WO2018038086A1 - Dispersion aqueuse de nanoparticules métalliques - Google Patents

Dispersion aqueuse de nanoparticules métalliques Download PDF

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Publication number
WO2018038086A1
WO2018038086A1 PCT/JP2017/029888 JP2017029888W WO2018038086A1 WO 2018038086 A1 WO2018038086 A1 WO 2018038086A1 JP 2017029888 W JP2017029888 W JP 2017029888W WO 2018038086 A1 WO2018038086 A1 WO 2018038086A1
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aqueous dispersion
metal
metal nanoparticle
organic compound
acid group
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PCT/JP2017/029888
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English (en)
Japanese (ja)
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昭太 新林
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Dic株式会社
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Priority to JP2017558511A priority Critical patent/JP6269909B1/ja
Priority to CN201780043376.2A priority patent/CN109478442B/zh
Priority to KR1020197002080A priority patent/KR102283387B1/ko
Publication of WO2018038086A1 publication Critical patent/WO2018038086A1/fr

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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
    • 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
    • B22F1/0545—Dispersions or suspensions of nanosized particles
    • 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
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • B22F1/147—Making a dispersion
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • 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
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • 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

Definitions

  • the present invention has excellent dispersion stability even when a thermal load such as heating or thawing after freezing, which can occur during storage or transportation, and has sufficient adsorptivity to a substrate, and
  • the present invention relates to an aqueous dispersion of metal nanoparticles having surface activity.
  • Metal nanoparticles are used industrially as catalysts, antibacterials, conductive materials and the like.
  • the main forms are pastes, inks and paints in which metal nanoparticles are dispersed and stabilized, and metal nanoparticles can be applied to any location of the target substrate by printing, coating, dipping treatment, etc. .
  • Both organic solvents and aqueous solvents have been studied as a solvent for dispersing metal nanoparticles, and can be selected depending on the purpose and process of applying metal nanoparticles on a substrate. From the viewpoint, it is preferable to use an aqueous solvent.
  • One of the basic properties required for such an aqueous dispersion of metal nanoparticles is long-term dispersion stability. This can generally be increased by increasing the amount of dispersant in the dispersion, but the excess dispersant tends to adversely affect the surface activity of the metal nanoparticles and the adsorptivity to the substrate. There is a concern that the original functions (catalytic activity, antibacterial activity, conductivity, etc.) of the material may be impaired.
  • Patent Document 1 As a technique for achieving both dispersion stability and function, a method of using a polymer dispersant having high dispersion performance instead of increasing the amount of the dispersant has been disclosed (for example, see Patent Document 1). It has been disclosed that the aqueous dispersion of metal nanoparticles can be used as a catalyst for electroless plating and has an adsorptivity to a substrate and surface activity (see, for example, Patent Document 2).
  • the problem to be solved by the present invention is that it has excellent dispersion stability even when a thermal load such as temperature rise or melting after freezing, which may occur during storage or transportation, and is sufficient for the substrate. It is to provide a metal nanoparticle aqueous dispersion having excellent adsorptivity and surface activity.
  • the present inventors have found that the above problems can be solved by configuring the metal nanoparticle aqueous dispersion with a specific composition, and have completed the present invention.
  • the present invention contains a composite of metal nanoparticles (X) and an organic compound (Y) (excluding a composite in which the organic compound (Y) is polyvinyl pyrrolidone) and polyvinyl pyrrolidone (Z).
  • the present invention provides a metal nanoparticle aqueous dispersion characterized by the above.
  • the metal nanoparticle aqueous dispersion of the present invention can improve the dispersion stability without deteriorating the adsorptivity and activity of the silver nanoparticles to the substrate. For this reason, characteristic deterioration (aggregation and deterioration of liquid appearance) can be prevented even if a thermal load such as heating or melting after freezing is applied without impairing the usefulness as an industrial material. As described above, since the metal nanoparticle aqueous dispersion of the present invention has excellent dispersion stability against thermal load, the temperature management cost in transportation (land transportation, sea transportation, air transportation) and storage can be reduced. .
  • FIG. 1 is an ultraviolet-visible absorption spectrum of an aqueous silver nanoparticle dispersion before heating (Example 1) and after heating (Example 1 and Comparative Example 1).
