WO2014024721A1 - 銀ナノ粒子の製造方法及び銀ナノ粒子、並びに銀塗料組成物 - Google Patents
銀ナノ粒子の製造方法及び銀ナノ粒子、並びに銀塗料組成物 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/02—Obtaining noble metals by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
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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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
Definitions
- the present invention relates to a method for producing silver nanoparticles and silver nanoparticles. Moreover, this invention relates to the silver coating composition containing the said silver nanoparticle. Furthermore, this invention is applied also to the manufacturing method of metal nanoparticle containing metals other than silver, and this metal nanoparticle.
- Silver nanoparticles can be sintered even at low temperatures. Utilizing this property, in the manufacture of various electronic devices, a silver coating composition containing silver nanoparticles is used to form electrodes and conductive circuit patterns on a substrate. Silver nanoparticles are usually dispersed in an organic solvent. Silver nanoparticles have an average primary particle size of about several nanometers to several tens of nanometers, and the surface thereof is usually coated with an organic stabilizer (protective agent). When the substrate is a plastic film or sheet, it is necessary to sinter the silver nanoparticles at a low temperature (for example, 200 ° C. or less) lower than the heat resistance temperature of the plastic substrate.
- a low temperature for example, 200 ° C. or less
- Japanese Patent Application Laid-Open No. 2010-265543 discloses a silver compound that decomposes by heating to produce metallic silver, a medium / short chain alkylamine having a boiling point of 100 ° C. to 250 ° C., and a medium / short chain alkyl diamine having a boiling point of 100 ° C. to 250 ° C.
- a method for producing coated silver ultrafine particles comprising a first step of preparing a complex compound containing a silver compound, the alkylamine and the alkyldiamine, and a second step of thermally decomposing the complex compound is disclosed. (Claim 3, paragraphs [0061] and [0062]).
- Silver nanoparticles have an average primary particle diameter of about several nanometers to several tens of nanometers, and are more likely to aggregate than micron ( ⁇ m) size particles. Therefore, the reduction reaction of the silver compound (thermal decomposition reaction in the above patent document) is organic so that the surface of the obtained silver nanoparticles is coated with an organic stabilizer (protective agent such as aliphatic amine or aliphatic carboxylic acid). It is carried out in the presence of a stabilizer.
- an organic stabilizer protecting agent such as aliphatic amine or aliphatic carboxylic acid
- the silver nanoparticles are a silver coating composition (silver ink, silver paste) containing the particles in an organic solvent.
- the organic stabilizer In order to develop conductivity, it is necessary to remove the organic stabilizer covering the silver nanoparticles and sinter the silver particles at the time of firing after application on the substrate. If the firing temperature is low, the organic stabilizer is difficult to remove. If the degree of sintering of the silver particles is not sufficient, a low resistance value cannot be obtained. That is, the organic stabilizer present on the surface of the silver nanoparticles contributes to the stabilization of the silver nanoparticles, but prevents the silver nanoparticles from being sintered (particularly, sintering at low temperature firing).
- an aliphatic amine compound and / or an aliphatic carboxylic acid compound having a relatively long chain for example, having 8 or more carbon atoms
- the distance between the individual silver nanoparticles is easily secured. Nanoparticles are easy to stabilize.
- long-chain aliphatic amine compounds and / or aliphatic carboxylic acid compounds are difficult to remove if the firing temperature is low.
- an oleylamine having 18 carbon atoms and a saturated aliphatic amine having 1 to 18 carbon atoms are used in combination as the aliphatic amine compound.
- oleylamine is used as the main component of the protective agent, sintering of silver nanoparticles during low-temperature firing is hindered.
- the reaction rate of the complex compound formation reaction between oleylamine and silver oxalate is not sufficient.
- a medium / short chain alkylamine having a boiling point of 100 ° C. to 250 ° C. (paragraph [0061]) and a medium / short chain having a boiling point of 100 ° C. to 250 ° C.
- An alkyldiamine (paragraph [0062]) is used in combination. According to this method, problems caused by using oleylamine as the main component of the protective agent are improved. However, further improvement of the production process of silver nanoparticles and improvement of the performance of silver nanoparticles produced (expression of a low resistance value at low temperature firing) are desired.
- an object of the present invention is a silver nanoparticle that exhibits excellent stability and exhibits excellent conductivity (low resistance value) by low-temperature baking, and in particular, low-temperature baking of a silver fired film having a thickness of 1 ⁇ m or more, for example. It is in providing the silver nanoparticle which electroconductivity (low resistance value) expresses, and its manufacturing method, even when formed by. Moreover, the objective of this invention is providing the silver coating composition containing the said silver nanoparticle.
- the present inventors have studied an aliphatic amine compound that functions as a complexing agent and / or a protective agent, and is excellent in stability, at a low temperature of 200 ° C. or lower (eg, 150 ° C. or lower, preferably 120 ° C. or lower) and for 2 hours. Excellent conductivity (low resistance value) is exhibited even when a relatively thick silver film of, for example, 1 ⁇ m or more is formed by firing in a short time (for example, 1 hour or less, preferably 30 minutes or less). We have found a method for obtaining silver nanoparticles.
- the present invention includes the following inventions.
