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WO2016013219A1 - Solution de placage et son procédé de production, matériau composite, matériau composite de cuivre, et procédé de production associé - Google Patents

Solution de placage et son procédé de production, matériau composite, matériau composite de cuivre, et procédé de production associé Download PDF

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Publication number
WO2016013219A1
WO2016013219A1 PCT/JP2015/003679 JP2015003679W WO2016013219A1 WO 2016013219 A1 WO2016013219 A1 WO 2016013219A1 JP 2015003679 W JP2015003679 W JP 2015003679W WO 2016013219 A1 WO2016013219 A1 WO 2016013219A1
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Prior art keywords
composite material
plating solution
copper
carbon
dispersion
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English (en)
Japanese (ja)
Inventor
新井　進
貢 上島
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Zeon Corp
Shinshu University NUC
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Zeon Corp
Shinshu University NUC
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Priority to JP2016535798A priority Critical patent/JP6606076B2/ja
Publication of WO2016013219A1 publication Critical patent/WO2016013219A1/fr
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the present invention relates to a plating solution and a method for producing the same, and particularly relates to a plating solution containing carbon nanofibers and a method for producing the plating solution.
  • the present invention also relates to a composite material formed using a plating solution containing carbon nanofibers.
  • the present invention also relates to a copper composite material in which copper and a carbon nanostructure are combined, and a method for producing the copper composite material.
  • Carbon nanostructures such as carbon nanotubes (hereinafter sometimes referred to as “CNT”) are excellent in conductivity, thermal conductivity, sliding properties, mechanical properties, etc. Has been. Therefore, in recent years, by utilizing the excellent properties of carbon nanostructures, we have provided composite materials that have further improved conductivity and thermal conductivity by combining carbon and other metals with carbon nanostructures. The development of technology is underway.
  • Patent Document 1 fine carbon fibers such as CNT are mixed in a plating solution, and a plating film is formed by the plating solution, whereby metal and fine carbon are formed.
  • a technique for satisfactorily combining fibers is proposed.
  • the metal and CNT are well compounded by using an electrolytic plating solution containing metal ions that can be plated, polyacrylic acid as a dispersant, and CNTs.
  • a technique for manufacturing an electronic component or the like having a plated film is proposed.
  • the composite material described in Patent Document 1 has room for improvement in terms of further improving the performance (for example, conductivity and thermal conductivity) of the composite material.
  • the inventors of the present invention made extensive studies to solve the above problems.
  • the inventors have found that carbon nanofibers can be well dispersed in the plating solution by blending the ionic surfactant and the polymeric surfactant into the plating solution. Completed the invention.
  • the present inventors have found that a composite material excellent in conductivity and thermal conductivity can be obtained by using a plating solution in which carbon nanofibers are well dispersed, and have completed the present invention.
  • the present invention aims to advantageously solve the above-mentioned problems, and the plating solution of the present invention comprises metal ions that can be plated, a chelating agent, an ionic surfactant, and a polymer system.
  • the plating solution of the present invention comprises metal ions that can be plated, a chelating agent, an ionic surfactant, and a polymer system.
  • One of the characteristics is that it contains a surfactant and carbon nanofibers.
  • the carbon nanofibers can be favorably dispersed in the plating solution.
  • “fiber” refers to those having an aspect ratio of 10 or more.
  • the plating solution of the present invention preferably has an average diameter of the carbon nanofibers of 5 nm or less. Since carbon nanofibers having an average diameter of 5 nm or less have a strong interaction between the carbon nanofibers, it is usually difficult to disperse them well in the plating solution. However, if an ionic surfactant and a polymeric surfactant are blended, even carbon nanofibers having an average diameter of 5 nm or less can be favorably dispersed in the plating solution.
  • the “average diameter of carbon nanofibers” can be determined by measuring the diameter (outer diameter) of 100 carbon nanofibers selected at random using a transmission electron microscope.
  • the metal ion capable of plating is preferably a copper ion. Since copper is highly conductive and excellent in rollability, a composite material having excellent performance (for example, conductivity and thermal conductivity) can be obtained by compounding with carbon nanofibers.
  • the plating solution of the present invention is preferably alkaline. If an alkaline plating solution is used, a composite material can be satisfactorily prepared by electroless plating.
  • the carbon nanofibers are preferably carbon nanotubes. If carbon nanotubes are used as the carbon nanofibers, the performance (for example, conductivity and thermal conductivity) of the composite material obtained using the plating solution can be further improved.