  • FIG. 2 is an ultraviolet-visible absorption spectrum of an aqueous silver nanoparticle dispersion before freezing (Example 1) and after a freeze-thaw cycle (Example 1 and Comparative Example 1).
  • the aqueous dispersion of metal nanoparticles of the present invention comprises a composite of metal nanoparticles (X) and an organic compound (Y) (excluding a composite in which the organic compound (Y) is polyvinyl pyrrolidone) and polyvinyl pyrrolidone (Z ).
  • Examples of the metal constituting the metal nanoparticles (X) include silver, copper, palladium alone, and alloys thereof.
  • Examples of the metal nanoparticles (X) include silver core copper shell particles, copper shell silver core particles, particles in which silver is partially substituted with palladium, and particles in which copper is partially substituted with palladium. These metals or alloys can be used alone or in combination of two or more. These metals or alloys may be appropriately selected according to the purpose. However, when used for the purpose of forming a wiring or a conductive layer, silver and copper are preferable. From the viewpoint of the catalytic function, silver, copper Palladium is preferred. From the viewpoint of cost, silver, copper, alloys thereof, partially substituted products, or mixtures thereof are preferable.
  • the shape of the metal nanoparticles (X) is not particularly limited as long as the dispersion stability in an aqueous medium is not impaired, and various shapes of nanoparticles can be appropriately selected according to the purpose. Specific examples include spherical, polyhedral, plate-like, rod-like, and combinations of these particles. As said metal nanoparticle (X), the thing of a single shape or a thing of a some shape can be mixed and used. Among these shapes, spherical or polyhedral particles are preferable from the viewpoint of dispersion stability.
  • the metal constituting the metal nanoparticle (X) is an organic compound (Y) as a dispersant on the surface of the metal nanoparticle (X) in order to maintain a uniform dispersed state for a long period of time in an aqueous dispersion medium.
  • Y organic compound
  • the organic compound (Y) may be appropriately selected and used according to the purpose, but from the viewpoint of dispersion stability, the compound (Y1) having an anionic functional group is preferable.
  • the organic compound (Y) is other than polyvinylpyrrolidone (Z) described later.
  • the compound having an anionic functional group (Y1) is a compound having at least one anionic functional group in the molecule. Further, a compound having a cationic functional group in addition to an anionic functional group in the molecule may be used as long as the dispersion stability is not inhibited.
  • the compound (Y1) having an anionic functional group can be used alone or in combination of two or more.
  • the polymer (Y2) of the monomer mixture (I) is particularly preferable.
  • the polymer (Y2) may be a homopolymer or a copolymer. Moreover, when it is a copolymer, it may be a random copolymer or a block copolymer.
  • the polymer (Y2) has one or more anionic functional groups selected from the group consisting of carboxy group, phosphoric acid group, phosphorous acid group, sulfonic acid group, sulfinic acid group and sulfenic acid group, Since it has the function of adsorbing to the metal nanoparticle (X) through the unshared electron pair of the atom and at the same time, a negative charge is imparted to the surface of the metal nanoparticle (X), Aggregation can be prevented, and the composite of polymer (Y2) and metal nanoparticles (X) can be stably dispersed in water.
  • anionic functional groups selected from the group consisting of carboxy group, phosphoric acid group, phosphorous acid group, sulfonic acid group, sulfinic acid group and sulfenic acid group
  • the polymer (Y2) preferably has three or more anionic functional groups in one molecule because the adsorption to the metal nanoparticles (X) and the dispersion stability in the aqueous dispersion can be further improved.
  • the weight average molecular weight of the polymer (Y2) is preferably in the range of 3,000 to 20,000 because the adsorption to the metal nanoparticles (X) and the dispersion stability in the aqueous dispersion can be further improved.
  • a range of 4,000 to 8,000 is more preferable.
  • the monomer mixture (I) is copolymerized with a (meth) acrylic acid monomer having a polyethylene glycol chain and a (meth) acrylic acid monomer having an anionic group.
  • the polymer (Y2) having a polyethylene glycol chain can be easily obtained.
  • the polymer (Y2) polymerized using a (meth) acrylic acid monomer having a polyethylene glycol chain with an average unit number of ethylene glycol of 20 or more stabilizes nanoparticles of noble metals, particularly silver and copper.