- a method for producing silver nanoparticles An aliphatic amine comprising at least a branched aliphatic hydrocarbon monoamine (D) consisting of a branched aliphatic hydrocarbon group and one amino group, wherein the branched aliphatic hydrocarbon group has 4 or more carbon atoms;
- D branched aliphatic hydrocarbon monoamine
- the complex compound is heated and thermally decomposed to form silver nanoparticles.
- the manufacturing method of the silver nanoparticle containing this.
- the aliphatic amine is further composed of a linear aliphatic hydrocarbon monoamine (B) consisting of a linear aliphatic hydrocarbon group and one amino group, the total number of carbons of the aliphatic hydrocarbon group being 5 or less. ), And at least one of the aliphatic hydrocarbon diamines (C) consisting of an aliphatic hydrocarbon group and two amino groups, wherein the aliphatic hydrocarbon group has a total carbon number of 8 or less, (1)
- B linear aliphatic hydrocarbon monoamine
- C aliphatic hydrocarbon diamines
- the aliphatic amine is a linear aliphatic hydrocarbon monoamine (A) further comprising a linear aliphatic hydrocarbon group and one amino group, and the total number of carbons of the aliphatic hydrocarbon group is 6 or more.
- the branched aliphatic hydrocarbon amine (D) is contained in an amount of 10 mol% to 50 mol% based on the total of the aliphatic amines.
- Silver nanoparticles whose surface is coated with a protective agent, the protective agent being the branched aliphatic hydrocarbon amine (D) and the linear aliphatic hydrocarbon monoamine (B) having 5 or less carbon atoms. And coated silver nanoparticles comprising at least one of the aliphatic hydrocarbon diamines (C).
- a metal coating composition containing the coated metal nanoparticles and an organic solvent can take various forms without limitation.
- a metal coating composition in which metal nanoparticles are dispersed in an organic solvent in a suspended state is a metal coating composition in which metal nanoparticles are dispersed in a kneaded state in an organic solvent.
- At least the branched aliphatic hydrocarbon monoamine (D) is used as an aliphatic amine compound that functions as a complex-forming agent and / or a protective agent.
- a branched aliphatic hydrocarbon amine compound compared with the case of using a straight aliphatic hydrocarbon amine compound having the same carbon number, the steric factor of the branched aliphatic hydrocarbon group causes more A larger area on the surface of the silver particles can be coated with a small amount of adhesion. Therefore, moderate stabilization of the silver nanoparticles can be obtained with a smaller amount of adhesion on the surface of the silver particles. Since the amount of protective agent (organic stabilizer) to be removed at the time of firing is small, the organic stabilizer can be efficiently removed even when firing at a low temperature of 200 ° C. or less, and the silver particles are sufficiently sintered. To do.
- an aliphatic hydrocarbon monoamine (A) consisting of a linear aliphatic hydrocarbon group and one amino group, wherein the aliphatic hydrocarbon group has a total carbon number of 6 or more
- An aliphatic hydrocarbon monoamine (B) consisting of a linear aliphatic hydrocarbon group and one amino group, the total number of carbons of the aliphatic hydrocarbon group being 5 or less
- An aliphatic hydrocarbon diamine (C) comprising an amino group and the aliphatic hydrocarbon group having a total carbon number of 8 or less
- the aliphatic hydrocarbon amine compound selected from can be used independently.
- the linear aliphatic hydrocarbon monoamine (B) and the aliphatic hydrocarbon diamine (C) are effective in promoting complex formation.
- the linear aliphatic hydrocarbon monoamine (A) includes primary amines, secondary amines, and tertiary amines.
- the primary amine include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n -Saturated straight chain aliphatic hydrocarbon monoamines (ie, straight chain alkyl monoamines) such as tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine.
- unsaturated linear aliphatic hydrocarbon monoamines such as oleylamine (that is, linear alkenyl monoamines) can be mentioned.
- Secondary amines include N, N-di (n-propyl) amine, N, N-di (n-butyl) amine, N, N-di (n-pentyl) amine, N, N-di (n -Hexyl) amine, N, N-di (n-peptyl) amine, N, N-di (n-octyl) amine, N, N-di (n-nonyl) amine, N, N-di (n-decyl) ) Amine, N, N-di (n-undecyl) amine, N, N-di (n-dodecyl) amine, N-methyl-N- (n-propyl) amine, N-ethyl-N- (n-propyl) And dialkyl monoamines such as N- (n-propyl) -N- (n-butyl) amine.
- the tertiary amine
- alkyl monoamines having 6 to 12 carbon atoms such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine and n-dodecylamine are preferably used. Only 1 type may be used among the said linear aliphatic hydrocarbon monoamine (A), and it may be used in combination of 2 or more type.
- the straight chain aliphatic hydrocarbon monoamine (B) having a total carbon number of 5 or less has a shorter carbon chain length than the straight chain aliphatic monoamine (A) having a total number of carbon atoms of 6 or more, it itself serves as a protective agent (stabilizer).
- the function is higher in polarity than the aliphatic monoamine (A) and has a high coordination ability to the silver of the silver compound, and is therefore effective in promoting complex formation.
- the carbon chain length is short, it can be removed from the surface of the silver particles in a short time of 30 minutes or less or 20 minutes or less even in low-temperature firing of 120 ° C. or less, or about 100 ° C. or less. Effective for low-temperature firing of silver nanoparticles.
