WO2011034079A1 - Dispersion de microparticules électriquement conductrices, composition photodurcissable contenant des microparticules électriquement conductrices et film durci contenant ces microparticules - Google Patents

Dispersion de microparticules électriquement conductrices, composition photodurcissable contenant des microparticules électriquement conductrices et film durci contenant ces microparticules Download PDF

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Publication number
WO2011034079A1
WO2011034079A1 PCT/JP2010/065919 JP2010065919W WO2011034079A1 WO 2011034079 A1 WO2011034079 A1 WO 2011034079A1 JP 2010065919 W JP2010065919 W JP 2010065919W WO 2011034079 A1 WO2011034079 A1 WO 2011034079A1
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Prior art keywords
conductive fine
fine particles
parts
metal complex
refractive index
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PCT/JP2010/065919
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English (en)
Japanese (ja)
Inventor
聖人 室内
賢児 林
薫 鈴木
大剛 溝口
雅昭 村上
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大日本塗料株式会社
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Application filed by 大日本塗料株式会社 filed Critical 大日本塗料株式会社
Priority to KR1020127009864A priority Critical patent/KR101752221B1/ko
Priority to CN201080036039.9A priority patent/CN102473475B/zh
Publication of WO2011034079A1 publication Critical patent/WO2011034079A1/fr

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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

Definitions

  • the present invention relates to a conductive fine particle dispersion excellent in storage stability, a conductive fine particle-containing photocurable composition, and a conductive fine particle-containing cured film obtained from the composition, and more specifically, plastic, metal, wood, A photocurable composition that can form a conductive fine particle-containing cured film having excellent transparency and an antistatic function on the surface of various substrates such as paper, glass, and slate, and the transparency obtained from the composition
  • the present invention relates to a cured film having an excellent antistatic function and a conductive fine particle dispersion having excellent storage stability used for preparing such a photocurable composition.
  • a curable composition that can form a cured film such as a transparent conductive film that is excellent in transparency and has an antistatic function. Things are required.
  • antireflection films are used in image display devices such as liquid crystal displays and cathode ray tube display devices and optical products.
  • the antireflection film is required to have a scratch resistance and a function of preventing adhesion of foreign matters such as dust and dirt. Therefore, the high refractive index layer of the antireflection film is required to have excellent scratch resistance and antistatic properties in addition to high transparency and high refractive index properties.
  • a method of adding a surfactant, a conductive polymer, or conductive fine particles mainly composed of a metal oxide to the curable composition is known.
  • a method of adding conductive fine particles is common.
  • a method for adding such conductive fine particles there is a method in which a chelating agent is blended in a resin solution or a solvent, and an inorganic oxide is dispersed in the blend (for example, see Patent Documents 1 and 2).
  • the conductive fine particle dispersion and the curable composition used for the above-mentioned applications it is required that the conductive fine particles have a small particle diameter and that the dispersion is excellent in storage stability. Since the chelating agents described in Patent Documents 1 and 2 form chelates with metals, there is a problem of corroding metal equipment and coating equipment used in the dispersion treatment process.
  • a cured film having excellent transparency and an antistatic function can be formed on the surface of a substrate and used in a dispersion treatment process.
  • Conductive fine particle-containing photocurable composition that does not corrode metallic equipment and coating equipment to be used,
  • Various cured films such as a transparent conductive film obtained from the conductive fine particle-containing photocurable composition, (3)
  • the present inventors have obtained a conductive fine particle dispersion having excellent storage stability by dispersing conductive fine particles and a metal complex in a dispersion medium.
  • the present inventors have found that by using such a conductive fine particle dispersion, a photocurable composition containing conductive fine particles can be obtained without corroding metal equipment or coating equipment in the course of dispersion treatment. Completed the invention.
  • the conductive fine particle dispersion of the present invention is characterized by comprising conductive fine particles, a metal complex, and a dispersion medium.
  • the content of the metal complex is 2 to 45 parts by mass per 100 parts by mass of the conductive fine particles.
  • the content of the dispersion medium is 40 to 1000 parts by mass.
  • the conductive fine particle dispersion when a high refractive index characteristic is required in addition to the transparent conductive characteristic, contains high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, and alkoxide.
  • a metal complex comprising no metal complex and a dispersion medium, and having a moisture content of 3% by mass or less.
