CN102473475A - Electrically conductive microparticle dispersion, photocurable composition containing electrically conductive microparticles, and cured film containing electrically conductive microparticles - Google Patents

Electrically conductive microparticle dispersion, photocurable composition containing electrically conductive microparticles, and cured film containing electrically conductive microparticles Download PDF

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Publication number
CN102473475A
CN102473475A CN2010800360399A CN201080036039A CN102473475A CN 102473475 A CN102473475 A CN 102473475A CN 2010800360399 A CN2010800360399 A CN 2010800360399A CN 201080036039 A CN201080036039 A CN 201080036039A CN 102473475 A CN102473475 A CN 102473475A
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electrically conductive
conductive microparticle
mass parts
metal complex
photocurable composition
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CN102473475B (en
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室内圣人
林贤儿
铃木薰
沟口大刚
村上雅昭
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NIPPON TORYO CO Ltd
Dai Nippon Toryo KK
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NIPPON TORYO CO Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • 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
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/023—Alloys based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Paints Or Removers (AREA)
  • Inorganic Chemistry (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Laminated Bodies (AREA)
  • Polymerisation Methods In General (AREA)
  • Non-Insulated Conductors (AREA)

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

Electrically conductive microparticle dispersion liquid, the cured film that contains the Photocurable composition of electrically conductive microparticle and contain electrically conductive microparticle
Technical field
The present invention relates to the excellent electrically conductive microparticle dispersion liquid of bin stability, contain the Photocurable composition of electrically conductive microparticle and the cured film that contains electrically conductive microparticle that obtains by said composition; More particularly; Relate to and to form the Photocurable composition that the transparency is excellent and have the cured film that contains electrically conductive microparticle of electrostatic-proof function on the surface of various base materials such as plastics, metal, timber, paper, glass, slabstone; The transparency that is obtained by said composition is excellent and have the cured film of electrostatic-proof function and an excellent electrically conductive microparticle dispersion liquid of bin stability that is used for the modulation of such Photocurable composition.
Background technology
In recent years; As the binder material of the antisitic defect that is used for various substrate surfaces (scratch) and antipollution protective finish material, printing-ink, require to have the excellent solidification compound that is coated with worker's property and can forms the excellent in curing films such as outward appearance of hardness, marresistance, abrasion performance, low curl (カ one Le) property, adaptation, the transparency, chemical resistance, coated surface on the surface of various base materials.
In addition, in the purposes that is used for flat-panel monitor, touch pad, plastics optics parts etc., beyond above-mentioned requirements, also requirement can form the solidification compound that the transparency is excellent and have the cured film such as nesa coating of electrostatic-proof function.
Further, in image display devices such as LCD, 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 foreign matters such as dust and rubbish adhere to.For this reason, for the high refractive index layer of antireflection film,, also require excellent marresistance and antistatic characteristic at high transparent with beyond the high index of refraction characteristic.
So; As the means of giving electrostatic-proof function for such cured film; Known method of in solidification compound, adding electrically conductive microparticle; It as the metal oxide of main component, is under the situation of purpose at the film that has the permanent antistatic effect with making particularly perhaps that said electrically conductive microparticle comprises surfactant, electric conductive polymer, and the method for adding electrically conductive microparticle is general.As the method for such interpolation electrically conductive microparticle, exist in fusion chelating agent in resin solution or the solvent, make inorganic oxide be scattered in the method (referring to for example patent documentation 1 and 2) in this admixture.
The prior art document
Patent documentation
Patent documentation 1: the spy opens 2001-139, No. 847 communiques
Patent documentation 2: the spy opens 2001-139, No. 889 communiques
Summary of the invention
The problem that invention will solve
For the electrically conductive microparticle dispersion liquid and the solidification compound thereof that are used for such use, require the little and dispersion liquid bin stability excellence of particle diameter of electrically conductive microparticle.Because the chelating agent of above-mentioned patent documentation 1 and 2 records and metal form chelate, exist in the problem of the metallic equipment and the coating machine material corrosion of use in the dispersion treatment process.
The present invention makes in view of the above problems; Its objective is provides (1) to contain the Photocurable composition of electrically conductive microparticle; Said composition can be formed on the cured film that the transparency has electrostatic-proof function in excellent on the surface of base material; And in the dispersion treatment process, do not corrode the metallic equipment and the coating machine material of use; (2) the various cured film such as nesa coating that obtain by this Photocurable composition that contains electrically conductive microparticle; (3) display, this display have the cured film that is obtained by this Photocurable composition that contains electrically conductive microparticle, and (4) are used for the excellent electrically conductive microparticle dispersion liquid of bin stability of the modulation of such Photocurable composition that contains electrically conductive microparticle.
The means that are used to deal with problems
As for reaching the result of the wholwe-hearted research of above-mentioned each purpose; The inventor finds, is scattered in the decentralized medium through making electrically conductive microparticle and metal complex, obtains the excellent electrically conductive microparticle dispersion liquid of bin stability; Find in addition; Through using such electrically conductive microparticle dispersion liquid, obtain in the dispersion treatment process, not corroding the Photocurable composition that contains electrically conductive microparticle of metallic equipment and coating machine material, thereby accomplish the present invention.