  • the carbon nanotube preferably has an average diameter (Av) and a standard deviation ( ⁇ ) of the diameter satisfy a relational expression: 0.20 ⁇ (3 ⁇ / Av) ⁇ 0.60. If carbon nanotubes having 3 ⁇ / Av of more than 0.20 and less than 0.60 are used, the conductivity and thermal conductivity of the composite material can be sufficiently improved even if the blending amount is small.
  • average diameter (Av) of carbon nanotubes” and “standard deviation of carbon nanotube diameter ( ⁇ : sample standard deviation)” are carbons selected at random using a transmission electron microscope, respectively. It can be obtained by measuring the diameter (outer diameter) of 100 nanotubes.
  • the manufacturing method of the plating solution of this invention is any manufacturing method of the plating solution mentioned above, Comprising:
  • One of the characteristics is that it includes a dispersion step of dispersing in a solvent by a dispersion treatment in which a cavitation effect or a crushing effect is obtained in the presence of an ionic surfactant and a polymeric surfactant.
  • a dispersion treatment is performed in the presence of the ionic surfactant and the polymer surfactant, a plating solution in which carbon nanofibers are well dispersed in the solution can be obtained.
  • the carbon nanofibers are dispersed by a dispersion treatment that can obtain a cavitation effect or a crushing effect, the carbon nanofibers are prevented from being damaged during the dispersion treatment, and a composite material prepared using a plating solution is desired. Performance can be demonstrated.
  • this invention aims at solving the said subject advantageously, and the composite material of this invention uses either one of the plating solutions mentioned above, and electroplating treatment or electroless plating on the substrate surface
  • One of the characteristics is that it is obtained by processing.
  • the composite material excellent in electroconductivity and heat conductivity will be obtained.
  • a copper composite material using copper as a metal among the composite materials includes a conventional copper composite material that has a much higher electrical resistance than that of unoxidized copper.
  • copper oxide may be contained, and as a result, it has been found that the conductivity and thermal conductivity of the copper composite material are not sufficiently excellent, and the present invention has been completed.
  • the present invention aims to advantageously solve the above problems, and the copper composite material of the present invention is a copper composite material in which copper and a carbon nanostructure are combined.
  • the copper composite material is a copper composite material in which copper and a carbon nanostructure are combined.
  • One characteristic of the copper composite material is that the diffraction intensity of the X-ray diffraction peak attributed to cuprous oxide is below the detection limit in the X-ray diffraction analysis.
  • the diffraction intensity of the X-ray diffraction peak attributed to cuprous oxide is below the detection limit, excellent conductivity and thermal conductivity can be exhibited.
  • the carbon nanostructure includes single-walled carbon nanotubes having a specific surface area of 600 m 2 / g or more. If single-walled carbon nanotubes with a specific surface area of 600 m 2 / g or more are contained, the conductivity and thermal conductivity of the copper composite material can be further improved.
  • the “specific surface area” refers to the nitrogen adsorption specific surface area measured using the BET method.
  • the average diameter (Av) and the diameter distribution (3 ⁇ ) of the single-walled carbon nanotube satisfy 0.20 ⁇ (3 ⁇ / Av) ⁇ 0.60. If single-walled carbon nanotubes having 3 ⁇ / Av of more than 0.20 and less than 0.60 are used, the conductivity and thermal conductivity of the copper composite material can be sufficiently improved even if the blending amount is small.
  • “diameter distribution (3 ⁇ )” refers to a value obtained by multiplying the sample standard deviation ( ⁇ ) of the diameter of the single-walled carbon nanotube by 3.
  • the “average diameter (Av) of single-walled carbon nanotubes” and “sample standard deviation ( ⁇ ) of diameter of single-walled carbon nanotubes” are 100 carbon nanotubes randomly selected using a transmission electron microscope, respectively. It can be determined by measuring the diameter (outer diameter).
  • Another object of the present invention is to advantageously solve the above-mentioned problems, and the method for producing a copper composite material according to the present invention comprises cavitation of carbon nanostructures in a dispersion medium in the presence of a dispersant.
  • a carbon nanostructure-dispersed copper plating solution is prepared by mixing the carbon nanostructure dispersion liquid and the copper plating material, it can be obtained by plating using the carbon nanostructure-dispersed copper plating solution.
  • the amount of cuprous oxide generated in the copper composite material can be significantly reduced. Accordingly, it is possible to obtain a copper composite material having excellent conductivity and thermal conductivity.
  • the plating treatment is preferably an electrolytic plating treatment. If electrolytic plating is used, the generation of cuprous oxide can be further suppressed.
  • a plating solution in which carbon nanofibers are well dispersed in the solution can be provided.
  • a composite material having excellent conductivity and thermal conductivity can be provided.