  • the content of conductive fine particles is 30 to 900 parts by mass per 100 parts by mass of high refractive index fine particles.
  • the content is 3 to 450 parts by mass and the content of the dispersion medium is 60 to 9000 parts by mass.
  • the conductive fine particle-containing photocurable composition of the present invention is characterized by comprising conductive fine particles, a metal complex, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, preferably conductive fine particles.
  • the content of the metal complex is from 2 to 45 parts by mass per 100 parts by mass
  • the content of the dispersion medium is from 40 to 1000 parts by mass
  • the content of the active energy ray-curable compound is from 10 to 1000 parts by mass.
  • the content of the photopolymerization initiator is 0.1 to 20 parts by mass per 100 parts by mass of the active energy ray-curable compound.
  • the conductive fine particle-containing photocurable composition for forming a transparent conductive film that requires high refractive index characteristics includes high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, and alkoxide.
  • the conductive fine particle content is 30 to 900 parts by mass
  • the metal complex content is 3 to 450 parts by mass
  • the dispersion medium content is 60 to 70000 parts by mass per 100 parts by mass of the high refractive index fine particles.
  • the content of the active energy ray-curable compound is 14 to 10,000 parts by mass
  • the content of the photopolymerization initiator per 100 parts by mass of the active energy ray-curable compound is 0.1 to 20 parts by mass.
  • the conductive fine particle-containing cured film of the present invention is characterized by being obtained by applying or printing the above-mentioned conductive fine particle-containing photocurable composition on a substrate and curing, preferably,
  • the refractive index is 1.45 to 1.90
  • the light transmittance is 75% or more
  • the haze is 2.0% or less
  • the surface resistance value is 10 12 ⁇ / ⁇ or less.
  • a cured film containing conductive fine particles for forming a transparent conductive film which requires high refractive index characteristics, is obtained by applying the above-described photocurable composition containing conductive fine particles for forming a transparent conductive film on a substrate.
  • a transparent conductive film obtained by coating or printing and curing, preferably having a refractive index of 1.55 to 1.90 and a light transmittance of 85% or more, A transparent conductive film having a haze of 1.5% or less and a surface resistance value of 10 12 ⁇ / ⁇ or less.
  • a conductive fine particle dispersion excellent in storage stability of a dispersion is provided, and (2) a cured film having excellent transparency and an antistatic function is formed on the surface of a substrate.
  • a cured film containing conductive fine particles having an antistatic function is provided.
  • a transparent conductive film having excellent transparency, a high refractive index, and an antistatic function can be formed on the surface of a substrate, and metal equipment and coating used in the dispersion treatment process.
  • a dispersion having excellent storage stability used for the preparation of a film, (3) a display having the transparent conductive film, and (4) such a composition for forming a transparent conductive film is provided.
  • the conductive fine particle dispersion of the present invention contains conductive fine particles, a metal complex, and a dispersion medium.
  • the shape of the conductive fine particles used in the present invention is not particularly limited.
  • the conductive fine particles have a volume resistivity of 10 7 ⁇ ⁇ cm or less, preferably 10 3 ⁇ ⁇ cm or less.
  • the size of the conductive fine particles those having a primary particle diameter of usually 1 to 500 nm, preferably 10 to 100 nm can be used.
  • the conductive fine particle dispersion is composed of high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, and alkoxide. It contains a metal complex and a dispersion medium that are not included, and has a moisture content of 3% by mass or less.
  • the shape of the high refractive index fine particles and conductive fine particles used in the present invention is not particularly limited. As for the sizes of the high refractive index fine particles and the conductive fine particles, those having a primary particle diameter of usually 1 to 500 nm, preferably 10 to 100 nm can be used.
  • the type of conductive fine particles used in the present invention is not particularly limited as long as the object can be achieved, and known products such as commercially available products can be used.
  • metal oxides such as ITO, ATO, tin oxide, zinc oxide, indium oxide, zinc antimonate, and antimony pentoxide, and metal hydroxides constituting these metal oxides can be used.
  • tin oxide one doped with an element such as phosphorus can also be used.
  • zinc oxide one doped with gallium or aluminum can also be used.
  • metal fine particles such as gold, silver, copper, platinum, and aluminum and organic conductive fine particles may be used. These conductive fine particles may be used alone or in combination of two or more.
  • the high refractive index fine particles blended in the conductive fine particle dispersion for applications requiring particularly high refractive index characteristics such as a transparent conductive film is used for controlling the refractive index of the formed transparent conductive film.
