parts of ATO, 10 parts of titanium acetylacetones, 10 parts of BYK-142,250 parts of 2-butanols and 400 parts of beades are all added in container, use coating rocker mix 3 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 1, making thickness is the nesa coating of 3 μ m.
[embodiment 3]
With respect to 100 parts of ATO, 10 parts of dibutyl tin diacetyl acetonate, 250 parts of 2-butanols and 400 parts of beades are all added in container, use coating rocker mix 3 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 1, making thickness is the nesa coating of 3 μ m.
[embodiment 4]
With respect to 50 parts of ATO, 50 parts of ITO, 10 parts of dibutyl tin diacetyl acetonate, 250 parts of 2-butanols and 400 parts of beades are all added in container, use coating rocker mix 3 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 1, making thickness is the nesa coating of 3 μ m.
[embodiment 5]
With respect to 60 parts of ITO, 40 parts of aluminium oxide, 25 parts of dibutyl tin diacetyl acetonate, 250 parts of 2-butanols and 400 parts of beades are all added in container, use coating rocker mix 3 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 67 parts of DPHA, 6.7 parts of IRGACURE 184 and 170 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 1, making thickness is the nesa coating of 3 μ m.
[comparative example 1]
With respect to 100 parts of tin oxide, 20 parts of BYK-142,250 parts of 2-butanols and 400 parts of beades are all added in container, use coating rocker mix 3 hours.Dispersion liquid tackify in mix process.
[comparative example 2]
Except adding the acetylacetone,2,4-pentanedione of 20 parts, replace the titanium acetylacetone of 20 parts, by the processing identical with embodiment 2, making thickness is the nesa coating of 3 μ m.
< evaluation method >
(1) median diameter of inorganic particles
The median diameter that is scattered in dispersion liquid that embodiment and comparative example make and the inorganic particles in Photocurable composition use day machine dress (strain) Microtrac particle size distribution processed meter just, make rear, (40 ℃ of preservations) after 3 months, after 6 months (40 ℃ of preservations) by following condition, measure.
(2) transmitance of nesa coating, mist degree
The nesa coating obtaining for embodiment and comparative example, Japanese electric look industry (strain) NDH 5000 mensuration processed for transmitance and mist degree.Measured value is the value that comprises base material.
(3) sheet resistance value
The nesa coating obtaining for embodiment and comparative example, measures with the Ha イ レ ス タ IP MCP-HT260 of Mitsubishi chemical Co., Ltd's system.
(4) refractive index
The nesa coating obtaining for embodiment and comparative example, measures with the ア Star ベ refractometer DRM4 (20 ℃) of (strain) ア タ go system.
(5) corrosion of metal container made
The dispersion liquid of embodiment and comparative example making is added to rustless steel container (SUS304; Fe-Cr-Ni is stainless steel), after standing 1 month, pass through the etch state of visual valuation rustless steel container.
Together with the composition of above-mentioned each measurement result, evaluation result and each composition, be illustrated in table 1.
[table 1]
From the data shown in table 1, in the situation that containing metal complex (embodiment 1～5), no matter whether there is dispersing aid, all obtain having the dispersion liquid of excellent bin stability, even if also do not find corrosion in metal container made in the situation that being stored in metal container made.Further, the Photocurable composition that uses embodiment 1～5 gained dispersion liquid is coated with and the nesa coating that obtains, and refractive index is 1.45～1.90, and transmitance is more than 75%, and mist degree is below 2.0%, and sheet resistance value is 10
12below Ω/, there is electrostatic-proof function, high transparent and excellent electric conductivity.In the situation that not adding metal complex (comparative example 1), be difficult to disperse and can not get uniform dispersion liquid.In addition,, in the situation that the dispersion liquid (comparative example 2) that has added acetylacetone,2,4-pentanedione and disperseed is stored in to metal container made, recognize significantly the corrosion of container.
Below, by embodiment and reference example, specifically describe of the present invention for require the purposes of high index of refraction characteristic electrically conductive microparticle dispersion liquid, be used to form the composition that contains electrically conductive microparticle and the nesa coating of nesa coating.It is pointed out that in embodiment and reference example, " part " is all " mass parts ".
