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WO2015111755A1 - Procédé pour fabriquer une nanofibre conductrice - Google Patents

Procédé pour fabriquer une nanofibre conductrice Download PDF

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Publication number
WO2015111755A1
WO2015111755A1 PCT/JP2015/052192 JP2015052192W WO2015111755A1 WO 2015111755 A1 WO2015111755 A1 WO 2015111755A1 JP 2015052192 W JP2015052192 W JP 2015052192W WO 2015111755 A1 WO2015111755 A1 WO 2015111755A1
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WIPO (PCT)
Prior art keywords
group
hyperbranched polymer
plating
fine particles
nanofiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2015/052192
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English (en)
Japanese (ja)
Inventor
島田　直樹
幸治 中根
信男 小形
小島　圭介
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
University of Fukui NUC
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Nissan Chemical Corp
University of Fukui NUC
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Application filed by Nissan Chemical Corp, University of Fukui NUC filed Critical Nissan Chemical Corp
Priority to JP2015559164A priority Critical patent/JP6571008B2/ja
Publication of WO2015111755A1 publication Critical patent/WO2015111755A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • C23C18/1641—Organic substrates, e.g. resin, plastic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/22—Polymers or copolymers of halogenated mono-olefins

Definitions

  • the present invention relates to a method for producing conductive nanofibers by using a resin composition in which a hyperbranched polymer and metal fine particles are blended in a thermoplastic resin as a spinning material, and subjecting the resin composition to electrostatic spinning and electroless plating.
  • conductive fibers can be cited as materials that satisfy these properties.
  • an electroless plating process on the surface of the fiber material is known.
  • electroless plating usually requires a pre-plating process including etching, conditioning, catalyzing, acceleration, and other processes, so that the manufacturing process is complicated and expensive.
  • a chemical etching process since a chemical such as chromic acid or an alkali metal hydroxide solution is used, a waste liquid process is required.
  • Non-patent Document 1 a method of imparting conductivity by irradiating the nanofibers with ions (Patent Document 1), and spinning by the electrospinning method.
  • Nylon 6 nanofibers are electrolessly plated (Non-patent Document 1)
  • a conductive polymer polypyrrole is used to produce nanofibers by electrospinning (Non-patent Document 2)
  • palladium chloride is used.
  • Patent Document 2 An example (Patent Document 2) in which electroless nickel plating is performed on nanofibers mixed with a resin and manufactured by an electrospinning method is disclosed.
  • the nanofiber surface is treated with iodine to form metal iodide composite organic nanofibers, and further, the metal iodide is reduced to a metal body, followed by electroless plating treatment. Examples are also disclosed (Patent Document 3).
  • the surface resistance of the conductive nanofiber obtained by the technique of Patent Document 1 is large, and the electrical conductivity is insufficient for use as a conductive material.
  • etching of the nanofiber surface is performed by low-temperature oxygen plasma treatment, and this plasma treatment apparatus is very expensive, and the plasma treatment performed under vacuum is a batch type, Not suitable for industrial mass production.
  • the conductivity of the conductive polymer disclosed in Non-Patent Document 2 is lower than that of metal, and the electrical conductivity is still insufficient as a conductive material.
  • the method of Patent Document 2 cannot be plated depending on the type of plating solution or the type of metal to be plated.
  • the process before plating is complicated.
  • the electroless plating method using a complex as a catalyst is an activation treatment such as a reduction treatment. And the operation is complicated, and there is a problem that plating cannot be performed depending on the type of plating metal and the type of plating solution. That is, there has been a demand for a method for producing conductive nanofibers that can use various kinds of plating metal species and plating solutions for conductive nanofibers having sufficient conductivity without complicated operations.
  • the present inventors have obtained a result obtained by mixing a hyperbranched polymer having an ammonium group at the molecular terminal and a metal fine particle with a thermoplastic resin as a matrix polymer and electrostatic spinning.
  • electroless plating By applying electroless plating to the nanofibers, it is possible to obtain nanofibers with sufficient electrical conductivity as a conductive material, and electroless plating can be performed without restricting the type of plating metal or plating solution As a result, the present invention was completed.
  • the present invention provides the first aspect as follows: A resin composition comprising (a) a thermoplastic resin, (b) a hyperbranched polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000, and (c) metal fine particles.
  • the present invention relates to a method for producing conductive nanofibers, which includes a spinning step of producing nanofibers according to an electrospinning method as a spinning material, and a plating step of performing electroless plating treatment of the nanofibers produced in the step.
  • the present invention relates to the production method according to the first aspect, in which the ammonium group of the (b) hyperbranched polymer is attached to the metal fine particles (c) to form a complex.
  • the said (b) hyperbranched polymer is related with the manufacturing method as described in a 1st viewpoint or a 2nd viewpoint which is a hyperbranched polymer represented by Formula [1].
  • each R 1 independently represents a hydrogen atom or a methyl group
  • R 2 to R 4 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
  • the alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxyl group, or a cyano group), or two groups of R 2 to R 4 may be bonded together.
  • a number of by unit structure represents an integer of 5 to 100,000
  • a 1 represents a structure represented by the formula [2].)
  • a 2 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond
  • Y 1 to Y 4 are each independently hydrogen.
  • And represents an atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.
  • the said (b) hyperbranched polymer is related with the manufacturing method as described in a 3rd viewpoint which is a hyperbranched polymer represented by Formula [3].