  • a metal oxide having a refractive index of 1.8 to 3.0 is preferably used.
  • the refractive index of each high refractive index fine particle is a value peculiar to material, and is described in various literatures. When a high refractive index fine particle having a refractive index of less than 1.8 is used, a film having a high refractive index cannot be obtained, and when a high refractive index fine particle having a refractive index exceeding 3.0 is used, Transparency tends to decrease.
  • the kind of high refractive index fine particles used in the present invention is not particularly limited as long as the object can be achieved, and known products such as commercially available products can be used.
  • known products such as commercially available products can be used.
  • These high refractive index fine particles may be used alone or in combination of two or more.
  • a metal complex is blended in the dispersion medium in addition to the above-mentioned conductive fine particles and particularly the high refractive index fine particles to be blended for applications requiring high refractive index characteristics.
  • This metal complex functions as a dispersant in the dispersion, a conductive fine particle dispersion having excellent storage stability of the dispersion can be obtained. Further, the metal complex hardly corrodes metal equipment and coating equipment used in the dispersion process.
  • the metal complex used in the present invention is a metal selected from the group consisting of zirconium, titanium, chromium, manganese, iron, cobalt, nickel, copper, vanadium, aluminum, zinc, indium, tin and platinum, preferably the color of the dispersion.
  • a metal complex containing an alkoxide reacts with the moisture contained in the solvent or moisture in the air over time, and the conductive fine particle-containing photocurable resin for forming the conductive fine particle dispersion and the transparent conductive film. There is a tendency to reduce the storage stability and film properties of the composition.
  • a metal complex that does not contain an alkoxide is used for a metal complex to be blended in a case where a particularly high refractive index characteristic such as a transparent conductive film is required.
  • a metal complex containing an alkoxide reacts with the moisture contained in the solvent or moisture in the air over time, and the conductive fine particle-containing photocurable resin for forming the conductive fine particle dispersion and the transparent conductive film.
  • the storage stability and film properties of the composition may be reduced.
  • another dispersant may be added as a dispersion aid.
  • the kind of the dispersion aid is not particularly limited, but as such a dispersion aid, a phosphate ester nonionic dispersant having a polyoxyethylene alkyl structure can be preferably exemplified.
  • Examples of the dispersion medium used in the present invention include alcohols such as water, methanol, ethanol, isopropanol, normal butanol, 2-butanol, and octanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2- Ketones such as pentanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; benzene , Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; amides such as dimethylformamide, N, N-dimethylacetoacetamide and N-
  • ethanol isopropanol, normal butanol, 2-butanol, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, ethyl acetate, butyl acetate, toluene, xylene, and ethylbenzene are preferable, and methyl ethyl ketone Butanol, xylene, ethylbenzene, and toluene are more preferable.
  • the dispersion medium may be used alone or in combination of two or more.
  • the dispersion medium to be blended in the case of applications requiring particularly high refractive index characteristics such as a transparent conductive film, a conductive fine particle-containing photocurable composition for forming a conductive fine particle dispersion or a transparent conductive film.
  • the amount of water contained is 3% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less. .
  • the blending ratio of each component can be appropriately set according to the use of the conductive fine particle dispersion, but the metal complex content is preferably 2 to 100 parts by weight of the conductive fine particles. It is 45 parts by mass, more preferably 5 to 20 parts by mass, and the content of the dispersion medium is preferably 40 to 1000 parts by mass, more preferably 60 to 600 parts by mass.
  • the amount of the metal complex is less than the above lower limit value, the conductive fine particles are poorly dispersed.
  • the amount is more than the above upper limit value, the metal complex does not dissolve in the dispersion medium and precipitation may occur.
  • the amount of the dispersion medium is less than the above lower limit value, the dissolution of the metal complex and the dispersion of the conductive fine particles are insufficient, and when the amount is more than the above upper limit value, the concentration of the conductive fine particle dispersion is too thin. Become impractical.
  • the content of conductive fine particles is preferably 30 to 900 per 100 parts by mass of the high refractive index fine particles. Parts by mass, more preferably 40 to 500 parts by mass, the content of the metal complex is preferably 3 to 450 parts by mass, more preferably 7 to 200 parts by mass, and the content of the dispersion medium is preferably 60 to 9000 parts by mass. More preferably, it is 100 to 5000 parts by mass.
