WO2014172856A1 - Metal nanoparticle-protecting polymer and metal colloidal solution, and method for producing the same - Google Patents

Metal nanoparticle-protecting polymer and metal colloidal solution, and method for producing the same Download PDF

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Publication number
WO2014172856A1
WO2014172856A1 PCT/CN2013/074612 CN2013074612W WO2014172856A1 WO 2014172856 A1 WO2014172856 A1 WO 2014172856A1 CN 2013074612 W CN2013074612 W CN 2013074612W WO 2014172856 A1 WO2014172856 A1 WO 2014172856A1
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Prior art keywords
metal
segment
metal nanoparticle
protecting polymer
colloidal solution
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PCT/CN2013/074612
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English (en)
French (fr)
Inventor
Seungtaeg EE
Zongwu YAO
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Dic Corporation
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Application filed by Dic Corporation filed Critical Dic Corporation
Priority to KR1020157023902A priority Critical patent/KR101927766B1/ko
Priority to KR1020177008889A priority patent/KR20170040368A/ko
Priority to CN201380075890.6A priority patent/CN105164183B/zh
Priority to JP2015512999A priority patent/JP5811430B2/ja
Priority to PCT/CN2013/074612 priority patent/WO2014172856A1/en
Priority to TW103114604A priority patent/TWI613255B/zh
Publication of WO2014172856A1 publication Critical patent/WO2014172856A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0206—Polyalkylene(poly)amines

Definitions

  • the present invention relates to a metal colloidal solution that uses, as a protecting agent for metal nanoparticles, a polymer that contains an acetylated polyalkylenimine segment and a hydrophilic segment or a polymer that contains a hydrophobic segment in addition to the aforementioned two segments, and a method for producing the metal colloidal solution. It also relates to the aforementioned polymers and a method for producing the polymers,
  • Metal nanoparticles are nanoparticles having a particle diameter of one to several hundred nanometers and a significantly large specific surface area. Metal nanoparticles having such properties are drawing much attention from, various fields and there is a nigh expectation for use in electronic materials, catalysts, magnetic materials, optical materials, various sensors, coloring materials, and medical examination.
  • a printable electronic device production technology involves preparing ink compositions by dispersing recently developed metal nanoparticles in media, forming patterns by printing using the ink compositions, and assembling the patterns into devices.
  • Print electro ics offer prospects for roll-to-roll mass production of electronic circuit patterns and semiconductor elements and economical efficiency since the technology is suited for on-demand production, simplification of processes, and resource conservation. The technology is also expected to pave the way toward low-cost production processes for display devices, light-emitting devices, IC tags (RFTDs) , etc.
  • Conductive material inks used in the printed electronics can contain metal nanoparticles of gold, silver, platinum, copper, and the like. Due to economical reasons and ease of handling, development of silver nanoparticles and. inks containing the silver nanoparticles has preceded .
  • Silver in form of nanometer-order particles exhibits a significantly large specific surface area and an increased surface energy compared to bulk silver.
  • Silver nanopar icles show a strong tendency to fuse with each other to lower the surface energy.
  • particles fuse with each other at a temperature far below the melting point of bulk silver.
  • This phenomenon is called a quantum size effect (Kubo effect ⁇ and presents an advantage of using silver nanoparticles as a conductive material on one hand.
  • the strong tendency of metal nanoparticles to fuse with each other impairs the stability of the metal nanoparticles and degrades storage stability.
  • the metal nanoparticles need to be protected with a protecting agent that prevents fusion.
  • a liquid phase reduction process is a process for obtaining metal nanoparticles by causing a metal compound to react with a reductant in a solvent. According to a known technology, reduction is performed in the presence of a compound called a dispersion stabilizer or a protecting agent in order: to control the shape and particle size of the metal nanoparticles to be generated and to achieve a stable dispersion state.
  • the protecting agent is often a polymeric compound designed to have a functional group (such as a tertiary amino group, a quaternary ammonium group, a heterocyclic group having a basic nitrogen atom, a hydroxyl group, or a carboxyl group) capable of coordinating with a metal particle (for example, refer to PTL 1 ⁇ .
  • a functional group such as a tertiary amino group, a quaternary ammonium group, a heterocyclic group having a basic nitrogen atom, a hydroxyl group, or a carboxyl group
  • an appropriate protecting agent that controls the shape and particle size of the metal nanoparticles and stabilizes the dispersion is used.
  • a protecting- agent functions as a resistive component for bulk metal and lowers the conductive performance.
  • a desirable low-temperature sintering property the property that the specific resistance of a thin film obtained by firing a thin film of a metal-nanoparticle-containing conductive ink at.
  • the protecting agent is required to exhibit an ability to produce small particles, an ability to stably disperse these particles, and an ability to rapidly detach from the particle surfaces during sintering so as not to inhibit fusion between the metal nanoparticles.
  • the protecting agent is required to exhibit an ability to facilitate purification and separation of metal nanoparticles produced. The protecting agent desirably exhibits all these abilities .