Promptly; 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 per 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, beyond the electrically conducting transparent characteristic, also require under the situation of high index of refraction characteristic; This electrically conductive microparticle dispersion liquid is characterised in that comprising refractive index is high index of refraction particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide and decentralized medium more than 1.8; Water content is below the 3 quality %, preferably, it is characterized in that; High index of refraction particulate for per 100 mass parts; The content of electrically conductive microparticle is 30～900 mass parts, and 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 per 100 mass parts; The content of metal complex is 2～45 mass parts, and the content of decentralized medium is 40～1000 mass parts, and the content of active energy ray-curable compound is 10～1000 mass parts; And for the active energy ray-curable compound of per 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 the high index of refraction characteristic; Be the Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating with following characteristic: comprising refractive index is high index of refraction particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide, active energy ray-curable compound, Photoepolymerizationinitiater initiater and the decentralized medium more than 1.8, and water content is below the 3 quality %; Preferably; It is the Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating with following characteristic: for the high index of refraction particulate of per 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 60～70000 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 per 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 and contains the Photocurable composition coating of electrically conductive microparticle or be printed on the base material, solidify and obtain above-mentioned; 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 the high index of refraction characteristic is the nesa coating with following characteristic: it is used to form the Photocurable composition coating that contains electrically conductive microparticle of nesa coating or is printed on the base material, solidifies and obtain above-mentioned; Preferably, it is the nesa coating with following characteristic: 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/.
The invention effect
Through the present invention; (1) the excellent electrically conductive microparticle dispersion liquid of bin stability of dispersion liquid is provided; (2) Photocurable composition that contains electrically conductive microparticle is provided; Said composition can form transparency excellence on the surface of base material and have the cured film of electrostatic-proof function; And in the dispersion treatment process, do not corrode the metallic equipment and the coating machine material of use, and (3) transparency excellence that is obtained by said composition and the cured film that contains electrically conductive microparticle with electrostatic-proof function are provided.
In addition; Through the present invention; Provide (1) to be used to form the composition of photo-curable nesa coating; Said composition can form the nesa coating that the transparency is excellent and have high index of refraction, electrostatic-proof function on the surface of base material, and in the dispersion treatment process, does not corrode metallic equipment and the coating machine material of use, transparency excellence that (2) are obtained by this composition that is used to form nesa coating and the nesa coating with high index of refraction and electrostatic-proof function; (3) have the display of this nesa coating, and (4) be used for such composition that is used to form nesa coating modulation, the excellent dispersion liquid of bin stability.
Embodiment
Embodiment of the present invention is described below particularly.
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 does not receive special restriction.As the conductivity of electrically conductive microparticle, specific insulation is 10 7Below the Ω cm, be preferably 10 3Below the 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; Under the situation of the high index of refraction characteristic of special demands nesa coating etc.; It is high index of refraction particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide and decentralized medium more than 1.8 that its electrically conductive microparticle dispersion liquid contains refractive index, and water content is below the 3 quality %.For the high index of refraction particulate of the present invention's use and the shape of electrically conductive microparticle, do not receive special restriction.In addition, for the size of high index of refraction 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 that uses for the present invention does not promptly receive special restriction if can achieve the goal, and can use commercially available article etc. known.For example, can use metal oxides such as ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonates, antimony pentoxide and constitute the hydroxide of the metal of these metal oxides.For tin oxide, also can use the elements such as phosphorus that mixed.For zinc oxide, also can use mixed gallium and aluminium.In addition, the metal particle and the organic conductive particulate of gold, silver, copper, platinum, aluminium etc. also can.These electrically conductive microparticles can only use a kind, also can more than 2 kinds and use.
In addition; In the present invention; Fusion is for the refractive index of the nesa coating of controlling formation and the particulate that adds in the high index of refraction particulate of electrically conductive microparticle dispersion liquid; The preferred refractive index of using is 1.8～3.0 metal oxide, and said electrically conductive microparticle dispersion liquid is used for the purposes of the high index of refraction characteristic of special demands nesa coating etc.In addition, the refractive index of various high index of refraction particulates is the intrinsic values of material, is recorded in the various documents.Under the situation of the high index of refraction particulate that uses refractive index less than 1.8, can not get the film of high index of refraction, in addition, using refractive index to surpass under the situation of 3.0 high index of refraction particulate, the tendency that exists the transparency of film to reduce.The kind of the high index of refraction particulate that uses for the present invention does not promptly receive special restriction if can achieve the goal, and can use commercially available article etc. known.For example, can use zirconia (n=2.2), titanium oxide (n=2.76) and cerium oxide (n=2.2) etc.These high index of refraction particulates can only use a kind, also can more than 2 kinds and use.
In electrically conductive microparticle dispersion liquid of the present invention, beyond the high index of refraction particulate of fusion under the purposes situation of above-mentioned electrically conductive microparticle and special demands high index of refraction characteristic, fusion metal complex in decentralized medium.This metal complex can obtain the excellent electrically conductive microparticle dispersion liquid of bin stability of dispersion liquid owing in dispersion liquid, work as dispersant.In addition, metal complex does not corrode the metallic equipment and the coating machine material of use basically in dispersion process.
Metal complex as the present invention's use; 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.Contain in use under the situation of metal complex of alkoxide; Exist contained moisture of alkoxide and solvent or airborne moisture along with the time reacts, make the bin stability of electrically conductive microparticle dispersion liquid and the Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating and the tendency that membrane property reduces.
In the present invention, the metal complex for fusion under the purposes situation of the high index of refraction characteristic of special demands nesa coating etc. uses the metal complex that does not comprise alkoxide.Contain in use under the situation of metal complex of alkoxide; Exist contained moisture of alkoxide and solvent or airborne moisture along with the time reacts, make the bin stability of electrically conductive microparticle dispersion liquid and the Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating and the situation that membrane property reduces.
In addition, in order further to improve the purpose of the bin stability of dispersion liquid, also can further add other dispersant as dispersing aid.The kind of such dispersing aid does not receive special restriction, and as such dispersing aid, preferably can enumerate the phosphate with polyxyethylated structure is non-ionic dispersing agent.