  • the amount of the conductive fine particles is less than the above lower limit value, the refractive index of the formed film increases, but the conductivity decreases.
  • the amount of conductive fine particles is higher than the above upper limit, the conductivity of the formed film increases, but the refractive index decreases. Further, when the amount of the metal complex is less than the above lower limit value, the dispersion of the high refractive index fine particles and the conductive fine particles becomes poor, and when more than the above upper limit value, the metal complex is not dissolved in the dispersion medium, Precipitation may occur.
  • the amount of the dispersion medium is less than the above lower limit value, the dissolution of the metal complex, the dispersion of the high refractive index fine particles and the conductive fine particles becomes insufficient, and when the amount is more than the above upper limit value, the high refractive index fine particles and The concentration of the conductive fine particles is too thin to be practical.
  • the conductive fine particle dispersion of the present invention can be obtained by adding conductive fine particles, metal complexes and dispersion media, and in particular, high refractive index fine particles to be blended in an arbitrary order for applications requiring high refractive index characteristics. Obtained by mixing. Usually, it is produced by dispersing conductive fine particles and high refractive index fine particles in a dispersion medium in which a metal complex is dissolved. It is even better to perform a pre-dispersion operation before performing the dispersion operation. In the pre-dispersion operation, the conductive fine particles and the high refractive index fine particles are gradually added to the dispersion medium in which the metal complex is dissolved while stirring with a disper or the like. Stir well until no longer confirmed.
  • a dispersion liquid composed of the high refractive index fine particles, the metal complex and the dispersion medium, and a dispersion liquid composed of the conductive fine particles, the metal complex and the dispersion medium are prepared in advance, These dispersions can also be mixed and produced.
  • the dispersion operation of the conductive fine particles and the high refractive index fine particles can be performed using a paint shaker, a ball mill, a sand mill, a sentry mill or the like.
  • it is preferable to use dispersed beads such as glass beads and zirconia beads.
  • the bead diameter is not particularly limited, but is usually about 0.05 to 1 mm, preferably 0.05 to 0.65 mm.
  • the thickness is more preferably 0.08 to 0.65 mm, and particularly preferably 0.08 to 0.5 mm.
  • the particle diameter of the conductive fine particles and the high refractive index fine particles is a median diameter, preferably 120 nm or less, more preferably 80 nm or less.
  • the median diameter is larger than that, the haze of the conductive fine particle-containing cured film obtained from the conductive fine particle-containing photocurable composition tends to increase.
  • conductive fine particles and high refractive index fine particles are stably dispersed over a long period of time, and since it does not contain acetylacetone or the like that corrodes metal, it can be stored in a metal container. Is possible.
  • the conductive fine particle dispersion of the present invention can be used in a protective film-forming composition, an antireflection film-forming composition, an adhesive, a sealing material, a binder material, etc., and in particular, a reflective film having an antistatic function. It can use suitably for the composition which forms a prevention film.
  • the photocurable composition containing conductive fine particles of the present invention contains conductive fine particles, a metal complex, an active energy ray-curable compound, a photopolymerization initiator, and a dispersion medium, and the conductive fine particles, the metal complex, and the dispersion medium. Is as described above.
  • the photocurable composition containing conductive fine particles for forming a transparent conductive film of the present invention includes high refractive index fine particles having a refractive index of 1.8 or more, conductive fine particles, metal complexes not containing alkoxide, active energy ray curing.
  • the high-refractive-index fine particles, the conductive fine particles, and the dispersion medium are as described above.
  • the conductive fine particle-containing photocurable composition of the present invention imparts scratch resistance, abrasion resistance, low curling properties, adhesion, transparency, refractive index, chemical resistance, and antistatic properties of the cured film. Therefore, fine particles other than the conductive fine particles can be used.
  • the type of fine particles is not particularly limited as long as the object can be achieved, and known products such as commercially available products can be used.
  • inorganic fine particles or organic fine particles such as zirconium oxide, titanium oxide, aluminum oxide, and silicon oxide can be used. These fine particles may be used alone or in combination of two or more.
  • Examples of the active energy ray-curable compound used in the present invention include radical polymerizable monomers and radical polymerizable oligomers.
  • Specific examples of the radical polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofluorine Furyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene Monofunctional (meth) acrylates such as glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol poly
  • radical polymerizable oligomer examples include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, oligo (meth) acrylate, alkyd (meth) acrylate, polyol Examples thereof include prepolymers having at least one (meth) acryloyl group such as (meth) acrylate and silicone (meth) acrylate.