  • Examples of the protective agents disclosed so far include commercially available polymeric pigment dispersants such as Solsperse (trademark, produced by Zeneca) and FLOWLEN (trademark, produced by Kyoeisha Chemical Co. , Ltd. ) , polymers that have a pigment-compatible group (amine) in a main/side chain and two or more solvation segments, and copolymers that nave polyethylene imine segments and polyethylene oxide segments.
  • Solsperse trademark, produced by Zeneca
  • FLOWLEN trademark, produced by Kyoeisha Chemical Co. , Ltd.
  • these dispersants rarely achieve all of the desired abilities described above and further improvements are needed (for example . , refer to PTL 2 to 4 ⁇ .
  • An object of the present invention is to provide a metal nanoparticle-protecting polymer to which various properties, such as an ability to control metal nanopartides, high dispersion stability, a good low-temperature sintering property,, and ease of purifying and separating metal nanoparticles, are intentionally adjusted and imparted, so that a more practical electrical conductivity is exhibited,
  • a metal colloidal solution and methods for producing the metal nanoparticle-protecting polymer and the metal colloidal solution are also provided.
  • the inventors of the present invention have already disclosed (refer to PTL 4 ⁇ that a binary system polymer in which a polyalkylenirnine segment containing polyethyienimine is linked with a hydrophilic segment containing a polyoxyalkylene chain and a ternary system polymer in which a hydrophobic segment such as an epoxy resin is linked to the binary system polymer are useful for producing metal nanoparticles.
  • a binary system polymer in which a polyalkylenirnine segment containing polyethyienimine is linked with a hydrophilic segment containing a polyoxyalkylene chain and a ternary system polymer in which a hydrophobic segment such as an epoxy resin is linked to the binary system polymer are useful for producing metal nanoparticles.
  • the properties described above have not been sufficiently achieved.
  • the inventors have found that it is effective to use a polymer in which nitrogen atoms in the polyalkylenimine segment are acetylated, and. made the present invention.
  • the present invention provides a metal nanoparticle-protecting polymer that includes , in a molecule, a polyacetylalkylenimine segment (A) in which 5 to 100 mol% of primary amines in polyalkylenimine are acetylated and 0 to 50 mol% of secondary amines in polyalkylenimine are acetylated; and a hydrophilic segment (B) .
  • the present invention also provides a. method for producing the metal nanoparticle-protecting polymer, a metal colloidal solution that contains metal nanoparticle-containing composite bodies dispersed in a medium, the composite bodies being prepared, by using the metal nanoparticle-protecting- polymer as a protecting agent, and a method for producing the metal colloidal solution.
  • a metal colloidal solution obtained, in the present invention exhibits a good low-temperature sintering property.
  • a thin film of obtained by firing the metal colloidal solution at low temperature exhibits good, cond.uct.ive performance since the protecting polymer used in. the present invention readily detaches from the surfaces of the metal nanoparticles at low temperature.
  • the size of the metal nanoparticles obtained in the presence of this particula protecting polymer is sufficiently small, monodisperse, and narrow in particle size distribution.
  • the storage stability is also high. This is because the acetylalkylenimine structural units in the protecting polymer protect the metal nanoparticles well and the hydrophilic segment or the hydrophobic segment in the polymer causes the particles to disperse in the medium.
  • the dispersion stability of the dispersion is not impaired and the dispersion retains a stable dispersion state in a solvent for a long time.
  • metal nanoparticles are obtained by reduction and, in the following purification and separation step of removing irapurit ies , coraposi te bodies con st. itut.ed by met.a.1 nan.opartic1es and the protecting polymer easily settle and become separated by a simple operation of adding a poor solvent to a dispersion of the composite bodies. This is achieved due to strong association torce of thie protect in.g polymer . Since coraplicated steps and elaborate condition settings are rarely needed, this method is industriously advantageous .
  • the metal nanoparticles in the metal colloidal solution obtained in the present invention have a large specific surface area, high surface energy, and plasmon absorption, which are the characteristics of metal nanoparticles.
  • the dispersion stability and storage stability can be efficiently exhibited because the polymer dispersion is of a self assembly type .
  • the metal colloidal solution has various chemical, electrical, and magnetic properties required of the conductive paste or the like and can be used in a wide variety of fields, such as catalysts, electronic materials, magnetic materials, optical materials, various sensors, coloring materials, and medical examination use.
  • a metal nanoparticle-protecting polymer of the present invention is a polymeric compound that has a hydrophiiic segment (B) and a polyacetylalkylenimine segment (A) in which 5 to 100 mol% of primary amines and 0 to 50 mol% of secondary amines in polyalkylenimine are acetylated or a polymeric compound, that has the polyacetylalkylenimine segment (A), the hydrophiiic segment (B) , and a hydrophobic segment. (C) .
  • a dispersion (metal colloidal solution) of metal nanoparticl.es protected with a. protecting polymer having such a structure has high dispersion stability and good conductive properties and exhibits various functions of metal-containing functional dispersion derived from metal, nanoparticl.es such as coloring, catalyzing, and. electrical functions.
