WO2016125581A1 - Fines particules composites, dispersion liquide, procédé de production et utilisation desdites fines particules composites et procédé de production et utilisation de ladite dispersion liquide - Google Patents

Fines particules composites, dispersion liquide, procédé de production et utilisation desdites fines particules composites et procédé de production et utilisation de ladite dispersion liquide Download PDF

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WO2016125581A1
WO2016125581A1 PCT/JP2016/051398 JP2016051398W WO2016125581A1 WO 2016125581 A1 WO2016125581 A1 WO 2016125581A1 JP 2016051398 W JP2016051398 W JP 2016051398W WO 2016125581 A1 WO2016125581 A1 WO 2016125581A1
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group
fine particles
acid
polymer
dispersion
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PCT/JP2016/051398
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English (en)
Japanese (ja)
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徹 米澤
洋己 田中
拓也 尾坂
和樹 岡本
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国立大学法人北海道大学
株式会社ダイセル
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Priority to JP2016573266A priority Critical patent/JP6661128B2/ja
Publication of WO2016125581A1 publication Critical patent/WO2016125581A1/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
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • 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
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Definitions

  • the present invention relates to composite fine particles useful for the formation of fine wiring (or wiring patterns) and the like, and dispersions (or pastes) containing the composite fine particles, and production methods and uses thereof (ink, coating film, fired film, wiring substrate, Electronic devices).
  • Patent Document 1 discloses copper composed of copper fine particles having a particle diameter of 100 nm or less coated with a water-soluble polymer and hydroxycarboxylic acid, and hydroxycarboxylic acid, polyhydric alcohol and / or polar solvent. Fine particle dispersions have been proposed. This document describes that the dispersion liquid is formed and then baked at 250 to 300 ° C.
  • Patent Document 2 discloses a method for producing copper nanoparticles in which a reducing agent is added to a solution containing an organic acid copper salt and a monoamine having 8 to 16 carbon atoms to form and grow a copper metal nucleus. Is disclosed. This document describes that the conductive composition containing the obtained copper nanoparticles is applied to a substrate and heat-treated at 50 ° C. or higher and lower than 500 ° C. to form a coating layer.
  • Patent Document 3 discloses a method of producing copper nanoparticles by adding a reducing agent after dissolving a copper source in a solvent containing citric acid to produce copper ions. Yes.
  • a copper test piece is bonded under heating conditions of 400 ° C. using the oxidation-resistant copper nanoparticles obtained by the above method.
  • the base material is limited to hard inorganic materials such as glass and ceramics.
  • the heat resistance is low such as polyethylene terephthalate (PET), and wiring is performed on the base material formed of a flexible resin. It becomes difficult to form a pattern.
  • Patent Document 4 discloses a fired paste composition containing a resin having an acyclic acetal structural unit, a powder, and a solvent.
  • various inorganic particles and organic particles are exemplified as the powder.
  • glass fine particles having an average particle diameter of 2 ⁇ m, silver powder, carbon nanotubes having a particle diameter of 40 to 70 nm, crosslinked organic particles, average particles Alumina fine particles having a diameter of 1 ⁇ m and magnesia are used.
  • the paste composition is heated to 1500 ° C. and sintered.
  • a resin having an acetal structure is blended in the composition as a binder resin, and the particle size of the metal powder is not described.
  • Japanese Patent No. 4978844 (Claim 1, Paragraph [0039], Example) Japanese Patent No. 5063003 (Claim 1, paragraph [0023]) Japanese Patent No. 5227828 (Claim 1, Example) Japanese Patent No. 5403740 (Claim 1, paragraphs [0002] [0003] [0044] [0045], Example)
  • an object of the present invention is to provide composite microparticles that can be sintered at a low temperature, a dispersion (or paste) containing the composite microparticles, and a method and application thereof (ink, coating film, fired film, wiring board, electronic device, etc.) Is to provide.
  • Another object of the present invention is to provide composite fine particles capable of being sintered at a low temperature of 200 ° C. or lower and having excellent stability by suppressing oxidation and aggregation despite containing a nano-sized metal. It is to provide a dispersion liquid containing them and a production method and use thereof.
  • Still another object of the present invention is to provide composite fine particles capable of forming a high-density conductor such as a fine wiring pattern on a flexible resin substrate, a dispersion containing the composite fine particles, and a production method and use thereof. There is.
  • Another object of the present invention is to provide composite fine particles having excellent solubility in an organic solvent, a dispersion containing the composite fine particles, and a production method and use thereof.
  • the present inventors have found that the surface of the metal fine particles can be sintered at a low temperature by coating with the acid-decomposable polymer, thereby completing the present invention.
  • the composite fine particles of the present invention include metal fine particles and a protective layer that covers at least a part of the surface of the metal fine particles and includes an acid-decomposable polymer.
  • the composite fine particles may have an average particle size of 3000 nm or less.
  • the metal fine particles may be copper fine particles.
  • the acid-decomposable polymer may have an acetal bond.
  • the acid-decomposable polymer includes a polymer having a repeating unit represented by the following formula (1), a polymer having a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3). It may be a polymer or a polymer having two types of repeating units represented by the following formulas (4a) and (4b).
  • R 1 to R 3 are the same or different and each represents a hydrogen atom, a halogen atom, a hydroxy group, a hydroperoxy group, an amino group, a mercapto group (or thiol group), a sulfo group or an organic group, And two or more of R 1 to R 3 may be bonded to each other to form a ring, and R 4 represents a halogen atom, a hydroxy group, a hydroperoxy group, an amino group, a mercapto group, a sulfo group or an organic group.
  • ring Z may have a substituent and represents a saturated heterocycle containing an oxygen atom as a heteroatom, and ring Z may be the same saturated heterocycle, It may be a combination of different saturated heterocycles
  • a 1 represents a hydrocarbon group which may have a substituent, or —A 2 — (OA 3 ) n — group (wherein A 2 and A 3 are the same or different, respectively) And n represents an integer of 1 or more.
  • a 4 represents a hydrocarbon group which may have a substituent, or —A 6 — (OA 7 ) m — group (wherein A 6 and A 7 are the same or different, respectively) A hydrocarbon group which may have a substituent, and m is an integer of 1 or more)
  • a 5 represents a hydrocarbon group which may have a substituent, or —A 8 — (OA 9 ) k — group (wherein A 8 and A 9 are the same or different, And k is an integer of 1 or more) A 4 and A 5 are different groups].
  • the present invention also includes a method for producing the composite fine particle, which includes a coating step of covering at least a part of the surface of the metal fine particle with an acid-decomposable polymer.
  • a coating step of covering at least a part of the surface of the metal fine particle with an acid-decomposable polymer.
  • at least one raw material metal compound selected from the group consisting of metal oxides, metal salts and metal halides may be reduced in the presence of an acid-decomposable polymer.
  • the raw material metal compound may be at least one selected from the group consisting of copper oxide, copper sulfate, copper formate, copper acetate, and copper chloride.
  • hydrazine may be used as a reducing agent.
  • the present invention includes a dispersion containing the composite fine particles and a dispersion medium.
  • the dispersion medium may be an organic solvent.
  • the dispersion of the present invention may further contain an acidic compound and / or an acid generator.
  • the dispersion of the present invention may further contain a reducing agent.
  • the dispersion of the present invention may be a conductive ink or a conductive paste.
  • the present invention also includes a method for producing the dispersion, which includes a dispersion step of dispersion treatment under pressure.
  • the present invention includes a method for producing a coating film including a coating step of coating the dispersion on a substrate.
  • the present invention also includes a method for producing a fired film including a firing step in which the coating film is heated and fired.
  • the firing temperature may be 200 ° C. or lower, and the firing may be performed in an inert gas atmosphere.
  • the obtained fired film may have an electrical resistivity of 0.5 ⁇ / ⁇ or less.
  • the present invention also includes a method of using this fired film as a wiring board.
  • the surface of the metal fine particles is coated with an acid-decomposable polymer which has excellent protective ability and can be easily removed, it can be sintered at a low temperature.
  • oxidation and aggregation are suppressed and the stability is excellent, and sintering can be performed at a low temperature of 200 ° C. or lower.
  • the metal fine particles have a nanometer size and a high-concentration dispersion liquid (ink or paste) can be prepared, a high-density conductor such as a fine wiring pattern can be formed on a flexible resin substrate.
  • the acid-decomposable polymer having excellent solubility in an organic solvent, in particular, having a repeating unit represented by the formula (3) or two kinds of repeating units represented by the formulas (4a) and (4b).
  • the composite fine particles can be dissolved in various organic solvents.
  • FIG. 1 is a chart of the 1 H-NMR spectrum of the polymer obtained in Synthesis Example 1 of the polymer of the example.
  • FIG. 2 is a chart of 1 H-NMR spectrum of the polymer obtained in Synthesis Example 2 of the polymer of Example.
  • FIG. 3 is a chart of 1 H-NMR spectrum of the polymer obtained in Synthesis Example 3 of the polymer of Example.
  • FIG. 4 shows the measurement results of TG-DTA of the polymer obtained in Synthesis Example 3 of the polymer of Example.
  • FIG. 5 is a scanning electron microscope (SEM) photograph (50000 times) of the composite fine particles obtained in Synthesis Example 1 of composite fine particles of Example.
  • SEM scanning electron microscope
  • FIG. 6 is a scanning electron microscope (SEM) photograph (50000 times) of the composite fine particles obtained in Synthesis Example 2 of composite fine particles of Example.
  • FIG. 7 is a scanning electron microscope (SEM) photograph (25000 times) of the composite fine particles obtained in Synthesis Example 3 of the composite fine particles of Example.
