WO2015068540A1 - Dispersion de nanofils métalliques ayant une stabilité de dispersion supérieure, film conducteur transparent et conducteur transparent - Google Patents

Dispersion de nanofils métalliques ayant une stabilité de dispersion supérieure, film conducteur transparent et conducteur transparent Download PDF

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WO2015068540A1
WO2015068540A1 PCT/JP2014/077382 JP2014077382W WO2015068540A1 WO 2015068540 A1 WO2015068540 A1 WO 2015068540A1 JP 2014077382 W JP2014077382 W JP 2014077382W WO 2015068540 A1 WO2015068540 A1 WO 2015068540A1
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silver nanowire
metal nanowire
dispersion
copolymer
dispersion liquid
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PCT/JP2014/077382
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English (en)
Japanese (ja)
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雄也 寺尾
長谷川　俊之
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星光Pmc株式会社
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Priority to JP2015546578A priority Critical patent/JP6119873B2/ja
Publication of WO2015068540A1 publication Critical patent/WO2015068540A1/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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer

Definitions

  • the present invention relates to a metal nanowire dispersion having excellent dispersion stability. More specifically, by adding a polymer having a hydrophilic group and a hydrophobic group, the dispersion stability of the metal nanowire component can be improved, and a conductive film that has good adhesion to the substrate and the laminated resin can be formed.
  • the present invention relates to a metal nanowire dispersion liquid.
  • ITO indium tin oxide
  • ITO indium, which is a component of ITO, is a rare metal with a small amount of output, and there is a large bias in the region of production, so there are problems such as anxiety of supply and rising prices.
  • ITO currently forms a conductive film by a dry process typified by sputtering, a large-scale high-vacuum manufacturing apparatus is required, and production speed and cost are problematic.
  • a method using a fine fibrous conductor such as a conductive polymer such as sulfonic acid (PEDOT / PSS) or a metal nanowire such as silver nanowire has attracted attention. Processing by a wet process can form a large-area conductive film in a short time, and can reduce manufacturing costs.
  • the conductive film containing metal nanowires of c) is noted to have low resistance and high light transmittance, and has been put into practical use as a transparent electrode material for touch panels and the like.
  • various prescriptions have been developed as described in the following patent documents.
  • metal nanowires having a wire length of several ⁇ m or more tend to be entangled with each other and easily generate aggregates.
  • the thermal stability of the nano metal crystal is lowered, when the entangled wires are in direct contact with each other, they are fused to each other over time and easily become agglomerated foreign matters that cannot be redispersed.
  • the metal nanowire may be damaged, and the average major axis length may be shortened, resulting in deterioration of the properties of the metal nanowire. There is.
  • Patent Document 1 discloses a method of reducing the aggregation of metal nanowires by using a low molecular weight surfactant as part of the dispersion composition.
  • the low molecular weight surfactant easily moves in the conductive film, and may bleed out over time and impair the physical properties of the conductive film.
  • Patent Documents 2 and 3 disclose polyvinyl alcohol and polyvinyl pyrrolidone, which are polymer type dispersants, as metal nanowire dispersants, but their redispersibility and anti-aggregation effects are still unsatisfactory.
  • the present invention solves the above-mentioned problems in the prior art, is a system in which metal nanowires are blended in a dispersion solvent, and is difficult to produce aggregates that are difficult to re-disperse metal nanowires in the production stage or product stage.
  • An object of the present invention is to provide a dispersion having excellent coating suitability and good adhesion between the obtained conductive film and a substrate or a laminated resin.
  • a metal nanowire dispersion liquid having the following constitution and its use are provided.
  • Nonionic hydrophobic monomer (b): Nonionic hydrophilic monomer (c) 1: 99 to 50:50
  • Metal nanowire (a): Copolymer (d) 1: 1 to 100: 1
  • the metal nanowire dispersion liquid according to (8) or (9), wherein the polysaccharide and its derivative (e) are guar gum and its derivative.
  • (11) The metal nanowire dispersion liquid according to any one of (1) to (10), wherein the metal nanowire is a silver nanowire.
  • a transparent conductor comprising a substrate and the transparent conductive film according to (12) formed on the substrate.
  • the metal nanowire dispersion liquid of the present invention contains at least a copolymer (d) obtained by copolymerizing the metal nanowire (a), the nonionic hydrophobic monomer (b) and the nonionic hydrophilic monomer (c). Further, it contains other components as necessary.
  • the metal in the metal nanowire of the present invention include gold, silver, copper, nickel, platinum, palladium, cobalt, tin, lead and the like. Further, alloys of these metals, metal compounds, or plated metals can also be used for the metal nanowires of the present invention.