As the decentralized medium that the present invention uses, can enumerate alcohols such as water, methyl alcohol, ethanol, isopropyl alcohol, n-butanol, 2-butanols, octanol; Ketones such as acetone, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, 4-hydroxy-4-methyl-2 pentanone; Ester classes such as ethyl acetate, butyl acetate, ethyl lactate, gamma-butyrolacton, propylene glycol monomethyl ether, propane diols list ethylether acetic acid esters; Ethers such as glycol monomethyl methyl ether, diethylene glycol single-butyl ether; Benzene,toluene,xylene, ethylbenzene etc. are aromatic hydrocarbon based; Dimethyl formamide, N, amide-types such as N-dimethyl aceto-acetamide, N-methyl pyrrolidone etc.In these; Preferred alcohol, isopropyl alcohol, n-butanol, 2-butanols, MEK, methyl iso-butyl ketone (MIBK), cyclohexanone, 4-hydroxy-4-methyl-2 pentanone, ethyl acetate, butyl acetate, toluene, xylenes, ethylbenzene, more preferably MEK, butanols, xylenes, 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 under the purposes situation of the high index of refraction characteristic of special demands nesa coating etc.; In order to prevent that electrically conductive microparticle dispersion liquid and the particle diameter that is used to form the particulate that contains in the Photocurable composition that contains electrically conductive microparticle of nesa coating are along with the time becomes big; Making that the contained water yield is below the 3 quality %, be preferably below the 1 quality %, more preferably is below the 0.5 quality %.
In electrically conductive microparticle dispersion liquid of the present invention; The mix proportions of each composition can be set according to the purposes of electrically conductive microparticle dispersion liquid aptly; And for the electrically conductive microparticle of per 100 mass parts, the content of metal complex is preferably 2～45 mass parts, more preferably is 5～20 mass parts; The content of decentralized medium is preferably 40～1000 mass parts, more preferably is 60～600 mass parts.Amount at metal complex is less than under the situation of above-mentioned lower limit, and electrically conductive microparticle disperses bad, and under the situation more than above-mentioned higher limit, metal complex is not dissolved in the decentralized medium, can produce deposition.In addition, be less than under the situation of above-mentioned lower limit in the amount of decentralized medium, the dissolving of metal complex, the dispersion of electrically conductive microparticle are insufficient, and under the situation more than above-mentioned higher limit, the concentration of electrically conductive microparticle dispersion liquid is rare excessively, becomes impracticable.
In addition, in the present invention, at the electrically conductive microparticle dispersion liquid of the purposes of the high index of refraction characteristic that is used for special demands nesa coating etc.; For the high index of refraction particulate of per 100 mass parts, the content of electrically conductive microparticle is preferably 30～900 mass parts, more preferably is 40～500 mass parts; The content of metal complex is preferably 3～450 mass parts; More preferably be 7～200 mass parts, the content of decentralized medium is preferably 60～9000 mass parts, more preferably is 100～5000 mass parts.Amount at electrically conductive microparticle is less than under the situation of above-mentioned lower limit, though the refractive index of the film that forms is high, conductivity reduces.On the contrary, be higher than under the situation of above-mentioned higher limit in the amount of electrically conductive microparticle, though the conductivity of the film that forms is high, refractive index reduces.In addition, be less than under the situation of above-mentioned lower limit in the amount of metal complex, the dispersion of high index of refraction particulate and electrically conductive microparticle becomes bad, and under the situation more than above-mentioned higher limit, metal complex is not dissolved in the decentralized medium, can produce deposition.In addition; Amount at decentralized medium is less than under the situation of above-mentioned lower limit, and the dispersion of the dissolving of metal complex, high index of refraction particulate and electrically conductive microparticle is insufficient, under the situation more than above-mentioned higher limit; The concentration of high index of refraction particulate and electrically conductive microparticle is rare excessively, becomes impracticable.
Electrically conductive microparticle dispersion liquid of the present invention, through with electrically conductive microparticle, metal complex and decentralized medium and further under the purposes situation of special demands high index of refraction characteristic the high index of refraction particulate of fusion add, fully mix and obtain with random order.Usually, make electrically conductive microparticle and high index of refraction microparticulate in the decentralized medium that has dissolved metal complex and make.Carrying out also can carrying out pre-dispersed operation before the scatter operation.Pre-dispersed operation can be carried out as follows: in the decentralized medium that has dissolved metal complex; In with stirrings such as dispersion machines; Conductive particle and high index of refraction particulate are slowly added, fully stir up to through the visual piece that can not recognize these electrically conductive microparticles and high index of refraction particulate.In addition; Under the situation of fusion high index of refraction particulate; The dispersion liquid that also can modulate the dispersion liquid that comprises high index of refraction particulate, metal complex and decentralized medium in advance and comprise electrically conductive microparticle, metal complex and decentralized medium mixes these dispersion liquids then and makes.
The scatter operation of electrically conductive microparticle and high index of refraction particulate can use coating rocker (ペ イ Application ト シ エ one カ one), ball mill, sand mill, centrifugal eddy current dispersion machine etc. to carry out.When scatter operation, preferably use dispersions such as bead, zirconium oxide bead to use pearl.The bead footpath does not receive special restriction, is generally about 0.05～1mm, is preferably 0.05～0.65mm.Under the situation of fusion high index of refraction particulate, more preferably 0.08～0.65mm is preferably 0.08～0.5mm especially.
In electrically conductive microparticle dispersion liquid of the present invention, the particle diameter of electrically conductive microparticle and high index of refraction particulate is preferably below the 120nm as median diameter (メ ジ ア Application footpath), further is preferably below the 80nm.If the tendency that median diameter more than it, exists the mist degree of the cured film that contains electrically conductive microparticle that is 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 index of refraction particulate are long-term, in addition, owing to do not comprise the acetylacetone,2,4-pentanedione that makes corrosion of metals etc., can in metal container, preserve.