  • R 1 , R 2 to R 4 and n represent the same meaning as described above.
  • the metal fine particles (c) include iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver (Ag), tin (Sn), platinum ( The manufacturing method according to any one of the first aspect to the fourth aspect, wherein the fine particles are at least one metal selected from the group consisting of Pt) and gold (Au).
  • the present invention relates to the manufacturing method according to the fifth aspect, wherein the metal fine particles (c) are palladium fine particles.
  • the present invention relates to the production method according to any one of the first to sixth aspects, wherein the (c) metal fine particles are fine particles having an average particle diameter of 1 to 100 nm.
  • the present invention relates to the production method according to any one of the first aspect to the seventh aspect, wherein the (a) thermoplastic resin is polyvinylidene fluoride.
  • the present invention relates to the production method according to any one of the first aspect to the eighth aspect, wherein the nanofiber has an average diameter of 50 to 2,000 nm.
  • the present invention relates to the manufacturing method according to the tenth aspect, in which the plating step is an electroless copper plating treatment and the second plating step is an electroless tin plating treatment.
  • the spinning step relates to the production method according to any one of the first aspect to the eleventh aspect, which is a process of producing a nanofiber aggregate as a nanofiber.
  • the present invention relates to the conductive nanofiber assembly according to the fourteenth aspect, which has a volume resistance value of 1 ⁇ 10 4 ⁇ ⁇ cm or less.
  • the resulting nanofibers are immersed in an electroless plating bath.
  • Conductive nanofibers excellent in electrical conductivity can be easily obtained. For this reason, it is not bothered by the necessity of the complicated pre-processing process required for the conventional electroless-plating process, the complexity of a manufacturing process, and cost increase.
  • the manufacturing method of this invention can be electroless-plated with various plating metal seed
  • a conductive nanofiber having a very low volume resistance value of 1 ⁇ 10 4 ⁇ ⁇ cm or less and satisfying electrical conductivity as a conductive material and an aggregate thereof are provided. be able to.
  • the conductive nanofiber aggregate of the present invention has a very low volume resistance as described above, it can be suitably used for high capacity battery electrodes, sensor electrodes, antistatic sheets, electromagnetic wave shields and the like.
  • FIG. 1 is a diagram showing a 1 H NMR spectrum of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end obtained in Production Example 1.
  • FIG. 2 is a diagram showing a 13 C NMR spectrum of a hyperbranched polymer (HPS-N (Me) 2 OctCl) having a dimethyloctylammonium group at the molecular end obtained in Production Example 2.
  • FIG. 3 is a diagram showing a 13 C NMR spectrum of a hyperbranched polymer (HPS-NOct 3 Cl) having a trioctylammonium group at the molecular end obtained in Production Example 4.
  • FIG. 4 is a diagram showing an SEM image of the nanofiber mat obtained in Example 1.
  • 5 is a view showing an SEM image of the nanofiber mat obtained in Example 7.
  • FIG. 1 is a diagram showing a 1 H NMR spectrum of a hyperbranched polymer (HPS-Cl) having a chlorine atom at the mo
  • the method for producing conductive nanofibers of the present invention includes a spinning step of producing nanofibers according to an electrospinning method using a resin composition described later as a spinning material, and a plating step of performing electroless plating treatment of the nanofibers produced in the above steps. It is characterized by including.
  • Conductive nanofibers produced by the production method of the present invention are also objects of the present invention.
  • the resin composition used in the method for producing conductive nanofibers of the present invention comprises (a) a thermoplastic resin, (b) an ammonium group at the molecular end, and a weight average molecular weight of 1,000 to 5,000,000. A hyperbranched polymer, and (c) metal fine particles.
  • thermoplastic resin used in the present invention is not particularly limited.
  • PE polyethylene
  • PP polypropylene
  • EVA ethylene-vinyl acetate copolymer
  • EVOH ethylene-vinyl alcohol copolymer
  • PVA polyvinyl
  • the hyperbranched polymer used in the resin composition used in the present invention is a polymer having an ammonium group at the molecular end and a weight average molecular weight of 1,000 to 5,000,000.
  • the hyperbranched polymer represented by [1] is mentioned.
  • R 1 represents a hydrogen atom or a methyl group independently.
  • R 2 to R 4 are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or — ( CH 2 CH 2 O) m R 5 (wherein R 5 represents a hydrogen atom or a methyl group, and m represents an arbitrary integer of 2 to 100).
  • the alkyl group and arylalkyl group may be substituted with an alkoxy group, a hydroxy group, an ammonium group, a carboxyl group, or a cyano group.
  • R 2 to R 4 together represent a linear, branched or cyclic alkylene group, or R 2 to R 4 together with the nitrogen atom to which they are attached.
  • X ⁇ represents an anion
  • n represents the number of repeating unit structures, and represents an integer of 5 to 100,000.
  • Examples of the linear alkyl group having 1 to 20 carbon atoms in R 2 to R 4 include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group and the like.
  • the hyperbranched polymer in the resin composition used as the spinning material is less likely to elute into the electroless plating solution and has 8 or more carbon atoms.
  • Group is preferable, and n-octyl group is particularly preferable.
  • the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
  • the cyclic alkyl group include a cyclopentyl ring and a group having a cyclohexyl ring structure.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms in R 2 to R 4 include a benzyl group and a phenethyl group. Further, examples of the linear alkylene group in which two of R 2 to R 4 are combined include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, and an n-hexylene group. It is done. Examples of the branched alkylene group include an isopropylene group, an isobutylene group, and a 2-methylpropylene group.