  • the polyacetylalkylen.im.ine segment (A) in the protect ing polymer of the present invention is acetylated to a particular degree. Since the acetylalkylenimine units in the segment can form coordinate bonds with a metal or a metal ion, the polyacetylaIkylend,mine segment (A) is a segment that can immobilize the metal as nanopart icles , When the metal nanoparticles obtained in the present invention are protected with the protecting polymer to form composite bodies and the composite bodies are produced and. stored in hydrophilic solvents, a. metal colloidal, solution obtained, can exhibit excellent dispersion stability and storage stability due to incorporation of the polyacetylalkylenimine segment (A) and the hydrophilic segment (B) that exhibit hydrophilicity in the solvents.
  • this purification and separation method involves settling achieved by adding a poor solvent such as acetone to the solution after the reaction.
  • the acetylalkylenimine units in the protecting polymer of the present invention have high polarity and thus promote rapid association of the metal-nanoparticle-containing composite bodies. Accordingly, settling easily occurs while blocks of large 3. S S O Ciated particles are formed.
  • a metal colloidal, solution which is a dispersion of metal nanoparticle-containing composite bodies or a conductive material obtained by using the metal colloidal solution to form a conductive ink is printed on or applied to a substrate.
  • the acetylalkylenimine units in the protecting polymer easily decouple from the metal nanoparticle surfaces even at low temperature because coordinate bonds between the units and the metal are weak. As a result, a good low-temperature sintering property is exhibited.
  • the particle size of the dispersed bodies (composite bodies ⁇ in the metal colloidal solution of the present invention is dependent not only on the molecular weight of the protecting polymer used and the degree of polymerization of the polyacetylalkylenimine segment (A) but also on the structure and compositional ratios of the components constituting the protecting polymer, namely, the polyacetylalkylenimine segment
  • the degree of polymerization of the polyacetylalkylenimine segment (A) is not particularly limited. At an excessively low degree of polymerization, the protecting polymer may not exhibit sufficient ability to protect metal nanoparticles . At an excessively high degree of polymerization, the size of the composite particles constituted by the metal nanopartides and the protecting polymer may become excessively large, thereby degrading storage stability. Accordingly, in order to enhance the metal nanoparticle immobilizing ability and prevent generation of gigantic dispersed particles, the number of alkylenimine units (degree of polymerization) in the polyacetylalkylenimine segment (A) is usually in the range of 1 to 10,000, preferably in the range of 5 to 2,500, and most preferably in the range of 5 to 300.
  • the polyacetylalkylenimine segment (A) can be easily obtained by acetylating the alkylenimine portion i the precursor structure which is a polyalkylenimine segment.
  • the polyacetylalkyleniitiine segment (A) can be obtained by reaction using an acetylating agent.
  • a segment constituted by polyalkylenimine may be any commercially available or synthesizable segment. From the viewpoint of industrial availability, the segment is preferably constituted by branched polyethylenimine or branched polypropylenimine and more preferably branched polyethylenimine .
  • hydrophilic segment In the case where a hydrophilic solvent such as water is used to prepare a metal colloidal solution, the hydrophilic segment
  • the hydrophilic segment (B) in the protecting polymer of the present invention exhibits high compatibility with the solvent and retains storage stability of the colloidal solution.
  • the hydrophilic segment (B) having strong intramolecular or intermolecular association force helps form cores of dispersed particles .
  • the degree of polymerization of the hydrophilic segment (B) is not part.icula.rly limited.
  • the storage stability is degraded at an excessively low degree of polymerization and. aggregation may occur at an excessively high degree of polymerization.
  • the degree of polymerization of the hydrophilic segment ( B ) is usually 1 to 10,000, preferably 3 to 3,000, and, based on ease of production, more preferably 5 to 1, 000.
  • the degree of polymerization is particularly preferably 5 to 500.
  • the hydrophilic segment (B) may be any segment composed, of a hydrophilic polymer chain that is commercially available or synthesizable. In the where a hydrophilic solvent is used, the hydrophilic segment (B) is preferably composed of a nonionic polymer since a highly stable colloidal solution is obtained. [0024]
  • hydrophilic segment (B) examples include polyoxyalkylene chains such as a polyoxyethylene chain and polyoxypropylene chain f polymer chains composed of polyvinyl alcohols such as polyvinyl alcohol and partially saponified polyvinyl alcohol, polymer chains composed of water-soluble poly (meth) acrylic acid esters such as polyhydroxyethyl acrylate, polyhydroxyethyl methacrylate , dimethylaminoethyl acrylate, and dimet.hy.1aminoethy1 methacry1ate, hydrophilic-subs tituent-containing poiyacylalkylenimine chains such as polyacetylethylenimine, polyacetylpropylenimine, polypropionylethylenimine , and polypropionylpropylenimine, and polymer chains composed of polyacrylamides such as po1yacry1arnide , po1yisopropy1acry1amide , and polyvinylpyrrolidone
  • the protecting polymer may further contain a hydrophobic segment (C) .