Electrically conductive microparticle dispersion liquid of the present invention can be included in the composition that is used to form diaphragm, the composition that is used to form antireflection film, adhesive, encapsulant, the adhesive material etc. and use, and particularly can be used to form the composition of the antireflection film with electrostatic-proof function suitably.
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 high index of refraction particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide, active energy ray-curable compound, Photoepolymerizationinitiater initiater and decentralized medium more than 1.8 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 high index of refraction particulate, electrically conductive microparticle and decentralized medium are as previously discussed below the 3 quality %.
Further; For the Photocurable composition that contains electrically conductive microparticle of the present invention; Marresistance, abrasion performance, low crimpiness, adaptation, the transparency, refractive index, chemical resistance, static electricity resistance in order to give cured film can use the particulate beyond the above-mentioned electrically conductive microparticle.For the kind of particulate,, can use commercially available article etc. known if can achieve the goal and promptly do not receive special restriction.Can use for example inorganic particles such as zirconia, titanium oxide, aluminium oxide and silica and organic fine particles etc.These particulates can only use a kind, also can more than 2 kinds and use.
As the active energy ray-curable compound that the present invention uses, can enumerate free radical polymerization monomer, radical polymerization oligomers etc.
As the instantiation of free radical polymerization monomer, can enumerate simple function (methyl) acrylic acid ester such as (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) acrylic acid ester, methoxy poly (ethylene glycol) list (methyl) acrylic acid ester, polypropylene glycol list (methyl) acrylic acid ester, polyethylene glycol polypropylene glycol list (methyl) acrylic acid ester, single (methyl) acrylic acid ester of polyethylene glycol polytetramethylene glycol, (methyl) glycidyl acrylate; Ethylene glycol bisthioglycolate (methyl) acrylic acid ester, diethylene glycol two (methyl) acrylic acid ester, triethylene glycol two (methyl) acrylic acid ester, TEG two (methyl) acrylic acid ester, polyethylene glycol two (methyl) acrylic acid ester, polypropylene glycol two (methyl) acrylic acid ester, neopentyl glycol two (methyl) acrylic acid ester, pi-allyl two (methyl) acrylic acid ester, bisphenol-A two (methyl) acrylic acid ester, oxirane modified bisphenol A two (methyl) acrylic acid ester, PEO modified bisphenol A two (methyl) acrylic acid ester, oxirane modified bisphenol S two (methyl) acrylic acid ester, bisphenol S two (methyl) acrylic acid ester, 1; 4-butanediol two (methyl) acrylic acid ester, 1, two senses (methyl) acrylic acid ester such as 3-butanediol two (methyl) acrylic acid ester; (methyl) acrylic acid ester that trifunctionals such as trimethylolpropane tris (methyl) acrylic acid ester, glycerine three (methyl) acrylic acid ester, pentaerythrite three (methyl) acrylic acid ester, pentaerythrite four (methyl) acrylic acid ester, ethene modification trimethylolpropane tris (methyl) acrylic acid ester, dipentaerythritol five (methyl) acrylic acid ester, dipentaerythritol six (methyl) acrylic acid ester are above; Free radical polymerization monomers such as styrene, vinyltoluene, vinylacetate, N-vinyl pyrrolidone, acrylonitrile, propenyl.
In addition; As the instantiation of radical polymerization oligomers, can enumerate the prepolymer that polyester (methyl) acrylic acid ester, polyurethane (methyl) acrylic acid ester, epoxy resin (methyl) acrylic acid ester, polyethers (methyl) acrylic acid ester, oligomeric (methyl) acrylic acid ester, alkyd (methyl) acrylic acid ester, polyalcohol (methyl) acrylic acid ester, organosilicon (methyl) acrylic acid ester etc. have at least 1 (methyl) acryloyl group.Preferred especially radical polymerization oligomers is each (methyl) acrylic acid ester of polyester, epoxy resin, polyurethane.In the present invention, the active energy ray-curable compound can use a kind of separately, also can two or more and usefulness.
In the Photocurable composition that contains electrically conductive microparticle of the present invention,, the Photocurable composition that contains electrically conductive microparticle is solidified owing to contain Photoepolymerizationinitiater initiater (photosensitizer).
As the Photoepolymerizationinitiater initiater (photosensitizer) that the present invention uses, 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 use a kind of separately, also can two or more and usefulness.
In the Photocurable composition that contains electrically conductive microparticle of the present invention; The mix proportions of each composition can be set according to the purposes of the Photocurable composition that contains electrically conductive microparticle aptly, and for the electrically conductive microparticle of per 100 mass parts, the content of metal complex is preferably 2～45 mass parts; More preferably be 5～20 mass parts; The content of decentralized medium is preferably 40～1000 mass parts, more preferably is 60～600 mass parts, and the content of active energy ray-curable compound is preferably 10～1000 mass parts; More preferably be 25～150 mass parts; And for the active energy ray-curable compound of per 100 mass parts, the content of Photoepolymerizationinitiater initiater is preferably 0.1～20 mass parts, more preferably is 1～15 mass parts.