  • FIG. 8 is an X-ray diffraction chart of the composite fine particles obtained in Synthesis Example 3 of the composite fine particles of Example.
  • FIG. 9 is an X-ray diffraction chart of the coating film and the fired film obtained in Example 1.
  • FIG. 10 is an X-ray diffraction chart of the coating film and the fired film obtained in Example 2.
  • FIG. 11 is an X-ray diffraction chart of the coating film and the fired film obtained in Example 3.
  • the composite fine particles of the present invention include metal fine particles and a protective layer covering at least a part of the surface of the metal fine particles.
  • Metal fine particles examples of the metal constituting the metal fine particle include transition metals (for example, periodic table Group 4A metals such as titanium and zirconium; periodic table Group 5A metals such as vanadium and niobium; periodic table Group 6A such as molybdenum and tungsten).
  • Metal Periodic Table Group 7A metal such as manganese; Periodic Table Group 8 metal such as iron, nickel, cobalt, ruthenium, rhodium, palladium, rhenium, iridium, platinum; Periodic Table Group 1B such as copper, silver, gold, etc.
  • Periodic Table Group 2B metal eg, zinc, cadmium, etc.
  • Periodic Table Group 3B metal eg, aluminum, gallium, indium, etc.
  • Periodic Table Group 4B metal eg, germanium, tin, lead
  • periodic table Group 5B metals for example, antimony, bismuth, etc.
  • the metal fine particles may be fine particles formed of these alloys, or a combination of a plurality of types of metal fine particles.
  • fine metal particles fine particles formed of a group 1B metal of the periodic table such as copper, silver, and gold are preferable from the viewpoint of excellent conductivity, and migration is unlikely to occur. Particulates are particularly preferred.
  • the shape of the metal fine particles is not particularly limited, and examples thereof include a spherical shape, an ellipsoidal shape, a polygonal shape (polygonal pyramid shape, a rectangular parallelepiped shape, a rectangular parallelepiped shape, etc.), a plate shape, a rod shape, and an indefinite shape.
  • a spherical shape an ellipsoidal shape, a polygonal shape (polygonal pyramid shape, a rectangular parallelepiped shape, a rectangular parallelepiped shape, etc.), a plate shape, a rod shape, and an indefinite shape.
  • an isotropic shape such as a substantially spherical shape is preferable from the viewpoint of excellent dispersibility.
  • the metal fine particles may have an average particle size (number average primary particle size) of 3000 nm or less.
  • the average particle size of the metal fine particles is preferably a nanometer size, for example, about 1 to 1000 nm, preferably about 10 to 500 nm (for example, 20 to 400 nm), more preferably about 30 to 300 nm (particularly about 50 to 200 nm). If the particle size of the metal fine particles is too large, the firing temperature for sintering becomes high, and it may be difficult to form a fine wiring pattern. On the other hand, if it is too small, the preparation becomes difficult and the specific surface area increases, so that it becomes easy to oxidize and redispersion in a paste or ink may be difficult. Furthermore, it may be difficult to improve the conductivity due to these complex factors.
  • the average particle diameter of the metal fine particles can be measured by a method such as image analysis using a scanning electron microscope (SEM).
  • the protective layer contains an acid-decomposable polymer having a property of being easily decomposed by an acid. Although this acid-decomposable polymer is decomposed by heat at a predetermined temperature in the absence of an acid, the decomposability is further improved in the presence of an acid.
  • the acid-decomposable polymer having such properties may be any polymer that can lower the firing temperature for sintering the metal fine particles. For example, a polymer having an ester bond, a carbonate bond, a urethane bond, an acetal bond, etc. For example). Among these polymers, a polymer having an acetal bond is preferable from the viewpoint of excellent acid decomposability.
  • the acid-decomposable polymer having an acetal bond includes a polymer [polymer (1)] having a repeating unit represented by the formula (1), a polymer [polymer (2) having a repeating unit represented by the formula (2). ], A polymer having a repeating unit represented by the formula (3) [polymer (3)], or a polymer having two repeating units represented by the formulas (4a) and (4b) [polymer (4) ].
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the organic group in R 1 to R 4 is not particularly limited as long as it contains a carbon atom, and examples thereof include a hydrocarbon group, alkoxy group, alkenyloxy group, aryloxy group which may have a substituent.
  • hydrocarbon group examples include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.
  • Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.
  • Examples of the alkyl group include C 1-20 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, and dodecyl group (preferably C 1-1 10 alkyl group, more preferably C 1-4 alkyl group).
  • alkenyl group examples include C 2-20 alkenyl groups such as vinyl group, allyl group, methallyl group, 1-propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group (preferably C 2-10 alkenyl group). And more preferably a C 2-4 alkenyl group).
  • alkynyl group examples include C 2-20 alkynyl groups such as ethynyl group and propynyl group (preferably C 2-10 alkynyl group, more preferably C 2-4 alkynyl group).
  • Examples of the alicyclic hydrocarbon group include a C 3-12 cycloalkyl group (particularly a C 5-8 cycloalkyl group) such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group; a cyclohexenyl group And C 3-12 cycloalkenyl groups such as C 4-15 bridged cyclic hydrocarbon groups such as bicycloheptanyl group and bicycloheptenyl group.
  • a C 3-12 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group
  • C 3-12 cycloalkenyl groups such as C 4-15 bridged cyclic hydrocarbon groups such as bicycloh
  • aromatic hydrocarbon group examples include C 6-14 aryl groups (particularly C 6-10 aryl groups) such as a phenyl group and a naphthyl group.
  • examples of the hydrocarbon group include a group in which an aliphatic hydrocarbon group such as a cyclohexylmethyl group or a methylcyclohexyl group is bonded to an alicyclic hydrocarbon group; a C 7-18 aralkyl such as a benzyl group or a phenethyl group.
  • Groups (especially C 7-10 aralkyl groups), C 6-10 aryl-C 2-6 alkenyl groups such as cinnamyl groups, C 1-4 alkyl substituted aryl groups such as tolyl groups, C 2-4 such as styryl groups And a group in which an aliphatic hydrocarbon group such as an alkenyl-substituted aryl group and an aromatic hydrocarbon group are bonded.
  • alkoxy group examples include C 1-10 alkoxy groups such as methoxy group, ethoxy group, propoxy group, isopropyloxy group, butoxy group, isobutyloxy group (preferably C 1-6 alkoxy group, more preferably C 1- 1 4 alkoxy group).
  • alkenyloxy group examples include a C 2-10 alkenyloxy group such as an allyloxy group (preferably a C 2-6 alkenyloxy group, more preferably a C 2-4 alkenyloxy group).
  • aryloxy group examples include a C 6-20 aryloxy group (particularly a C 6-14 aryloxy group) such as a phenoxy group, a tolyloxy group, and a naphthyloxy group.
  • the aryloxy group may have a substituent such as a C 1-4 alkyl group, a C 2-4 alkenyl group, a halogen atom, or a C 1-4 alkoxy group on the aromatic ring.
  • aralkyloxy group include a C 6-20 aralkyloxy group such as a benzyloxy group and a phenethyloxy group (particularly a C 7-18 aralkyloxy group).
  • acyl group examples include C 1-20 acyl groups such as acetyl group, propionyl group, (meth) acryloyl group, and benzoyl group (particularly, C 1-12 acyl group).
  • acyloxy group examples include C 1-20 acyloxy groups such as acetyloxy group, propionyloxy group, (meth) acryloyloxy group, and benzoyloxy group (particularly, C 1-12 acyloxy group).
  • alkylthio group examples include a C 1-6 alkylthio group such as a methylthio group and an ethylthio group (particularly a C 1-4 alkylthio group).
  • alkenylthio group examples include a C 2-6 alkenylthio group such as an allylthio group (particularly a C 2-4 alkenylthio group).
  • arylthio group examples include 6-20 arylthio groups (particularly C 6-14 arylthio groups) such as a phenylthio group, a tolylthio group, and a naphthylthio group.
  • the arylthio group may have a substituent such as a C 1-4 alkyl group, a C 2-4 alkenyl group, a halogen atom, or a C 1-4 alkoxy group on the aromatic ring.
  • aralkylthio group examples include a C 6-20 aralkylthio group (particularly a C 7-18 aralkylthio group) such as a benzylthio group and a phenethylthio group.
  • alkoxycarbonyl group examples include C 1-10 alkoxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group (particularly a C 1-6 alkoxy-carbonyl group).
  • aryloxycarbonyl group examples include a C 6-20 aryloxy-carbonyl group such as a phenoxycarbonyl group, a tolyloxycarbonyl group, and a naphthyloxycarbonyl group (particularly a C 6-14 aryloxy-carbonyl group).
  • aralkyloxycarbonyl group examples include a C 6-20 aralkyloxy-carbonyl group (particularly a C 7-18 aralkyloxy-carbonyl group) such as a benzyloxycarbonyl group.
  • Examples of the epoxy-containing group include a glycidyl group and a glycidyloxy group.
  • Examples of the oxetanyl-containing group include a C 1-10 alkyl-oxetanyloxy group such as an ethyl oxetanyloxy group.
  • substituted amino group examples include mono- or dialkylamino groups (particularly mono- or di-C 1-6 alkylamino groups) such as methylamino group, ethylamino group, dimethylamino group, and diethylamino group, acetylamino group, and propionylamino.
  • acylamino groups such as benzoylamino group (particularly C 1-11 acylamino group).
  • the organic group may have a substituent.