- linear aliphatic hydrocarbon monoamine (B) examples include saturated linear aliphatic hydrocarbon monoamines having 2 to 5 carbon atoms such as ethylamine, n-propylamine, n-butylamine, and n-pentylamine (that is, linear Alkyl monoamine). Further, dialkyl monoamines such as N, N-dimethylamine and N, N-diethylamine are also included.
- n-butylamine, n-pentylamine and the like are preferable, and the above-mentioned n-butylamine is particularly preferable.
- aliphatic hydrocarbon monoamines (B) only one type may be used, or two or more types may be used in combination.
- Aliphatic hydrocarbon diamine (C) having a total carbon number of 8 or less has high coordination ability to silver of silver compounds and is effective in promoting complex formation.
- the aliphatic hydrocarbon diamine generally has a higher polarity than the aliphatic hydrocarbon monoamine, and the coordination ability of silver compounds to silver is increased.
- the aliphatic hydrocarbon diamine (C) has an effect of promoting thermal decomposition at a lower temperature and in a shorter time in the thermal decomposition step of the complex compound, and can produce silver nanoparticles more efficiently. .
- the aliphatic hydrocarbon diamine (C) is not particularly limited, but includes ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1 , 3-propanediamine, 2,2-dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N′-dimethyl-1,3-propanediamine, N, N— Diethyl-1,3-propanediamine, N, N′-diethyl-1,3-propanediamine, 1,4-butanediamine, N, N-dimethyl-1,4-butanediamine, N, N′-dimethyl- 1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N′-diethyl-1,4-butanediamine 1,5-pentanediamine, 1,5-d
- alkylene diamines having a total carbon number of 8 or less, in which at least one of the two amino groups is a primary amino group or a secondary amino group, and the ability of the silver compound to coordinate to silver is high, Effective in promoting complex formation.
- a linear aliphatic hydrocarbon diamine is exemplified.
- one of the two amino groups is a primary amino group
- An alkylenediamine having a total carbon number of 8 or less, wherein —NH 2 ) and the other one is a tertiary amino group (—NR 1 R 2 ) is preferred.
- a preferred alkylenediamine is represented by the following structural formula.
- R represents a divalent alkylene group
- R 1 and R 2 may be the same or different and represent a linear alkyl group, provided that the total number of carbon atoms of R, R 1 and R 2 Is 8 or less.
- the alkylene group usually does not contain a hetero atom (an atom other than carbon and hydrogen) such as an oxygen atom or a nitrogen atom, but may optionally have a substituent containing the hetero atom.
- the alkyl group usually does not contain a heteroatom such as an oxygen atom or a nitrogen atom, but may optionally have a substituent containing the heteroatom.
- one of the two amino groups is a primary amino group
- the ability of the silver compound to coordinate to silver is increased, which is advantageous for complex formation
- the other is a tertiary amino group. Since the tertiary amino group has poor coordination ability to silver atoms, the complex formed is prevented from having a complex network structure.
- a high temperature may be required for the thermal decomposition process of the complex.
- a diamine having a total carbon number of 6 or less is preferable, and a diamine having a total carbon number of 5 or less is more preferable from the viewpoint that it can be removed from the surface of the silver particles in a short time even in low-temperature firing.
- the aliphatic hydrocarbon diamine (C) only one type may be used, or two or more types may be used in combination.
- the branched aliphatic hydrocarbon monoamine (D) may be contained, for example, in an amount of 10 mol% to 50 mol% based on the total of the aliphatic amines. The remainder may be occupied by other amine components [(A), (B), (C)]. Due to its steric factors, the branched amine (D) has a smaller amount of adhesion on the surface of the silver particle than the other amine components [(A), (B), (C)]. Large areas can be covered. By using the branched amine (D) in such an amount, the steric factor can cover a larger area of the silver particle surface with a smaller amount of adhesion on the surface of the silver particle. Moderate stabilization is obtained.
- the protective agent organic stabilizer
- an organic stabilizer can be removed efficiently and silver particle sintering is enough Proceed to.
- the amount of the branched amine (D) used is less than 10 mol%, it is difficult to obtain a coating effect on the surface of the silver particles.
- the minimum of the usage-amount 10 mol% or more is preferable and 15 mol% or more is more preferable.
- the upper limit of the amount of the branched amine (D) used may exceed 50 mol%, but if the amount used exceeds 50 mol%, a long time may be required for complex formation.
- each amine component may be appropriately determined in consideration of the action of each amine component described above.
- the total of the aliphatic amines [(D) + (B)] (100% )
- the complex formation effect by the component (C) can be easily obtained, and the component (C) itself can be obtained at a low temperature for a short time. Can contribute to firing.
- the function of protecting and stabilizing the surface of the generated silver particles can be easily obtained by the carbon chain of the component (A).
- the content of the component (A) is less than 5 mol%, the expression of the protective stabilization function by the component (A) may be weak.
- the content of the component (A) is sufficient to be 60 mol% or less.
- content of the said (A) component exceeds 60 mol%, it will become difficult to remove this (A) component by low-temperature baking.
- the content of the component (A) is preferably 5 mol% to 50 mol%.