  • a (meth) acrylic acid monomer having a polyethylene glycol chain with an average unit number of ethylene glycol of 20 or more stabilizes nanoparticles of noble metals, particularly silver and copper.
  • This is preferable because it is a suitable protective agent.
  • Synthesis of such a polymer having an anionic functional group and a polyethylene glycol chain can be easily carried out by the methods described in, for example, Japanese Patent No. 4697356, Japanese Patent Application Laid-Open No. 2010-209421, and the like.
  • the weight average molecular weight of the (meth) acrylic acid monomer having a polyethylene glycol chain having an average unit number of ethylene glycol of 20 or more is preferably in the range of 1,000 to 2,000. When the weight average molecular weight is within this range, the water dispersibility of the composite with the metal nanoparticles (X) becomes better.
  • polymer (Y2) having a phosphate group and a polyethylene glycol chain for example, commercially available 2-methacryloyloxyphosphate (for example, “Light Ester P-1M” manufactured by Kyoeisha Chemical Co., Ltd.). )) And a commercially available methacrylic acid ester monomer having a polyethylene glycol chain (for example, “Blenmer PME-1000” manufactured by NOF Corporation) as a polymerization initiator (for example, oil-soluble azo polymerization initiator “V-59”). And a method of copolymerization using these.
  • 2-methacryloyloxyphosphate for example, “Light Ester P-1M” manufactured by Kyoeisha Chemical Co., Ltd.
  • methacrylic acid ester monomer having a polyethylene glycol chain for example, “Blenmer PME-1000” manufactured by NOF Corporation
  • a polymerization initiator for example, oil-soluble azo polymerization initiator “V-59”.
  • the ratio of the (meth) acrylic acid ester monomer having a phosphate group is less than 30% by mass in the monomer mixture (I)
  • the monomer mixture (I) contains a third polymerizable monomer other than the (meth) acrylic acid monomer having an anionic group and the (meth) acrylic acid monomer having a polyethylene glycol chain. May be.
  • the third polymerizable monomer is a hydrophobic monomer
  • the amount used thereof can maintain good water dispersibility, so that the amount of the (meth) acrylic acid monomer having a polyethylene glycol chain is 100 parts by mass.
  • the amount is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.
  • the 3rd polymeric monomer is not a hydrophobic monomer, it is not limited to this range.
  • the weight average molecular weight of the polymer (Y2) is preferably in the range of 3,000 to 20,000, but when a (meth) acrylic acid monomer having a polyethylene glycol chain is used in combination,
  • the polymer (Y2) obtained by the polymerization reaction has a molecular weight distribution.
  • the weight average molecular weight of the polymer (Y2) is more preferably 4,000 or more.
  • the weight average molecular weight of the complex with the metal nanoparticle (X) is likely to be coarsened, and the weight average molecular weight of the polymer (Y2) is 8, from the viewpoint of easily causing precipitation in the catalyst solution. More preferably, it is 000 or less.
  • a chain transfer agent described in known literature for example, JP 2010-209421 A may be used. You may control by polymerization conditions, without using.
  • a composite used for the aqueous dispersion of metal nanoparticles of the present invention a composite with metal nanoparticles (X) such as silver, copper, palladium, etc., produced using the polymer (Y2) as a colloid protective agent is used. be able to.
  • the polymer (Y2) is dissolved or dispersed in an aqueous medium, and then silver nitrate, copper acetate, palladium nitrate is added thereto.
  • a metal compound such as a complexing agent as necessary to obtain a uniform dispersion
  • the metal compound is reduced by mixing a reducing agent, and the reduced metal is nanosized particles ( And a method of obtaining an aqueous dispersion of metal nanoparticles (X) combined with the polymer (Y2) at the same time.
  • a complexing agent you may mix simultaneously with a reducing agent.
  • the composite of the metal nanoparticles (X) and the organic compound (Y) used in the present invention is advantageous from the viewpoints of fusion property at low temperatures and catalytic activity, which is advantageous for wiring and conductive layer formation.
  • the average particle size of (X) is preferably in the range of 0.5 to 100 nm.