  • the metal compound include metal oxides, and examples of the plated metal include gold-plated metal. Among these metals, silver is more preferable.
  • silver nanowires may be read as “other metal nanowires” in the following description.
  • ⁇ Silver nanowire reaction solution> There is no restriction
  • the thing manufactured by the conventionally well-known method can be used.
  • it can be synthesized by a method of reducing silver nitrate by a polyol method in the presence of polyvinylpyrrolidone as in (Chem. Mater., 2002, 14, 4736).
  • it can be synthesized by a method of reducing a silver compound by a polyol method in the presence of a polymer containing N-substituted (meth) acrylamide instead of polyvinylpyrrolidone. it can.
  • the silver nanowire (a) in the present invention is a structure having a cross-sectional diameter of less than 1 ⁇ m and an aspect ratio (major axis length / diameter) of 2 or more, and is obtained by purifying the silver nanowire reaction solution. .
  • the diameter of the silver nanowire (a) is smaller in order to increase transparency.
  • the diameter of the silver nanowire (a) is preferably less than 250 nm, more preferably less than 150 nm, and even more preferably less than 100 nm.
  • the diameter of silver nanowire (a) can be calculated
  • the transparent conductive film containing silver nanowires (a) exhibits conductivity when the silver nanowires come into contact with each other and a three-dimensional conductive network structure is spatially widely distributed. Therefore, the silver nanowire (a) having an optimum long axis length according to the use of the transparent conductive film is preferable.
  • the major axis length of the silver nanowire (a) used in the present invention is preferably 0.5 to 1000 ⁇ m.
  • the major axis length of the silver nanowire (a) can be obtained from the arithmetic average value of 100 silver nanowires observed using a scanning electron microscope.
  • the compounding ratio of the silver nanowire (a) is not limited as long as the desired performance such as conductivity and electromagnetic shielding properties can be obtained. For example, 0.01 to 30% by mass, preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass in the finished dispersion. If it is less than 0.01%, the amount of coating for expressing the performance becomes very large, and coating and drying become difficult. When it is higher than 30%, the entanglement between the silver nanowires increases, and the amount of aggregated foreign matter is increased.
  • the nonionic hydrophobic monomer (b) in the present invention is an unsaturated group-containing nonionic hydrophobic organic compound having a solubility in water at 20 ° C. of 3 g / 100 g or less.
  • nonionic hydrophobic monomer (b) examples include styrene, methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and (meth) acrylic.
  • N-butyl acid i-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, dodecyl (meth) acrylate, octadecyl (meth) acrylate, isobornyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl cinnamate, vinyl naphthalene and the like.
  • styrene and (meth) acrylic acid esters are preferable, alkyl (meth) acrylic acid esters having 4 to 12 carbon atoms are more preferable, and alkyl methacrylic acid esters having 4 to 12 carbon atoms are more preferable.
  • the nonionic hydrophobic monomers can be used alone or in combination of two or more.
  • the nonionic hydrophilic monomer (c) in the present invention is an unsaturated group-containing nonionic hydrophilic organic compound having a solubility in water at 20 ° C. of 50 g / 100 g or more.
  • nonionic hydrophilic monomer (c) examples include N-substituted acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, acryloylmorpholine, 2-hydroxyethylacrylamide, N-methoxymethylacrylamide and the like.
  • the nonionic hydrophilic monomer (c) can be used alone or in combination of two or more, and the nonionic hydrophilic monomer (c) contains a compound having an amide structure in the molecule with respect to the total mass.
  • the amount is preferably 10% by mass to 100% by mass, more preferably 30% by mass to 100% by mass, and further preferably 50% by mass to 100% by mass.
  • the copolymer (d) in the present invention is a copolymer obtained by copolymerizing at least one nonionic hydrophobic monomer (b) and at least one nonionic hydrophilic monomer (c).
  • the molecular structure of the copolymer may be a linear structure or a crosslinked structure to the extent that the solubility in the silver nanowire-dispersed solvent is not impaired. Further, other copolymerizable monomers may be copolymerized to such an extent that the effects of the present invention are not impaired.
  • copolymerizable monomers include (meth) acrylic acid and salts thereof, hydrogen succinate (2- (meth) acryloyloxyethyl) and salts thereof, 2-acrylamido-2-methylpropanesulfone Acids and their salts, dimethylaminoethyl (meth) acrylate and their salts, dimethylaminopropyl (meth) acrylamide and their salts, 2-vinylpyridine and its salts, 4-vinylpyridine and its salts, N-vinyl Imidazole and its salts, methylenebis (meth) acrylamide, triacryl formal, hydrogen maleate (2- (meth) acryloyloxyethyl) and its salts, vinyltrimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, etc. Can be mentioned.