  • Examples of the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic or bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms. These alkylene groups may contain a nitrogen atom, a sulfur atom or an oxygen atom in the group.
  • the ring formed by R 2 to R 4 together with the nitrogen atom bonded to them in the structure represented by the formula [1] may contain a nitrogen atom, a sulfur atom or an oxygen atom in the ring.
  • R 2 to R 4 examples include [methyl group, methyl group, methyl group], [methyl group, methyl group, ethyl group], [methyl group, methyl group, n-butyl group], [methyl group] Group, methyl group, n-hexyl group], [methyl group, methyl group, n-octyl group], [methyl group, methyl group, n-decyl group], [methyl group, methyl group, n-dodecyl group], [Methyl group, methyl group, n-tetradecyl group], [methyl group, methyl group, n-hexadecyl group], [methyl group, methyl group, n-octadecyl group], [ethyl group, ethyl group, ethyl group],
  • a 1 represents a structure represented by the following formula [2].
  • a 2 represents a linear, branched or cyclic alkylene group having 1 to 30 carbon atoms which may contain an ether bond or an ester bond.
  • Y 1 to Y 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a nitro group, a hydroxy group, an amino group, a carboxyl group, or a cyano group.
  • alkylene group of A 2 examples include linear alkylene groups such as methylene group, ethylene group, n-propylene group, n-butylene group and n-hexylene group, isopropylene group, isobutylene group, 2-methyl group.
  • examples include branched alkylene groups such as propylene groups.
  • the cyclic alkylene group include alicyclic aliphatic groups having a monocyclic, polycyclic and bridged cyclic structure having 3 to 30 carbon atoms. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo, or pentacyclo structure having 4 or more carbon atoms.
  • structural examples (a) to (s) of the alicyclic portion of the alicyclic aliphatic group are shown below.
  • Examples of the alkyl group having 1 to 20 carbon atoms of Y 1 to Y 4 in the above formula [2] include a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, and an n-pentyl group.
  • Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, isopropoxy group, cyclohexyloxy group, n-pentyloxy group and the like.
  • Y 1 to Y 4 are preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • the A 1 is a structure represented by the following formula [4].
  • the hyperbranched polymer used in the present invention includes a hyperbranched polymer represented by the following formula [3].
  • R 1, R 2 to R 4 and n are as defined above.
  • the hyperbranched polymer having an ammonium group at the molecular end used in the present invention can be obtained, for example, by reacting an amine compound with a hyperbranched polymer having a halogen atom at the molecular end.
  • a hyperbranched polymer having a halogen atom at the molecular end can be produced from a hyperbranched polymer having a dithiocarbamate group at the molecular end in accordance with the description in WO 2008/029688.
  • As the hyperbranched polymer having a dithiocarbamate group at the molecular end a commercially available product can be used, and Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd. can be preferably used.
  • the amine compounds that can be used in this reaction are, as primary amines, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n -Hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine , N-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosylamine and other aliphatic amines;
  • Secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-n-pentylamine, ethylmethylamine, methyl- n-propylamine, methyl-n-butylamine, methyl-n-pentylamine, methyl-n-octylamine, methyl-n-decylamine, methyl-n-dodecylamine, methyl-n-tetradecylamine, methyl-n- Hexadecylamine, methyl-n-octadecylamine, ethylisopropylamine, ethyl-n-butylamine, ethyl-n-pentylamine, ethyl-n-octylamine, di-n-hexylamine, di-n-
  • Tertiary amines include trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-octylamine, tri-n-dodecyl.
  • Amine dimethylethylamine, dimethyl-n-butylamine, dimethyl-n-hexylamine, dimethyl-n-octylamine, dimethyl-n-decylamine, diethyl-n-decylamine, dimethyl-n-dodecylamine, dimethyl-n-tetradecyl Aliphatic amines such as amine, dimethyl-n-hexadecylamine, dimethyl-n-octadecylamine, dimethyl-n-eicosylamine; pyridine, pyrazine, pyrimidine, quinoline, 1-methylimidazole, 4,4′-bipyridyl, 4-methyl-4,4 - Nitrogen-containing heterocyclic compounds such as bipyridyl and the like.
  • the amount of the amine compound that can be used in these reactions is 0.1 to 20 molar equivalents, preferably 0.5 to 10 molar equivalents, based on 1 mol of the halogen atom of the hyperbranched polymer having a halogen atom at the molecular end. Preferably, it is 1 to 5 molar equivalents.
  • the reaction between the hyperbranched polymer having a halogen atom at the molecular end and the amine compound can be carried out in water or an organic solvent in the presence or absence of a base.
  • the solvent to be used is preferably a solvent capable of dissolving a hyperbranched polymer having a halogen atom at the molecular end and an amine compound.
  • a hyperbranched polymer having a halogen atom at the molecular end and an amine compound can be dissolved, but a solvent that does not dissolve the hyperbranched polymer having an ammonium group at the molecular end is more preferable because it can be easily isolated.
  • Solvents that can be used in this reaction are not particularly limited as long as they do not significantly inhibit the progress of this reaction.
  • the amides can be used. These solvents may be used alone or in combination of two or more.