  • a hydrophobic segment (C) when an organic solvent is used as a medium for the metal colloidal solution, it is preferable to use a polymer containing a hydrophobic segment (C) as a protecting agent.
  • the hydrophobic segment (C) may be any segment composed of a residue of a hydrophobic compound that is commercially available or synthesizafole .
  • the hydrophobic segment (C) include those composed of residues of polymers such as polystyrenes, e.g., polystyrene, polymethylstyrene, polychloromethylstyrene, and polybromomethylstyrene, water-insoluble poly (meth) acrylic acid esters, e.g., po1ymet.hy.1 acry1ate, po1ymethy1 metha.cry1ate, po1y (2-ethy1hexy1 acry1ate ⁇ , and po1 y (2-ethy1hexy1 methacrylate) , and hydrophofoic-substituent-containing polyacylalkylenimines such as polybenzoylethylenimine , po.1yben zoy.
  • the hydrophobic segment (C) maybe composed of a residue of a. single compound or a residue of a compound obtained by preliminarily reacting two or more different types of compounds.
  • the hydrophobic segment (C) preferably has a structure derived from an epoxy resin and more preferably has a structure derived from a bisphenol A-type epoxy resin since a protecting polymer can be easily industrially synthesized and a metal colloidal solution obtained therewith exhibits high adhesion to a substrate when printed or applied.
  • the degree of polymerization of the hydrophobic segment (C) is not particularly limited but is usually 1 to 10, 000, and preferably 3 to 3,000 and more preferably 10 to 1,000 if the hydrophobic segment (C) is a polystyrene, a poly (meth) acrylic acid ester, a ydrop obic-substi tuent-containing polyacylalkylenimine, or the like.
  • the hydrophobic segment (C) is composed of a residue of a resin such as an epoxy resin, a polyurethane, a polycarbonate, or the like
  • the degree or polymerization is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20.
  • the metal nanoparticie-pro ecting polymer of the present invention may be made by allowing an acetylation agent to react with a precursor compound (I) which is either a compound having a polyalkylenimine segment and a. hydrophilic segment (B) or a compound having a polyalkylenimine segment, a hydrophilic segment (B) , and a hydrophobic segment (C) .
  • a precursor compound (I) which is either a compound having a polyalkylenimine segment and a. hydrophilic segment (B) or a compound having a polyalkylenimine segment, a hydrophilic segment (B) , and a hydrophobic segment (C) .
  • an acetylating agent may be used during performance of a reaction for preparing a precursor compound (I) from a. polyalkylenimine segment and a hydrophilic segment (B) .
  • an as-designed protecting polymer can be easily obtained.
  • the nitrogen ato s of the primary amines and/or secondary amines in the polyalkylenimine segment are acetylated.
  • the nitrogen atoms of primary amines and/or secondary amines in the polyalkylenimine segment are acetylated.
  • the acetylation reaction is performed by adding an acetylating agent that has an acetyl structure (CH 3 -CO-) .
  • a common industrial acetylating agent can be used as the acetylating agent.
  • the acetylating agent include acetic anhydride, acetic acid, dimethylacetamide, ethyl acetate, and chlorinated acetic acid.
  • acetic anhydride, acetic acid, and dimethylacetamide are particularly preferable from the viewpoints of availability and ease of hand1 ing .
  • the polyalkylenimine segment is derived from a branched polyalkylenimine compound, primary, secondary, and tertiary amines are contained homogeneously and at random.
  • this polyalkylenimine segment is reacted with any of the acetylating agent described above, one acetyl group oxygen is offered per nitrogen atom in the primary amines and/or secondary amines while leaving the tertiary amine un-acetylated .
  • the acetylation reaction proceeds on the primary amine and the secondary amine that have higher quantitative reactivity with the acetylating- agent used.
  • the acetylation ratio for the acetylation reaction in terms of the acetylation ratio of the primary amine and secondary amine is investigated. As a result, it has been found that a protecting polymer having good electrical conductivity, dispersion stability, and an ability to facilitate purification and separation is obtained when 5 to 100 mol% of the primary amines in the polyalkylenimine segment and 0 to 50 mol% of the secondary ami es in the polyalkylenimine segment are acetylated. [0032]
  • the acetylalkylenimine units smoothly decouple from the metal nanoparticle surfaces even at low temperature due to weak coordination bonding force with the metal compa ed to the alkylenimine units and a good low-temperature sintering- property is exhibited as a result.
  • the resulting metal nanoparticle-protecting polymer has lower dispersion stability (ability to stabilize metal nanoparticles) than that formed by using alkylenimine units.
  • the dispersion stability is degraded by stronger association force.
  • the dispersion stability and the low-temperature sintering property are in a trade-off relationship.
  • the ranges of the acetylation described above have been limited from, the viewpoints of the storage stability of the metal colloidal solution obtained and the low-temperature sintering property of the coating films formed of the metal colloidal solution.