[embodiment 6～11 and reference example 1～6]
The composition that embodiment 6～11 and reference example 1～6 are used is the following stated.
< high-refractive index particulate >
Zirconia (refractive index 2.2, primary particle size 0.02 μ m)
Titanium oxide (refractive index 2.76, primary particle size 0.02 μ m)
< electrically conductive microparticle >
ATO (refractive index 2.0, specific insulation 10 Ω cm, primary particle size 0.06 μ m)
Tin oxide (refractive index 2.0, specific insulation 100 Ω cm, primary particle size 0.06 μ m)
Zinc oxide (refractive index 1.95, specific insulation 100 Ω cm, primary particle size 0.06 μ m)
< metal complex >
Acetylacetone,2,4-pentanedione zirconium [Zr (C
5h
7o
2)
4]
Titanium acetylacetone [Ti (C
5h
7o
2)
4]
Aluminium acetylacetonate [Al (C
5h
7o
2)
3]
Zinc acetylacetonate [Zn (C
5h
7o
2)
2]
Indium Tris acetylacetonate [In (C
5h
7o
2)
3]
Dibutyl tin diacetyl acetonate [(C
4h
9)
2sn (C
5h
7o
2)
2]
Single acetyl acetone three butoxy zirconium [(C
4h
9o)
3zr (C
5h
7o
2)]
< dispersing aid >
PVC Star Network ケ ミ mono-ジ ヤ パ Application (strain) system, BYK-142
< active energy ray-curable compound >
Japan's chemical drug (strain) system, KAYARAD DPHA
< Photoepolymerizationinitiater initiater >
チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ (strain) system, IRGACURE 184
< chelating agent >
ダ イ セ Le chemical industry (strain) system, acetylacetone,2,4-pentanedione
[embodiment 6]
With respect to 100 parts of zirconias, 100 parts of tin oxide, 40 parts of acetylacetone,2,4-pentanedione zirconiums, 500 parts of 2-butanols and 800 parts of beades are all added in container, use coating rocker mix 7 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 86 parts of DPHA, 4.3 parts of IRGACURE 184 and 130 parts of 2-butanols and obtain Photocurable composition.The PET film ((strain) A4100 processed spins in Japan) of this Photocurable composition being coated to thickness 100 μ m with roll coater is upper, makes after organic solvent evaporation, uses high-pressure mercury light irradiation 300mJ/cm under air
2light, making thickness is the nesa coating of 3 μ m.The Photocurable composition that is produced on of film has just been made and has carried out after 6 months.
[embodiment 7]
With respect to 100 parts of titanium oxide, 43 parts of ATO, 6 parts of titanium acetylacetones, 14.3 parts of BYK-142,500 parts of 2-butanols and 800 parts of beades are all added in container, use coating rocker mix 7 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 143 parts of DPHA, 7.2 parts of IRGACURE 184 and 160 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 6, making thickness is the nesa coating of 3 μ m.
[embodiment 8]
With respect to 100 parts of zirconias, 233 parts of tin oxide, 33 parts of aluminium acetylacetonates, 880 parts of 2-butanols and 800 parts of beades are all added in container, use coating rocker mix 7 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 143 parts of DPHA, 7.2 parts of IRGACURE 184 and 160 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 6, making thickness is the nesa coating of 3 μ m.
[embodiment 9]
With respect to 100 parts of titanium oxide, 100 parts of zinc oxide, 20 parts of zinc acetylacetonates, 500 parts of 2-butanols and 800 parts of beades are all added in container, use coating rocker mix 7 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 86 parts of DPHA, 4.3 parts of IRGACURE 184 and 130 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 6, making thickness is the nesa coating of 3 μ m.
[embodiment 10]
Except adding the dibutyl tin diacetyl acetonate of 20 parts, replace the zinc acetylacetonate of 20 parts, by the processing identical with embodiment 9, making thickness is the nesa coating of 3 μ m.
[embodiment 11]
Except adding the Indium Tris acetylacetonate of 20 parts, replace the zinc acetylacetonate of 20 parts, by the processing identical with embodiment 9, making thickness is the nesa coating of 3 μ m.