  • substituents include the above-mentioned groups such as a halogen atom (for example, fluorine), an oxo group, a hydroxy group, and a hydroperoxy group.
  • the substituent may be a group in which two or more substituents are bonded via a C 1-6 alkylene group.
  • R 1 to R 3 may be bonded to each other to form a ring, but is usually a monovalent group.
  • R 1 and R 2 a linear or branched C 1-6 alkyl group is preferable, and a C 1-3 alkyl group (particularly a methyl group) such as a methyl group is particularly preferable.
  • R 3 is preferably a hydrogen atom or a linear or branched C 1-6 alkyl group, particularly preferably a hydrogen atom.
  • R 4 is an exemplified monovalent group, preferably a linear or branched C 1-6 alkyl group, particularly preferably a C 1-3 alkyl group such as a methyl group (particularly a methyl group). .
  • Polymer (1) having a repeating unit represented by formula (1) is a monomer comprising an oxirane compound that is a monomer for forming the repeating unit represented by formula (1). It is obtained by cationic polymerization of the body.
  • the structure of the polymer (1) is not particularly limited, and may be any structure such as a linear type, a branched type, and a star type.
  • the polymer (1) may be a homopolymer or a copolymer.
  • the copolymer may be a copolymer in which a plurality of (two or more) repeating units represented by the formula (1) are combined, and the repeating unit represented by the formula (1) and other copolymerization properties. It may be a copolymer with a repeating unit formed of a monomer (another cationically polymerizable monomer). Furthermore, the copolymer may be a random copolymer or a block copolymer.
  • Examples of other copolymerizable monomers include vinyl ether compounds, cyclic ether compounds, benzaldehyde compounds, ⁇ -olefin compounds, chain conjugated diene compounds, olefinic hydrocarbons having a ring structure of five or more members, and cyclopentadiene. Examples thereof include a compound, a cyclic olefin compound, a cyclic conjugated diene compound, a heterocyclic ring-containing vinyl compound, a silane compound having an ethylenically unsaturated bond, and a lactone compound. These monomers can be used alone or in combination of two or more. Specifically, these other copolymerizable monomers may be other copolymerizable monomers described in, for example, JP2013-237755A.
  • the proportion of the repeating unit represented by the formula (1) may be 50 mol% or more (for example, 70 to 100 mol%), for example, 80 mol% or more (for example, 80 to 100 mol%). ), Preferably 90 mol% or more (for example, 90 to 100 mol%), more preferably 95 mol% or more (particularly 99 mol% or more). If the ratio of the repeating unit (1) is too small, the treatment of the residue after decomposing the polymer with an acid may be complicated.
  • the terminal structure of the polymer (1) is not particularly limited.
  • the terminal structure is composed of an atomic group derived from a starting species of a cationic polymerization reaction (for example, a hydrogen halide adduct of vinyl ether), derived from a polymerization terminator.
  • Examples include terminal structures composed of atomic groups.
  • the terminal group of the polymer (1) may be a hydroxyl group formed when the polymerization reaction starts from protons due to impurities in the system, transfer reaction, or the like.
  • the number average molecular weight (Mn) of the polymer (1) may be, for example, 2000 or more in terms of polystyrene when measured by the GPC method (gel permeation chromatography method), for example, 2000 to 100,000, preferably 2500. It is about 50,000, more preferably about 3,000 to 15,000. If the number average molecular weight is too small, the protective ability against metal fine particles may be reduced, and the heat resistance and mechanical strength of the polymer before decomposition may be insufficient. On the other hand, if it is too large, the productivity of the polymer may decrease, or the solubility may be insufficient and handling may be difficult.
  • the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymer (1) is, for example, 1.3 or less (for example, 1.0 to 1.3), preferably 1.25 or less (for example, 1 0.02 to 1.25), more preferably about 1.2 or less (for example, 1.05 to 1.20). If the molecular weight distribution is too large, the particle size distribution of the composite fine particles may increase, or the heat resistance and mechanical strength of the polymer before decomposition may be insufficient.
  • the molecular weight distribution of the polymer can also be calculated in terms of polystyrene by, for example, the GPC method.
  • Polymer (1) can be produced by conventional cationic polymerization, and can be produced, for example, by the production method described in JP2013-237755A.
  • the ring Z may be a saturated heterocycle containing an oxygen atom as a hetero atom.
  • the saturated heterocycle may be a saturated monocyclic heterocycle (heteromonocycle) or a saturated condensed heterocycle.
  • saturated heteromonocycle examples include oxacyclobutane, tetrahydrofuran (oxacyclopentane), tetrahydropyran (oxacyclohexane), oxacycloheptane, oxacyclooctane, and the like. Of these, tetrahydrofuran and tetrahydropyran (particularly tetrahydrofuran) are preferred.
  • the number of condensed condensed heterocyclic rings may be two or more, and may be three or more (for example, 3 to 4 rings). It is a formula.
  • the number of saturated condensed heterocycles (total number of condensed rings) is, for example, about 6 to 20 members, preferably 7 to 15 members, more preferably 8 to 12 members (particularly 8 to 10 members).
  • the number of oxygen atoms contained in the saturated condensed heterocycle may be 2 or more, for example, 2 to 6, preferably 2 to 4, and more preferably about 2 to 3. Two or more oxygen atoms may be contained in the same ring, but usually one or more (for example, 1 to 2, particularly 1) is contained in each ring.
  • Examples of the basic skeleton of the saturated condensed heterocycle include the saturated heteromonocyclic ring.
  • saturated heteromonocycles tetrahydrofuran and tetrahydropyran (particularly tetrahydrofuran) are preferred.
  • the condensed ring is composed of a combination of these rings, and may be a combination of the same ring or a combination of different rings.
  • a saturated condensed heterocycle is preferable as the ring Z from the viewpoint of adhesion and the like.
  • Examples of the substituent contained in the ring Z include an organic group exemplified in the formula (1), a substituent of the organic group exemplified in the formula (1), and the like.
  • Such a repeating unit (2) may be a repeating unit represented by the following formula (2a).
  • R 5 to R 12 represent a hydrogen atom or a substituent
  • R 5 to R 12 may be a single group selected from these substituents and a hydrogen atom, or may be a group in which two or more kinds are combined.
  • R 5 to R 12 a C 1-4 alkyl group such as a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable, from the viewpoint of ease of production and availability of raw materials.
  • the polymer (2) [the polymer (2) having a repeating unit represented by the formula (2)] includes a reaction between a divinyl ether having an oxygen-containing saturated heterocyclic skeleton and a diol having an oxygen-containing saturated heterocyclic skeleton, It can be obtained by polymerization of hydroxy vinyl ether having an oxygen saturated heterocyclic skeleton.
  • the structure of the polymer (2) is not particularly limited, and may be any structure such as a linear type, a branched type, and a star type.
  • the polymer (2) may be a homopolymer or a copolymer.
  • the copolymer is a repeating unit represented by the formula (2), wherein the ring Z is a combination of different saturated heterocycles, for example, a combination of different saturated heteromonocycles, a combination of different saturated condensed heterocycles, saturation It may be a copolymer such as a combination of a heteromonocycle and a saturated condensed heterocycle. That is, in the formula (2), the rings Z may be the same saturated heterocycle or a combination of different saturated heterocycles.
  • the copolymer is a copolymer of the repeating unit represented by the formula (2) and a unit formed of another copolymerizable monomer (another divinyl ether and / or another diol). It may be. Furthermore, the copolymer may be a random copolymer or a block copolymer.
  • the proportion of the repeating unit represented by the formula (2) may be 50 mol% or more (for example, 70 to 100 mol%), for example, 80 mol% or more (for example, 80 to 100 mol%). ), Preferably 90 mol% or more (for example, 90 to 100 mol%), more preferably 95 mol% or more (particularly 99 mol% or more). If the ratio of the repeating unit (2) is too small, the treatment of the residue after decomposing the polymer with an acid may be complicated.
  • the terminal group of the polymer (2) is either a vinyl ether group or a hydroxyl group, and may be either alone or a combination of both groups.
  • the polymer of the present invention since the polymer of the present invention has a hydroxyl group and / or a vinyl group at the terminal, it is possible to impart adhesion to a substrate formed of an inorganic material or the like by the hydroxyl group, or to perform other polymerization by the vinyl group. It is also possible to obtain a resin having an acid-decomposable crosslinked structure by polymerizing with a functional group.
  • the weight average molecular weight (Mw) of the polymer (2) may be, for example, 1000 or more in terms of polystyrene when measured by the GPC method, for example, 1000 to 100,000, preferably 2000 to 50000, more preferably 3000 to It may be about 30000 (particularly 4000 to 10,000).
  • the polymer (2) has a high molecular weight despite having an oxygen-containing saturated heterocycle. If the weight average molecular weight is too small, the protective ability against metal fine particles may be reduced, and the heat resistance and mechanical strength of the polymer before decomposition may be insufficient. On the other hand, if it is too large, the productivity of the polymer may decrease, or the solubility may be insufficient and handling may be difficult.
  • the molecular weight distribution (Mw / Mn) of the polymer (2) is, for example, about 1 to 5, preferably about 1.1 to 3, more preferably about 1.2 to 2.8 (especially 1.5 to 2.5). May be. If the molecular weight distribution is too large, the particle size distribution of the composite fine particles may increase, or the heat resistance and mechanical strength of the polymer before decomposition may be insufficient.
  • the molecular weight distribution of the polymer can also be calculated in terms of polystyrene by, for example, the GPC method.