  • Particularly preferred radical polymerizable oligomers are (meth) acrylates of polyester, epoxy, and polyurethane.
  • an active energy ray hardening compound can be used individually by 1 type, or can also use 2 or more types together.
  • the photocurable composition containing conductive fine particles of the present invention contains a photopolymerization initiator (photosensitizer), the photocurable composition containing conductive fine particles is cured by irradiation with a small amount of active energy rays. be able to.
  • a photopolymerization initiator photosensitizer
  • a photoinitiator can be used individually by 1 type, or can also use 2 or more types together.
  • the blending ratio of each component can be appropriately set according to the use of the photocurable composition containing conductive fine particles, but the metal complex per 100 parts by mass of the conductive fine particles.
  • the content of is preferably 2 to 45 parts by mass, more preferably 5 to 20 parts by mass
  • the content of the dispersion medium is preferably 40 to 1000 parts by mass, more preferably 60 to 600 parts by mass
  • the active energy The content of the linear curable compound is preferably 10 to 1000 parts by mass, more preferably 25 to 150 parts by mass
  • the content of the photopolymerization initiator per 100 parts by mass of the active energy ray curable compound is preferably 0.00. 1 to 20 parts by mass, more preferably 1 to 15 parts by mass.
  • the conductive fine particles tend to be poorly dispersed, and when the amount is more than the above upper limit value, the metal complex does not dissolve in the dispersion medium and precipitates. May occur.
  • the amount of the dispersion medium is less than the above lower limit value, the metal complex tends to be dissolved and the dispersion of the conductive fine particles tends to be insufficient.
  • the concentration of the conductive fine particle dispersion is low. There exists a tendency for the addition effect of electroconductive fine particles to become inadequate and to become inadequate.
  • the amount of the active energy ray-curable compound When the amount of the active energy ray-curable compound is less than the above lower limit value, the refractive index of the cured film increases, but the transparency tends to decrease, and when it exceeds the above upper limit value, the refractive index of the cured film. Is not as high as desired.
  • the amount of the photopolymerization initiator when the amount of the photopolymerization initiator is less than the above lower limit value, the curing rate of the photocurable composition tends to decrease, and even if the amount exceeds the above upper limit value, an effect commensurate with it cannot be obtained. .
  • the content of conductive fine particles is preferably 30 to 900 parts by mass, more preferably 40 to 500 parts per 100 parts by mass of the high refractive index fine particles.
  • the content of the mass part and the metal complex is preferably 3 to 450 parts by mass, more preferably 7 to 200 parts by mass, and the content of the dispersion medium is preferably 60 to 70000 parts by mass, more preferably 100 to 50000 parts by mass.
  • the content of the active energy ray-curable compound is preferably 14 to 10,000 parts by mass, more preferably 35 to 2000 parts by mass, and the content of the photopolymerization initiator per 100 parts by mass of the active energy ray-curable compound Is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass.
  • this photocurable composition containing conductive fine particles for forming a transparent conductive film when the amount of conductive fine particles is less than the above lower limit value, the refractive index of the formed film increases, but the conductivity decreases. . Conversely, when the amount of conductive fine particles is higher than the above upper limit, the conductivity of the formed film increases, but the refractive index decreases.
  • the amount of the metal complex is less than the above lower limit value, the dispersion of the high refractive index fine particles and the conductive fine particles tends to be poor, and when the amount is more than the above upper limit value, the metal complex is dissolved in the dispersion medium. And precipitation may occur.
  • the amount of the dispersion medium is less than the above lower limit, dissolution of the metal complex, and dispersion of the high refractive index fine particles and conductive fine particles tend to be insufficient.
  • the concentration of the composition is too low to be practical.
  • the amount of the active energy ray-curable compound is less than the above lower limit value, the refractive index of the transparent conductive film increases, but the transparency tends to decrease. The refractive index is not as high as desired, and the antistatic function is insufficient.
  • the amount of the photopolymerization initiator is less than the above lower limit value, the curing rate of the photocurable composition tends to decrease, and even if the amount exceeds the above upper limit value, an effect commensurate with it cannot be obtained. .
  • the conductive fine particle-containing photocurable composition of the present invention may be blended with various conventional additives other than those described above within a range not impairing the purpose.