  • the metal nanoparticle-protecting polymer of the present invention contains a hydrophilic segment (B) and, optionally, a hydrophobic segment (C) in addition to the polyacetylalkylenimine segment (A ) that can stabilize the metal nanoparticles.
  • the hydrophilic segment (B) exhibits strong association force in a hydrophobic solvent and high compatibility with a hydrophilic solvent
  • the hydrophobic segment (C) exhibits strong association force in a hydrophilic solvent and high compatibility with a hydrophobic solvent.
  • the hydrophobic segment (C) contains a aromatic ring, the pi electron of the aromatic ring interacts with the metal and contributes to stabilization the metal nanoparticles.
  • the ratio of the number of moles of the polymer constituting the chain of the polyacetylalkylenimine segment (A) to the number of moles of the polymer constituting the chain of the hydrophilic segment ( B ) , that is, the molar ratio (A) : (B) , is not particularly limited.
  • the ratio is usually i the range of 1: (1 to 100 ⁇ and preferably 1: (1 to 30) from the viewpoints of the dispersion stability and. storage stability of a metal colloidal solution ob ained.
  • the protecting polymer also contains a hydrophobic segment (C) , the ratio of the number of moles of the polymer constituting the chain of the polyacetylalkylenimine segment (A) , the number of moles of the polymer constituting the chain of the hydrophilic segment (B) , and the number of moles of the polymer constituting the chain of the hydrophobic segment
  • the weight -average molecular weight of the metal nanoparticle-protecting polymer of the present invention is preferably in the range of 1,000 to 500,000 and more preferably in the range of 1,000 to 100,000.
  • the protecting polymer of the present invention is dispersed or dispersed in various media and used in production of metal colloidal solutions.
  • the material used as the media is not particularly limited and the dispersion may be of an oil/water (O/W) system or of a water/oil (W/O) system.
  • the medium may be selected according to the metal colloidal solution production process and/or usage of the metal colloidal solution.
  • a hydrophilic solvent, a hydrophobic solvent, a mixed solvent containing hydrophilic and hydrophobic solvents, or a mixed solvent that contains other solvent in addition to the foregoing as described below may be selected and used.
  • the amount of the hydrophilic solvent is adjusted to be larger than that of the hydrophobic solvent for an O/W system and the amount of the hydrophobic solvent is adjusted to be larger than that of the hydrophilic solvent for a W/O system.
  • the mixing ratio is not particularly limited since the ratio depends on the types of the solvents used.
  • the volume of the hydrophilic solvent is preferably 5 times or more larger than that of the hydrophobic solvent and for a W/O system, the volume of the hydrophobic solvent is preferably 5 times or more larger than that of the hydrophi1 ic so1 ent .
  • hydrop ilic solvent examples include methanol, ethanol, isopropyl alcohol, tetrahydrofuran, acetone, dimethylacetamide, dimethylformamide, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, dimethyl sulfone oxide, dioxirane, and N-methylpyrrolidone . These can be sed alone or in combination.
  • hydrophobic solvent examples include hexane, cyclohexane, ethyl acetate, butanol, methylene chloride, chloroform, chlorobenze e, nitrobe zene, methoxybenze e, toluene, and xylene. These can be sed alone or in combi ation.
  • hydrophobic solvent examples include ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monomethy1 et.her acetate.
  • the metal nanoparticle-protecting polymer may be dispersed in a medium by any method. Typically, the metal nanoparticle-protecting polymer is easily dispersed by leaving the polymer to stand still or by stirring at room temperature. If needed, a ultrasonic treatment or a neat treatment may be carried out. In the case where the protecting polymer is not readily compatible with the medium due to its crystal linity or the like, the protecting polymer may be dissolved or allowed to swell in a small amount of a good solvent and then dispersed in a desired medium. It is effective to employ an ultrasonic treatment or heat treatment during this process.
  • a mixture of a hydrophilic solvent and a hydrophobic solvent may be prepared by any mixing method and mixing order, etc . Since the compatibility of the protecting polymer with various solvents and the dispersibility of the protecting polymer differ depending on the type, composition, and. other factors of the protecting polymer, the solvent mixing ratio, the order of mixing the solvents, the method for mixing the solvents, mixing conditions, and the like may be appropriate selected based on the purpose.
  • metal ions are reduced in the solution or dispersion of the protecting polymer to form metal nanoparticles .
  • the source of the metal ions maybe a salt or an ionic solution of a metal.
  • the source of the metal ion may be any water-soluble metal compound, for example, a salt of a. metal cation and an acid group anion or an acid group anion containing a metal.
  • metal ions that have metal species such as transition metals are preferably used.
  • the transition metal ion can be smoothly coordinated to form a complex irrespective of whether the ion is a transition metal cation (MTM) or an anion (ML x n ⁇ ) constituted by a halogen bond.
  • MTM transition metal cation
  • ML x n ⁇ anion constituted by a halogen bond.
  • a transition metal refers to a. transition metal element in 4 to 12 groups and 4 to 6 periods of the periodic table.