  • the method for producing the copolymer (d) in the present invention various conventionally known methods can be used.
  • a nonionic hydrophobic monomer (b), a nonionic hydrophilic monomer (c) and a solvent were charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, and a polymerization initiator was added. Thereafter, the reaction is carried out at a reaction temperature of 20 to 100 ° C. for 0.5 to 12 hours.
  • the polymerization form may be any of solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization and the like.
  • the reaction operation may be a batch reaction, a semi-batch reaction or a continuous reaction.
  • the reaction solvent may be a conventionally known solvent as long as it can perform a polymerization reaction. Specific examples include water, ethanol, 1-propanol, 2-propanol, methyl ethyl ketone, ethylene glycol, propylene glycol, and ethylene glycol monomethyl. Examples include ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.
  • the polymerization initiator may be a conventionally known substance.
  • persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide.
  • Peroxides such as oxide and lauroyl peroxide, persulfates and peroxides and sulfites, bisulfites, thiosulfates, sodium formaldehyde sulfoxylate, ferrous sulfate, ferrous ammonium sulfate, glucose Redox initiators in combination with reducing agents such as ascorbic acid, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylbutyronitrile), 2,2′-azobis (2-methylpropionic acid) dimethyl, Azo compounds such as' -azobis (2-amidinopropane) dihydrochloride, photopolymerization initiators such as
  • the weight average molecular weight of the polymer is preferably 1,000 to 1,000,000, more preferably 1,000 to 100,000. When the molecular weight is within the above range, the redispersibility of the silver nanowires becomes good.
  • a conventionally known chain transfer agent may be used. Specific examples include mercaptoethanol, lauryl mercaptan, thioglycerin, thioglycolic acid, thiols such as mercaptopropionic acid and thiomalic acid, alcohols such as 2-propanol, allylsulfonic acid and its salts, methallylsulfonic acid.
  • the copolymer (d) in the present invention may be used as it is containing a polymerization solvent, or may be used after being dried and solidified by heat drying, spray drying, reduced pressure drying, freeze drying or the like.
  • the blending ratio of the copolymer (d) may be 0.001 to 10% by mass, preferably 0.01 to 10% by mass in the finished dispersion.
  • the step of adding the copolymer (d) is not particularly limited at the time of silver nanowire synthesis, before silver nanowire purification, after silver nanowire purification, etc., but it is preferably added before silver nanowire purification.
  • the polysaccharide and its derivative (e) are used in gums such as guar gum, locust bean gum, tara gum, psyllium seed gum, xanthan gum and their derivatives, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylcellulose.
  • gums such as guar gum, locust bean gum, tara gum, psyllium seed gum, xanthan gum and their derivatives, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylcellulose.
  • Commercially available products such as celluloses can be suitably used.
  • guar gum is preferable, hydroxypropyl guar gum which is a derivative thereof is more preferable, and hydroxypropyl guar gum obtained by graft polymerization of (meth) acrylic acid ester is more preferable.
  • the Brookfield viscosity of a 0.6 mass% aqueous solution at 25 ° C. is preferably 10 mPa ⁇ s or more.
  • the polysaccharide and its derivative (e) improve the dispersibility of the silver nanowire, so that the storage stability of the silver nanowire dispersion, the coating suitability, the light transmittance of the conductive film coated with the silver nanowire dispersion, haze, It is thought that it contributes to the improvement of the surface resistivity.
  • the dispersion solvent used for the silver nanowire dispersion liquid of the present invention is not limited as long as it can dissolve the copolymer (d) and can disperse the silver nanowires.
  • arbitrary components such as a surface tension adjusting agent, a binder resin, and a corrosion inhibitor can be used in combination as long as the characteristics as the silver nanowire dispersion liquid are not impaired.
  • the optional components can be used alone or in combination of two or more.
  • the surface tension adjusting agent examples include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, polar liquids such as alcohols, glycols, and ketones. However, it is preferable to use a polar liquid that is volatile at the conductive film drying temperature and does not remain in the conductive film after being evaporated and dried when the conductive film is formed.
  • a substrate having a transparent conductive film can be produced using the silver nanowire dispersion liquid of the present invention. After applying the silver nanowire-containing composition of the present invention to the substrate, the solvent is removed, the transparency, turbidity, and conductivity are good on the substrate, and the water resistance, friction resistance, and alcohol resistance of the coating film And a coating film with high substrate adhesion can be formed.