At this, be less than under the situation of above-mentioned lower limit in the amount of metal complex, exist electrically conductive microparticle to become and disperse bad tendency, under the situation more than above-mentioned higher limit, metal complex is not dissolved in the decentralized medium, can produce deposition.Amount at decentralized medium is less than under the situation of above-mentioned lower limit; There is the dispersion of dissolving, the electrically conductive microparticle of the metal complex inadequate tendency that becomes; Under situation, exist the concentration of electrically conductive microparticle dispersion liquid to cross and additive effect electrically conductive microparticle becomes inadequate tendency rare more than above-mentioned higher limit.Amount at the active energy ray-curable compound is less than under the situation of above-mentioned lower limit, exists the refractive index of cured film to uprise and the tendency of transparency reduction, and under the situation more than above-mentioned higher limit, the refractive index of cured film can not high degree to expectation.In addition, be less than under the situation of above-mentioned lower limit in the amount of Photoepolymerizationinitiater initiater, the tendency that exists the curing rate of Photocurable composition to reduce, and also can not get the effect of its balance usually more than above-mentioned higher limit.
In addition, in being used to form the Photocurable composition that contains electrically conductive microparticle of nesa coating, for the high index of refraction particulate of per 100 mass parts; The content of electrically conductive microparticle is preferably 30～900 mass parts, more preferably is 40～500 mass parts, and the content of metal complex is preferably 3～450 mass parts; More preferably be 7～200 mass parts; The content of decentralized medium is preferably 60～70000 mass parts, more preferably is 100～50000 mass parts, and the content of active energy ray-curable compound is preferably 14～10000 mass parts; More preferably be 35～2000 mass parts; And for the active energy ray-curable compound of per 100 mass parts, the content of Photoepolymerizationinitiater initiater is preferably 0.1～20 mass parts, more preferably is 1～15 mass parts.
Be used to form in the Photocurable composition that contains electrically conductive microparticle of nesa coating at this, be less than under the situation of above-mentioned lower limit in the amount of electrically conductive microparticle, though the refractive index of the film that forms is high, conductivity reduces.On the contrary, be higher than under the situation of above-mentioned higher limit in the amount of electrically conductive microparticle, though the conductivity of the film that forms is high, refractive index reduces.Amount at metal complex is less than under the situation of above-mentioned lower limit, the tendency that exists the dispersion of high index of refraction particulate and electrically conductive microparticle to become bad, and under the situation more than above-mentioned higher limit, metal complex is not dissolved in the decentralized medium, can produce deposition.Amount at decentralized medium is less than under the situation of above-mentioned lower limit; There is the dispersion of dissolving, high index of refraction particulate and the electrically conductive microparticle of the metal complex inadequate tendency that becomes; Under the situation more than above-mentioned higher limit, the concentration of Photocurable composition is rare excessively, becomes impracticable.Amount at the active energy ray-curable compound is less than under the situation of above-mentioned lower limit; Exist the refractive index of nesa coating to uprise and the tendency of transparency reduction; Under situation more than above-mentioned higher limit; The refractive index of nesa coating can not be high to the degree of expecting, it is insufficient that electrostatic-proof function also becomes.In addition, be less than under the situation of above-mentioned lower limit in the amount of Photoepolymerizationinitiater initiater, the tendency that exists the curing rate of Photocurable composition to reduce, and also can not get the effect of its balance usually more than above-mentioned higher limit.
Further, in the Photocurable composition that contains electrically conductive microparticle of the present invention, in the scope of not damaging its purpose, the habitual various additives beyond also can fusion above-mentioned.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 the surface of various base materials such as 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, slabstone; Be solidified to form film, what for example can be used for plastics optics parts, touch pad, film-type liquid crystal cell, plastic containers, the flooring material as the building built-in material, wall material, artificial marble etc. is used 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 fusion under the situation of the Photocurable composition that contains electrically conductive microparticle of high index of refraction particulate, particularly can be used for the formation of the nesa coating of high index of refraction suitably.
The Photocurable composition that contains electrically conductive microparticle to the coating of base material or printing can according to conventional method for example means such as roller coat, spin coating, silk screen printing carry out.Heat as required and make decentralized medium (solvent) evaporation, make dried coating film, shine active energy beam (ultraviolet ray or electron ray) then.As the active energy beam source, can use ultraviolet source and 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 under ultraviolet situation 2Be suitable in the scope, 0.2～1000 μ C/cm under the electron ray situation 2Be suitable in the scope.Through the irradiation of this active energy beam, above-mentioned active energy ray-curable compound generation polymerization forms the film of electrically conductive microparticle through resin-bonded.The thickness of this film generally is preferably in 0.1～10.0 mu m range.
The feasible cured film that contains electrically conductive microparticle of the present invention that obtains with the Photocurable composition curing that contains electrically conductive microparticle of electrically conductive microparticle dispersion liquid modulation of the present invention, electrically conductive microparticle evenly disperses in cured film, the refractive index may command; 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 feasible nesa coating of the present invention that is used to form the composition curing that contains electrically conductive microparticle of the nesa coating that requires the high index of refraction characteristic and obtains; High index of refraction particulate and electrically conductive microparticle evenly disperse in nesa coating, and refractive index may command and refractive index are high, and 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 amount with the amount of active energy ray-curable compound of high index of refraction particulate and electrically conductive microparticle.Nesa coating can be used for the display surface of conductivity anti-reflection material and display etc.
Embodiment
Specify the present invention through embodiment and comparative example below.It is pointed out that in embodiment and comparative example " part " all is " mass parts ".
[embodiment 1～5 and comparative example 1～2]
Embodiment 1～5 is the following stated with the composition that comparative example 1～2 uses.
< 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 one 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 MEKs and 400 parts of beades are all added in the container, with coating rocker mix 3 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of MEKs and obtain Photocurable composition to this dispersion liquid.With scraping strip coating machine this Photocurable composition is coated on the PET film (Japan spin (strain) system A4100) of thickness 100 μ m, make organic solvent evaporation after, under air with high-pressure mercury light irradiation 300mJ/cm 2Light, making thickness is the nesa coating of 3 μ m.The Photocurable composition that is produced on of film has just been processed and has been 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 the container, with coating rocker mix 3 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, through 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 the container, with coating rocker mix 3 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, through 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 the container, with coating rocker mix 3 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, through 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 the container, with coating rocker mix 3 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 67 parts of DPHA, 6.7 parts of IRGACURE 184 and 170 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, through 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 the container, with coating rocker mix 3 hours.Dispersion liquid tackify in the mix process.