- the total amount of the amine component [(D) + optional component (A) + optional component (B) + optional component (C)] exceeds about 50 mol with respect to 1 mol of the silver atom, too much. There seems to be no merit.
- the total amount of the amine components is preferably about 2 mol or more, for example.
- the silver oxalate molecule contains two silver atoms.
- an aliphatic carboxylic acid (E) may be further used as a stabilizer.
- the aliphatic carboxylic acid (E) may be used together with the amine, and may be used by being included in the amine mixed solution.
- the stability of silver nanoparticles particularly the stability in a paint state dispersed in an organic solvent, may be improved.
- aliphatic carboxylic acid (E) a saturated or unsaturated aliphatic carboxylic acid is used.
- aliphatic carboxylic acid a saturated or unsaturated aliphatic carboxylic acid is used.
- saturated aliphatic monocarboxylic acids having 4 or more carbon atoms such as icosanoic acid and eicosenoic acid
- unsaturated aliphatic monocarboxylic acids having 8 or more carbon atoms such as oleic acid
- saturated or unsaturated aliphatic monocarboxylic acids having 8 to 18 carbon atoms are preferable.
- the number of carbon atoms By setting the number of carbon atoms to 8 or more, when the carboxylic acid group is adsorbed on the surface of the silver particle, a space between the silver particle and other silver particles can be secured, so that the effect of preventing aggregation of the silver particles is improved.
- saturated or unsaturated aliphatic monocarboxylic acid compounds having up to 18 carbon atoms are usually preferred.
- octanoic acid, oleic acid and the like are preferably used.
- the aliphatic carboxylic acids (E) only one type may be used, or two or more types may be used in combination.
- the method for producing silver nanoparticles of the present invention includes the branched aliphatic hydrocarbon monoamine (D), and the aliphatic component including the amine component (A) and / or (B) and / or (C) as an optional component.
- a step of mixing an amine and a silver compound to produce a complex compound containing the silver compound and the amine (a step of producing a complex compound), and a step of heating and complexing the complex compound (heat of the complex compound) Decomposition step).
- a metal compound containing the target metal is used instead of the silver compound.
- the complex compound formed by silver oxalate is generally colorless (observed as white when visually observed), but even in such a case, the complex compound is formed on the basis of a change in form such as a change in viscosity of the reaction mixture. The generation state can be detected. In this way, a silver-amine complex (or metal-amine complex) is obtained in a medium mainly composed of amines.
- a mixed liquid of the aliphatic amine component [(D) + optional component (A) + optional component (B) + optional component (C)] is prepared, and then silver A compound and the amine mixed solution may be mixed in the presence of a reaction solvent to form a complex compound containing the silver compound and the amine.
- a reaction solvent for example, an alcohol having 3 or more carbon atoms, preferably an alcohol having 3 to 10 carbon atoms can be used.
- Preferred examples of the alcohol include 1-butanol, isobutanol, sec-butanol, tert-butanol, 1-pentanol, 1-hexanol, 1-octanol, 2-ethylhexanol, 2-octanol and the like.
- reaction solvent By using the reaction solvent, mixing and stirring of the powdery silver compound and the amine can be facilitated, and the exothermic reaction can be performed mildly and safely.
- Each amine component may be sequentially mixed with the silver compound without using a mixed solution.
- a silver compound and an alcohol solvent are mixed to obtain a silver compound-alcohol slurry, and then, To the obtained silver compound-alcohol slurry, a mixed liquid of the aliphatic amine component [(D) + optional component (A) + optional component (B) + optional component (C)] is added, and the silver compound and A complex compound containing the amine may be generated.
- the alcohol solvent those described above may be used.
- the obtained complex compound is heated and pyrolyzed to form silver nanoparticles [complex compound pyrolysis step].
- a metal compound containing a metal other than silver is used, target metal nanoparticles are formed.
- Silver nanoparticles (metal nanoparticles) are formed without using a reducing agent. However, if necessary, an appropriate reducing agent may be used as long as the effects of the present invention are not impaired.
- amines control the manner in which atomic metals generated by the decomposition of metal compounds aggregate to form fine particles, and on the surface of the formed metal fine particles.
- a film By forming a film, it plays the role of preventing reaggregation between the fine particles. That is, by heating a complex compound of a metal compound and an amine, the metal compound is thermally decomposed while maintaining the coordinate bond of the amine to the metal atom to produce an atomic metal, and then the amine is coordinated. It is considered that the metal atoms are aggregated to form metal nanoparticles covered with an amine protective film.
- the thermal decomposition of the complex compound is preferably performed in an inert gas atmosphere such as argon, but the thermal decomposition can also be performed in the air.
- the complex compound Due to thermal decomposition of the complex compound, it becomes a suspension exhibiting blue gloss. From this suspension, removal of excess amine, etc., for example, precipitation of silver nanoparticles (or metal nanoparticles), decantation / washing with an appropriate solvent (water or organic solvent), Thus, stable coated silver nanoparticles (or coated metal nanoparticles) can be obtained. If it dries after washing
- Use water or organic solvent for decantation and cleaning operations examples include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, and tetradecane; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; toluene, xylene An aromatic hydrocarbon solvent such as mesitylene, etc .; an alcohol solvent such as methanol, ethanol, propanol, butanol, etc .; acetonitrile; and a mixed solvent thereof may be used.
- aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, and tetradecane
- alicyclic hydrocarbon solvents such as cyclo
- a silver coating composition can be prepared using the obtained silver nanoparticles.
- the silver coating composition can take various forms without limitation. For example, by dispersing silver nanoparticles in an appropriate organic solvent (dispersion medium) in a suspended state, a silver coating composition called a so-called silver ink can be produced. Alternatively, a silver coating composition called a so-called silver paste can be produced by dispersing silver nanoparticles in a state of being kneaded in an organic solvent.
- organic solvents for obtaining a silver coating composition include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, and tetradecane; alicyclic carbonization such as cyclohexane and methylcyclohexane Hydrogen solvent; aromatic hydrocarbon solvent such as toluene, xylene, mesitylene, etc .; methanol, ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n -Alcohol solvents such as decanol.
- aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, de
- Examples of the organic solvent for obtaining the silver coating composition include terpene solvents such as terpineol and dihydroterpineol to obtain a silver paste.
- the type and amount of the organic solvent may be appropriately determined according to the concentration and viscosity of the desired silver coating composition (silver ink, silver paste). The same applies to metal nanoparticles.
- the silver nanoparticle powder and silver coating composition obtained by the present invention are excellent in stability.
- silver nanoparticle powder is stable at room temperature storage for a period of one month or longer.
- the silver coating composition is stable without causing aggregation and fusion at room temperature for a period of one month or more, for example, at a silver concentration of 50 wt%.
- the protective agent includes the branched aliphatic hydrocarbon monoamine (D), and as optional components, a straight-chain aliphatic hydrocarbon monoamine (A) having 6 or more carbon atoms, and a straight-chain aliphatic hydrocarbon monoamine having 5 or less carbon atoms. (B) and / or an aliphatic hydrocarbon diamine (C) having 8 or less carbon atoms and / or an aliphatic carboxylic acid (E).
- Application is spin coating, inkjet printing, screen printing, dispenser printing, letterpress printing (flexographic printing), sublimation printing, offset printing, laser printer printing (toner printing), intaglio printing (gravure printing), contact printing, microcontact printing It can carry out by well-known methods, such as.
- a printing technique is used, a patterned silver coating composition layer is obtained, and a patterned silver conductive layer is obtained by firing.
- Calcination can be performed at a temperature of 200 ° C. or lower, for example, room temperature (25 ° C.) or higher and 150 ° C. or lower, preferably room temperature (25 ° C.) or higher and 120 ° C. or lower.
- a temperature of 60 ° C. to 200 ° C. for example, 80 ° C. to 150 ° C., preferably 90 ° C. to 120 ° C. .
- the firing time may be appropriately determined in consideration of the amount of silver ink applied, the firing temperature, etc., for example, within several hours (eg, 3 hours or 2 hours), preferably within 1 hour, more preferably within 30 minutes, More preferably, it is 10 minutes to 20 minutes, more specifically 10 minutes to 15 minutes.
- the substrate can be a glass substrate, a heat resistant plastic substrate such as a polyimide film, or a polyester film such as a polyethylene terephthalate (PET) film or a polyethylene naphthalate (PEN) film.
- a general-purpose plastic substrate having low heat resistance such as a polyolefin-based film such as polypropylene can also be suitably used.
- baking in a short time reduces the load on these general-purpose plastic substrates having low heat resistance, and improves production efficiency.
- the thickness of the silver conductive layer may be appropriately determined according to the intended use, and particularly high conductivity even when a silver conductive layer having a relatively large thickness is formed by using the silver nanoparticles according to the present invention. Can show.
- the thickness of the silver conductive layer may be selected from the range of, for example, 5 nm to 30 ⁇ m, preferably 100 nm to 25 ⁇ m, more preferably 500 nm to 20 ⁇ m.
- the obtained silver fired film was measured using a four-terminal method (Loresta GP MCP-T610).
- the measuring range limit of this device is 10 7 ⁇ cm.
- 1-Butanol Special grade dihydroterpineol manufactured by Wako Pure Chemical Industries, Ltd .: Silver oxalate (produced by Nippon Terpene Co., Ltd.) MW: 303.78): synthesized from silver nitrate (Wako Pure Chemical Industries, Ltd.) and oxalic acid dihydrate (Wako Pure Chemical Industries, Ltd.)
- the reaction product was heated and stirred at 100 ° C. to thermally decompose the silver oxalate-amine complex, and a suspension in which dark blue silver nanoparticles were suspended in the amine mixture was obtained. Obtained.
- the obtained suspension was cooled, 9 g of methanol was added thereto and stirred, and then silver nanoparticles were precipitated by centrifugation, and the supernatant was removed.
- 9 g of 1-butanol was added to the silver nanoparticles and stirred, and then the silver nanoparticles were precipitated by centrifugation, and the supernatant was removed. In this way, wet silver nanoparticles were obtained.
- the white material obtained during the preparation of the silver nanoparticles was subjected to IR spectrum measurement, absorption derived from the alkyl group of the alkyl amine (2900 cm around -1, around 1000 cm -1) were observed. This also shows that the viscous white substance obtained during the preparation of the silver nanoparticles is formed by the combination of silver oxalate and alkylamine, and the silver oxalate has silver atoms. On the other hand, it was presumed to be a silver oxalate-amine complex in which the amino group was coordinated.