  • substrate is suitably selected according to a use, and it may be hard and may bend easily. Moreover, it may be colored. Specific examples of the material of the substrate include glass, polyimide, polycarbonate, polyethersulfone, polyacrylate, polyester, polyethylene terephthalate, polyethylene naphthalate, polyolefin, and polyvinyl chloride.
  • More preferable base material materials are polyester and polyolefin.
  • examples of commercially available materials for these substrates include, for example, polyester, Cosmo Shine manufactured by Toyobo Co., Ltd., Lumirror manufactured by Toray Industries, Inc. and Tetron manufactured by Teijin DuPont Films, Ltd.
  • polyolefin Arton manufactured by JSR Corporation, ZEONOR manufactured by Nippon Zeon Co., Ltd., and the like can be used.
  • An organic functional material and an inorganic functional material may be further formed on the substrate. A large number of substrates may be stacked.
  • a known application method can be used as a method for applying the silver nanowire dispersion liquid of the present invention to a substrate.
  • Specific examples of the method for applying the silver nanowire-containing composition of the present invention to the substrate include spin coating, slit coating, dip coating, blade coating, bar coating, spraying, relief printing, and intaglio printing. , Screen printing method, flat plate printing method, dispensing method, ink jet method and the like. Moreover, you may apply several times using these application
  • the silver nanowire dispersion liquid of the present invention is excellent in redispersibility of silver nanowires, the form as a silver nanowire dispersion liquid is maintained for a long time, and the adhesiveness with a substrate or a resin to be laminated is excellent. Can be widely used in applications such as electrode materials, antistatic materials, and electromagnetic shielding materials.
  • Methyl cellulose Trade name Metroise SM-8000, Shin-Etsu Chemical Co., Ltd.
  • hydroxyethyl cellulose Trade name HEC Daicel SP400, Daicel Corporation hydroxypropyl methylcellulose: Trade name Metroze 65SH-15000, Shin-Etsu Chemical Guar gum: Trade name: Guar gum RG100, hydroxypropyl guar gum manufactured by MRC Polysaccharide Co., Ltd .: trade name JAGUAR HP-105, Sanki Co., Ltd.
  • PVP polyvinylpyrrolidone (K-30), Kanto Chemical Co., Ltd.
  • New Call 2308 non Ionic surfactants, Nippon Emulsifier Co., Ltd. Ethanol: Reagent grade, Junsei Chemical Co., Ltd. BTA: 1,2,3-benzotriazole, Kanto Chemical Co., Ltd. dimethyl sulfoxide: Reagent grade, Junsei Chemical Co., Ltd. ) Made
  • Preparation Example e-5 A polysaccharide and its derivative aqueous solution (e-5) were prepared in the same manner as in Preparation Example (e-4) except that the types of components were changed as shown in Table 2.
  • Example 1 20 parts of a silver nanowire reaction solution having a silver nanowire content of 0.4%, 0.1 part of 40% copolymer (d-1) and 79.9 parts of water were weighed into a beaker and stirred. The obtained mixed solution was centrifuged at 500 G for 10 minutes using a centrifuge J2-MC (manufactured by Beckman Coulter, Inc.), and the supernatant was discarded to obtain silver nanowires. Water and 40% copolymer (d-1) were added thereto and stirred to adjust the silver nanowire content to 0.4% and the copolymer (d-1) content to 0.2%.
  • the silver nanowire component was purified to prepare a silver nanowire liquid having a silver nanowire content of 0.4% and a copolymer (d-1) content of 0.2%.
  • a silver nanowire dispersion liquid having a silver nanowire content of 0.2% and a copolymer (d-1) content of 0.1% 50 parts of silver nanowire liquid after purification and 50 parts of water was weighed into a beaker and stirred.
  • AG-1) was prepared.
  • Table 3 shows the concentration and mass ratio of each component of the silver nanowire dispersion (AG-1).
  • evaluation methods The evaluation method and measurement method in each evaluation item of the obtained silver nanowire dispersion were in accordance with the following methods.
  • the silver nanowire dispersion (AG-1) is weighed into a beaker, centrifuged at 2000 G for 1 hour using a centrifuge, the supernatant is discarded, the silver nanowire is taken out, and water is added so that the silver nanowire content becomes 10%. It was adjusted.
  • the resulting 10% silver nanowire was adjusted by adding a copolymer (d-1) and water so that the concentration and mass ratio of each component were as shown in Table 3, followed by stirring for 30 seconds. .