[comparative example 2]
Except the acetylacetone,2,4-pentanedione that adds 20 parts replaced 20 parts titanium acetylacetone, through the processing identical with embodiment 2, making thickness was 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 the Photocurable composition use day machine dress (strain) system Microtrac particle size distribution meter after just making, after 3 months (40 ℃ of preservations), after 6 months (40 ℃ of preservations) measure through following condition.
(2) transmitance of nesa coating, mist degree
For the nesa coating that embodiment and comparative example obtain, transmitance and mist degree are measured with Japanese electric look industry (strain) system NDH 5000.Measured value is the value that comprises base material.
(3) sheet resistance value
The nesa coating that obtains for embodiment and comparative example is measured with the Ha イ レ ス タ IP MCP-HT260 of Mitsubishi chemical Co., Ltd's system.
(4) refractive index
The nesa coating that obtains for embodiment and comparative example is measured with the ア Star ベ refractometer DRM4 (20 ℃) of (strain) ア タ go system.
(5) corrosion of metallic container
The dispersion liquid of embodiment and comparative example making is added rustless steel container (SUS304; Fe-Cr-Ni is stainless steel), leave standstill the etch state that passes through the visual valuation rustless steel container after 1 month.
Above-mentioned each measured the result, evaluation result is illustrated in the table 1 with the composition of each composition.
[table 1]
Figure BPA00001513975000141
Figure BPA00001513975000151
Can know from the data shown in the table 1; Containing (embodiment 1～5) under the situation of metal complex; Whether no matter dispersing aid arranged, and the dispersion liquid that all obtains having excellent in storage stability is not even finding corrosion yet in the metallic container under the situation that is stored in the metallic container.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/, have electrostatic-proof function, high transparent and excellent electric conductivity.Under the situation of not adding metal complex (comparative example 1), be difficult to disperse and can not get uniform dispersion liquid.In addition, in that the dispersion liquid (comparative example 2) that has added acetylacetone,2,4-pentanedione and disperseed is stored under the situation of metallic container, recognize the corrosion of container significantly.
Below, through embodiment and reference example, the electrically conductive microparticle dispersion liquid that is used for the purposes of requirement high index of refraction characteristic of the present invention is described particularly, is 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 " all is " mass parts ".
[embodiment 6～11 and reference example 1～6]
Embodiment 6～11 is the following stated with the composition that reference example 1～6 uses.
< high index of refraction 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 one 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 the container, with coating rocker mix 7 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 86 parts of DPHA, 4.3 parts of IRGACURE 184 and 130 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.With roll coater this Photocurable composition is coated on the PET film (Japan spin (strain) system A4100) of thickness 100 μ m, make organic solvent evaporation after, under air with high-pressure mercury light irradiation 300mJ/cm 2Light, making thickness is the nesa coating of 3 μ m.The Photocurable composition that is produced on of film has just been processed and has been 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 the container, with coating rocker mix 7 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 143 parts of DPHA, 7.2 parts of IRGACURE 184 and 160 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, be the nesa coating of 3 μ m through making thickness with embodiment 6 identical methods.
[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 the container, with coating rocker mix 7 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 143 parts of DPHA, 7.2 parts of IRGACURE 184 and 160 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, be the nesa coating of 3 μ m through making thickness with embodiment 6 identical methods.
[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 the container, with coating rocker mix 7 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 86 parts of DPHA, 4.3 parts of IRGACURE 184 and 130 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, be the nesa coating of 3 μ m through making thickness with embodiment 6 identical methods.
[embodiment 10]
Except the dibutyl tin diacetyl acetonate of adding 20 parts replaced 20 parts zinc acetylacetonate, through the processing identical with embodiment 9, making thickness was the nesa coating of 3 μ m.
[embodiment 11]
Except the Indium Tris acetylacetonate of adding 20 parts replaced 20 parts zinc acetylacetonate, through the processing identical with embodiment 9, making thickness was 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 the container, with coating rocker mix 7 hours.Dispersion liquid tackify in the mix process.
[reference example 2]
Except the acetylacetone,2,4-pentanedione that adds 6 parts replaced 6 parts titanium acetylacetone, through the processing identical with embodiment 7, making thickness was 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 the container, with coating rocker mix 7 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 150 parts of DPHA, 5 parts of IRGACURE 184 and 100 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, be the nesa coating of 3 μ m through making thickness with embodiment 6 identical methods.
[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 the container, with coating rocker mix 7 hours.Behind the mix, take out bead and obtain dispersion liquid.Add 43 parts of DPHA, 2.2 parts of IRGACURE 184 and 60 parts of 2-butanols and obtain Photocurable composition to this dispersion liquid.After this, be the nesa coating of 3 μ m through making thickness with embodiment 6 identical methods.
[reference example 5]
Except the single acetyl acetone three butoxy zirconiums that add 40 parts replaced 40 parts acetylacetone,2,4-pentanedione zirconium, through the processing identical with embodiment 6, making thickness was the nesa coating of 3 μ m.
[reference example 6]
Except replacing 40 parts acetylacetone,2,4-pentanedione zirconium, the 2-butanols that adds 90 parts water and 410 parts, the single acetyl acetone three butoxy zirconiums that add 40 parts replace 500 parts the 2-butanols; Through the processing identical with embodiment 6, making thickness is the nesa coating of 3 μ m.