  • the amount used is 0.2 to 1,000 times, preferably 1 to 500 times, more preferably 5 to 100 times, most preferably the mass of the hyperbranched polymer having a halogen atom at the molecular end. It is preferable to use a solvent having a mass of 5 to 50 times.
  • Suitable bases generally include alkali metal hydroxides and alkaline earth metal hydroxides (eg sodium hydroxide, potassium hydroxide, calcium hydroxide), alkali metal oxides and alkaline earth metal oxides (eg lithium oxide). Calcium oxide), alkali metal hydrides and alkaline earth metal hydrides (eg sodium hydride, potassium hydride, calcium hydride), alkali metal amides (eg sodium amide), alkali metal carbonates and alkaline earth metal carbonates Inorganic compounds such as salts (eg lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate), alkali metal bicarbonates (eg sodium bicarbonate), and alkali metal alkyls, alkylmagnesium halides, alkali metal alkoxides, alkaline earth metals Alkoki De, organometallic compounds such as dimethoxy magnesium was used.
  • alkali metal hydroxides and alkaline earth metal hydroxides eg sodium hydroxide, potassium hydroxide,
  • potassium carbonate and sodium carbonate are particularly preferred.
  • the amount used is 0.2 to 10 molar equivalents, preferably 0.5 to 10 molar equivalents, most preferably 1 to 5 molar equivalents per mole of halogen atoms of the hyperbranched polymer having a halogen atom at the molecular end. It is preferable to use the base.
  • reaction conditions are appropriately selected from a reaction time of 0.01 to 100 hours and a reaction temperature of 0 to 300 ° C.
  • the reaction time is 0.1 to 72 hours, and the reaction temperature is 20 to 150 ° C.
  • a hyperbranched polymer represented by the formula [1] can be obtained regardless of the presence / absence of a base.
  • a hyperbranched polymer having a halogen atom at the molecular end is reacted with a primary amine or secondary amine compound in the absence of a base, the terminal secondary amine and tertiary tertiary of the corresponding hyperbranched polymer are respectively reacted.
  • a hyperbranched polymer having ammonium groups terminated with protonated primary amines is obtained.
  • the terminal secondary amine of the corresponding hyperbranched polymer can be obtained by mixing with an aqueous solution of an acid such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an organic solvent. And a hyperbranched polymer having an ammonium group terminated with a tertiary amine protonated.
  • the hyperbranched polymer has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography of 1,000 to 5,000,000, preferably 1,000 to 500,000, more preferably 2 3,000 to 200,000, most preferably 3,000 to 100,000. Further, the dispersity Mw (weight average molecular weight) / Mn (number average molecular weight) is 1.0 to 7.0, preferably 1.1 to 6.0, and more preferably 1.2 to 5. 0.
  • the metal fine particles used in the resin composition used in the present invention are not particularly limited, and the metal species are iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), palladium (Pd), silver. (Ag), tin (Sn), platinum (Pt), and gold (Au) may be mentioned, and one kind of these metals or two or more kinds of alloys may be used. Among these, preferable metal fine particles include palladium fine particles.
  • the metal oxide may be used as the metal fine particles.
  • the metal fine particles can be obtained by reducing metal ions by, for example, a method of irradiating an aqueous solution of a metal salt with a high-pressure mercury lamp or a method of adding a compound having a reducing action (so-called reducing agent) to the aqueous solution.
  • a compound having a reducing action for example, an aqueous solution of a metal salt is added to a solution in which the hyperbranched polymer is dissolved and irradiated with ultraviolet light, or an aqueous solution of a metal salt and a reducing agent are added to the solution to reduce metal ions.
  • a resin composition containing the hyperbranched polymer and the metal fine particles and other components described later can be prepared while forming a composite of the hyperbranched polymer and the metal fine particles.
  • the reducing agent is not particularly limited, and various reducing agents can be used, and it is preferable to select the reducing agent according to the metal species to be contained in the resin composition (that is, nanofiber) obtained later.
  • the reducing agent that can be used include metal borohydrides such as sodium borohydride and potassium borohydride; lithium aluminum hydride, potassium aluminum hydride, cesium aluminum hydride, aluminum beryllium hydride, hydrogenation
  • Aluminum hydride salts such as aluminum magnesium and calcium aluminum hydride; hydrazine compounds; citric acid and salts thereof; succinic acid and salts thereof; ascorbic acid and salts thereof; primary or secondary such as methanol, ethanol, isopropanol and polyol Tertiary alcohols; tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, diethylmethylamine, tetramethylethylenediamine [TMEDA], ethylenediaminet
  • the average particle size of the metal fine particles is preferably 1 to 100 nm. The reason is that when the average particle diameter of the metal fine particles exceeds 100 nm, the surface area decreases and the catalytic activity decreases.
  • the average particle size is more preferably 75 nm or less, and particularly preferably 1 to 30 nm.
  • the amount of (b) hyperbranched polymer added to (c) metal fine particles is preferably 50 to 2,000 parts by mass with respect to 100 parts by mass of (c) metal fine particles.
  • the amount is less than 50 parts by mass, the dispersibility of the metal fine particles is insufficient, and when the amount exceeds 2,000 parts by mass, the organic matter content increases, and problems such as physical properties tend to occur. More preferably, it is 100 to 1,000 parts by mass.
  • the hyperbranched polymer and the metal fine particles form a composite.