  • the obtained dispersion was subjected to suction filtration with a 100-mesh metal filter, and the captured silver nanowire aggregates were dried at 150 ° C. ⁇ 3 hr, and the mass was measured.
  • the aggregation preventing effect of the copolymer (d-1) on the aggregate formed by the entanglement of the silver nanowires at a high concentration was evaluated.
  • Aggregate mass / total silver nanowire mass ⁇ 100 aggregate generation rate (%) Evaluation criteria ⁇ : Aggregate generation rate of less than 10% ⁇ : Aggregate generation rate of 10% or more and less than 30% ⁇ : Aggregate generation rate of 30% or more and less than 50% ⁇ : Aggregate generation rate of 50% or more XX: Mostly Aggregates (approximately 80% or more) and silver nanowires are aggregated
  • a commercially available polyester film or cyclic polyolefin film (hereinafter sometimes referred to as a substrate) having a thickness of 100 ⁇ m is used as a coating substrate, and the above silver nanowire dispersion (AG-1) is coated using a bar coater # 4. did. Immediately after coating, it is dried for 3 minutes with a natural convection type electric dryer adjusted to 110 ° C., and the portion of the obtained silver nanowire-containing conductive film is not coated with silver nanowires due to insufficient wettability Was determined visually.
  • ⁇ A portion where silver nanowire is not applied is not recognized.
  • ⁇ A portion where the silver nanowire is not applied to the end portion of the substrate is observed slightly.
  • the surface resistivity of the conductive film obtained above was measured at 10 points with a resistivity meter Loresta GP MCP-T610 (manufactured by Mitsubishi Chemical Corporation), and the average value was used as the surface resistivity for evaluation. The smaller the numerical value of the surface resistivity, the higher the performance.
  • Total light transmittance of conductive film The total light transmittance of the conductive film obtained above was measured with a haze meter NDH 5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) at five points, and the average value was taken as the total light transmittance for evaluation.
  • the total light transmittance of the coated substrate before coating was subtracted from the total light transmittance of the conductive film after coating, and the difference value was used as an index of the total light transmittance of the silver nanowire coating layer. The smaller the absolute value of this difference, the higher the performance.
  • the haze of the conductive film obtained above was measured with a haze meter NDH 5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) at five points, and the average value was used as the haze for evaluation.
  • the haze of the coated substrate before coating was subtracted from the haze of the conductive film after coating, and the numerical value of the difference was used as an index of haze of the silver nanowire coating layer. The smaller the difference value, the higher the performance.
  • Table 4 shows the aggregate generation rate and redispersibility test results of the silver nanowire dispersion liquid of Example 1, a commercially available polyester film (Examples 1 to 39, Comparative Examples 1 to 10) having a thickness of 100 ⁇ m as a coating substrate, and The coating aptitude test result to a commercially available cyclic polyolefin film (Example 40), the physical property of a silver nanowire containing electrically conductive film, and the evaluation result of adhesiveness with a base material are shown.
  • Examples 2 to 21, 23, 26 to 29 Silver nanowire dispersions were prepared in the same manner as in Example 1 except that the types and contents of the components were changed as shown in Table 3 (AG-2 to 21, AG23, AG-26 to 29). The obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • Example 22 20 parts of a silver nanowire reaction solution having a silver nanowire content of 0.4% and 80 parts of water were weighed into a beaker and stirred. The obtained mixture was centrifuged at 500 G for 10 minutes using a centrifuge, the supernatant was discarded, and water was added to the silver nanowires and stirred to adjust the silver nanowire content to 0.4%. By repeating this operation three times, the silver nanowire component was purified to prepare a 0.4% silver nanowire solution. Weighed 50 parts of silver nanowire liquid after purification, 0.25 part of 40% copolymer (d-17) and 49.75 parts of water into a beaker and stirred to give a silver nanowire content of 0.2% and copolymerization.
  • a silver nanowire dispersion liquid (AG-22) having a product (d-17) content of 0.1% was prepared.
  • Table 3 shows the concentration and mass ratio of each component of the silver nanowire dispersion (AG-22).
  • the obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • Example 24 20 parts of a silver nanowire reaction solution having a silver nanowire content of 0.4%, 0.1 part of 40% copolymer (d-17) and 79.9 parts of water were weighed into a beaker and stirred. The obtained mixed solution is centrifuged at 500 G for 10 minutes using a centrifuge, and the supernatant is discarded. Water and 40% copolymer (d-17) are added to the silver nanowire and stirred, thereby stirring the silver nanowire. The content was adjusted to 0.4%, and the copolymer (d-17) content was adjusted to 0.2%.