  • transition metal cation examples include the cations (M lt ) of the transition metals such as monovalent, divalent, trivalent, or tetravalent cations of Cr, Co, Ni, Cu, Pd, Ag, Pt, Au, and the like.
  • the counter anion of the metal cation may be CI, NO3, SO 4 , or an organic anion of a. carboxylic acid.
  • An anion in which a metal is coordinated with a halogen such as a metal-containing anion (ML x n ⁇ ) , e.g., AgNOs, AUCI 4 , PtCl 4 , or CuF ⁇ 5, can also smoothly coordinate to form a. complex.
  • a metal-containing anion e.g., AgNOs, AUCI 4 , PtCl 4 , or CuF ⁇ 5
  • the ions of silver, gold, and platinum are preferred since these are spontaneously reduced at room temperature or under heating into nonionic metal nanoparticles.
  • silver ions are preferably used to develop electrical conductivity and prevent oxidation of a coating film obtained by printing or applying the metal colloidal solution ,
  • the number of metal species to be contained may be two or more.
  • salts or ions of plural metals are added either simultaneously or separately so that the metal ions of different species undergo a reduction reaction in a medium and metal particles of different species are generated.
  • a colloidal solution that contains plural species of metals can be obtained.
  • metal ions may be reduced by using a reductant .
  • the reductant may be any of a variety of reductants. The selection may be made based, on the usage of the metal colloidal solution obtained, metal species contained, etc.
  • the reductant include hydrogen, boron compounds such as sodium borohydride and. ammonium borohydride, alcohols such as methanol, ethanol, propanol, isopropyl alcohol, ethylene glycol, and propylene glycol, aldehydes such as formaldehyde, acetaldehyde, and propionaldehyde, acids such as ascorbic acid, citric acid, and sodium citrate, amines such as propylamine, butylamine, diethy1a ine , dipropylamine, dimethylethylamine, triethylamine, ethylenediamine, triethylenetetramine, methy1aminoethano1 , dimethylaminoethanol, and triethanolamine, and hydrazines such, as hydrazine and hyd.raz
  • the ratio of the metal ion source to the protecting polymer used is not particularly limited.
  • the amount of the metal is usually in the range of 1 to 20, 000 rnol, preferably in the range of 1 to 10 , 000 mol, and more preferably in the range of 50 to 7,000 mol .
  • the medium in which the protecting polymer is dispersed or dissolved may be mixed with a metal salt or an ionic solution by any method.
  • a metal salt or an ionic solution may be added to a medium in which the protecting polymer is dispersed or dissolved or vice versa, or a protecting polymer and a metal salt or ionic solution may be simultaneously fed to a separate container and mixed.
  • the mi ing method is not particularly limited and may be stirring.
  • the reductant may be added by any method.
  • a reductant. may be directly added or a reductant. may be dissolved or dispersed in an aqueous solution or other solvent and then mixed.
  • the order of adding the reductant is not particularly limited.
  • A. reductant. may be preliminarily added to a dispersion or solution of a protecting polymer or a reductant may be added to the protecting polymer together with a metal salt or an ionic solution.
  • a solution or dispersion of a protecting polymer may be mixed, with a metal salt or an ionic solution and then a reductant may be added thereto after several days or several weeks.
  • the metal salt or ionic solution thereof is preferably added either directly or in the form of an aqueous solution irrespective of whether the system is O./W or W/O.
  • the metal ion coordinates to the acetylalkylenimine unit in the polymer and then sponta.neou.sly reduced at room temperature or under heating.
  • a reductant is preferably used as discussed above and a metal colloidal solution can be obtained by leaving the ions still or stirring the ions at room temperature or under heating.
  • the reductant is preferably used as is or prepared into an aqueous solution in advance.
  • the temperature at which heating is conducted differs depending on the types of the protecting polymer and types of the metal, medium, and reductant used, for example. Generally speaking, the temperature is 100 deg C or less and preferably 80 deg C or less.
  • Metal nanoparticles precipitate as a result of reduction of metal ions described above and, at the same time, surfaces of these particles are protected with the protecting polymer that stabilizes the particles.
  • the solution after the reduction contains impurities such as the reductant, counter io s of the metal ions, and the protecting polymer not contributing- to the protection of the metal nanoparticles and thus cannot perform sufficiently as a conductive material. Accordingly, a purification step of removing the impurities is needed. Since the protecting polymer of the present invention has high protecting performance, a poor solvent can be added to the solution after the reaction to efficiently settle the composite bodies constituted by metal nanoparticles protected, with the protecting polymer. The settled composite bodies can be concentrated or isolated through centrifugation or the like. After concentration, an appropriate medium is added to control the nonvolatile content (concentration) to suite the usage of the metal colloidal solution and the resulting product is used in various usages.