  • the composite is a particle that is in contact with or close to the metal fine particles due to the action of the ammonium group at the end of the hyperbranched polymer to form a particulate form. It is expressed as a composite having a structure in which the ammonium group of the polymer is attached or coordinated to the metal fine particles. Therefore, in the “composite” in the present invention, not only the metal fine particles and the hyperbranched polymer are combined to form one composite as described above, but also the metal fine particles and the hyperbranched polymer have bonding portions. Those that are present independently without being formed may also be included.
  • the hyperbranched polymer and metal fine particle composite may be formed in advance by combining the hyperbranched polymer and metal fine particles, or may be performed simultaneously with the preparation of the resin composition used in the production method of the present invention. .
  • the ligand is exchanged with a hyperbranched polymer, or by directly reducing metal ions in a hyperbranched polymer solution. There are methods of forming a complex.
  • the metal fine particles stabilized to some extent by the lower ammonium ligand used as a raw material can be synthesized by the method described in Journal of Organometallic Chemistry 1996, 520, 143-162 and the like.
  • a hyperbranched polymer is dissolved in the resulting reaction mixture solution of metal fine particles, and the target metal fine particle composite can be obtained by room temperature (approximately 25 ° C.) or heating and stirring.
  • the solvent to be used is not particularly limited as long as it is a solvent capable of dissolving the metal fine particles and the hyperbranched polymer at a required concentration or higher.
  • alcohols such as ethanol, n-propanol, and isopropanol; methylene chloride, Halogenated hydrocarbons such as chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile; and mixtures of these solvents, preferably tetrahydrofuran.
  • the temperature at which the metal fine particle reaction mixture and the hyperbranched polymer are mixed is usually in the range of 0 ° C. to the boiling point of the solvent, preferably in the range of room temperature (approximately 25 ° C.) to 60 ° C.
  • the metal fine particles can be stabilized to some extent in advance by using a phosphine dispersant (phosphine ligand) in addition to the amine dispersant (lower ammonium ligand).
  • a metal ion and a hyperbranched polymer are dissolved in a solvent and reduced with a primary or secondary alcohol such as methanol, ethanol, isopropanol, polyol, etc.
  • a primary or secondary alcohol such as methanol, ethanol, isopropanol, polyol, etc.
  • a primary or secondary alcohol such as methanol, ethanol, isopropanol, polyol, etc.
  • the metal ion source used here the above-mentioned metal salts can be used.
  • the solvent to be used is not particularly limited as long as it can dissolve the metal ion and the hyperbranched polymer at a required concentration or more.
  • alcohols such as methanol, ethanol, n-propanol, and isopropanol; methylene chloride Halogenated hydrocarbons such as chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile and butyronitrile; N, N-dimethylformamide (DMF), N-methyl- Amides such as 2-pyrrolidone (NMP); Sulfoxides such as dimethyl sulfoxide and the like, and mixtures of these solvents are preferable, and alcohols, halogenated hydrocarbons, and cyclic ethers are preferable, and more preferable.
  • methylene chloride Halogenated hydrocarbons such as chloroform
  • cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran, tetrahydropyran
  • the Etano Le, isopropanol, chloroform, and the like and tetrahydrofuran can usually be in the range of 0 ° C. to the boiling point of the solvent, preferably in the range of room temperature (approximately 25 ° C.) to 60 ° C.
  • a target metal fine particle composite can be obtained by dissolving a metal ion and a hyperbranched polymer in a solvent and reacting them in a hydrogen gas atmosphere.
  • a metal ion source used here the above-mentioned metal salt, hexacarbonyl chromium [Cr (CO) 6 ], pentacarbonyl iron [Fe (CO) 5 ], octacarbonyl dicobalt [Co 2 (CO) 8 ].
  • a metal carbonyl complex such as tetracarbonyl nickel [Ni (CO) 4 ] can be used.
  • zero-valent metal complexes such as metal olefin complexes, metal phosphine complexes, and metal nitrogen complexes can also be used.
  • the solvent to be used is not particularly limited as long as it can dissolve the metal ion and the hyperbranched polymer at a required concentration or more.
  • alcohols such as ethanol and n-propanol; methylene chloride, chloroform and the like Halogenated hydrocarbons; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; and a mixture of these solvents, preferably tetrahydrofuran.
  • the temperature at which the metal ions and the hyperbranched polymer are mixed can usually be in the range of 0 ° C. to the boiling point of the solvent.
  • a target metal fine particle composite can be obtained by dissolving a metal ion and a hyperbranched polymer in a solvent and causing a thermal decomposition reaction.
  • the metal ion source used here the above metal salts, metal carbonyl complexes, other zero-valent metal complexes, and metal oxides such as silver oxide can be used.
  • the solvent to be used is not particularly limited as long as it can dissolve the metal ion and the hyperbranched polymer at a required concentration or more. Specifically, alcohols such as methanol, ethanol, n-propanol, isopropanol, and ethylene glycol are used.
  • Halogenated hydrocarbons such as methylene chloride and chloroform; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran and tetrahydropyran; nitriles such as acetonitrile and butyronitrile; aromatic hydrocarbons such as benzene and toluene; And a mixture of these solvents, preferably toluene.
  • the temperature at which the metal ions and the hyperbranched polymer are mixed usually ranges from 0 ° C. to the boiling point of the solvent, preferably around the boiling point of the solvent, for example, 110 ° C. (heated reflux) in the case of toluene.
  • the hyperbranched polymer / metal fine particle composite thus obtained can be in the form of a solid such as a powder through a purification treatment such as reprecipitation.