  • the silver nanowire component was purified to prepare a silver nanowire liquid having a silver nanowire content of 0.4% and a copolymer (d-17) content of 0.2%.
  • 50 parts of purified silver nanowire liquid, 4 parts of 0.5% BTA, and 46 parts of water are weighed into a beaker and stirred to obtain a silver nanowire content of 0.2% and a copolymer (d-17) content of 0.1. %, And a silver nanowire dispersion (AG-24) having a BTA content of 0.02% was prepared.
  • Table 3 shows the concentration and mass ratio of each component of the silver nanowire dispersion liquid (AG-24). The obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • Example 25 A silver nanowire dispersion was prepared in the same manner as in Example 24 except that the types and contents of the components were changed as shown in Table 3 (AG-25). The obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • Example 30 20 parts of a silver nanowire reaction solution having a silver nanowire content of 0.4%, 0.1 part of 40% copolymer (d-17) and 79.9 parts of water were weighed into a beaker and stirred. The obtained mixed solution is centrifuged at 500 G for 10 minutes using a centrifuge, and the supernatant is discarded. Water and 40% copolymer (d-17) are added to the silver nanowire and stirred, thereby stirring the silver nanowire. The content was adjusted to 0.4%, and the copolymer (d-17) content was adjusted to 0.2%.
  • the silver nanowire component was purified to prepare a silver nanowire liquid having a silver nanowire content of 0.4% and a copolymer (d-17) content of 0.2%.
  • 50 parts of purified silver nanowire solution and 50 parts of 1% polysaccharide and its derivative aqueous solution (e-1) were weighed into a beaker and stirred to give a silver nanowire content of 0.2%, copolymer (d-17) )
  • a silver nanowire dispersion (AG-30) having a content of 0.1% and an aqueous solution of polysaccharides and derivatives thereof (e-1) of 0.5% was prepared.
  • Table 3 shows the concentration and mass ratio of each component of the silver nanowire dispersion (AG-30).
  • the obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • Examples 31 to 39 Silver nanowire dispersions were prepared (AG-31 to AG-39) in the same manner as in Example 30, except that the types and contents of the components were changed as shown in Table 3. The obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • Example 40 A silver nanowire dispersion liquid was prepared in the same manner as in Example 1 except that the types and contents of the components were changed as shown in Table 3 (AG-50). The obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1 except that the coated substrate was changed from a polyester film to a cyclic polyolefin film.
  • Example 1 20 parts of a silver nanowire reaction solution having a silver nanowire content of 0.4% and 80 parts of water were weighed into a beaker and stirred. The obtained mixture was centrifuged at 500 G for 10 minutes using a centrifuge, the supernatant was discarded, and water was added to the silver nanowires and stirred to adjust the silver nanowire content to 0.4%. By repeating this operation three times, the silver nanowire component was purified to prepare a silver nanowire liquid having a silver nanowire content of 0.4%. A silver nanowire dispersion (AG-40) having a silver nanowire content of 0.2% was prepared by weighing 50 parts of the purified silver nanowire liquid and 50 parts of water into a beaker and stirring. Table 3 shows the concentration and mass ratio of each component of the silver nanowire dispersion (AG-40). The obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • Comparative Example 2 20 parts of a silver nanowire reaction solution having a silver nanowire content of 0.4%, 0.08 part of New Coal 2308, and 79.92 parts of water were weighed into a beaker and stirred. The resulting mixture is centrifuged at 500 G for 10 minutes using a centrifuge, and the supernatant is discarded. Water and New Coal 2308 are added to the silver nanowire and stirred, so that the silver nanowire content is 0.4%. New Coal 2308 content was adjusted to 0.2%. By repeating this operation three times, the silver nanowire component was purified to prepare a silver nanowire liquid having a silver nanowire content of 0.4% and a Newcol 2308 content of 0.2%.
  • Comparative Example 3 A silver nanowire dispersion was prepared in the same manner as in Comparative Example 2 except that the types of components were changed as shown in Table 3 (AG-42). The obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • the content was adjusted to 0.4%, and the copolymer (d-25) content was adjusted to 0.2%.
  • the silver nanowire component was purified to prepare a silver nanowire liquid having a silver nanowire content of 0.4% and a copolymer (d-25) content of 0.2%.
  • a silver nanowire dispersion liquid having a silver nanowire content of 0.2% and a copolymer (d-25) content of 0.1% 50 parts of silver nanowire liquid after purification and 50 parts of water was weighed into a beaker and stirred. AG-46) was prepared.