[reference example 1]
With respect to 100 parts of zirconias, 100 parts of tin oxide, 20 parts of BYK-142,600 parts of 2-butanols and 800 parts of beades are all added in container, use coating rocker mix 7 hours.Dispersion liquid tackify in mix process.
[reference example 2]
Except adding the acetylacetone,2,4-pentanedione of 6 parts, replace the titanium acetylacetone of 6 parts, by the processing identical with embodiment 7, making thickness is the nesa coating of 3 μ m.
[reference example 3]
100 parts of tin oxide, 10 parts of titanium acetylacetones, 600 parts of 2-butanols and 800 parts of beades are all added in container, use coating rocker mix 7 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 150 parts of DPHA, 5 parts of IRGACURE 184 and 100 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 6, making thickness is the nesa coating of 3 μ m.
[reference example 4]
100 parts of zirconias, 10 parts of acetylacetone,2,4-pentanedione zirconiums, 270 parts of 2-butanols and 400 parts of beades are all added in container, use coating rocker mix 7 hours.After mix, take out bead and obtain dispersion liquid.To this dispersion liquid, add 43 parts of DPHA, 2.2 parts of IRGACURE 184 and 60 parts of 2-butanols and obtain Photocurable composition.After this, by the method identical with embodiment 6, making thickness is the nesa coating of 3 μ m.
[reference example 5]
Except adding the single acetyl acetone three butoxy zirconiums of 40 parts, replace the acetylacetone,2,4-pentanedione zirconium of 40 parts, by the processing identical with embodiment 6, making thickness is the nesa coating of 3 μ m.
[reference example 6]
Except adding the single acetyl acetone three butoxy zirconiums of 40 parts, replace the acetylacetone,2,4-pentanedione zirconium of 40 parts, the 2-butanols that adds the water of 90 parts and 410 parts to replace the 2-butanols of 500 parts, by the processing identical with embodiment 6, making thickness is the nesa coating of 3 μ m.
< evaluation method >
In addition, the median diameter of inorganic particles and high-refractive index particulate, the corrosion of the transmitance of nesa coating, mist degree, sheet resistance value, refractive index and metal container made and embodiment 1～6 similarly carry out.
Together with the composition of above-mentioned each measurement result, evaluation result and each composition, be illustrated in table 2.
From the data shown in table 2, in the situation that containing metal complex (embodiment 6～11), no matter whether there is dispersing aid, all obtain having the dispersion liquid of excellent bin stability, even if also do not find corrosion in metal container made in the situation that being stored in metal container made.Further, the Photocurable composition that uses embodiment 6～11 gained dispersion liquids is coated with and the nesa coating that obtains, and refractive index is 1.55～1.90, and transmitance is more than 85%, and mist degree is below 1.5%, and sheet resistance value is 10
12below Ω/, there is high index of refraction, high transparent and excellent electric conductivity.In the situation that not adding metal complex (reference example 1), be difficult to disperse and can not get uniform dispersion liquid.In addition,, in the situation that the dispersion liquid (reference example 2) that has added acetylacetone,2,4-pentanedione and disperseed is stored in to metal container made, recognize significantly the corrosion of container.In the situation that not adding high-refractive index particulate (reference example 3), can not get meeting completely the film of high index of refraction, high transparent and conductivity.In the situation that not adding electrically conductive microparticle (reference example 4), identification is less than the conductivity of film.In the situation that comprising alkoxide as metal complex (reference example 5 and 6), particle diameter is along with the time becomes large, and membrane property is marked change also.In addition, a large amount of, moisture in the situation that (reference example 6), find that significantly particle diameter increases.
Claims (7)
1. nesa coating formation dispersion liquid, comprise electrically conductive microparticle, metal complex and decentralized medium, described metal complex does not comprise alkoxide, and the electrically conductive microparticle for every 100 mass parts, the content of metal complex is 2～45 mass parts, the content of decentralized medium is 40～1000 mass parts, by the solidification compound that comprises above-mentioned substance form that refractive index is 1.45～1.90, light transmission rate is more than 75%, mist degree is below 2.0% and sheet resistance value is 10
12nesa coating below Ω/, described electrically conductive microparticle is the a kind of metal oxide that is selected from ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonates and antimony pentoxide, and described metal complex consists of the metal of selected among zirconium, titanium, aluminium, zinc, indium and tin and the part that is selected from beta-diketon.