< evaluation method >
In addition, the corrosion of the transmitance of the median diameter of inorganic particles and high index of refraction particulate, nesa coating, mist degree, sheet resistance value, refractive index and metallic container and embodiment 1～6 likewise carry out.
Above-mentioned each measured the result, evaluation result is illustrated in the table 2 with the composition of each composition.
Can know from the data shown in the table 2; Containing (embodiment 6～11) under the situation of metal complex; Whether no matter dispersing aid arranged, and the dispersion liquid that all obtains having excellent in storage stability is not even finding corrosion yet in the metallic container under the situation that is stored in the metallic container.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/, have high index of refraction, high transparent and excellent electric conductivity.Under the situation of not adding metal complex (reference example 1), be difficult to disperse and can not get uniform dispersion liquid.In addition, in that the dispersion liquid (reference example 2) that has added acetylacetone,2,4-pentanedione and disperseed is stored under the situation of metallic container, recognize the corrosion of container significantly.Under the situation of not adding the high index of refraction particulate (reference example 3), can not get satisfying fully the film of high index of refraction, high transparent and conductivity.Do not adding (reference example 4) under the situation of electrically conductive microparticle, identification is less than the conductivity of film.Comprising (reference example 5 and 6) under the situation of alkoxide as metal complex, particle diameter is along with the time becomes big, and membrane property is marked change also.In addition, under a large amount of moisture situation (reference example 6), find that significantly particle diameter increases.
Figure BPA00001513975000191

Claims (32)

1. the electrically conductive microparticle dispersion liquid is characterized in that comprising electrically conductive microparticle, metal complex and decentralized medium.
2. the described electrically conductive microparticle of claim 1 is characterized in that said metal complex does not comprise alkoxide.
3. claim 1 or 2 described electrically conductive microparticle dispersion liquids is characterized in that, for the electrically conductive microparticle of per 100 mass parts, the content of metal complex is 2～45 mass parts, and the content of decentralized medium is 40～1000 mass parts.
4. each described dispersion liquid of claim 1～3 is characterized in that, electrically conductive microparticle is at least a kind of metal oxide that is selected from ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonates and antimony pentoxide.
5. each described electrically conductive microparticle dispersion liquid of claim 1～4 is characterized in that the part that metal complex comprises the metal of selected among zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminium, zinc, indium, tin and platinum and is selected from beta-diketon.
6. each described electrically conductive microparticle dispersion liquid of claim 1～5 is characterized in that the part that metal complex comprises the metal of selected among zirconium, titanium, aluminium, zinc, indium and tin and is selected from pivaloyl trifluoroacetone, acetylacetone,2,4-pentanedione, trifluoroacetylacetone (TFA) and hexafluoroacetylacetone.
7. the Photocurable composition that contains electrically conductive microparticle is characterized in that comprising electrically conductive microparticle, metal complex, active energy ray-curable compound, Photoepolymerizationinitiater initiater and decentralized medium.
8. the described Photocurable composition that contains electrically conductive microparticle of claim 7 is characterized in that said metal complex does not comprise alkoxide.
9. claim 7 or the 8 described Photocurable compositions that contain electrically conductive microparticle; It is characterized in that for the electrically conductive microparticle of per 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 for the active energy ray-curable compound of per 100 mass parts, the content of Photoepolymerizationinitiater initiater is 0.1～20 mass parts.
10. each described Photocurable composition that contains electrically conductive microparticle of claim 7～9 is characterized in that, electrically conductive microparticle is at least a kind of metal oxide that is selected from ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonates and antimony pentoxide.
11. each described Photocurable composition that contains electrically conductive microparticle of claim 7～10 is characterized in that the part that metal complex comprises the metal of selected among zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminium, zinc, indium, tin and platinum and is selected from beta-diketon.
12. each described Photocurable composition that contains electrically conductive microparticle of claim 7～11 is characterized in that the part that metal complex comprises the metal of selected among zirconium, titanium, aluminium, zinc, indium and tin and is selected from pivaloyl trifluoroacetone, acetylacetone,2,4-pentanedione, trifluoroacetylacetone (TFA) and hexafluoroacetylacetone.
13. contain the cured film of electrically conductive microparticle, it is characterized in that each described Photocurable composition coating that contains electrically conductive microparticle of claim 7～12 or be printed on the base material, solidify and obtain.
14. the described cured film that contains electrically conductive microparticle of claim 13 is characterized in that refractive index is 1.45～1.90, light transmission rate is more than 75%, and mist degree is below 2.0%, and sheet resistance value is 10 12Below Ω/.
15. the conductivity anti-reflection material is characterized in that on the transparent resin base material, having claim 13 or 14 described nesa coatings.
16. display is characterized in that on display surface, having claim 13 or the 14 described cured film that contain electrically conductive microparticle.
17. the electrically conductive microparticle dispersion liquid, it is characterized in that comprising refractive index is high index of refraction particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide and decentralized medium more than 1.8, and water content is below the 3 quality %.
18. the described electrically conductive microparticle dispersion liquid of claim 17; It is characterized in that for the high index of refraction particulate of per 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.
19. claim 17 or 18 described electrically conductive microparticle dispersion liquids is characterized in that the high index of refraction particulate is at least a kind of metal oxide that is selected from zirconia, titanium oxide and cerium oxide.
20. each described electrically conductive microparticle dispersion liquid of claim 17～19 is characterized in that electrically conductive microparticle is at least a kind of metal oxide that is selected from ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonates and antimony pentoxide.
21. each described electrically conductive microparticle dispersion liquid of claim 17～20 is characterized in that the part that metal complex comprises the metal of selected among zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminium, zinc, indium, tin and platinum and is selected from beta-diketon.