  • the polymer (2) is a production method including a reaction step in which a divinyl ether represented by the following formula (5) and a diol represented by the following formula (6) are reacted, and a hydroxy represented by the following formula (7). It is a polymer obtained by a production method including a reaction step of polymerizing vinyl ether.
  • ring Z may have a substituent and represents a saturated heterocycle containing an oxygen atom as a heteroatom, and ring Z may be the same saturated heterocycle, and are different. It may be a combination of the above saturated heterocycles).
  • the divinyl ether (5) may be any divinyl ether having the ring Z exemplified in the repeating unit (2) as a basic skeleton, and represented by the following formula (5a) (particularly, Divinyl ether having a substituent exemplified in the repeating unit (2a) is preferable.
  • the diol (6) may be a diol having the ring Z exemplified in the repeating unit (2) as a basic skeleton, and may be a diol represented by the following formula (6a) (particularly the repeating unit (2a)). Diols having a substituted group are preferred.
  • the hydroxy vinyl ether (7) may be any hydroxy vinyl ether having the ring Z exemplified in the repeating unit (2) as a basic skeleton.
  • the hydroxy vinyl ether represented by the following formula (7a) (especially the repeating unit (2a) is preferred.
  • R 5 to R 12 represent a hydrogen atom or a substituent
  • a copolymerizable monomer may be added in addition to divinyl ether (5) and diol (6), or hydroxy vinyl ether (7).
  • copolymerizable monomers include other divinyl ethers (for example, butylene divinyl ether, cyclohexane divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 2,2-norbornane dimethanol divinyl ether, etc.), other diols ( For example, ethylene glycol, propylene glycol, tetramethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, etc., other hydroxy vinyl ethers (eg, hydroxybutyl vinyl ether, hydroxycyclohexyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol mono Vinyl ether, 2,2-norbornane dimethanol monovinyli Ether and the like)
  • the reaction may be performed in the presence of a catalyst.
  • a catalyst a conventional catalyst can be used, but an acid catalyst is preferable from the viewpoint of high reaction acceleration.
  • the acid catalyst may be a strong acid such as hydrochloric acid, sulfuric acid or p-toluenesulfonic acid, but acetic acid, phosphoric acid, arenesulfonic acid (for example, A weak acid such as a salt of a base such as toluenesulfonic acid) and a base (for example, a weak base such as pyridine) is preferable, and toluene such as pyridinium paratoluenesulfonate is excellent in terms of excellent balance between stability and reactivity of the polymer. Sulfonate is preferred.
  • the ratio of the catalyst is, for example, 0.1 to 20 moles, preferably 0.3 to 15 moles with respect to 100 moles of the total moles of polymerization components (for example, the total moles of divinyl ether (5) and diol (6)). Mol, more preferably about 0.5 to 10 mol (especially 1 to 5 mol). If the ratio of the catalyst is too small, the reactivity decreases, and if it is too large, the physical properties of the polymer may be adversely affected.
  • the reaction may be performed in a solvent, and the solvent is not particularly limited as long as it is a non-reactive solvent with respect to the divinyl ether and diol.
  • the solvent is not particularly limited as long as it is a non-reactive solvent with respect to the divinyl ether and diol.
  • hydrocarbons toluene, xylene, etc.
  • halogenated solvents Methylene chloride, chloroform, etc.
  • ethers dialkyl ethers, such as diethyl ether, cyclic ethers, such as tetrahydrofuran
  • ketones acetone, methyl ethyl ketone, etc.
  • esters methyl acetate, ethyl acetate, butyl acetate, etc.
  • Cellosolve acetates C 1-4 alkyl cellosolve acetate such as ethyl cellosolve acetate, propylene glycol mono C 1-4 alkyl ether
  • solvents can be used alone or in combination of two or more.
  • cellosolve acetates for example, propylene glycol mono C 1-4 alkyl ether acetate such as propylene glycol monomethyl ether acetate
  • propylene glycol monomethyl ether acetate for example, propylene glycol monomethyl ether acetate
  • the amount of the solvent used is, for example, 10 to 1000 parts by weight, preferably 50 to 500 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the total amount of polymerization components (for example, the total amount of divinyl ether (3) and diol (4)). May be about 100 to 300 parts by weight (particularly 150 to 200 parts by weight).
  • the reaction may be performed by adding a conventional additive such as a polymerization accelerator or a polymerization inhibitor. Furthermore, moisture may be contained in the reaction system, and the reaction may be performed in the presence of moisture inevitably contained from raw materials.
  • the reaction can proceed without excessive heating or cooling, and the reaction temperature is, for example, 0 to 60 ° C., preferably 10 to 50 ° C., more preferably 20 to 45 ° C. (especially 30 to 30 ° C.). About 40 ° C.).
  • the reaction time may be, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably about 2 to 24 hours.
  • the reaction may be performed in an inert atmosphere (for example, an atmosphere of nitrogen, helium, argon, or the like).
  • the polymer obtained through the reaction step may be further subjected to a separation and purification step.
  • separation and purification may be performed by a conventional separation and purification treatment such as filtration, concentration, reprecipitation, extraction, crystallization (recrystallization, etc.).
  • an acid catalyst when used, it may be neutralized with an alkali by a conventional method.
  • examples of the hydrocarbon group of A 1 to A 9 include, for example, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, Aromatic hydrocarbon groups and groups in which two or more of these are bonded are exemplified.
  • Examples of the aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group.
  • Examples of the alkylene group include C 1 such as methylene group, ethylene group, propylene group, trimethylene group, butylene group, tetramethylene group, hexamethylene group, isohexylene group, octamethylene group, isooctylene group, decamethylene group, and dodecamethylene group.
  • a -20 alkylene group is a -20 alkylene group.
  • alkenylene group examples include C 2-20 alkenylene groups such as vinylene group, arylene group, metalrylene group, 1-propenylene group, isopropenylene group, butenylene group, pentenylene group, hexenylene group and the like.
  • alkynylene group examples include C 2-20 alkynylene groups such as ethynylene group and propynylene group.
  • Examples of the alicyclic hydrocarbon group include C 3-12 cycloalkyl groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclododecane-diyl group (especially C 5-8 cycloalkyl group). Group); C 3-12 cycloalkenylene group such as cyclohexenylene group; C 4-15 bridged cyclic hydrocarbon group such as bicycloheptanylene group and bicycloheptenylene group.
  • aromatic hydrocarbon group examples include C 6-14 arylene groups such as a phenylene group and a naphthylene group.
  • the hydrocarbon group may be, for example, a group in which two or more selected from an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group are bonded.
  • the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include, for example, a cyclohexylenemethylene group, a methylcyclohexylene group, a dicyclohexylmethane-4,4′-diyl group, and a dicyclohexylpropane-4,4.
  • Examples include a '-diyl group.
  • Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include a tolylene group, a xylylene group, a diphenylmethane-4,4′-diyl group, and a diphenylpropane-4,4′-diyl group. It is done.
  • substituent of these hydrocarbon groups include the substituent of the organic group exemplified in the above formula (1).
  • n, m and k are each an integer of 1 or more, preferably 1 to 10, more preferably 1 to 5 (particularly 1 to 3). .
  • an alkylene group having 3 or more carbon atoms eg, a C 3-10 alkylene group
  • a tri to octamethylene group particularly, a tri to hexamethylene group
  • the A 1 , A 4, and A 5 skeletons do not include a saturated heterocycle containing an oxygen atom as a hetero atom.
  • Polymers (3) and (4) are obtained by reacting a divinyl ether having an A 1 skeleton with a diol having an A 1 skeleton, a divinyl ether having an A 4 or A 5 skeleton, and a diol having an A 5 or A 4 skeleton. It can be obtained by reaction, polymerization of hydroxy vinyl ether having A 1 skeleton or the like.
  • the structures of the polymers (3) and (4) are not particularly limited, and may be any structure such as a linear type, a branched type, and a star type.
  • the polymer (3) may be a homopolymer or a unit formed with another copolymerizable monomer (formed with a monomer other than the monomer capable of forming the repeating unit (3)). Unit).
  • the copolymer may be a random copolymer or a block copolymer.
  • the polymer (4) is a copolymer containing the repeating units (4a) and (4b), but in the same manner as the polymer (3), units (repeating units) formed from other copolymerizable monomers.
  • (4a) and a copolymer containing (4b) may be sufficient as the copolymer containing a monomer other than the monomer which can form.
  • the copolymer may be a random copolymer or a block copolymer.
  • the other copolymerizable monomers in the polymers (3) and (4) also do not contain a saturated heterocycle containing an oxygen atom as a hetero atom.
  • the ratio of the repeating unit represented by the formula (3) or the two repeating units represented by the formulas (4a) and (4b) is 50 mol% or more (for example, 70 to 100 mol%), for example 80 mol% or more (for example 80 to 100 mol%), preferably 90 mol% or more (for example 90 to 100 mol%), more preferably 95 mol% or more (particularly 99 mol% or more). If the ratio of the repeating unit is too small, the treatment of the residue after decomposing the polymer with an acid may be complicated.
  • a 1 may be a tri to hexamethylene group, preferably a tetra to pentamethylene group, and more preferably a tetramethylene group.
  • the end groups of the polymers (3) and (4) are either a vinyl ether group or a hydroxyl group, and either of them may be used alone or a combination of both groups.
  • the polymers (3) and (4) since the polymers (3) and (4) have a hydroxyl group and / or a vinyl group at the terminal, the polymer (3) and (4) can have adhesion to a substrate formed of an inorganic material or the like by the hydroxyl group, It is also possible to obtain a resin having an acid-decomposable crosslinked structure by polymerizing with other polymerizable groups.