  • the blending amount of (b) the hyperbranched polymer and (c) the metal fine particles with respect to the thermoplastic resin is a composite formed from the hyperbranched polymer and the metal fine particles.
  • the amount is preferably 0.1 to 20 parts by weight, particularly 1 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.
  • additives generally added together with the thermoplastic resin for example, heat stabilizer, light stabilizer, antioxidant, ultraviolet absorber, lubricant, mold release agent, antistatic agent, melting Elastic modifiers, processing aids, crosslinking agents, reinforcing agents, flame retardants, antifoaming agents, dispersants, light diffusing agents, pigments, dyes, fluorescent dyes, and the like may be used in combination.
  • the spinning step in the method for producing a conductive nanofiber of the present invention is performed according to an electrospinning method using the resin composition containing (a) thermoplastic resin, (b) hyperbranched polymer, and (c) metal fine particles as a spinning material.
  • This is a process for producing nanofibers.
  • the composition is dissolved or dispersed in a solvent to form a varnish, which is electrospun to produce nanofibers.
  • the solvent used for the electrostatic spinning may be any solvent that can dissolve and disperse the thermoplastic resin, the hyperbranched polymer, and the metal fine particles.
  • acetone ethyl methyl ketone (MEK), isobutyl methyl ketone (MIBK), chloroform, tetrahydrofuran (THF), 1,4-dioxane, toluene, xylene, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP) ), Cyclohexanone, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, ethyl lactate, diethylene glycol monoethyl ether, butyl cello Lube, ethanol, hexafluoroisopropanol (HFIP), .gamm
  • the concentration of the thermoplastic resin, the hyperbranched polymer, and the metal microparticles is arbitrary with respect to the total mass (total mass) of the thermoplastic resin, the hyperbranched polymer, and the metal microparticles and the solvent. (Also referred to as solid content concentration) is 1 to 50% by mass, preferably 10 to 40% by mass, and more preferably 20 to 30% by mass.
  • a commercially available electrospinning apparatus can be used for the electrospinning.
  • the spinning conditions are appropriately selected. For example, nozzle length: 3 to 5 cm, spinning distance (electrode-collector distance): 5 to 30 cm, spinning amount: 0.1 to 5.0 mL / hour, applied voltage between electrodes : 5 to 40 kV.
  • the nanofibers obtained as described above preferably have an average diameter of 50 to 2,000 nm, more preferably 100 to 1,000 nm.
  • the plating step in the method for producing conductive nanofibers of the present invention is a step of electroless plating treatment of the nanofibers produced in the above-described ⁇ spinning step>.
  • the nanofibers produced by the spinning process described above are in a state where the hyperbranched polymer and metal fine particles (composites formed from these) are present on the fiber surface (interface).
  • the nanofiber obtained by the electrospinning method can be used for the electroless plating process as it is, without requiring the plating pretreatment which consists of each process of etching, conditioning, catalyzing, and acceleration.
  • the electroless plating treatment (process) is not particularly limited, and can be performed by any of the generally known electroless plating treatments.
  • a method of immersing nanofibers obtained in the spinning process in the plating solution (bath) is common.
  • the electroless plating solution mainly contains a metal ion (metal salt), a complexing agent, and a reducing agent, and a pH adjuster, a pH buffering agent, a reaction accelerator (second complexing agent) according to other uses.
  • a metal ion metal salt
  • a complexing agent complexing agent
  • a reducing agent a pH adjuster
  • a pH buffering agent pH buffering agent
  • a reaction accelerator second complexing agent
  • Stabilizers surfactants (use for imparting gloss to the plating film, use for improving wettability of the surface to be treated, etc.) and the like are appropriately included.
  • the metal used in the metal plating film formed by electroless plating include iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof, and are appropriately selected according to the purpose. Is done.
  • the complexing agent and the reducing agent may be appropriately selected according to the metal ion.
  • the electroless plating solution may be a commercially available plating solution.
  • an electroless nickel plating chemical (Melplate (registered trademark) NI series) manufactured by Meltex Co., Ltd., an electroless copper plating chemical (Melplate ( (Registered trademark) CU series); Electroless nickel plating solution (ICP Nicolon (registered trademark) series) manufactured by Okuno Pharmaceutical Industry Co., Ltd., Electroless copper plating solution (OPC-700 Electroless copper MK, ATS Addcopper IW) ), Electroless tin plating solution (Substar SN-5), electroless gold plating solution (flash gold 330, self gold OTK-IT); electroless palladium plating solution (pallet II) manufactured by Kojima Chemical Co., Ltd.
  • Electroless gold plating solution (Dip G series, NC gold series); Electroless silver plating solution manufactured by Sasaki Chemical Co., Ltd. ); Electroless nickel plating solution (Schumer (registered trademark) series, Schumer (registered trademark) crab black (registered trademark) series), Electroless palladium plating solution (S-KPD) manufactured by Nippon Kanisen Co., Ltd .; Dow Chemical Company Electroless copper plating solution (Cuposit (registered trademark) Coppermix series, Circuposit (registered trademark) series), Electroless palladium plating solution (Paramars (registered trademark) series), Electroless nickel plating solution (Duraposit ( (Registered trademark) series), electroless gold plating solution (Aurolectroles (registered trademark) series), electroless tin plating solution (Tinposito (registered trademark) series); electroless copper plating solution manufactured by Uemura Kogyo Co., Ltd. ( Surcup (registered trademark) ELC-SP
  • the electroless plating process adjusts the temperature, pH, immersion time, metal ion concentration, presence / absence of stirring, stirring speed, presence / absence of supply of air / oxygen, supply speed, etc. And the film thickness can be controlled.