  • additives include a polymerization inhibitor, a curing catalyst, an antioxidant, a leveling agent, and a coupling agent.
  • the photocurable composition containing conductive fine particles of the present invention is a plastic (polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetylcellulose resin, polyethylene terephthalate, ABS resin, AS resin, norbornene series. Resin, etc.), metal, wood, paper, glass, slate, etc. can be applied or printed on the surface of the substrate and cured to form a film.
  • plastic polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetylcellulose resin, polyethylene terephthalate, ABS resin, AS resin, norbornene series. Resin, etc.
  • metal, wood, paper, glass, slate, etc. can be applied or printed on the surface of the substrate and cured to form a film.
  • a photocurable composition containing conductive fine particles in which high refractive index fine particles are blended it can be suitably used particularly for forming a transparent conductive film having a high refractive index.
  • coating or printing of the electroconductive fine particle containing photocurable composition to a base material can be performed by methods, such as roll coating, spin coating, and screen printing, according to a conventional method. If necessary, the dispersion medium (solvent) is evaporated by heating, the coating film is dried, and then irradiated with active energy rays (ultraviolet rays or electron beams).
  • active energy ray source an ultraviolet ray source such as a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an excimer laser, or a dye laser, and an electron beam accelerator can be used.
  • the dose of the active energy ray when the ultraviolet rays 50 ⁇ 3000mJ / cm 2, when the electron beam is suitably in the range of 0.2 ⁇ 1000 ⁇ C / cm 2.
  • the active energy ray-curable compound is polymerized to form a film in which conductive fine particles are bonded with a resin.
  • the thickness of this film is preferably in the range of 0.1 to 10.0 ⁇ m.
  • the conductive fine particle-containing cured film of the present invention obtained by curing the conductive fine particle-containing photocurable composition prepared with the conductive fine particle dispersion of the present invention has conductive fine particles uniformly dispersed in the cured film.
  • the refractive index can be controlled, the transparency is high, and the haze is low.
  • the refractive index is 1.45 to 1.90
  • the light transmittance is 75% or more
  • the haze is 2. 0% or less and a surface resistance value of 10 12 ⁇ / ⁇ or less.
  • the transparent conductive film of the present invention obtained by curing a conductive fine particle-containing composition for forming a transparent conductive film, which requires high refractive index characteristics, has high refractive index fine particles and conductive fine particles that are transparent conductive.
  • the film is uniformly dispersed in the film, the refractive index can be controlled, and the refractive index is high, the transparency is high, the haze is low, specifically, the refractive index is 1.55 to 1.90.
  • the transmittance is 85% or more, the haze is 1.5% or less, and the surface resistance value is 10 12 ⁇ / ⁇ or less. It is.
  • the ratio of the amount of the high refractive index fine particles and conductive fine particles to the amount of the active energy ray-curable compound may be adjusted.
  • the transparent conductive film can be used for a conductive antireflection material, a display surface of a display, or the like.
  • Example 1 to 5 and Comparative Examples 1 and 2 The components used in Examples 1 to 5 and Comparative Examples 1 and 2 are as follows.
  • Example 1 All components were put into a container in an amount of 20 parts of zirconium acetylacetonate, 250 parts of methyl ethyl ketone and 400 parts of glass beads with respect to 100 parts of tin oxide, and kneaded with a paint shaker for 3 hours. After kneading, the glass beads were removed to obtain a dispersion. 43 parts of DPHA, 2 parts of IRGACURE 184 and 65 parts of methyl ethyl ketone were added to this dispersion to obtain a photocurable composition.
  • This photocurable composition was applied onto a 100 ⁇ m-thick PET film (A4100 manufactured by Toyobo Co., Ltd.) using a bar coater, the organic solvent was evaporated, and then 300 mJ / cm using a high-pressure mercury lamp under air.
  • a transparent conductive film having a thickness of 3 ⁇ m was produced by irradiating the light of No. 2 .
  • the film was prepared immediately after and 6 months after the photocurable composition.
  • Example 2 Add 100 parts of ATO to 10 parts of titanium acetylacetonate, 10 parts of BYK-142, 250 parts of 2-butanol and 400 parts of glass beads in a container and knead for 3 hours in a paint shaker. did. After kneading, the glass beads were removed to obtain a dispersion. To this dispersion, 43 parts DPHA, 2 parts IRGACURE 184 and 65 parts 2-butanol were added to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 1.