22. each described electrically conductive microparticle dispersion liquid of claim 17～21 is characterized in that the part that metal complex comprises the metal of selected among zirconium, titanium, aluminium, zinc, indium and tin and is selected from pivaloyl trifluoroacetone, acetylacetone,2,4-pentanedione, trifluoroacetylacetone (TFA) and hexafluoroacetylacetone.
23. be used to form the Photocurable composition that contains electrically conductive microparticle of nesa coating; It is characterized in that comprising refractive index is high index of refraction particulate, electrically conductive microparticle, the metal complex that does not comprise alkoxide, active energy ray-curable compound, Photoepolymerizationinitiater initiater and decentralized medium more than 1.8, and water content is below the 3 quality %.
24. the described Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating of claim 23; It is characterized in that; High index of refraction particulate for per 100 mass parts; The content of electrically conductive microparticle is 30～900 mass parts, and the content of metal complex is 3～450 mass parts, and the content of decentralized medium is that the content of 60～70000 mass parts and active energy ray-curable compound is 14～10000 mass parts; And for this active energy ray-curable compound of per 100 mass parts, the content of Photoepolymerizationinitiater initiater is 0.1～20 mass parts.
25. claim 23 or the 24 described Photocurable compositions that contain electrically conductive microparticle that are used to form nesa coating is characterized in that the high index of refraction particulate is at least a kind of metal oxide that is selected from zirconia, titanium oxide and cerium oxide.
26. each described Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating of claim 23～25 is characterized in that electrically conductive microparticle is at least a kind of metal oxide that is selected from ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonates and antimony pentoxide.
27. each described Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating of claim 23～26 is characterized in that the part that metal complex comprises the metal of selected among zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminium, zinc, indium, tin and platinum and is selected from beta-diketon.
28. each described Photocurable composition that contains electrically conductive microparticle that is used to form nesa coating of claim 23～27 is characterized in that the part that metal complex comprises the metal of selected among zirconium, titanium, aluminium, zinc, indium and tin and is selected from pivaloyl trifluoroacetone, acetylacetone,2,4-pentanedione, trifluoroacetylacetone (TFA) and hexafluoroacetylacetone.
29. nesa coating is characterized in that each describedly is used to form Photocurable composition coating that contains electrically conductive microparticle of nesa coating or is printed on the base material, solidifies and obtain with claim 23～28.
30. the described nesa coating of claim 29 is characterized in that refractive index is 1.55～1.90, light transmission rate is more than 85%, and mist degree is below 1.5%, and sheet resistance value is 10 12Below Ω/.
31. the conductivity anti-reflection material is characterized in that on the transparent resin base material, having claim 29 or 30 described nesa coatings.
32. display is characterized in that on display surface, having claim 29 or 30 described nesa coatings.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104508609A (en) * 2012-07-27 2015-04-08 奈米制作概念公司 Method of manufacturing a transparent tactile surface and tactile surface obtained by such a method
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5908287B2 (en) * 2012-01-24 2016-04-26 日立マクセル株式会社 Composition for forming transparent conductive film and transparent conductive film
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1871085A (en) * 2003-09-12 2006-11-29 独立行政法人产业技术综合研究所 Metal nano particle liquid dispersion capable of being sprayed in fine particle form and being applied in laminated state
JP2008010236A (en) * 2006-06-28 2008-01-17 Kyocera Corp Transparent conductive film and forming method therefor, photoelectric transfer device, and photovoltaic generator device
TW200824786A (en) * 2006-12-01 2008-06-16 Dainippon Toryo Kk Zirconium oxide particle dispersion liquid, photocurable composition containing zirconium 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

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3862042B2 (en) * 1997-05-08 2006-12-27 Ｔｄｋ株式会社 Conductive paste, ceramic structure using the same, and method for producing the same
JP2001139847A (en) * 1999-11-12 2001-05-22 Dainippon Toryo Co Ltd Active energy ray-curable coating composition
JP5309440B2 (en) * 2005-11-15 2013-10-09 三菱マテリアル株式会社 Composition for forming electrode of solar cell, method for forming the electrode, and method for producing solar cell using the electrode obtained by the forming method
JP4620634B2 (en) * 2006-06-06 2011-01-26 株式会社パワーシステム Electrode member for non-aqueous electronic parts
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1871085A (en) * 2003-09-12 2006-11-29 独立行政法人产业技术综合研究所 Metal nano particle liquid dispersion capable of being sprayed in fine particle form and being applied in laminated state
JP2008010236A (en) * 2006-06-28 2008-01-17 Kyocera Corp Transparent conductive film and forming method therefor, photoelectric transfer device, and photovoltaic generator device
TW200824786A (en) * 2006-12-01 2008-06-16 Dainippon Toryo Kk Zirconium oxide particle dispersion liquid, photocurable composition containing zirconium 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

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104508609A (en) * 2012-07-27 2015-04-08 奈米制作概念公司 Method of manufacturing a transparent tactile surface and tactile surface obtained by such a method
CN104508609B (en) * 2012-07-27 2017-08-25 奈米制作概念公司 The manufacture method of transparent tactile-surface and the tactile-surface obtained by methods described
CN105244081A (en) * 2013-10-16 2016-01-13 日立化成株式会社 Laminate containig conductive fiber, photosensitive conductive film, method for producing conductive pattern, conductive pattern substrate, and touch panel
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US10795469B2 (en) 2013-10-16 2020-10-06 Hitachi Chemical Company, Ltd. Laminate containing conductive fiber, photosensitive conductive film, method for producing conductive pattern, conductive pattern substrate, and touch panel
CN106104703A (en) * 2014-03-20 2016-11-09 E.I.内穆尔杜邦公司 The polymer thick film transparent conductor of thermoformable and the purposes in capacitance-type switch circuit thereof
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