  • the thickness of the plating film to be obtained is not particularly limited, but can generally be about 10 to 500 nm, for example, 30 to 300 nm.
  • the electroconductive nanofiber of this invention produced can have an aggregate shape (for example, mat shape).
  • the conductive nanofiber aggregate preferably has a volume resistance value of 1 ⁇ 10 4 ⁇ ⁇ cm or less, and desirably 1 ⁇ 10 2 ⁇ ⁇ cm or less.
  • SEM Sccanning Electron Microscope
  • Image Device 3D Real Surface View Microscope VE-9800 manufactured by Keyence Corporation
  • Volume resistance measurement device Loresta (registered trademark) AX MCP-T370 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
  • HPS Hyperbranched polystyrene [Hypertech (registered trademark) HPS-200 manufactured by Nissan Chemical Industries, Ltd.]
  • IPA 2-propanol IPE: diisopropyl ether
  • PVDF polyvinylidene fluoride [manufactured by Aldrich, product number: 427152, Mw (GPC): 180,000, Mn: 71,000]
  • PVDF / HFP Vinylidene fluoride-hexafluoropropylene copolymer [manufactured by Aldrich, product number: 427160, Mw (GPC): 400,000, Mn: 130,000]
  • PU Polyurethane [Elastolan (registered trademark) ET385, Mw (GPC): 146,000, manufactured by BASF Japan Ltd.]
  • DMAc N, N-dimethylacetamide
  • DMF N, N-dimethylformamide
  • THF tetrahydrofuran
  • the white powder obtained by filtering this precipitate was dissolved in 100 g of chloroform and added to 500 g of IPA to reprecipitate the polymer.
  • the precipitate was filtered under reduced pressure and vacuum dried to obtain 8.5 g of hyperbranched polymer (HPS-Cl) having a chlorine atom at the molecular end as a white powder (yield 99%).
  • the 1 H NMR spectrum of the obtained HPS-Cl is shown in FIG. Since the peak (4.0 ppm, 3.7 ppm) derived from the dithiocarbamate group disappeared, it was confirmed that the obtained HPS-Cl had almost all the dithiocarbamate groups at the HPS molecule terminals substituted with chlorine atoms. It became clear.
  • the weight average molecular weight Mw measured by polystyrene conversion by GPC of the obtained HPS-Cl was 14,000, and the dispersity Mw / Mn was 2.9.
  • HPS-N (Me) 2 OctCl obtained from the peak of the benzene ring and the peak of the methyl group at the end of the octyl group shows that the chlorine atom at the end of the HPS-Cl molecule is almost quantitatively substituted with an ammonium group. Became clear.
  • the weight average molecular weight Mw of HPS-N (Me) 2 OctCl calculated from Mw (14,000) of HPS-Cl and ammonium group introduction rate (100%) was 28,000.
  • the reaction mixture was added to 2,000 g of IPE at 0 ° C. and purified by reprecipitation.
  • the precipitated polymer was filtered under reduced pressure and vacuum dried at 60 ° C., and 9.8 g of a complex of a hyperbranched polymer and Pd particles having an ammonium group at the molecular end (Pd [HPS-N (Me) 2 OctCl]) was blackened. Obtained as a powder. From the results of ICP emission analysis, the Pd content of the obtained Pd [HPS-N (Me) 2 OctCl] was 10% by mass. Further, from the TEM (transmission electron microscope) image, the Pd particle diameter was about 2 to 4 nm.
  • HPS-NOct 3 Cl hyperbranched polymer having a trioctylammonium group at the molecular end as a pale yellow powder.
  • the 13 C NMR spectrum of the resulting HPS-NOct 3 Cl is shown in FIG. From the peak of the methylene group to which the chlorine atom is bonded and the peak of the methylene group to which the ammonium group is bonded, the obtained HPS-NOct 3 Cl has 71% of the chlorine atom at the end of the HPS-Cl molecule replaced with the ammonium group. Became clear.
  • the weight average molecular weight Mw of HPS-NOct 3 Cl calculated from Mw (14,000) of HPS-Cl and ammonium group introduction rate (71%) was 37,000.
  • the obtained residue was dissolved in 300 g of THF and cooled to 0 ° C. This solution was added to 6,000 g of IPE at 0 ° C. for reprecipitation purification.
  • the precipitated polymer was filtered under reduced pressure and vacuum dried at 60 ° C. to obtain 19.9 g of a complex of a hyperbranched polymer having an ammonium group at the molecular end and Pd particles (Pd [HPS-NOct 3 Cl]) as a black powder. It was. From the result of ICP emission analysis, the Pd content of the obtained Pd [HPS-NOct 3 Cl] was 11% by mass. Further, from the TEM (transmission electron microscope) image, the Pd particle diameter was about 2 to 4 nm.