  • the weight average molecular weight (Mw) of each of the polymers (3) and (4) may be 1000 or more in terms of polystyrene when measured by the GPC method, for example, 1000 to 100,000, preferably 2000 to 50000, Preferably, it may be about 3000 to 30000 (particularly 4000 to 10,000). If the weight average molecular weight is too small, the protective ability against metal fine particles may be reduced, and the heat resistance and mechanical strength of the polymer before decomposition may be insufficient. On the other hand, if it is too large, the productivity of the polymer may decrease, or the solubility may be insufficient and handling may be difficult.
  • the molecular weight distribution (Mw / Mn) of the polymers (3) and (4) is, for example, 1 to 5, preferably 1.1 to 3, more preferably 1.2 to 2.8 (especially 1.5 to 2). .5) may be sufficient. If the molecular weight distribution is too large, the heat resistance and mechanical strength of the polymer before decomposition may be insufficient.
  • the molecular weight distribution of the polymer can also be calculated in terms of polystyrene by, for example, the GPC method.
  • the polymers (3) and (4) are produced by a production method including a reaction step of reacting a corresponding divinyl ether and a corresponding diol, a production method including a reaction step of polymerizing a corresponding hydroxyvinyl ether, and the like. can get.
  • Examples of the divinyl ether having an A 1 , A 4 or A 5 skeleton in the reaction step include butylene divinyl ether, cyclohexane divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, 2,2-norbornane dimethanol divinyl ether, and the like. Is mentioned.
  • Examples of the diol having an A 1 , A 4 or A 5 skeleton include tetramethylene glycol, diethylene glycol, triethylene glycol, cyclohexane dimethanol, and bisphenol A.
  • hydroxy vinyl ether having A 1 , A 4 or A 5 skeleton examples include hydroxybutyl vinyl ether, hydroxycyclohexyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, 2,2-norbornane dimethanol monovinyl ether, and the like.
  • an alternating polymer of the corresponding divinyl ether and the corresponding diol is preferable.
  • the reaction may be performed in the presence of a catalyst.
  • a catalyst a conventional catalyst can be used, but an acid catalyst is preferable from the viewpoint of high reaction acceleration.
  • an acid catalyst the acid catalyst used with the manufacturing method of a polymer (2) can be utilized, and it can be used in the ratio similar to the manufacturing method of a polymer (2).
  • the reaction may be carried out in a solvent, and as the solvent, a solvent used in the production method of the polymer (2) can be used, and it can be used in the same amount as used in the production method of the polymer (2).
  • addition of additives, reaction temperature and time, and separation and purification steps of the obtained polymer are the same as in the method for producing the polymer (2).
  • the protective layer only needs to contain an acid-decomposable polymer, and may contain other components, for example, a catalyst, a solvent mixed in the production process, a reducing agent, and a conventional additive.
  • the ratio of the reducing agent is, for example, about 10% by weight or less (for example, 0.001 to 10% by weight), preferably about 5% by weight or less, and more preferably about 1% by weight or less with respect to the entire protective layer.
  • the ratio of the reducing agent is, for example, about 10% by weight or less (for example, 0.001 to 10% by weight), preferably about 5% by weight or less, and more preferably about 1% by weight or less with respect to the entire protective layer.
  • additives examples include other polymers (binders), stabilizers (antioxidants, UV absorbers, etc.), metal corrosion inhibitors, surfactants or dispersants, water-soluble polymers, waxes, dispersion stability Agents, thickeners or viscosity modifiers, humectants, thixotropic agents, leveling agents, antifoaming agents, fillers and the like may be included.
  • the ratio of the other components may be, for example, 50% by weight or less with respect to the entire protective layer, for example, about 0.01 to 10% by weight (particularly 0.1 to 5% by weight).
  • the protective layer only needs to cover at least a part of the surface of the metal fine particles, and the coverage of the surface of the metal fine particles may be 10% or more, for example, 30% or more, preferably 50% or more, more preferably May be 80% or more (particularly 90% or more), and may cover the entire surface of the metal fine particles. If the coverage of the protective layer is too low, the metal fine particles are likely to be oxidized or aggregated, and the stability of the metal fine particles may be reduced.
  • the composite fine particles of the present invention may have an average particle size (number average primary particle size) of 3000 nm or less.
  • the average particle diameter of the composite fine particles is preferably nanometer size, for example, about 1 to 1000 nm, preferably about 10 to 500 nm (for example, 20 to 400 nm), more preferably about 30 to 300 nm (particularly about 50 to 200 nm). If the particle size of the composite fine particles is too large, the firing temperature for sintering becomes high, and it may be difficult to form a fine wiring pattern.
  • the average particle diameter of the composite fine particles can be measured by measuring an arbitrary 100 to 300 particle diameters based on the SEM photograph and calculating the average value.
  • the composite fine particles of the present invention can be obtained by a production method including a coating step of covering at least a part of the surface of metal fine particles with an acid-decomposable polymer.
  • the method of coating the metal fine particles with the acid-decomposable polymer is not particularly limited, but usually a method of reducing the raw metal compound in the presence of the acid-decomposable polymer is used.
  • raw metal compounds include metal oxides, metal salts, and metal halides. These raw metal compounds can be used alone or in combination of two or more.
  • the raw metal compound can be selected according to the type of metal fine particles.
  • Metal halides include metal chlorides, metal bromides, metal iodides, and the like.
  • Metal salts include metal inorganic acid salts (sulfates, nitrates, carbonates, hydrochlorides, phosphates, etc.), metal organic acid salts (formates, acetates, lactates, etc.) and the like.
  • the metal salt may be a hydrate.
  • the copper oxide includes copper oxide (I) (cuprous oxide) and copper oxide (II) (cupric oxide).
  • Copper halides include copper chloride (I) (cuprous chloride), copper chloride (II) (cupric chloride), copper bromide (I) (cuprous bromide), copper bromide (II) (Cupric bromide) and the like are included.
  • Metal salts include copper sulfate, copper nitrate, copper formate, copper acetate, and the like. Among these, at least one selected from the group consisting of copper oxide, copper sulfate, copper formate, copper acetate, and copper chloride is preferable.
  • the ratio of the acid-decomposable polymer at the time of synthesis can be selected from a range of about 1 to 500 parts by weight (particularly 3 to 400 parts by weight) with respect to 100 parts by weight of the starting metal compound.
  • the ratio of the acid-decomposable polymer is, for example, 5 to 400 parts by weight, preferably 10 to 250 parts by weight with respect to 100 parts by weight of the starting metal compound. Part, more preferably about 15 to 200 parts by weight.
  • the ratio of the acid-decomposable polymer is, for example, 3 to 30 parts by weight, preferably 5 to 20 parts by weight with respect to 100 parts by weight of the starting metal compound. More preferably, it is about 6 to 10 parts by weight. If the ratio of the acid-decomposable polymer is too small, the stability of the metal fine particles may be reduced or coarse particles may be generated. If the ratio is too large, very fine particles are generated and a composite having a desired particle size is formed. Particles may not be obtained or sintering at low temperatures may be difficult.
  • the reducing agent examples include conventional reducing agents such as sodium borohydrides, lithium aluminum hydride, hypophosphorous acid or salts thereof, boranes, formalin, hydrazine, amines, alcohols, and carboxyl groups having a phenolic hydroxyl group. An acid etc. can be illustrated. These reducing agents can be used alone or in combination of two or more. Of these reducing agents, sodium borohydride, hydrazine, tertiary amine, ethylene glycol, tannic acid and the like are widely used, and hydrazine is preferred. Hydrazine may be a hydrate.
  • the ratio of the reducing agent can be selected from a range of, for example, about 0.1 to 50 mol (particularly 0.2 to 40 mol) with respect to 1 mol of the starting metal compound.
  • the ratio of the reducing agent is, for example, about 0.5 to 30 mol, preferably about 1 to 30 mol, and more preferably about 3 to 10 mol.
  • the ratio of the reducing agent is, for example, 0.2 to 30 mol, preferably 0.3 to 10 mol, more preferably about 0.5 to 5 mol. It is. If the ratio of the reducing agent is too small, the reduction of metal ions may be insufficient. If the ratio is too large, the particle size becomes small, and composite particles having a desired particle size cannot be obtained, or purification after the reaction is performed. May take time.
  • the reduction reaction using a reducing agent may be performed at normal temperature, but may be heated from the viewpoint of promoting the reduction reaction.
  • the heating temperature may be, for example, about 40 to 80 ° C., preferably 45 to 70 ° C., more preferably about 50 to 60 ° C.
  • the reaction time may be, for example, 10 minutes to 20 hours, usually 30 minutes to 10 hours, preferably about 1 to 5 hours.
  • the reduction reaction may be performed under stirring.
  • the reduction reaction may be performed in the presence of a solvent.
  • the solvent can be selected according to the type of the starting metal compound and the reducing agent, such as water, alcohols such as ethanol and isopropanol, ketones such as acetone, cyclic ethers such as dioxane and tetrahydrofuran, and amides such as dimethylacetamide. Etc. These solvents can be used alone or in combination of two or more. Of these solvents, cyclic ethers such as water and tetrahydrofuran are widely used.
  • the proportion of the solvent is, for example, about 10 to 5000 parts by weight, preferably about 30 to 4000 parts by weight, and more preferably about 50 to 3000 parts by weight with respect to 100 parts by weight of the starting metal compound.
  • the pH is adjusted using an acid (an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, an organic acid such as acetic acid) or an alkali (an inorganic base such as sodium hydroxide or ammonia) in a conventional manner. May be.