  • Table 3 shows the concentration and mass ratio of each component of the silver nanowire dispersion liquid (AG-46). The obtained silver nanowire dispersion was subjected to the test in the same manner as in Example 1.
  • Polyester film substrate used in Examples 1 to 39 and Comparative Examples 1 to 10 Cosmo Shine A-4100 (manufactured by Toyobo Co., Ltd.)
  • the silver nanowire dispersions of Examples 1 to 40 which are the present invention, are less likely to generate aggregates than the silver nanowire dispersions of Comparative Examples 1 to 10, have excellent redispersibility, are suitable for coating, Excellent physical properties and adhesion to the substrate. That is, by mixing the silver nanowire (a), which is an essential component of the silver nanowire aqueous dispersion of the present invention, and the copolymer (d), it is excellent in redispersibility, coating suitability, The silver nanowire dispersion liquid which can form the electrically conductive film excellent in the physical property and adhesiveness with a base material was able to be obtained.
  • Example 2 to 4 The silver nanowire dispersions of Examples 2 to 4 are more preferable as the nonionic hydrophobic monomer (b) than the dispersion of Example 1 as a copolymer (d) composed of styrene, octadecyl acrylate, or methyl methacrylate. ), The surface resistivity, the total light transmittance, the haze and the adhesion to the substrate of the conductive film were improved.
  • Examples 5 to 6 The silver nanowire dispersion liquids of Examples 5 to 6 are more preferable than the dispersion liquids of Examples 2 to 4 as a nonionic hydrophobic monomer (b) containing a more preferable alkyl acrylate ester having 4 to 12 carbon atoms. Since the polymer (d) was contained, aggregates were hardly generated, and the surface resistivity, total light transmittance, and haze of the conductive film were improved.
  • Example 7 to 8 The dispersions of Examples 7 to 8 are more preferable than the dispersions of Examples 5 to 6 as a nonionic hydrophobic monomer (b), which is a copolymer containing a more preferable alkyl methacrylate having 4 to 12 carbon atoms. Since (d) is contained, the total light transmittance, haze, and adhesion to the substrate of the conductive film were improved.
  • a nonionic hydrophobic monomer (b) which is a copolymer containing a more preferable alkyl methacrylate having 4 to 12 carbon atoms. Since (d) is contained, the total light transmittance, haze, and adhesion to the substrate of the conductive film were improved.
  • Example 9 to 10 The dispersions of Examples 9 to 10 contain a copolymer (d) composed of a monomer having a more preferable amide structure as the nonionic hydrophilic monomer (c) as compared with the dispersion of Example 8.
  • the redispersibility was excellent, and the surface resistivity, total light transmittance, and haze of the conductive film were improved.
  • Example 11 Compared with the dispersions of Examples 9 to 10, the dispersion of Example 11 contains a more preferable copolymer (d) composed of N-substituted (meth) acrylamide as the nonionic hydrophilic monomer (c). Therefore, the coating suitability was improved, and the surface resistivity, total light transmittance and haze of the conductive film were improved.
  • Example 12 to 29 The dispersions of Examples 12 to 29 contain a more preferable copolymer (d) composed of N, N-dimethylacrylamide as the nonionic hydrophilic monomer (c) as compared with the dispersion of Example 11. For this reason, aggregates are hardly generated, and the surface resistivity, total light transmittance, and haze of the conductive film are improved. Since the dispersions of Examples 15 to 17 contain a copolymer having a weight average molecular weight in a preferable range as compared with the dispersion of Example 14, the surface resistivity, total light transmittance, and Haze improved.
  • Example 23 Since the dispersion of Example 23 was before the silver nanowire purification, which is a preferable period of addition of the copolymer, compared with the dispersion of Example 22, the surface resistivity, total light transmittance, and haze of the conductive film Improved.
  • Example 30 to 33 Since the dispersions of Examples 30 to 33 contain the polysaccharide and its derivative (e) as compared with the dispersion of Example 23, the coating suitability is further improved, and the surface resistivity of the conductive film is improved. The light transmittance and haze were improved.
  • Examples 34 to 36 Since the dispersions of Examples 34 to 36 contain polysaccharides and their derivatives (e) in a preferable amount with respect to the silver nanowires (a), compared with the dispersions of Examples 32 and 33, The surface resistivity, total light transmittance and haze of the conductive film were improved.
  • Example 37 to 39 Since the dispersions of Examples 37 to 39 contain more preferable guar gum and its derivative as the polysaccharide and its derivative (e) compared to the dispersion of Example 36, the surface resistivity of the conductive film, Total light transmittance and haze were improved.