  • Example 2 is a photograph showing a state when the copper plating solution 1 obtained in Example 1-1 is dropped on a slide glass.
  • A is a photograph of the copper composite material of Example 2-1 taken using a scanning electron microscope, and
  • B is an enlarged view of the photograph shown in (A). It is a figure which shows the result when the copper composite material of Example 2-1 is analyzed using an X-ray diffractometer.
  • the plating solution of this invention can be used suitably for manufacture of the composite material containing a metal and carbon nanofiber.
  • the plating solution of this invention can be prepared, for example using the manufacturing method of the plating solution of this invention.
  • the 1st composite material of this invention is obtained by performing the electroplating process or the electroless-plating process, Preferably the electroless-plating process is performed to the base-material surface using the plating solution of this invention.
  • the second composite material of the present invention is capable of plating, and a composite of copper (Cu), which is a metal having excellent conductivity and thermal conductivity, and a carbon nanostructure. It is a copper composite material.
  • the 2nd composite material of this invention can be prepared using the manufacturing method of the copper composite material of this invention, for example.
  • the plating solution of the present invention includes metal ions that can be plated, a chelating agent, an ionic surfactant, a polymeric surfactant, and carbon nanofibers, and is optionally added to the plating solution in general. It further contains other additives. And since the plating solution of this invention contains both an ionic surfactant and polymeric surfactant, carbon nanofiber can be favorably disperse
  • the reason why the carbon nanofibers can be favorably dispersed in the plating solution by using the ionic surfactant and the polymeric surfactant in combination is not clear, but the above-mentioned two kinds of interfaces It is presumed that the action when the activator is used in combination is as follows. That is, the carbon nanofiber has strong interaction between the carbon nanofibers and is likely to aggregate in the plating solution. However, when only one of the ionic surfactant and the polymeric surfactant is used, even if a large amount of the ionic surfactant or the polymeric surfactant is blended, the carbon Nanofibers do not disperse well enough.
  • the plating solution in which the carbon nanofibers are well dispersed while the carbon nanofibers are sufficiently satisfactorily dispersed in a blending amount that does not affect the stability of the plating solution and the stability as the plating solution is ensured. It is guessed that can be obtained.
  • the metal ions that can be plated are not particularly limited, and examples include metal ions that can be plated, such as ions of copper, nickel, tin, platinum, chromium, and zinc. Among these, copper ions are preferred as metal ions that can be plated. Copper is excellent in conductivity, thermal conductivity, rollability, and the like, and if it is combined with carbon nanofiber, a composite material having excellent performance (for example, conductivity and thermal conductivity) can be obtained. Because.
  • the metal ions that can be plated are not particularly limited and can be introduced into the plating solution by dissolving a known metal compound such as copper sulfate pentahydrate or nickel sulfate hexahydrate. . Further, the concentration of metal ions that can be plated in the plating solution is not particularly limited.
  • chelating agent a known chelating agent capable of forming a chelate complex with the metal ion that can be plated can be used.
  • chelating agent for example, ethylenediaminetetraacetic acid (EDTA), ethylenediamine, triethanolamine, thiourea, Rochelle salt, tartaric acid and the like can be used.
  • EDTA ethylenediaminetetraacetic acid
  • ethylenediamine ethylenediamine
  • triethanolamine thiourea
  • Rochelle salt tartaric acid and the like
  • the ionic surfactant and the polymeric surfactant can function as a dispersant for assisting the dispersion of the carbon nanofibers in the plating solution. And in the plating solution of this invention, in order to disperse
  • the plating solution of the present invention may contain a known dispersant other than the ionic surfactant and the polymer surfactant.
  • any of a cationic surfactant and an anionic surfactant can be used.
  • a cationic surfactant is preferably used, and when an electroless plating process is performed using a plating solution, an anionic surfactant is preferably used.
  • an anionic surfactant is preferably used.
  • the cationic surfactant include quaternary ammonium salts and quaternary phosphonium salts.
  • anionic surfactant examples include sodium dodecyl sulfate, sodium deoxycholate, sodium cholate, sodium dodecylbenzenesulfonate, sodium dodecyldiphenyloxide disulfonate, and the like.
  • sodium dodecyl sulfate and sodium deoxycholate are preferable from the viewpoint of excellent dispersibility of carbon nanofibers.
  • polymer surfactant examples include polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polystyrene sulfonic acid, and salts thereof. Among these, hydroxypropylcellulose and polyvinylpyrrolidone are preferable from the viewpoint of excellent dispersibility of the carbon nanofibers.
  • the total compounding amount of the ionic surfactant and the polymer surfactant may be at least an amount that provides a critical micelle concentration.