  • an acid an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, an organic acid such as acetic acid
  • an alkali an inorganic base such as sodium hydroxide or ammonia
  • the composite fine particles obtained in the coating step may use the dispersion after completion of the reduction reaction as it is for ink or the like, but the dispersion is usually subjected to a separation and purification step.
  • the separation and purification step the produced composite fine particles are separated from the solvent by a conventional method (for example, filtration treatment such as centrifugation, membrane filter, ultrafiltration, etc.), and then the separated composite fine particles are washed and dried. You may refine
  • the dispersion of the present invention only needs to contain the composite fine particles and the dispersion medium.
  • the dispersion may be a dispersion obtained in the coating step. It is obtained by dispersing the composite fine particles obtained through the above in a dispersion medium.
  • the dispersion medium can be selected according to the type of the composite fine particles and may be water, but an organic solvent is preferable from the viewpoint that high concentration of the composite fine particles can be dispersed.
  • composite fine particles particularly composite fine particles coated with a protective layer containing the polymer (3) or (4)
  • organic solvent examples include alcohol solvents (for example, alkanols such as methanol, ethanol, isopropanol and butanol; aliphatic polyhydric alcohols such as ethylene glycol and glycerin; alicyclics such as cyclohexanol, terpineol and dihydroterpineol.
  • alcohol solvents for example, alkanols such as methanol, ethanol, isopropanol and butanol
  • aliphatic polyhydric alcohols such as ethylene glycol and glycerin
  • alicyclics such as cyclohexanol, terpineol and dihydroterpineol.
  • ester solvents eg, acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether monoacetate
  • ketone solvents eg, chain ketones such as acetone; cyclic ketones such as cyclohexanone
  • Ether solvents for example, chain ethers such as propylene glycol monomethyl ether and diethylene glycol dimethyl ether; cyclic ethers such as dioxane and tetrahydrofuran
  • Aromatic solvents for example, aromatic hydrocarbons such as toluene and xylene
  • halogen solvents for example, haloalkanes such as dichloromethane and chloroform
  • nitrile solvents for example, acetonitrile, benzonitrile, etc.
  • nitro solvents for example, nitrobenzene etc.
  • These dispersion media can be used alone or in combination of two or more.
  • a dispersion medium may be selected according to the type of the protective layer.
  • the dispersion medium may be a C 1-4 alkanol such as methanol, a cyclic ether such as tetrahydrofuran, an ethyl acetate or the like.
  • Acetic acid C 1-3 alkyl ester may be used.
  • the dispersion medium may be an alicyclic alcohol such as terpineol, a cyclic ether such as tetrahydrofuran, or an acetic acid C 1-3 alkyl ester such as ethyl acetate.
  • the dispersion medium is a C 1-4 alkanol such as methanol, an alicyclic alcohol such as terpineol, a cyclic ether such as tetrahydrofuran, or a C 1 -acetate such as ethyl acetate. It may be a trialkyl ester.
  • the ratio of the dispersion medium is, for example, about 10 to 1000 parts by weight, preferably 30 to 500 parts by weight, and more preferably 50 to 400 parts by weight (particularly 80 to 300 parts by weight) with respect to 100 parts by weight of the composite fine particles. If the proportion of the dispersion medium is too large, cracks and the like are likely to occur during drying after coating, and it may be difficult to form a highly conductive sintered film, and if it is too small, the coating properties of the dispersion will be reduced. There is a risk of doing.
  • the dispersion of the present invention may further contain an acidic compound and / or an acid generator as a decomposition aid for the acid-decomposable polymer in order to improve sintering at a low temperature.
  • Acidic compounds include inorganic acids, organic acids and the like.
  • the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid and the like.
  • the organic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, caprylic acid and stearic acid; aliphatics such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and maleic acid
  • dicarboxylic acids alicyclic carboxylic acids such as naphthenic acid
  • hydroxycarboxylic acids such as glycolic acid, lactic acid, tartaric acid, malic acid, and citric acid
  • arene sulfonic acids such as toluenesulfonic acid.
  • These inorganic acids and organic acids may be metal salts (for example, alkali metal salts such as sodium, alkaline earth metal salts such as calcium, and periodic table group 14 metal salts such as tin).
  • alkali metal salts such as sodium
  • alkaline earth metal salts such as calcium
  • periodic table group 14 metal salts such as tin
  • These acidic compounds can be used alone or in combination of two or more.
  • C 1-4 aliphatic monocarboxylic acids (particularly formic acid) such as formic acid are preferred because they do not inhibit the sinterability at low temperatures and are excellent in the decomposability of the acid-decomposable polymer.
  • the acid generator examples include conventional acid generators such as sulfonium salts (sulphonium ions and anions), iodonium salts (iodonium ions and anions), selenium salts (selenium ions and anions), Ammonium salts (salts of ammonium ions and anions), phosphonium salts (salts of phosphonium ions and anions), salts of transition metal complex ions and anions, allene-ion complexes, aluminum chelates, boron trifluoride amine complexes, etc. Can be mentioned. These acid generators can be used alone or in combination of two or more. Of these acid generators, sulfonium salts are preferred because of their high acidity.
  • sulfonium salt examples include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, and 2-naphthyldiphenylsulfonium salt.
  • Triarylsulfonium salts such as 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salt; diphenylphenacylsulfonium salt, diphenyl-4-nitrophenacylsulfonium salt, diphenylbenzyl Sulfonium salts, diaryl sulfonium salts such as diphenyl methyl sulfonium salts; phenylmethyl benzyl sulfonium salt, 4-hydroxyphenyl-methyl benzyl sulfonium salt, such as mono
  • anion (counter ion) for forming a salt with the sulfonium ion (cation) examples include SbF 6 ⁇ , PF 6 ⁇ , BF 4 ⁇ , fluorinated alkyl fluorophosphate ion [(CF 3 CF 2 ) 3 PF 3- , (CF 3 CF 2 CF 2 ) 3 PF 3- etc.], (C 6 F 5 ) 4 B ⁇ , (C 6 F 5 ) 4 Ga ⁇ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoro Ethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), (CF 3 SO 2 ) 3 C ⁇ , (CF 3 SO 2 ) 2 N ⁇ , Perhalogenate i
  • the acid generator may be a thermal acid generator or a photoacid generator.
  • thermal acid generators such as “Sun-Aid SI-60L”, “Sun-Aid SI-60S”, “Sun-Aid SI-80L”, “Sun-Aid” manufactured by Sanshin Chemical Industry Co., Ltd. "SI-100L”, “Sun-Aid SI-110L”, ADEKA “SP-66", “SP-77”, etc. can be used.
  • Commercially available products can also be used as the photoacid generator, for example, “HS-1”, “HS-1A”, “HS-1P”, “HS-1N”, “HS-1TF” manufactured by San Apro Co., Ltd.
  • HS-1NF HS-1NF
  • HHS-1MS HS-1CS
  • H-1PC HS-1PC
  • LW-S1 LW-S1
  • LW-S1NF K1-S
  • CPI CPI-100P
  • CPI300PG CPI300PG
  • the decomposition aid may be selected according to the type of the acid-decomposable polymer contained in the protective layer.
  • an acid generator may be used, and the polymer (2 ), An acidic compound may be used.
  • an acid generator is preferable from the viewpoint that the low-temperature sinterability can be easily improved, and a thermal acid generator is particularly preferable from the viewpoint that heat of the firing step can be used.
  • the proportion of the decomposition aid is, for example, from 0.01 to 100 parts by weight, preferably from 0.03 to 80 parts by weight, and more preferably from 0. About 05 to 50 parts by weight.
  • the ratio of the decomposition aid is, for example, 0.01 to 100 parts by weight with respect to 100 parts by weight of the composite fine particles.
  • the amount is about 10 parts by weight, preferably about 0.03 to 5 parts by weight, more preferably about 0.05 to 3 parts by weight (particularly 0.08 to 2 parts by weight).
  • the proportion of the decomposition aid (particularly acidic compound) is, for example, 1 to 100 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the composite fine particles. More preferably, it is about 10 to 50 parts by weight (particularly 20 to 40 parts by weight).
  • the ratio of the decomposition aid (particularly acidic compound) is, for example, about 1 to 30% by weight, preferably about 3 to 20% by weight, and more preferably about 5 to 15% by weight with respect to the entire dispersion (ink). .
  • the decomposition aid may remain after sintering and the conductivity may be lowered, or the stability of the dispersion may be lowered. If too small, the low temperature sinterability is lowered. In addition, there is a possibility that the conductivity is lowered due to insufficient decomposition of the acid-decomposable polymer.
  • the dispersion of the present invention may contain a conventional additive added to the conductive paste or the conductive ink depending on the application.
  • the conventional additive include a colorant (such as a dye / pigment), a hue improver, a dye fixing agent, and a gloss imparting agent in addition to the conventional additives exemplified in the section of the protective layer.
  • the proportion of conventional additives may be 50% by weight or less with respect to the total dispersion, for example, about 0.01 to 10% by weight (particularly 0.1 to 5% by weight).
  • the dispersion process may be a dispersion process in which the dispersion process is performed under pressure.
  • the pressure in the dispersing step may be 10 MPa or more, for example, about 30 to 500 MPa, preferably about 50 to 300 MPa, more preferably about 80 to 200 MPa (particularly 100 to 180 MPa).
  • Such dispersion under pressure may be dispersed using an ultrahigh pressure disperser. If the pressure is too low, it may be difficult to prepare a uniform dispersion with a high concentration. Dispersion treatment under pressure is particularly effective when the acid-decomposable polymer is the polymer (1) or (2).