- Example 2 Using the silver nanoparticle paste prepared in Example 1, a printing test was performed with a screen printing apparatus. Drawing with an average drawing line width of 99.9 ⁇ m was possible for a plate design of 100 ⁇ m.
- Example 3 In the preparation of silver nanoparticles, the composition of the amine mixture was 10.84 g (148.1 mmol) of n-butylamine, 3.83 g (29.6 mmol) of 2-ethylhexylamine, and 1.28 g (9. 9 of n-octylamine).
- a silver nanoparticle paste was prepared in the same manner as in Example 1 except that it was changed to 90 mmol), and a coating film was formed and fired on an alkali-free glass plate by an applicator. After the formation of the coating film, it was immediately fired at 120 ° C. for 15 minutes in a blast drying furnace to form a silver fired film. When the specific resistance value of the obtained silver fired film was measured by the four-terminal method, it was 7.2 ⁇ cm.
- n-hexylamine having a lower molecular weight was used instead of 2-ethylhexylamine of Example 1 in the same molar amount (that is, smaller weight) as in Example 1. Compared with Example 1, the conductivity was inferior.
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Abstract
Description
(1) 銀ナノ粒子の製造方法であって、
分枝脂肪族炭化水素基と1つのアミノ基とからなり且つ該分枝脂肪族炭化水素基の炭素数が4以上である分枝脂肪族炭化水素モノアミン(D)を少なくとも含む脂肪族アミンと、銀化合物とを混合して、前記銀化合物及び前記アミンを含む錯化合物を生成させ、
前記錯化合物を加熱して熱分解させて、銀ナノ粒子を形成する、
ことを含む銀ナノ粒子の製造方法。
シュウ酸銀分子は、銀原子2個を含んでいる。前記銀化合物がシュウ酸銀である場合には、シュウ酸銀1モルに対して、前記脂肪族アミンをその合計として2~100モル用いる、上記(1) ~(9) のうちのいずれかに記載の銀ナノ粒子の製造方法。
前記基板上に、上記(1) ~(10)のうちのいずれかに記載の方法により製造される銀ナノ粒子と有機溶剤とを含む銀塗料組成物が塗布され、焼成されてなる銀導電層と、
を含む銀導電材料。焼成は、200℃以下、例えば150℃以下、好ましくは120℃以下の温度で、2時間以下、例えば1時間以下、好ましくは30分間以下の時間で行われる。
分枝脂肪族炭化水素基と1つのアミノ基とからなり且つ該分枝脂肪族炭化水素基の炭素数が4以上である分枝脂肪族炭化水素モノアミン(D)を少なくとも含む脂肪族アミンと、金属化合物とを混合して、前記金属化合物及び前記アミンを含む錯化合物を生成させ、 前記錯化合物を加熱して熱分解させて、金属ナノ粒子を形成する、
ことを含む金属ナノ粒子の製造方法。
前記錯化合物を加熱して熱分解させて、銀ナノ粒子を形成する、
ことにより、銀ナノ粒子を製造する。
・直鎖脂肪族炭化水素基と1つのアミノ基とからなり且つ該脂肪族炭化水素基の炭素総数が6以上である脂肪族炭化水素モノアミン(A)、
・直鎖脂肪族炭化水素基と1つのアミノ基とからなり且つ該脂肪族炭化水素基の炭素総数が5以下である脂肪族炭化水素モノアミン(B)、及び
・脂肪族炭化水素基と2つのアミノ基とからなり且つ該脂肪族炭化水素基の炭素総数が8以下である脂肪族炭化水素ジアミン(C)
から選ばれる脂肪族炭化水素アミン化合物をそれぞれ別個独立に用いることができる。前記直鎖脂肪族炭化水素モノアミン(B)、及び前記脂肪族炭化水素ジアミン(C)は、錯体形成促進に効果がある。
ここで、Rは、2価のアルキレン基を表し、R1 及びR2 は、同一又は異なっていてもよく、直鎖アルキル基を表し、ただし、R、R1 及びR2 の炭素数の総和は8以下である。該アルキレン基は、通常は酸素原子又は窒素原子等のヘテロ原子(炭素及び水素以外の原子)を含まないが、必要に応じて前記ヘテロ原子を含む置換基を有していてもよい。また、該アルキル基は、通常は酸素原子又は窒素原子等のヘテロ原子を含まないが、必要に応じて前記ヘテロ原子を含む置換基を有していてもよい。