  • the average particle diameter of the metal nanoparticles (X) can be estimated by a transmission electron micrograph, and the average value of 100 particles in the range of 0.5 to 100 nm is, for example, the above-mentioned patent It can be easily obtained by methods described in Japanese Patent No. 4697356, Japanese Patent Application Laid-Open No. 2010-209421, and the like.
  • the metal nanoparticles (X) obtained in this manner are protected by the polymer (Y2) and are present one by one and can be obtained in a state of being dispersed in an aqueous dispersion medium.
  • the average particle diameter of the metal nanoparticles (X) is the type of metal compound, the molecular weight of the organic compound (Y) to be a colloid protective agent, the chemical structure and the amount used, the type and amount of complexing agent and reducing agent,
  • the temperature can be easily controlled by the temperature at the time of the reduction reaction. For these, reference may be made to the examples described in the above-mentioned patent documents.
  • the content ratio of the organic compound (Y) in the complex of the organic compound (Y) and the metal nanoparticles (X) is preferably in the range of 1 to 30% by mass, and in the range of 2 to 20% by mass. Is more preferable. That is, in the composite, the metal nanoparticle (X) occupies most of the mass is suitable for use in wiring, conductive layer formation, and various catalyst applications.
  • the composite in which the metal nanoparticles (X) are protected with the polymer (Y2) is 0.01 to 70% by mass in an aqueous medium, that is, a mixed solvent of water or an organic solvent compatible with water. Even if a thermal load such as heating or thawing after freezing is applied by further coexisting the polyvinylpyrrolidone (Z) in this dispersion, The composite of the metal nanoparticles (X) and the organic compound (Y) can maintain excellent dispersion stability, high adsorptivity to the substrate, and surface activity.
  • aggregation occurs due to freezing, when the metal nanoparticle dispersion is frozen, and when the water in the dispersion crystallizes to become ice, it is crystallized while eliminating metal nanoparticle complexes that are contaminants for water. It is thought that growth occurs and the metal nanoparticle composite is extremely concentrated. Therefore, in order to suppress irreversible aggregation of particles due to heating or freezing, it is effective to allow a compound having the property of adsorbing and protecting the metal nanoparticles (X) to coexist in the dispersion. it is conceivable that.
  • the driving force by which the metal nanoparticle composite is adsorbed to the base material is mainly an electrostatic interaction between the charge on the surface of the base material and the charge of the metal nanoparticle composite. For this reason, when an additive having the same charge as that of the metal nanoparticle composite is allowed to coexist, the additive and the metal nanoparticle composite compete with each other for the adsorption point on the base material. It is thought to inhibit the adsorption of the composite to the substrate. Conversely, when an additive having a charge opposite to that of the metal nanoparticle composite is allowed to coexist, the electrostatic repulsion between the metal nanoparticle composites is shielded, and aggregation of the metal nanoparticle composite is induced. Conceivable.
  • a nonionic compound as an additive as a compound having the property of adsorbing and protecting the metal nanoparticles (X). Conceivable.
  • the compound having the property of adsorbing and protecting the metal nanoparticles (X) is not too weak and not too strong for the metal nanoparticles (X), and is water-soluble.
  • nonionic properties are preferable for maintaining excellent dispersion stability, high adsorptivity to the substrate, and surface activity of the metal nanoparticles (X).
  • Polyvinylpyrrolidone (Z) meets this condition.
  • the aqueous dispersion of metal nanoparticles of the present invention contains polyvinylpyrrolidone (Z) as an essential component in addition to the composite of the metal nanoparticles (X) and the organic compound (Y).
  • polyvinylpyrrolidone (Z) as an essential component in addition to the composite of the metal nanoparticles (X) and the organic compound (Y).
  • Polyvinyl pyrrolidone (Z) may be added to the aqueous dispersion of the complex of the organic compound (Y) and metal nanoparticles (X) obtained by the above preparation method, or an excess complexing agent, reduced
  • a purification process in which various kinds of purification methods such as ultrafiltration, precipitation, centrifugation, vacuum distillation, and vacuum drying are used alone or in combination of two or more for counter ions contained in the metal compound used as an agent or raw material. You may add to what passed, and what was newly re-prepared as a dispersion by changing a density
  • the weight average molecular weight (hereinafter abbreviated as “Mw”) of the polyvinyl pyrrolidone (Z) used in the present invention is superior in dispersion stability, even when it is heated or thawed after freezing.