  • Example 1 100 parts by mass of PVDF, 5 parts by mass of Pd [HPS-N (Me) 2 OctCl] produced according to Production Example 3 (0.5 parts by mass as Pd), and 300 parts by mass of a DMF / acetone mixed liquid (mass ratio 9: 1) Were uniformly mixed to prepare a resin composition (spun material). This composition was spun under the conditions shown in Table 1 using an electrospinning apparatus to produce an assembly of nanofibers on the mat (hereinafter referred to as nanofiber mat). The obtained nanofiber mat was observed with an SEM, and the nanofiber diameter (average diameter) was calculated. The nanofiber diameter was determined by measuring the diameters of 100 nanofibers randomly selected from five different SEM images, and taking the average value.
  • FIG. 4 shows an SEM image of the obtained nanofiber mat subjected to the electroless plating treatment.
  • Example 2 100 parts by mass of PVDF, 4.5 parts by mass of Pd [HPS-NOct 3 Cl] produced according to Production Example 5 (0.5 parts by mass as Pd), and 300 parts by mass of a DMAc / acetone mixture (mass ratio 7: 3)
  • the resin composition was prepared by mixing uniformly. This composition was used and evaluated in the same manner as in Example 1 except that the plating solution shown in Table 1 was used. The results are also shown in Table 1.
  • Example 3 The same operation as in Example 2 was performed except that the plating solution was changed. The results are also shown in Table 1.
  • Example 4 100 parts by mass of PU, 5 parts by mass of Pd [HPS-N (Me) 2 OctCl] produced according to Production Example 3 (0.5 parts by mass as Pd), and 614 parts by mass of DMF were uniformly mixed to prepare a resin composition. .
  • This composition was used and evaluated in the same manner as in Example 1 except that the plating solution shown in Table 1 was used. The results are also shown in Table 1.
  • Example 5 100 parts by mass of PU, 4.5 parts by mass of Pd [HPS-NOct 3 Cl] produced according to Production Example 5 (0.5 parts by mass as Pd), and 614 parts by mass of DMF were uniformly mixed to prepare a resin composition. This composition was used and evaluated in the same manner as in Example 1 except that the plating solution shown in Table 1 was used. The results are also shown in Table 1.
  • Example 6 100 parts by mass of PVDF / HFP, 5 parts by mass of Pd [HPS-N (Me) 2 OctCl] produced according to Production Example 3 (0.5 parts by mass as Pd), and 400 parts by mass of DMF were uniformly mixed to obtain a resin composition. Prepared. This composition was used and evaluated in the same manner as in Example 1 except that the plating solution shown in Table 1 was used. The results are also shown in Table 1.
  • Example 7 The nanofiber mat obtained in Example 6 was immersed in the electroless tin plating solution A (Sn-A) prepared in Reference Example 5 at 20 ° C. for 5 minutes. Thereafter, the nanofiber mat taken out was washed with water and air-dried. The nanofiber diameter of the obtained electroless plating (substitution type) treated nanofiber mat was calculated in the same manner as described above. Moreover, the volume resistance value of the nanofiber mat was measured. The results are also shown in Table 1. Moreover, the SEM image of the obtained nanofiber mat subjected to electroless plating is shown in FIG.
  • Examples 1 to 7 a conductive material having a low volume resistance of 1 ⁇ 10 4 ⁇ ⁇ cm or less by a simple method without being restricted by the type of plating metal or the type of plating solution. An aggregate of nanofibers (nanofiber mat) could be obtained. On the other hand, in Comparative Example 1 using a spinning material in which palladium chloride was blended with PVDF, copper plating was not performed, and conductive nanofibers could not be obtained.

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Abstract

La présente invention vise à proposer un procédé pour fabriquer une nanofibre conductrice, qui peut produire une nanofibre conductrice qui a une conductivité suffisante à l'aide de différents types de métaux de placage et de fluides de placage, sans opérations compliquées. L'invention concerne un procédé pour fabriquer une nanofibre conductrice, caractérisé en ce qu'il comprend une étape de filature de fibre pour fabriquer la nanofibre selon un processus d'électrofilature avec une composition de résine qui comprend (a) une résine thermoplastique, (b) un polymère hyper-ramifié ayant des groupes ammonium aux extrémités moléculaires et une masse moléculaire moyenne en masse de 1 000-5 000 000, et (c) de fines particules métalliques comme matière de filature, et une étape de placage pour le placage autocatalytique de la nanofibre fabriquée dans l'étape de filature de fibre.
PCT/JP2015/052192 2014-01-27 2015-01-27 Procédé pour fabriquer une nanofibre conductrice Ceased WO2015111755A1 (fr)

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JP2021526595A (ja) * 2019-05-09 2021-10-07 ネイール テクノロジー 窒化ホウ素ナノチューブが分散された高分子複合圧電材料の製造方法及び装置、並びにその方法により製造される高分子複合圧電材料
CN117433672A (zh) * 2023-09-20 2024-01-23 华南理工大学 一种基于导电纳米纤维的柔性压阻传感器及其制备方法和应用

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KR102261388B1 (ko) 2018-11-22 2021-06-08 한국재료연구원 폴리비닐 알코올 고분자 섬유, 이의 제조방법, 및 폴리비닐 알코올 고분자 섬유의 강도 향상방법
JP2021526595A (ja) * 2019-05-09 2021-10-07 ネイール テクノロジー 窒化ホウ素ナノチューブが分散された高分子複合圧電材料の製造方法及び装置、並びにその方法により製造される高分子複合圧電材料
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CN117433672A (zh) * 2023-09-20 2024-01-23 华南理工大学 一种基于导电纳米纤维的柔性压阻传感器及其制备方法和应用

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