(D)+(B)
(D)+(C)
(D)+(B)+(C)
(D)+(B)+(A)
(D)+(C)+(A)
(D)+(B)+(C)+(A)
(D)+(A)
前記分枝モノアミン(D): 10モル%~50モル%
前記(C5-)直鎖モノアミン(B):50モル%~90モル%
とするとよい。あるいは、
前記分枝モノアミン(D): 20モル%~50モル%
前記(C5-)直鎖モノアミン(B):50モル%~80モル%
とするとよい。
前記分枝モノアミン(D): 10モル%~50モル%
前記脂肪族ジアミン(C): 50モル%~90モル%
とするとよい。あるいは、
前記分枝モノアミン(D): 20モル%~50モル%
前記脂肪族ジアミン(C): 50モル%~80モル%
とするとよい。
前記分枝モノアミン(D): 10モル%~50モル%
前記(C6+)直鎖モノアミン(A): 5モル%~60モル%
前記(C5-)直鎖モノアミン(B):30モル%~85モル%
とするとよい。
前記分枝モノアミン(D): 10モル%~50モル%
前記(C6+)直鎖モノアミン(A): 5モル%~60モル%
前記脂肪族ジアミン(C): 30モル%~85モル%
とするとよい。
得られた銀化合物-アルコールスラリーに、前記脂肪族アミン成分[(D)+任意成分(A)+任意成分(B)+任意成分(C)]の混合液を添加して、前記銀化合物及び前記アミンを含む錯化合物を生成させてもよい。アルコール溶剤としては、上述したものを用いるとよい。粉末状の銀化合物から、銀化合物-アルコールスラリーを得ておくことにより、銀化合物の取扱性が向上すると共に、銀化合物-アルコールスラリーと前記アミンとの混合攪拌が容易となり、また、発熱反応を温和に安全に遂行することができる。各アミン成分は、混合液としないで、逐次に銀化合物と混合してもよい。
得られた銀焼成膜について、4端子法(ロレスタGP MCP-T610)を用いて測定した。この装置の測定範囲限界は、107 Ωcmである。
2-エチルヘキシルアミン(MW:129.25):和光純薬社製試薬
n-ブチルアミン(MW:73.14):東京化成社製試薬
n-ヘキシルアミン(MW:101.19):東京化成社製試薬
n-オクチルアミン(MW:129.25):東京化成社製試薬
メタノール:和光純薬社製試薬特級
1-ブタノール:和光純薬社製試薬特級
ジヒドロターピネオール:日本テルペン株式会社製
シュウ酸銀(MW:303.78):硝酸銀(和光純薬社製)とシュウ酸二水和物(和光純薬社製)とから合成したもの
(銀ナノ粒子の調製)
100mLフラスコにシュウ酸銀3.0g(9.9mmol)を仕込み、その後、1-ブタノール4.5gを添加し、室温で攪拌することにより、シュウ酸銀の1-ブタノールスラリーを調製した。
次に、湿った銀ナノ粒子に、ジヒドロターピネオールを銀濃度70wt%となるように加えて混練し、銀ナノ粒子ペーストを調製した。
上記銀ナノ粒子の調製中に得られた白色物質について、DSC(示差走査熱量計)測定を行ったところ、熱分解による発熱開始平均温度値は102.5℃であった。一方、原料のシュウ酸銀について、同様に、DSC測定を行ったところ、熱分解による発熱開始平均温度値は218℃であった。このように、上記銀ナノ粒子の調製中に得られた白色物質は、原料のシュウ酸銀に比べて、熱分解温度が低下していた。このことから、上記銀ナノ粒子の調製中に得られた白色物質は、シュウ酸銀とアルキルアミンとが結合してなるものであることが示され、シュウ酸銀の銀原子に対してアルキルアミンのアミノ基が配位結合しているシュウ酸銀-アミン錯体であると推察された。
装置:DSC 6220-ASD2(エスアイアイ・ナノテクノロジー社製)
試料容器:15μL 金メッキ密封セル(エスアイアイ・ナノテクノロジー社製)
昇温速度:10℃/min (室温~600℃)
雰囲気ガス:セル内 大気圧 空気封じ込み
セル外 窒素気流(50mL/min)
実施例1において調製された銀ナノ粒子ペーストを用いて、スクリーン印刷装置にて印刷試験を実施した。版設計100μmに対して、描画線幅平均99.9μmでの描画が可能であった。
銀ナノ粒子の調製において、アミン混合液の組成を、n-ブチルアミン10.84g(148.1mmol)、2-エチルヘキシルアミン3.83g(29.6mmol)、及びn-オクチルアミン1.28g(9.90mmol)に変更した以外は、実施例1と同様にして、銀ナノ粒子ペーストを調製し、アプリケーターにより無アルカリガラス板上に塗膜の形成、焼成を行った。
塗膜の形成後、速やかに120℃にて15分間の条件で、送風乾燥炉にて焼成し、銀焼成膜を形成した。得られた銀焼成膜の比抵抗値を4端子法により測定したところ、7.2μΩcmであった。
銀ナノ粒子の調製において、アミン混合液の組成を、n-ブチルアミン10.84g(148.1mmol)、n-ヘキシルアミン3.00g(29.6mmol)、及び2-エチルヘキシルアミン3.83g(29.6mmol)に変更した以外は、実施例1と同様にして、銀ナノ粒子ペーストを調製し、アプリケーターにより無アルカリガラス板上に塗膜の形成、焼成を行った。
[1] 塗膜の形成後、速やかに120℃にて15分間の条件で、送風乾燥炉にて焼成し、銀焼成膜を形成した。得られた銀焼成膜の比抵抗値を4端子法により測定したところ、8.3μΩcmであった。