  • the total amount of ionic surfactant and polymer surfactant in the plating solution can be, for example, 1 to 20 times the amount of carbon nanofibers in the plating solution.
  • the ratio of the amount of the polymeric surfactant to the amount of the ionic surfactant (polymeric surfactant / ionic surfactant) is preferably 0.05 or more and 5 or less.
  • the ratio of the amount of the polymeric surfactant to the amount of the ionic surfactant is within the above range, the effect obtained by using the ionic surfactant and the polymeric surfactant together can be obtained. This is because it can be made sufficiently high.
  • Carbon nanotubes or carbon nanofibers can be used as the carbon nanofibers contained in the plating solution.
  • carbon nanotubes from the viewpoint of obtaining a composite material having excellent performance (for example, conductivity and thermal conductivity), it is preferable to use carbon nanotubes, and it is more preferable to use carbon nanotubes having an average diameter of 5 nm or less.
  • the average diameter of the carbon nanofibers contained in the plating solution is not particularly limited. However, from the viewpoint of improving the performance of the composite material obtained using the plating solution, the average diameter of the carbon nanofibers is preferably 15 nm or less, more preferably 10 nm or less, and 5 nm or less. Is more preferable.
  • carbon nanofibers having a small average diameter, particularly carbon nanofibers having an average diameter of 5 nm or less, are usually difficult to disperse well in the plating solution because of the strong interaction between the carbon nanofibers. . However, if an ionic surfactant and a polymeric surfactant are used in combination, even carbon nanofibers having a small average diameter can be favorably dispersed in the plating solution.
  • the CNT contained in the plating solution is not particularly limited, and single-walled carbon nanotubes and / or multi-walled carbon nanotubes can be used.
  • the CNT is preferably a single-walled to carbon-walled carbon nanotube, and more preferably a single-walled carbon nanotube. This is because if single-walled carbon nanotubes are used, the conductivity and thermal conductivity of the composite material can be improved better than when multi-walled carbon nanotubes are used.
  • a CNT having a ratio (3 ⁇ / Av) of a value (3 ⁇ ) obtained by multiplying the standard deviation ( ⁇ ) of the diameter by 3 with respect to the average diameter (Av) is more than 0.20 and less than 0.60. It is preferable to use CNTs with 3 ⁇ / Av exceeding 0.25, and it is even more preferable to use CNTs with 3 ⁇ / Av exceeding 0.50. This is because if 3CNT / Av is more than 0.20 and less than 0.60, the conductivity and thermal conductivity of the composite material can be sufficiently improved even if the amount of CNT is small.
  • the average diameter (Av) and standard deviation ( ⁇ ) of CNTs may be adjusted by changing the CNT manufacturing method and manufacturing conditions, or by combining multiple types of CNTs obtained by different manufacturing methods. May be.
  • CNT when measuring the diameter of 100 carbon nanotubes using a transmission electron microscope, the measured diameter is plotted on the horizontal axis, the frequency is plotted on the vertical axis, and approximated by Gaussian, A normal distribution is usually used.
  • the CNT preferably has a peak of Radial Breathing Mode (RBM) when evaluated using Raman spectroscopy. Note that there is no RBM in the Raman spectrum of multi-walled carbon nanotubes of three or more layers.
  • RBM Radial Breathing Mode
  • CNTs preferably have a G-band peak intensity ratio (G / D ratio) of 1 to 20 in the Raman spectrum. This is because if the G / D ratio is 1 or more and 20 or less, the conductivity and thermal conductivity of the composite material can be sufficiently improved even if the blending amount of CNT is small.
  • G / D ratio G-band peak intensity ratio
  • the average diameter (Av) of the CNTs is preferably 0.5 nm or more, and more preferably 1 nm or more. This is because, if the average diameter (Av) of CNTs is 0.5 nm or more, aggregation of CNTs can be suppressed and the dispersibility of CNTs in the plating solution can be further enhanced.
  • the average length of the structure during synthesis is preferably 100 ⁇ m or more and 5000 ⁇ m or less, and more preferably 300 ⁇ m or more and 2000 ⁇ m or less. This is because if the average length of the structure during synthesis is 100 ⁇ m or more, the conductivity and thermal conductivity of the composite material are improved. In addition, as the length of the structure at the time of synthesis is longer, damage such as breakage or cutting tends to occur in the CNT during dispersion. Therefore, the average length of the structure during synthesis is preferably 5000 ⁇ m or less.