  • the range of 10,000 to 1,000,000 is preferable, and the range of 30,000 to 500,000 is more preferable from the viewpoint of providing an aqueous dispersion of metal nanoparticles having high adsorptivity and surface activity at the same time.
  • the weight average molecular weight is a value obtained by measurement by gel permeation chromatography (GPC) method.
  • the polyvinyl pyrrolidone used in the present invention may be synthesized using a known and commonly used method, or a commercially available product may be used.
  • Examples of the commercially available products include “Pittscall K-30” (Mw: 40,000), “Pittscall K-90” (Mw: 360,000) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.
  • the added amount of the polyvinyl pyrrolidone (Z) is the metal from the viewpoint of simultaneously satisfying excellent dispersion stability, high adsorptivity to the substrate, and surface activity even when heated or thawed after freezing.
  • the range of 0.1 to 20% by mass is preferable with respect to 100 parts by mass of the composite of the nanoparticles (X) and the organic compound (Y), more preferably 0.5 to 15 parts by mass.
  • the range of 10 parts by mass is more preferable, and the range of 2 to 8 is particularly preferable.
  • the concentration of the composite in the aqueous dispersion is in the range of 0.5 to 40% by mass.
  • the range of 1 to 30% by mass is more preferable.
  • a method of applying a composite of the metal nanoparticles (X) and the organic compound (Y) on a substrate when wiring and conductive layer formation are performed using the metal nanoparticle aqueous dispersion of the present invention as an ink and a coating liquid.
  • the metal nanoparticle aqueous dispersion of the present invention as an ink and a coating liquid.
  • various known and commonly used printing / coating techniques may be appropriately selected depending on the shape, size, degree of flexibility, and the like of the substrate to be used.
  • gravure method Specifically, gravure method, offset method, gravure offset method, letterpress method, letterpress inversion method, flexo method, screen method, microcontact method, reverse method, air doctor coater method, blade coater method, air knife coater method, squeeze coater Method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, ink jet method, die method, spin coater method, bar coater method and the like.
  • the composite is printed or coated on a substrate and the composite is applied on the substrate to form a wiring or conductive layer, the printed or coated substrate is dried and fired.
  • the wiring and the conductive layer may be directly formed, or electroless or electrolytic plating may be performed.
  • the metal nanoparticle aqueous dispersion of the present invention can also be used as a catalyst solution for electroless plating used in a normal plating treatment step by immersion treatment.
  • the metal nanoparticle aqueous dispersion of the present invention is used as a catalyst for electroless plating, the amount of adsorption to the object to be plated can be secured, and the adhesion of the plating film to the object to be plated can be improved.
  • the concentration of the composite in the metal nanoparticle aqueous dispersion is preferably in the range of 0.05 to 5 g / L, and more preferably in the range of 0.02 to 2 g / L in view of economy.
  • the object to be plated with the composite in the metal nanoparticle aqueous dispersion of the present invention attached to the surface thereof is subjected to a known electroless plating treatment, whereby a metal film is efficiently applied to the surface. Can be formed.
  • Examples of the aqueous medium used in the metal nanoparticle aqueous dispersion of the present invention include water alone and a mixed solvent of water and an organic solvent compatible with water.
  • the organic solvent can be selected without particular limitation as long as it does not impair the dispersion stability of the composite and does not damage the object to be plated.
  • Specific examples of the organic solvent include methanol, ethanol, isopropanol, acetone and the like. These organic solvents can be used alone or in combination of two or more.
  • the mixing ratio of the organic solvent is preferably 50% by mass or less from the viewpoint of dispersion stability of the composite, and more preferably 30% by mass or less from the viewpoint of convenience in the plating step.
  • the base material to which the composite of the metal nanoparticles (X) and the organic compound (Y) is applied using the metal nanoparticle aqueous dispersion of the present invention is not particularly limited.
  • the metal nanoparticle aqueous dispersion of the present invention provides a composite of metal nanoparticles and an organic compound on a substrate by a simple method such as printing, coating, or dipping. It can be formed and can be suitably used as a catalyst solution for electroless plating.