  • the metal nanoparticle content in the metal colloidal solution obtained in the present invention is not particularly limited. However, if the content is excessively low, the properties of the metal nanoparticles in the colloidal solution are not sufficiently exhibited. If the content is excessively high, the relative weight of the metal nanoparticles in the colloidal solution is increased and the stability of the colloidal solution is anticipated to be poor due to the imbalance between the excessively large relative weight of the metal nanoparticles and the dispersing ability of the protecting polymer .
  • the nonvolatile content in the metal colloidal solution is preferably within the range of 10 to 80 massl and more preferably within the range of 20 to 70 mass%.
  • the metal nanoparticle content in the nonvolatile matter is preferably 93 mass% or more and more preferably 95 mass% or more in order for the colloidal solution used as a conductive material to exhibit satisfactory electrical conductivity.
  • the size of the metal nanoparticles contained in the nonvolatile matter in the metal colloidal solution obtained, in the present, invention is not particularly limited.
  • the metal nanoparticles are preferably fine particles 1 to 70 nm in particle size and more preferably 5 to 50 nm in particle size.
  • metal nanoparticles several ten nanometers in size have characteristic optical absorption induced by surface plasmon excitation dependent on the metal species. Accordingly, whether metals are present by taking a form of nanometer-order fine particles in the solution can be confirmed through measuring the plasmon absorption of the metal colloidal solution obtained in the present invention. Moreover, it is possible to determine the average particle size and the distribution width by using a transmission electron microscope
  • the metal colloidal solution obtained in the present invention stays stably dispersed for a long time in all types of media and thus the usage thereof is not limited.
  • the metal colloidal solution finds its usage in various fields including catalysts, electronic materials, magnetic materials, optical materials, various sensors, coloring materials, and medical exa.mina.tion. uses. Since the metal species and the ratio thereof to be contained are also easily adjustable, the effects desired for the usage can be efficiently exhibited. Moreover, since the solution stays stably dispersed for a long time, the solution can withstand long-term use and long-term storage, which makes the solution highly useful. Moreover, the method for producing the metal colloidal solution according to the present invention does not require complicated steps and elaborate condition settings and. is thus a highly advantageous industrial process.
  • a portion of a metal colloidal solution was diluted with purified water and the particle size distribution and average particle size were determined with FPAR-1000 concentrated-system particle analyzer produced by Otsuka Electronics Co . , Ltd.
  • a coating film was formed by using a bar coater No. 8, The coating film was air-dried and then heated in a hot air drier at 125 deg C and at 180 deg C for 30 minutes to form a fired coating film.
  • the thickness of the fired coating film was measured with an O telics C130 Real Color Confocal microscope (produced by Lasertec Corporation) and the surface resistivity (ohms per square) was measured with Loresta-EP MCP-T360 low resistivity meter (produced by Mitsubishi Chemical Corporation) in accordance with Japanese Indus rial Standard (JIS) K7194 "Testing method for resistivity of conductive plastics with a four-point probe array".
  • JIS Japanese Indus rial Standard
  • the resulting mixture was stirred for 4 more hours at 40 deg C.
  • 50 mL of chloroform was added to dilute the reaction solution .
  • the diluted reaction solution was then washed sequentially with 100 rnL of a 5% aqueous hydrochloric acid solution, 100 mL of an aqueous saturated sodium hydrogen carbonate solution, and 100 mL of a saturated saline, dried over magnesium sulfate, filtered, and concentrated at a reduced pressure.
  • the solid matter obtained was washed with hexane several times, filtered, and dried at 80 deg C at a reduced pressure. As a result, 22.0 g of a tosylated product was obtained .
  • the residue was dried at a reduced pressure and a modified bisphenol A-type epoxy resin was obtained as a result.
  • the yield of the product was 98%.
  • the integrated ratio of the epoxy group was investigated through 1 H- MR measurement . It was found that 0.95 epoxy rings remained per molecule of the bisphenol A-type epoxy resin and that the product was a monof nctional epoxy resin having a bisphenol A skeleton.
  • Delta (ppm) 3.57 (br s, PEGM methylene ⁇ , 3.25 (s, 3H, methoxy group at PEGM chain terminal ⁇ , 3.16 (m, 2H, methylene group next to acetyl N) , 2.65-2.40 (m, branched PEI ethylene ⁇ , 1.90 (br s, 3H, acetyl group of primary N) .
  • Delta (ppm) 21.4 (s) (acetyl group of secondary N) , 22.9 (s) (acetyl group of primary N) , 39.9 (s) , 41.8 (s) , 47.6 (m) , 49.5 (m) , 52.6 (m) , 54.7 (m) , 57.8 (ra) (branched PEI ethylene up to here), 59.0 (s) , 70.5 (m) , 71.8 (s) (PEGM methylene and terminal methoxy group up to here), 173.4 (m) (acetyl group).
  • Delta (ppm) 3.57 (br s, PEGM methylene) , 3.25 (s, 3H, met oxy group at PEGM chain terminal), 3.16 (m, 2H, methylene N next to acetyl N) , 2.65-2.40 (m, branched PET ethylene), 2.11 (br s, 3H, acetyl group of secondary N) , 1,90 (br s, 3H, acetyl group of primary N) .