  • Example 40 Compared with the dispersion liquid of Example 11, the dispersion liquid of Example 40 contains a copolymer (d) containing isobornyl methacrylate as the nonionic hydrophobic monomer (b). Improved.
  • Comparative Example 1 Unlike the dispersion liquid of Example 1, the dispersion liquid of Comparative Example 1 does not contain the copolymer (d), so there are very many aggregates, the redispersibility is poor, and the conductive film cannot be formed. It was.
  • Comparative Example 2 Unlike the dispersion liquid of Example 1, the dispersion liquid of Comparative Example 2 contains a low-molecular-weight surfactant instead of the copolymer (d), so there are many aggregates and the redispersibility is poor. It was impossible to form a conductive film.
  • Comparative Examples 3 to 5 Unlike the dispersions of Examples 1 and 9 and Example 23, the dispersions of Comparative Examples 3 to 5 are homopolymers of nonionic hydrophilic monomers (c) or nonionic hydrophilics instead of the copolymer (d). Since it contains a copolymer consisting only of the polymerizable monomer (c), there are many aggregates, and the redispersibility, coating suitability, surface resistivity of the conductive film, total light transmittance, haze and adhesion are inferior. .
  • Comparative Example 6 Unlike the dispersion liquid of Example 1, the dispersion liquid of Comparative Example 6 contains a copolymer composed of an anionic hydrophilic monomer instead of the nonionic hydrophilic monomer (c). Redispersibility, coating suitability, surface resistivity of the conductive film, total light transmittance, haze and adhesion were inferior.
  • Comparative Examples 7 to 8 Unlike the dispersion liquid of Example 1, the dispersion liquids of Comparative Examples 7 to 8 are copolymers in which the copolymerization ratio of the nonionic hydrophobic monomer (b) and the nonionic hydrophilic monomer (c) is in an unfavorable range ( Since d) was contained, there were many aggregates, and redispersibility, coating suitability, surface resistivity of the conductive film, total light transmittance, haze and adhesion were inferior.
  • Comparative Examples 9 to 10 Unlike the dispersion liquid of Example 1, the dispersion liquids of Comparative Examples 9 to 10 contain the copolymer (d) having a ratio with respect to the silver nanowires (a) which is not preferable, and thus there are many aggregates. Redispersibility, coating suitability, surface resistivity of the conductive film, total light transmittance, haze and adhesion were inferior.
  • a transparent conductive film is formed using the metal nanowire dispersion liquid of the present invention, and an electrode material for a liquid crystal display, an electrode material for a plasma display, an electrode material for an organic electroluminescence display, an electrode material for electronic paper, and a touch panel
  • an electrode material for a liquid crystal display an electrode material for a plasma display
  • an electrode material for an organic electroluminescence display an electrode material for electronic paper
  • a touch panel It is widely applied to various devices such as electrode materials, electrode materials for thin-film amorphous Si solar cells, electrode materials for dye-sensitized solar cells, electromagnetic wave shielding materials, and antistatic materials.

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  • Engineering & Computer Science (AREA)
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  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une dispersion moins susceptible de produire un agrégat de nanofils métalliques peu redispersibles de nanofils métalliques dans le stade de fabrication ou le stade produit dans un système de formulation de nanofils métalliques dans un solvant de dispersion, présentant une excellente aptitude au revêtement lors de la fabrication d'un film conducteur et qui présente une adhérence favorable avec un matériau de base ou une résine stratifiée. L'invention concerne une dispersion de nanofils métalliques contenant des nanofils métalliques (a) et un copolymère (d) obtenu par copolymérisation d'un monomère hydrophobe non ionique (b) et d'un monomère hydrophile non ionique (c), la dispersion de nanofils métalliques étant caractérisée en ce que le copolymère (d) satisfait aux rapports de masse (i) et (ii). (i) monomère hydrophobe non ionique (b)/monomère hydrophile non ionique (c) = 1/99 à 50/50 (ii) nanofils métalliques (a)/copolymère (d) = 1/1 à 100/1
PCT/JP2014/077382 2013-11-06 2014-10-15 Dispersion de nanofils métalliques ayant une stabilité de dispersion supérieure, film conducteur transparent et conducteur transparent WO2015068540A1 (fr)

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WO2023126576A1 (fr) * 2021-12-31 2023-07-06 Åbo Akademi Procédé de préparation d'une émulsion à base de polysaccharide pour des applications de liaison et de revêtement

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