  • sample analysis The sample was analyzed using the following apparatus. Observation with a transmission electron microscope (TEM) was performed with “JEM-1400” manufactured by JEOL Ltd. Ultraviolet-visible absorption spectrum measurement was performed with ThermoFisher Scientific (“Nanodrop ND-1000”).
  • Light Ester P-1M methoxypolyethylene glycol methacrylate (Nippon Corporation “Blenmer PME-1000”, molecular weight 1,000) 80 parts by mass , A mixture of 4.1 parts by weight of methyl 3-mercaptopropionate and 80 parts by weight of MEK and a polymerization initiator (Wako Pure Chemical Industries, Ltd. “V-65”, 2,2′-azobis (2,4-dimethylvaleronitrile) ) A mixture of 0.5 parts by mass and 5 parts by mass of MEK was added dropwise over 2 hours.
  • a polymerization initiator (“Perbutyl O” manufactured by NOF Corporation) was added twice every 4 hours, and the mixture was stirred at 80 ° C. for 12 hours. Water was added to the obtained resin solution for phase inversion emulsification, and after desolvation under reduced pressure, water was added to adjust the concentration to obtain an aqueous solution of a polymer (Y2-1) having a nonvolatile content of 76.8% by mass. It was.
  • This polymer (Y2-1) has a methoxycarbonylethylthio group, a phosphoric acid group and a polyethylene glycol chain, and its weight average molecular weight (polystyrene conversion value measured by gel permeation chromatography) is 4. 300, and the acid value was 97.5 mgKOH / g.
  • Example 1 To 272.5 parts by mass of the silver nanoparticle aqueous dispersion obtained in Preparation Example 1 (100 parts by mass as a silver nanoparticle-containing complex), polyvinyl pyrrolidone (“Pitscol K-30” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) After adding 20 parts by mass of a 20% by mass aqueous solution (Mw: 40,000) (4 parts by mass as polyvinylpyrrolidone), the mixture is stirred uniformly and ion-exchanged so that the concentration of the silver nanoparticle-containing complex is 10% by mass. Water was added to obtain a silver nanoparticle aqueous dispersion (1).
  • Pitscol K-30 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • a slide glass is prepared as a base material.
  • the slide glass is immersed in a 2% by weight aqueous solution of polyethyleneimine (“Epomin SP-200” manufactured by Nippon Shokubai Co., Ltd.) for 1 minute, taken out, washed with running water for 1 minute, and then air blown.
  • the surface-treated slide glass was obtained by draining with
  • an aqueous solution containing copper sulfate pentahydrate 0.04 mol / L, formaldehyde 0.04 mol / L, and ethylenediaminetetraacetic acid disodium 0.08 mol / L was adjusted to pH with sodium hydroxide.
  • a solution adjusted to 12.3 was prepared, and a solution heated to 55 ° C. was prepared.
  • the slide glass surface-treated above is immersed in a 200-fold diluted silver nanoparticle aqueous dispersion (1) obtained above at 25 ° C. for 10 minutes to adsorb the silver nanoparticles on the surface of the slide glass. It was. Since the silver nanoparticles were colored at this time, the slide glass colored yellow as the amount of silver nanoparticles adsorbed on the slide glass surface increased. The degree of coloring was visually observed, and the adsorptivity to the base material was evaluated according to the following criteria with the additive-free additive (Comparative Example 1) described below as a standard. ⁇ : Equivalent to those without additives. (Triangle
  • the glass was immersed in the electroless copper plating bath prepared above for 30 minutes with air stirring, then taken out and washed with water for 1 minute. And electroless copper plating was applied.
  • Black and white binarization was performed on the basis of lightness by image processing of a slide glass plated with electroless copper, and the plating coverage was calculated from the area of the plated portion.
  • the activity of the silver nanoparticle composite was evaluated from the obtained plating coverage.
  • the catalytic activity is sufficiently high, plating is deposited on the entire surface of the substrate, and when the activity is reduced, the deposition area of the plating is reduced. Therefore, it was judged that the activity of the silver nanoparticle composite was good when the entire surface of the slide glass was plated (plating coverage: 100%).