2. nesa coating formation dispersion liquid claimed in claim 1, is characterized in that, the beta-diketon that forms the part of metal complex is the beta-diketon that is selected from pivaloyl trifluoroacetone, acetylacetone,2,4-pentanedione, trifluoroacetylacetone (TFA) and hexafluoroacetylacetone.
3. nesa coating formation Photocurable composition, it is characterized in that, in the dispersion liquid described in claim 1 or 2, contain with respect to the content of every 100 mass parts electrically conductive microparticles is the active energy ray-curable compound of 10～1000 mass parts, and for the active energy ray-curable compound of every 100 mass parts, the content of Photoepolymerizationinitiater initiater is 0.1～20 mass parts.
4. nesa coating, it is characterized in that nesa coating claimed in claim 3 is formed with Photocurable composition coating or is printed on base material, solidifies and obtain.
5. nesa coating claimed in claim 4, is characterized in that refractive index is 1.45～1.90, and light transmission rate is more than 75%, and mist degree is below 2.0%, and sheet resistance value is 10
12below Ω/.
6. conductivity anti-reflection material, is characterized in that having the nesa coating described in claim 4 or 5 on transparent resin base material.
7. display, is characterized in that having the nesa coating described in claim 4 or 5 on display surface.
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| JP2009217991A JP4995878B2 (en) | 2009-09-18 | 2009-09-18 | Transparent conductive film forming dispersion, transparent conductive film forming photocurable composition, and transparent conductive film |
| JP2009-217991 | 2009-09-18 | ||
| PCT/JP2010/065919 WO2011034079A1 (en) | 2009-09-18 | 2010-09-15 | Electrically conductive microparticle dispersion, photocurable composition containing electrically conductive microparticles, and cured film containing electrically conductive microparticles |
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| FR2993999B1 (en) * | 2012-07-27 | 2014-09-12 | Nanomade Concept | METHOD FOR MANUFACTURING A TRANSPARENT TOUCH SURFACE AND TOUCH SURFACE OBTAINED BY SUCH A METHOD |
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| JP6436487B2 (en) * | 2014-12-29 | 2018-12-12 | 小林 博 | Manufacturing method for manufacturing transparent conductive film |
| WO2019049609A1 (en) * | 2017-09-05 | 2019-03-14 | 富士フイルム株式会社 | Curable composition, cured product, and lens unit |
| CN113861729B (en) * | 2021-10-14 | 2022-12-09 | 新纶新能源材料(常州)有限公司 | High-corrosion-resistance environment-friendly coating and preparation method thereof |
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| JP4817254B2 (en) * | 2006-12-01 | 2011-11-16 | 大日本塗料株式会社 | Zirconium oxide particle dispersion, photocurable composition containing zirconium oxide particles, and cured film |
| JP2009135098A (en) * | 2007-10-31 | 2009-06-18 | Sumitomo Metal Mining Co Ltd | Coating liquid for translucent conductive film formation, and translucent conductive film |
| JP5020130B2 (en) * | 2008-03-13 | 2012-09-05 | 日立マクセル株式会社 | Transparent conductive film forming ink and transparent conductive film |
| JP5077950B2 (en) * | 2008-03-19 | 2012-11-21 | 大日本塗料株式会社 | Dispersion, transparent conductive film forming composition, transparent conductive film and display |
| JP5598892B2 (en) * | 2008-04-21 | 2014-10-01 | 大日本塗料株式会社 | Laminated transparent film |
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2009
- 2009-09-18 JP JP2009217991A patent/JP4995878B2/en active Active
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- 2010-09-15 CN CN201080036039.9A patent/CN102473475B/en active Active
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| Publication number | Publication date |
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| KR20120087921A (en) | 2012-08-07 |
| TWI529225B (en) | 2016-04-11 |
| TW201124490A (en) | 2011-07-16 |
| JP2011065966A (en) | 2011-03-31 |
| WO2011034079A1 (en) | 2011-03-24 |
| KR101752221B1 (en) | 2017-06-29 |
| JP4995878B2 (en) | 2012-08-08 |
| CN102473475A (en) | 2012-05-23 |
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