  • Delta (ppm) 21.4 (s) (acetyl group of secondary N) , 22.9 (s) (acetyl group of primary N) , 39.9 (s) , 41.8 (s) , 47,6 (m) , 49.5 (m) , 52.6 (m) , 54.7 (m) , 57.8 (m) (branched PEI ethylene up to here), 59.0 (s) , 70.5 (m) , 71.8 (s) (PEGM methylene and terminal methoxy group up to here) , 173.4 (m) (acetyl group).
  • Delta (ppm) 3.57 (br s, PEGM methylene) , 3.25 (s, 3H, methoxy group at PEGM chain terminal) , 3.16 (m, 2H, methylene group next to acetyl N) , 2.65-2.40 (m, branched PEI ethylene), 2.11 (br s, 3H, acetyl group of secondary N) , 1.90 (br s, 3H, acetyl group of primary N) .
  • Delta (ppm) 3.57 (br s, PEGM methylene) , 3.25 (s, 3H, methoxy group at PEGM chain terminal) , 3.16 (m, 2H, methylene group next to acetyl M) , 2.65-2.40 (m, branched PET ethylene), 2.11 (br s, 3H, acetyl group of secondary ) , 1.90 (br s, 3H, acetyl group of primary N) .
  • Delta (ppm) 21.4 (s) (acetyl group of secondary ) , 22.9 (s) (acetyl group of primary N) , 39.9 (s) , 41,8 (s) , 47.6 ( ) , 49,5 (m) , 52.6 (m) , 54.7 (m) , 57.8 (m) (branched ⁇ ethylene up to here), 59.0 is) , 70.5 (m) , 71.8 (s) (PEGM methylene and terminal methoxy group up to here), 173.4 (m) (acetyl group).
  • Example 7 synthesis of silver colloidal solution using protecting polymer (1-1) of Example 1]
  • Example 8 synthesis of silver colloidal solution using protecting polymer (1-2) of Examp1e 2 ⁇
  • Example 9 synthesis of silver colloidal solution using protecting polymer (1-3) of Example 3]
  • Example 10 synthesis of silver colloidal solution using protecting polymer (1-4) of Example 4]
  • Example 75.0 g of an aqueous silver colloidal solution (45.6 g in terms of nonvolatile matter, yield: 95%) having a nonvolatile content of about 60% was obtained as in Example 7 except that 17.0 g of an aqueous solution of the protecting polymer (1-4) obtained in Example 4 was used instead of 13.5 g of an aqueous solution of the protecting polymer (1-1) obtained in Example 1.
  • Results of the thermal analysis (Tq/DTA) snowed that the silver content in the nonvolatile matter was 96.1%.
  • Example 11 synthesis of silver colloidal solution using protecting polymer (1-5) of Example 5]
  • Example 12 synthesis of silver colloidal solution using protecting polymer (2-1 ⁇ of Example 6]
  • Example 7 77.0 g of an aqueous silver colloidal solution (45.5 g in terms of nonvolatile matter, yield: 95%) having a nonvolatile content of about 60% was obtained as in Example 7 except that, an aqueous solution prepared by dissolving 4.1 g of the compound obtained in Synthetic Example 3 in 9.5 g of pure water was used instead of 13.5 g of an aqueous solution of the protecting polymer (1-1) obtained in Example 1. Results of the thermal analysis (Tg/DTA) showed that the silver content in the nonvolatile matter was 95.5%, [0102]
  • the resistivity and average particle size of metal thin films prepared by using the silver colloidal solutions obtained in Examples 7 to 12 and Comparative Examples 2 to 4 were measured as described above.
  • the amount of acetone used in the settling treatment during- synthesis and the time taken for the treatment are shown in Table 2.
  • the silver colloidal solutions obtained were left to stand for one week at room temperature (25 to 35 deg C) and the stability of the solutions was evaluated, from the appearance. The results are shown in Tables 1 and 2. In Table l f O.L. means overload.
  • Results show that, good electrical conductivity, dispersion, stability, and ease of purification and separation are exhibited when protecting polymers in which the primary amine acetylation ratio is 5 to 100 mol% and the secondary amine acetylation ratio is 0 to 50 m.ol% in the polyalkylenimine segment are used.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Dispersion Chemistry (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
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KR102312406B1 (ko) * 2020-07-08 2021-10-13 유한회사 대동 스크린 인쇄용 도전성 수성 잉크 조성물, 이를 이용하여 제조되는 도전성 패턴 및 이를 포함하는 도전성 디바이스
KR102552064B1 (ko) * 2020-10-16 2023-07-06 유한회사 대동 음각 미세패턴 충전용 도전성 수성 잉크 조성물, 이를 이용하여 제조되는 도전체 충전 미세패턴 및 이를 포함하는 도전성 디바이스
CN115194171B (zh) * 2022-05-27 2023-09-26 氢电中科（广州）新能源设备有限公司 一种高度分散铂纳米粒子溶液及其制备方法

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