  • Example 2 Silver nanoparticle water dispersion was carried out in the same manner as in Example 1 except that the 20% by mass aqueous polyvinylpyrrolidone solution used in Example 1 was changed from 20 parts by mass to 10 parts by mass (2 parts by mass as polyvinylpyrrolidone). A liquid (2) was obtained. Further, the obtained silver nanoparticle aqueous dispersion (2) was measured and evaluated in the same manner as in Example 1.
  • Example 3 Silver nanoparticle water dispersion was carried out in the same manner as in Example 1 except that the 20% by mass aqueous polyvinylpyrrolidone solution used in Example 1 was changed from 20 parts by mass to 50 parts by mass (10 parts by mass as polyvinylpyrrolidone). A liquid (3) was obtained. Further, the obtained silver nanoparticle aqueous dispersion (3) was measured and evaluated in the same manner as in Example 1.
  • Example 4 The polyvinyl pyrrolidone used in Example 1 was changed to polyvinyl pyrrolidone (Daiichi Kogyo Seiyaku Co., Ltd. “Pitzkor K-90”, Mw: 360,000), and the concentration of the aqueous solution was changed to 10% by mass. The same operation as in Example 1 was carried out to obtain a silver nanoparticle aqueous dispersion (4). Further, the obtained silver nanoparticle aqueous dispersion (4) was measured and evaluated in the same manner as in Example 1.
  • Silver nanoparticle aqueous dispersions (R2) to (R15) were prepared in the same manner as in Example 1 except that polyvinylpyrrolidone used in Example 1 was changed to the additives and addition amounts shown in Table 1. did.
  • the obtained silver nanoparticle aqueous dispersions (R2) to (R15) were subjected to measurement and evaluation of dispersion stability and activity in the same manner as in Example 1.
  • Table 1 shows the additives of the silver nanoparticle aqueous dispersions (1) to (4) and (R1) to (R15) obtained in Examples 1 to 4 and Comparative Examples 1 to 15, their addition amounts, and evaluation results. Shown in In addition, the addition amount of Table 1 represents the quantity of the additive with respect to 100 mass parts of silver nanoparticle containing composites (complex of a metal nanoparticle (X) and an organic compound (Y)).
  • the appearance change after the heating test that is “present” indicates that the particles are suspended in gray due to aggregation of silver nanoparticles.
  • “existence” in the appearance change after the freeze-thaw test indicates that the liquid color changed from yellow to black-green due to the change in plasmon absorption based on the aggregation of silver nanoparticles.
  • the metal nanoparticle dispersions of Examples 1 to 4 of the present invention were excellent even when subjected to a thermal load such as heating or repeated thawing operations after freezing. It was confirmed that it had dispersion stability and sufficient adsorptivity to the substrate.

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Abstract

La présente invention concerne une dispersion aqueuse de nanoparticules métalliques qui contient des corps composites de nanoparticules métalliques (X) et un composé organique (Y) (à l'exclusion de corps composites dans lesquels le composé organique (Y) est un polyvinyl pyrrolidone) et un polyvinyl pyrrolidone (Z). La présente invention concerne également la dispersion aqueuse de nanoparticules métalliques dans laquelle le composé organique (Y) est un polymère d'un mélange de monomères qui contient un monomère acide (méth)acrylique comprenant un ou plusieurs groupes fonctionnels anioniques choisis dans le groupe constitué par un groupe carboxy, un groupe acide phosphorique, un groupe acide phosphoreux, un groupe acide sulfonique, un groupe acide sulfinique et un groupe acide sulfénique. Ladite dispersion aqueuse de nanoparticules métalliques présente une excellente stabilité de dispersion même dans des cas où une charge thermique telle qu'un chauffage ou une congélation suivie d'une fusion susceptibles de se produire pendant le stockage ou le transport lui sont appliquées, tout en présentant une activité de surface et une adsorption suffisante à un substrat.
PCT/JP2017/029888 2016-08-25 2017-08-22 Dispersion aqueuse de nanoparticules métalliques WO2018038086A1 (fr)

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CN113649587A (zh) * 2021-07-14 2021-11-16 上海涂固安高科技有限公司 一种包含金属纳米颗粒的无机/聚合物复合纳米颗粒及应用

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