  • a stirring process such as a stirring process using a rotation / revolution stirrer
  • an ultrasonic process for example, an ultrasonic process of about 10 to 100 kHz
  • the coating film of this invention is obtained through the application
  • the base material may be an inorganic material or an organic material.
  • inorganic materials include glasses (soda glass, borosilicate glass, crown glass, barium-containing glass, strontium-containing glass, boron-containing glass, low alkali glass, alkali-free glass, crystallized transparent glass, silica glass, and quartz glass.
  • metal oxides alumina, sapphire, zirconia, titania, yttrium oxide, indium oxide-tin oxide composite oxide (ITO), fluorine-doped tin oxide (FTO), etc.
  • organic materials include polymethyl methacrylate resin, polypropylene resin, cyclic polyolefin resin, styrene resin, vinyl chloride resin, polyester resin [polyalkylene arylate resin (polyethylene terephthalate, etc.), polyarylate. And other resins such as polyamide resins, polycarbonate resins, polysulfone resins, polyethersulfone resins, polyimide resins, cellulose derivatives, and fluororesins.
  • the average thickness of the substrate is, for example, about 0.001 to 10 mm, preferably about 0.01 to 5 mm, and more preferably about 0.05 to 3 mm.
  • a coating method As a coating method, a conventional method can be used.
  • a pattern such as a wiring pattern on a wiring board
  • a coating film for example, a screen printing method, an ink jet printing method, an intaglio printing method (for example, a gravure printing method, etc.) ), Offset printing method, intaglio offset printing method (for example, gravure offset printing method), relief printing method, flexographic printing method, reverse printing, and the like can be used.
  • the average thickness of the coating film may be, for example, about 0.5 to 100 ⁇ m (eg 1 to 20 ⁇ m), preferably 1 to 80 ⁇ m (eg 3 to 10 ⁇ m), more preferably about 5 to 50 ⁇ m (particularly 10 to 40 ⁇ m).
  • the average line width of the coating film is, for example, 0.5 to 30 ⁇ m, preferably 1 to 20 ⁇ m, more preferably 2 to 10 ⁇ m (particularly 3 to 3 ⁇ m). It may be about 8 ⁇ m).
  • a dispersion (paste or ink) containing nanometer-sized metal fine particles at a high concentration can be prepared, a fine wiring pattern can be easily formed.
  • the fired film of the present invention is obtained through a firing process in which the obtained coating film is heated and fired.
  • the heating temperature may exceed 200 ° C., but when the dispersion contains a decomposition aid, sintering at a low temperature is possible and may be 200 ° C. or less, for example, 60 to 200. It is about 80 to 180 ° C. (eg 100 to 175 ° C.), more preferably about 120 to 170 ° C. (especially 130 to 160 ° C.).
  • the acid-decomposable polymer is polymer (3) or (4) and the dispersion contains a decomposition aid (particularly an acid generator)
  • sintering at a lower temperature is possible, and the heating temperature is 120.
  • the temperature may be not higher than 60 ° C., for example, 60 to 120 ° C., preferably 80 to 110 ° C., and more preferably about 90 to 105 ° C.
  • the firing time is, for example, about 10 minutes to 10 hours, preferably 15 minutes to 8 hours, more preferably 20 minutes to 6 hours (particularly 30 minutes to 5 hours) depending on the firing temperature and the like. .
  • the firing step may be performed in an active gas atmosphere containing oxygen such as air, but is preferably fired in an inert gas atmosphere such as hydrogen, nitrogen, or argon from the viewpoint that oxidation of metal fine particles can be suppressed.
  • the inert gas may be a combination of two or more inert gases containing hydrogen.
  • the present invention it becomes possible to sinter at a low temperature by decomposing the acid-decomposable polymer.
  • the dispersion contains a thermal acid generator, an acid is generated by heating in the baking step, and the acid-decomposable polymer is decomposed.
  • the polymer may be degraded.
  • a polymer decomposition step for decomposing the acid-decomposable polymer may be separately provided as a pre-step of the baking step depending on the presence or type of the acid-decomposable polymer.
  • a polymer decomposition step of heating at, for example, 35 to 100 ° C., preferably 40 to 80 ° C., more preferably about 45 to 60 ° C. may be provided.
  • a polymer decomposing step for decomposing the acid-decomposable polymer may be separately provided as a pre-step of the baking step.
  • the heating temperature in the polymer decomposition step is, for example, about 40 to 200 ° C., preferably 50 to 180 ° C., more preferably about 70 to 150 ° C.
  • a polymer decomposition step for generating acid by irradiating visible light or ultraviolet light may be provided.
  • the coating film that has undergone the coating step may be irradiated with light and then subjected to a baking step.
  • the polymer decomposition step may be a step of irradiating light simultaneously with the baking in the baking step.
  • an acid may be generated by irradiating ultraviolet rays or visible light at the stage of the dispersion, and thereafter, it may be subjected to a coating step and a baking step.
  • the light source for light irradiation a conventional light source can be used. In the case of ultraviolet rays, ultrahigh to low pressure mercury lamps, LEDs, xenon lamps and the like can be mentioned.
  • the fired film of the present invention is excellent in conductivity and may have an electrical resistivity of 0.5 ⁇ / ⁇ or less, for example, 0.01 to 0.5 ⁇ / ⁇ , preferably 0.02 to 0.3 ⁇ . / ⁇ , more preferably about 0.03 to 0.1 ⁇ / ⁇ .
  • the fired film of the present invention may have a specific resistivity of 1 ⁇ 10 ⁇ 5 ⁇ ⁇ cm or less, for example, 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, preferably 1 ⁇ 10 ⁇ It is about 8 to 3 ⁇ 10 ⁇ 6 ⁇ ⁇ cm, more preferably about 5 ⁇ 10 ⁇ 8 to 2 ⁇ 10 ⁇ 6 ⁇ ⁇ cm.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymers obtained in Synthesis Examples 2 and 3 were connected to three columns (“TSKgel-superHZM-M” manufactured by Tosoh Corporation) to transfer tetrahydrofuran.
  • the phase was obtained in terms of polystyrene using a high-speed gel permeation column chromatography apparatus (“HLC-8220GPC” manufactured by Tosoh Corporation) equipped with an RI8020 detector at a flow rate of 0.6 mL / min at 40 ° C.
  • TG-DTA was measured under the following conditions using a differential thermothermal gravimetric simultaneous measurement apparatus (“TG-DTA6200” manufactured by SII Nanotechnology Co., Ltd.).
  • X-ray diffraction (XRD) of composite fine particles, coating film and fired film [X-ray diffraction (XRD) of composite fine particles, coating film and fired film] Using a desktop X-ray diffractometer (“MiniFlex II” manufactured by Rigaku Corporation), a start angle of 10 °, an end angle of 110.005 °, a sampling width of 0.015 °, a scan speed of 10.0 ° per minute, and a voltage of 30 kV , Measured at a current of 15 mA.
  • XRD X-ray diffraction
  • Polymer synthesis example 1 Synthesis of Polymer for Protective Layer (p-MOMPO)] Under a dry nitrogen atmosphere, 3.1 mL of purified toluene, 0.25 mL of purified heptane, 0.4 mL of tetrahydrofuran (THF), and 0.28 mL of 2-methoxy-1-methylpropylene oxide are added to the container 1 so as to be uniform. Was stirred.
  • the containers are all glass containers equipped with three-way stopcocks, and heated for 10 minutes using an industrial blaster that emits hot air at about 400 ° C. in a dry nitrogen atmosphere. The one from which adsorbed water was removed as much as possible was used.
  • the conversion rate of the monomer (2-methoxy-1-methylpropylene oxide) in the polymerization was 89% (polymerization time: 4 hours). Moreover, the weight average molecular weight (Mw) of the obtained polymer was 5300, and molecular weight distribution (Mw / Mn) was 1.30.
  • FIG. 1 shows a chart of 1 H-NMR spectrum of the obtained polymer.
  • FIG. 1 shows to which proton of the polymer the 1 H-NMR spectrum peak belongs.
  • the integration ratio [g: (b, c, h, k): (g, proton peak of b, c, h, and k, proton peak of a, f, and i] a, f, i)] was 1: 3: 6.
  • the NMR data of the obtained polymer are shown below.
  • Polymer synthesis example 2 [Synthesis of protective layer polymer (p-ISB)] Add 5 g of isosorbide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.43 g of pyridinium p-toluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) to 20 g of propylene glycol monomethyl ether acetate (manufactured by Daicel Co., Ltd.) and add 30 g or less. Then, 6.78 g of isosorbide divinyl ether (manufactured by Daicel Corporation) was added dropwise. After dropping, the mixture was stirred at 40 ° C. for 4 hours.
  • p-ISB protective layer polymer
  • the polymer had a weight average molecular weight Mw of 5200 and a molecular weight distribution (Mw / Mn) of 2.2.
  • Mw / Mn molecular weight distribution
  • Polymer synthesis example 3 [Synthesis of protective layer polymer (p-BDO)] 1,7-butanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.59 g of pyridinium paratoluenesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to molecular sieves (manufactured by Wako Pure Chemical Industries, Ltd.). 4A 1/16 ") was added to 265 g of propylene glycol monomethyl ether acetate (Daicel Co., Ltd.) dehydrated, and 100.2 g of 1,4-butanediol divinyl ether (Sigma Aldrich) was added dropwise at 40 ° C.