[2] また、別途、塗膜の形成後、速やかに220℃にて5分間の条件で、送風乾燥炉にて焼成し、銀焼成膜を形成した。得られた銀焼成膜の比抵抗値を4端子法により測定したところ、3.0μΩcmであった。
銀ナノ粒子の調製において、アミン混合液の組成を、n-ブチルアミン10.84g(148.1mmol)、n-ヘキシルアミン3.00g(29.6mmol)、及びn-オクチルアミン1.28g(9.90mmol)に変更した以外は、実施例1と同様にして、銀ナノ粒子ペーストを調製し、アプリケーターにより無アルカリガラス板上に塗膜の形成、焼成を行った。
塗膜の形成後、速やかに120℃にて15分間の条件で、送風乾燥炉にて焼成し、銀焼成膜を形成した。得られた銀焼成膜の比抵抗値を4端子法により測定したところ、14.2μΩcmであった。
銀ナノ粒子の調製において、アミン混合液の組成を、n-ブチルアミン10.84g(148.1mmol)、n-ヘキシルアミン3.00g(29.6mmol)、及びn-オクチルアミン3.83g(29.6mmol)に変更した以外は、実施例1と同様にして、銀ナノ粒子ペーストを調製し、アプリケーターにより無アルカリガラス板上に塗膜の形成、焼成を行った。
[1] 塗膜の形成後、速やかに120℃にて15分間の条件で、送風乾燥炉にて焼成し、銀焼成膜を形成した。得られた銀焼成膜の比抵抗値を4端子法により測定したところ、導電性が得られなかった。
[2] また、別途、塗膜の形成後、速やかに220℃にて5分間の条件で、送風乾燥炉にて焼成し、銀焼成膜を形成した。得られた銀焼成膜の比抵抗値を4端子法により測定したところ、32.0μΩcmであった。
これに対して、比較例2では、2-エチルヘキシルアミンの代わりに、これと同分子量のn-オクチルアミンを実施例4におけるのと同量(重量、モル)用いたが、実施例4に比べて導電性は大きく劣っていた。
また、比較例1では、実施例1の2-エチルヘキシルアミンの代わりに、これよりも分子量の小さいn-ヘキシルアミンを実施例1におけるのと同モル量(すなわち、より小さい重量)用いたが、実施例1に比べて導電性は劣っていた。
Claims (13)
- 銀ナノ粒子の製造方法であって、
分枝脂肪族炭化水素基と1つのアミノ基とからなり且つ該分枝脂肪族炭化水素基の炭素数が4以上である分枝脂肪族炭化水素モノアミン(D)を少なくとも含む脂肪族アミンと、銀化合物とを混合して、前記銀化合物及び前記アミンを含む錯化合物を生成させ、
前記錯化合物を加熱して熱分解させて、銀ナノ粒子を形成する、
ことを含む銀ナノ粒子の製造方法。 - 前記銀化合物は、シュウ酸銀である、請求項1に記載の銀ナノ粒子の製造方法。
- 前記分枝脂肪族炭化水素モノアミン(D)における分枝脂肪族炭化水素基は、炭素数が4~16である、請求項1又は2に記載の銀ナノ粒子の製造方法。
- 前記脂肪族アミンは、さらに、直鎖脂肪族炭化水素基と1つのアミノ基とからなり且つ該脂肪族炭化水素基の炭素総数が5以下である直鎖脂肪族炭化水素モノアミン(B)、及び脂肪族炭化水素基と2つのアミノ基とからなり且つ該脂肪族炭化水素基の炭素総数が8以下である脂肪族炭化水素ジアミン(C)のうちの少なくとも一方を含んでいる、請求項1~3のうちのいずれかに記載の銀ナノ粒子の製造方法。
- 前記脂肪族炭化水素モノアミン(B)は、炭素数2以上5以下のアルキルモノアミンである、請求項4に記載の銀ナノ粒子の製造方法。
- 前記脂肪族炭化水素モノアミン(B)は、ブチルアミンである、請求項4又は5に記載の銀ナノ粒子の製造方法。
- 前記脂肪族アミンは、さらに、直鎖脂肪族炭化水素基と1つのアミノ基とからなり且つ該脂肪族炭化水素基の炭素総数が6以上である直鎖脂肪族炭化水素モノアミン(A)を含んでいる、請求項1~6のうちのいずれかに記載の銀ナノ粒子の製造方法。
- 前記脂肪族炭化水素モノアミン(A)は、炭素数6以上12以下のアルキルモノアミンである、請求項7に記載の銀ナノ粒子の製造方法。
- 前記分枝脂肪族炭化水素アミン(D)は、前記脂肪族アミンの合計を基準として、10モル%~50モル%含まれる、請求項1~8のうちのいずれかに記載の銀ナノ粒子の製造方法。
- 前記銀化合物の銀原子1モルに対して、前記脂肪族アミンをその合計として1~50モル用いる、請求項1~9のうちのいずれかに記載の銀ナノ粒子の製造方法。
- 請求項1~10のうちのいずれかに記載の方法により製造される銀ナノ粒子。
- 請求項1~10のうちのいずれかに記載の方法により製造される銀ナノ粒子と、有機溶剤とを含む銀塗料組成物。
- 基板と、
前記基板上に、請求項1~10のうちのいずれかに記載の方法により製造される銀ナノ粒子と有機溶剤とを含む銀塗料組成物が塗布され、焼成されてなる銀導電層と、
を含む銀導電材料。
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EP2883634A4 (en) | 2016-03-30 |
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US20150224578A1 (en) | 2015-08-13 |
NO2883634T3 (ja) | 2018-05-12 |
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