  • Example 3 All components in 10 parts of ATO, 10 parts dibutyl-tin bisacetylacetonate, 250 parts 2-butanol and 400 parts glass beads were placed in a container and kneaded for 3 hours with a paint shaker. After kneading, the glass beads were removed to obtain a dispersion. To this dispersion, 43 parts DPHA, 2 parts IRGACURE 184 and 65 parts 2-butanol were added to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 1.
  • Example 4 Put all ingredients in a container in an amount of 50 parts ITO, 10 parts dibutyl-tin bisacetylacetonate, 250 parts 2-butanol and 400 parts glass beads for 50 parts of ATO and knead for 3 hours in a paint shaker. did. After kneading, the glass beads were removed to obtain a dispersion. To this dispersion, 43 parts DPHA, 2 parts IRGACURE 184 and 65 parts 2-butanol were added to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 1.
  • Example 5 Put all ingredients in a container in 60 parts of ITO, 40 parts of aluminum oxide, 25 parts of dibutyl-tin bisacetylacetonate, 250 parts of 2-butanol and 400 parts of glass beads, 3 hours in a paint shaker Kneaded. After kneading, the glass beads were removed to obtain a dispersion. 67 parts DPHA, 6.7 parts IRGACURE 184 and 170 parts 2-butanol were added to this dispersion to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 1.
  • Example 2 A transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 2 except that 20 parts of acetylacetone was added instead of 20 parts of titanium acetylacetonate.
  • ⁇ Evaluation method> Median diameter of inorganic fine particles The median diameter of inorganic fine particles dispersed in the dispersions and photocured compositions prepared in Examples and Comparative Examples was measured immediately using a Microtrac particle size distribution meter manufactured by Nikkiso Co., Ltd. After 3 months (40 ° C storage) and 6 months (40 ° C storage), the measurement was performed under the following conditions.
  • the conductive fine particle dispersion, the conductive fine particle-containing composition for forming a transparent conductive film, and the transparent conductive film will be specifically described with reference to Examples and Reference Examples for applications in which the high refractive index characteristics of the present invention are required. To do.
  • “parts” are all “parts by mass”.
  • Example 6 to 11 and Reference Examples 1 to 6 The components used in Examples 6 to 11 and Reference Examples 1 to 6 are as follows.
  • Example 6 Add 100 parts of zirconium oxide to 100 parts of tin oxide, 40 parts of zirconium acetylacetonate, 500 parts of 2-butanol and 800 parts of glass beads in a container and knead in a paint shaker for 7 hours. Combined. After kneading, the glass beads were removed to obtain a dispersion. To this dispersion was added 86 parts DPHA, 4.3 parts IRGACURE 184 and 130 parts 2-butanol to obtain a photocurable composition.
  • This photocurable composition was applied onto a 100 ⁇ m-thick PET film (A4100 manufactured by Toyobo Co., Ltd.) using a roll coater, the organic solvent was evaporated, and then 300 mJ / cm using a high-pressure mercury lamp under air.
  • a transparent conductive film having a thickness of 3 ⁇ m was produced by irradiating the light of No. 2 .
  • the film was prepared immediately after and 6 months after the photocurable composition.
  • Example 7 In 100 parts of titanium oxide, all components in containers in amounts of 43 parts ATO, 6 parts titanium acetylacetonate, 14.3 parts BYK-142, 500 parts 2-butanol and 800 parts glass beads. And kneaded for 7 hours in a paint shaker. After kneading, the glass beads were removed to obtain a dispersion. To this dispersion was added 143 parts DPHA, 7.2 parts IRGACURE 184 and 160 parts 2-butanol to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 6.
  • Example 8 Add 100 parts of zirconium oxide to 233 parts of tin oxide, 33 parts of aluminum acetylacetonate, 880 parts of 2-butanol and 800 parts of glass beads in a container and mix for 7 hours in a paint shaker. Combined. After kneading, the glass beads were removed to obtain a dispersion. To this dispersion was added 143 parts DPHA, 7.2 parts IRGACURE 184 and 160 parts 2-butanol to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 6.