  • p-BDO protective layer polymer
  • Synthesis example 1 of composite fine particles [Synthesis of copper particles coated with p-MOMPO] After dissolving 1.2802 g of the p-MOMPO obtained in Polymer Synthesis Example 1 in 20 mL of a tetrahydrofuran solution containing 0.4 M ammonia at room temperature, copper (II) oxide (“N-130 manufactured by Nisshin Chemco Co., Ltd.) was dissolved. ] 0.8094 g was added and heated to 60 ° C. with stirring, and 24 mL of a tetrahydrofuran solution containing 1M hydrazine was added while stirring. Foaming from the reaction solution was confirmed 12 minutes after the addition. After completion of foaming, the reaction was continued at 60 ° C.
  • the produced particles are filtered through a filter having a diameter of 0.2 ⁇ m, and the filtered particles are washed with tetrahydrofuran and water and vacuum dried at room temperature to obtain copper fine particles (composite fine particles) 0 coated with p-MOMPO. .5 g was obtained.
  • the composite fine particles were observed with an SEM (50000 times) and the particle diameter was measured. As a result, the median diameter was 123.8 nm.
  • the measurement result of SEM is shown in FIG.
  • Synthesis example 2 of composite fine particles [Synthesis of copper particles coated with p-ISB] 3.3 g of p-ISB obtained in Synthesis Example 2 of the polymer and 12.5 g of copper (II) sulfate pentahydrate were added to 10 mL of distilled water, and stirred at 50 ° C. for 1 hour to dissolve. 12.5 mL of hydrazine monohydrate was added to this mixed solution, and the mixture was reacted at 50 ° C. for 3 hours. Distilled water was added to the reaction solution, centrifuged for 5 minutes at 5000 rpm, washed twice by decantation, further added with ethanol, centrifuged for 5 minutes at 5000 rpm, and washed twice by decantation.
  • the obtained particles were dried at room temperature under a nitrogen atmosphere to obtain 3.2 g of copper fine particles (composite fine particles) coated with p-ISB.
  • the composite fine particles were observed with an SEM (50000 times) and the particle diameter was measured. As a result, the median diameter was 90 nm.
  • the measurement result of SEM is shown in FIG.
  • Synthesis example 3 of composite fine particles [Synthesis of copper particles coated with p-BDO] After dissolving 1.67 g of p-BDO obtained in Polymer Synthesis Example 3 in 500 mL of tetrahydrofuran at room temperature, 20 g of copper (II) oxide (“N-130” manufactured by Nisshin Chemco Co., Ltd.) was added and stirred. While heating to 50 ° C., 12.5 mL of hydrazine monohydrate was added to this mixed solution, and the mixture was stirred at 50 ° C. for 3 hours to be reacted. Distilled water was added to the reaction solution, and centrifugal sedimentation was performed at 5000 rpm for 5 minutes.
  • copper (II) oxide (“N-130” manufactured by Nisshin Chemco Co., Ltd.
  • Example 1 Manufacture and baking evaluation of copper ink
  • Copper fine particles (composite fine particles) coated with p-MOMPO were sieved with a 60-mesh sieve, and the composite fine particles that passed through the sieve were pulverized in a mortar.
  • 50 ml of methanol was added to 0.1260 g of the composite fine particles, and the mixture was stirred for 8 minutes with a mixer (“Spinky / Revolution Hybrid-Mixer” manufactured by Shinkey Co., Ltd.), then irradiated with 40 kHz ultrasonic waves for 10 minutes, and a 400 mesh filter. And filtered.
  • Example 2 After adding 3.0 g of copper fine particles (composite fine particles) coated with p-ISB and 7.0 g of ⁇ -terpineol to 30 mL of methanol, 32 minutes with a mixer (“Spinning / Revolving Hybrid-Mixer” manufactured by Sinky Corp.) Stir. After stirring, using an ultra-high pressure disperser (“Starburst” manufactured by Sugino Machine Co., Ltd.), dispersion treatment was performed 5 times at an injection pressure of 150 MPa to obtain a dispersion of composite fine particles. The dispersion was concentrated under reduced pressure to remove methanol, and 0.13 mL of formic acid was added to 1.4 mL of the concentrated solution to obtain a copper ink.
  • a mixer Spinning / Revolving Hybrid-Mixer” manufactured by Sinky Corp.
  • This copper ink was applied to an alumina plate with a doctor blade with a film thickness of 40 ⁇ m, desorbed at 60 ° C. under nitrogen for 2 hours, and then baked at 150 ° C. under 3% hydrogen mixed nitrogen for 2 hours.
  • the electrical resistivity of the coating film after baking was 0.3036 ⁇ / ⁇ .
  • X-ray diffraction (XRD) of the composite fine particles, the coating film after coating, and the fired film were measured. The measurement result of XRD is shown in FIG.
  • Example 3 A copper ink was obtained in the same manner as in Example 1 except that the acid generator was not added in Example 1. This copper ink was applied to an alumina plate with a doctor blade with a film thickness of 20 ⁇ m, desorbed at 200 ° C. under air for 4 hours, and then baked at 200 ° C. under 3% hydrogen mixed nitrogen for 2 hours. The electrical resistivity of the coating film after firing was 0.071 ⁇ / ⁇ .
  • X-ray diffraction (XRD) of the composite fine particles, the coating film after coating, the coating film after removal of the solvent and the fired film were measured. The measurement result of XRD is shown in FIG.
  • Example 4 Evaluation of conductivity by hot pressing of copper particles
  • 1 g of the composite fine particles obtained in Synthesis Example 3 of the composite fine particles and 10 mg of an acid generator (“SI-100” manufactured by Sanshin Chemical Industry Co., Ltd.) are mixed, and the temperature shown in Table 2 is kept under air at 100 MPa for 30 minutes. Hot pressing ( ⁇ 13 mm) was performed.
  • 1 g of the composite fine particles obtained in Synthesis Example 3 of composite fine particles were hot-pressed ( ⁇ 13 mm) at 100 MPa for 30 minutes under air at each temperature shown in Table 2.
  • Table 2 shows the film thickness and specific resistivity of the obtained copper film.
  • the composite fine particles of the present invention can be used as conductive inks or conductive pastes for the formation of various conductors.
  • the metal fine particles are nanometer-sized and high-concentration inks or pastes can be prepared, the fine particles to be densified. It can be effectively used for forming a wiring pattern. Therefore, the composite fine particles of the present invention are preferably used for a transparent wiring board on which a fine wiring pattern is formed, and an electronic device equipped with this wiring board.

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Abstract

La présente invention porte sur de fines particules composites, chacune étant préparée par recouvrement d'au moins une partie de la surface d'une fine particule métallique avec une couche protectrice qui contient un polymère décomposable en milieu acide. Les fines particules composites ainsi obtenues peuvent être frittées à de basses températures. Les fines particules composites peuvent avoir un diamètre moyen de particule inférieur ou égal à 3 000 nm. La fine particule métallique peut être une fine particule de cuivre. Le polymère décomposable en milieu acide peut avoir une liaison acétal. Selon l'invention, une carte de câblage peut être produite par : préparation d'une encre conductrice ou d'une pâte conductrice par ajout d'un composé acide et/ou d'un générateur d'acide dans une dispersion des fines particules composites; et cuisson de l'encre conductrice ou de la pâte conductrice à 200 °C ou moins.
PCT/JP2016/051398 2015-02-06 2016-01-19 Fines particules composites, dispersion liquide, procédé de production et utilisation desdites fines particules composites et procédé de production et utilisation de ladite dispersion liquide WO2016125581A1 (fr)

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JP2019007032A (ja) * 2017-06-20 2019-01-17 住友金属鉱山株式会社 ニッケルペースト及びその製造方法、並びにニッケル有機スラリーの製造方法
JP7091611B2 (ja) 2017-06-20 2022-06-28 住友金属鉱山株式会社 ニッケルペースト及びその製造方法、並びにニッケル有機スラリーの製造方法
WO2022045252A1 (fr) * 2020-08-28 2022-03-03 国立大学法人北海道大学 Particules fines de cuivre contenant de l'oxyde, leur procédé de fabrication et procédé de fabrication d'un comprimé fritté à partir de fines particules de cuivre contenant de l'oxyde
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CN115461173A (zh) * 2020-08-28 2022-12-09 国立大学法人北海道大学 含氧化物的铜微粒及其制造方法、以及使用该含氧化物的铜微粒的烧结体的制造方法
JP7507511B2 (ja) 2020-08-28 2024-06-28 国立大学法人北海道大学 酸化物含有銅微粒子およびその製造方法、ならびにそれを用いた焼結体の製造方法
JPWO2023013572A1 (fr) * 2021-08-03 2023-02-09
WO2023013572A1 (fr) * 2021-08-03 2023-02-09 三菱マテリアル株式会社 Encre métallique, procédé de fabrication d'encre métallique et procédé de fabrication de couche métallique
JP7517615B2 (ja) 2021-08-03 2024-07-17 三菱マテリアル株式会社 金属インク、金属インクの製造方法、及び金属層の製造方法
WO2023140300A1 (fr) * 2022-01-19 2023-07-27 三菱マテリアル株式会社 Encre métallique, procédé de production d'encre métallique, procédé de production de couche métallique, et couche métallique
JPWO2023140300A1 (fr) * 2022-01-19 2023-07-27
JP7464202B2 (ja) 2022-01-19 2024-04-09 三菱マテリアル株式会社 金属インク、金属インクの製造方法、金属層の製造方法、及び金属層
CN116851770A (zh) * 2023-07-23 2023-10-10 长江师范学院 一种利用水溶性碱性柱[5]芳烃合成金纳米粒子的方法

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TW201631607A (zh) 2016-09-01
JP6661128B2 (ja) 2020-03-11

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