  • Example 9 100 parts of titanium oxide, 100 parts of zinc oxide, 20 parts of zinc acetylacetonate, 500 parts of 2-butanol, and 800 parts of glass beads are placed in a container and mixed for 7 hours in a paint shaker. Combined. After kneading, the glass beads were removed to obtain a dispersion. To this dispersion was added 86 parts DPHA, 4.3 parts IRGACURE 184 and 130 parts 2-butanol to obtain a photocurable composition. Thereafter, a transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 6.
  • Example 10 A transparent conductive film having a thickness of 3 ⁇ m was prepared in the same manner as in Example 9 except that 20 parts of dibutyl-tin bisacetylacetonate was added instead of 20 parts of zinc acetylacetonate.
  • Example 11 A transparent conductive film having a thickness of 3 ⁇ m was produced in the same manner as in Example 9, except that 20 parts of indium acetylacetonate was added instead of 20 parts of zinc acetylacetonate.
  • Example 5 A transparent conductive film having a thickness of 3 ⁇ m was prepared in the same manner as in Example 6 except that 40 parts of tributoxy-zirconium monoacetylacetonate was added instead of 40 parts of zirconium acetylacetonate.

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Abstract

L'invention concerne une dispersion de microparticules électriquement conductrices qui présente une excellente stabilité au stockage, une composition photodurcissable, contenant ces microparticules, qui permet la formation d'un film durci qui présente une excellente transparence et une fonction antistatique à la surface d'un matériau de base, et un film durci contenant des microparticules électriquement conductrices, fabriqué en durcissant la composition photodurcissable. En particulier, il est possible de fournir une dispersion utile à la formation d'un film électriquement conducteur et transparent avec un indice de réfraction élevé, une composition et un film électriquement conducteur transparent. L'invention concerne plus précisément une dispersion de microparticules électriquement conductrices comportant des microparticules électriquement conductrices, un complexe métallique et un milieu de dispersion, et contenant facultativement des microparticules à indice de réfraction élevé, dont l'indice de réfraction est égal ou supérieur à 1,8, une composition photodurcissable, contenant des microparticules électriquement conductrices, qui comporte des microparticules électriquement conductrices, un complexe métallique, un composé durcissant sous l'effet d'un rayonnement d'énergie d'activation, un initiateur de photopolymérisation et un milieu de dispersion, et contenant facultativement des microparticules à indice de réfraction élevé, dont l'indice de réfraction est égal ou supérieur à 1,8, et un film durci, contenant des microparticules électriquement conductrices, qui est obtenu en durcissant la composition photodurcissable contenant des microparticules électriquement conductrices.
PCT/JP2010/065919 2009-09-18 2010-09-15 Dispersion de microparticules électriquement conductrices, composition photodurcissable contenant des microparticules électriquement conductrices et film durci contenant ces microparticules WO2011034079A1 (fr)

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JP2016027084A (ja) * 2014-07-04 2016-02-18 富士フイルム株式会社 硬化性組成物、硬化膜の製造方法、硬化膜、タッチパネル及び表示装置
US20220251397A1 (en) * 2014-09-26 2022-08-11 The Boeing Company Compositions and coatings with non-chrome corrosion inhibitor particles

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CN103360854A (zh) 2012-03-28 2013-10-23 厦门纳诺泰克科技有限公司 一种高透明、低辐射、节能的玻璃用组合材料及其制备方法
FR2993999B1 (fr) * 2012-07-27 2014-09-12 Nanomade Concept Procede pour la fabrication d'une surface tactile transparente et surface tactile obtenue par un tel procede
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
US9587132B2 (en) * 2014-03-20 2017-03-07 E I Du Pont De Nemours And Company Thermoformable polymer thick film transparent conductor and its use in capacitive switch circuits
JP6436487B2 (ja) * 2014-12-29 2018-12-12 小林　博 透明導電性膜を製造する製造方法
DE112018004743T5 (de) * 2017-09-05 2020-06-18 Fujifilm Corporation Härtbare zusammensetzung, gehärtetes produkt und linseneinheit
CN113861729B (zh) * 2021-10-14 2022-12-09 新纶新能源材料(常州)有限公司 一种高耐腐蚀性的环保涂料及其制备方法

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JP2016027084A (ja) * 2014-07-04 2016-02-18 富士フイルム株式会社 硬化性組成物、硬化膜の製造方法、硬化膜、タッチパネル及び表示装置
US20220251397A1 (en) * 2014-09-26 2022-08-11 The Boeing Company Compositions and coatings with non-chrome corrosion inhibitor particles

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