  • the BET specific surface area of the CNT is preferably 600 m 2 / g or more in an unopened state, more preferably 800 m 2 / g or more, and preferably 2500 m 2 / g or less, and 1200 m 2. / G or less is more preferable. Furthermore, when the CNT is mainly opened, the BET specific surface area is preferably 1300 m 2 / g or more. This is because if the BET specific surface area of CNT is 600 m 2 / g or more, the conductivity and thermal conductivity of the composite material can be improved satisfactorily.
  • the BET specific surface area of CNT is 2500 m ⁇ 2 > / g or less, it can suppress the aggregation of CNT and can improve the dispersibility of CNT in a plating solution.
  • the “BET specific surface area” refers to a nitrogen adsorption specific surface area measured using the BET method.
  • CNTs are obtained as aggregates (CNT aggregates) oriented in a direction substantially perpendicular to the base material on a base material having a catalyst layer for carbon nanotube growth on the surface according to the super growth method described later.
  • the mass density of the CNTs as the aggregate is preferably 0.002 g / cm 3 or more and 0.2 g / cm 3 or less. If the mass density is 0.2 g / cm 3 or less, the CNTs are weakly bonded, so that the CNTs can be uniformly dispersed. In addition, if the mass density is 0.002 g / cm 3 or more, the integrity of the CNTs can be improved and the variation can be suppressed, so that handling becomes easy.
  • the CNT preferably has a plurality of micropores.
  • the CNT preferably has micropores having a pore diameter smaller than 2 nm, and the abundance thereof is a micropore volume determined by the following method, preferably 0.40 mL / g or more, more preferably 0.43 mL. / G or more, more preferably 0.45 mL / g or more, and the upper limit is usually about 0.65 mL / g.
  • the CNTs have the above micropores, aggregation of the CNTs is suppressed, the dispersibility of the CNTs is increased, and a plating solution in which the CNTs are highly dispersed can be obtained very efficiently.
  • the micropore volume can be adjusted, for example, by appropriately changing the CNT preparation method and preparation conditions.
  • P is a measurement pressure at the time of adsorption equilibrium
  • P0 is a saturated vapor pressure of liquid nitrogen at the time of measurement
  • M is an adsorbate (nitrogen) molecular weight of 28.010
  • ⁇ is an adsorbate (nitrogen).
  • micropore volume can be determined using, for example, “BELSORP (registered trademark) -mini” (manufactured by Nippon Bell Co., Ltd.).
  • the CNT having the above-described properties is obtained by, for example, supplying a raw material compound and a carrier gas onto a base material having a catalyst layer for producing carbon nanotubes on the surface, and performing chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • a catalyst is synthesized, a method of dramatically improving the catalytic activity of the catalyst layer by making a small amount of an oxidizing agent (catalyst activating substance) present in the system (super growth method; see International Publication No. 2006/011655) ),
  • the catalyst layer is formed on the surface of the substrate by a wet process, and a raw material gas containing acetylene as a main component (for example, a gas containing 50% by volume or more of acetylene) can be used for efficient production. it can.
  • the carbon nanotube obtained by the super growth method may be referred to as “SGCNT”.
  • the compounding quantity of the carbon nanofiber in a plating solution is not specifically limited, According to the characteristic of the plating film according to a use, it can adjust suitably.
  • the plating solution of this invention may contain known additives, such as a pH adjuster and a brightener other than the component mentioned above in the range which does not impair the effect of this invention.
  • the pH of the plating solution containing the above components is adjusted to be alkaline, preferably pH 9 or higher, using a pH adjuster such as potassium hydroxide, particularly when used for preparing a composite material by electroless plating. It is preferable that
  • the plating solution of the present invention can be prepared by dissolving or dispersing the above-described components in a known solvent such as water.
  • the plating solution may be prepared by simultaneously adding all of the above-described components into a solvent and performing a dispersion treatment.
  • the ionic surfactant and After carbon nanofibers are dispersed in a solvent in the presence of a polymeric surfactant the metal nanofiber dispersion is prepared by adding a metal compound and a chelating agent that give a metal ion that can be plated. It is preferable.
  • the plating solution is obtained by subjecting a coarse dispersion containing carbon nanofibers, an ionic surfactant, a polymer surfactant, and a solvent to a dispersion treatment, It is preferable to prepare by adding a metal compound and a chelating agent to the nanofiber dispersion and mixing them.
  • mixing with a carbon nanofiber dispersion liquid, a metal compound, and a chelating agent can be performed using a known stirring apparatus.
  • distributing carbon nanofiber in a solvent it is preferable to use the dispersion process from which a cavitation effect or a crushing effect is acquired. If a dispersion treatment that provides a cavitation effect or a crushing effect is used, the carbon nanofibers can be prevented from being damaged during the dispersion treatment, and the composite material prepared using the plating solution can exhibit the desired performance. It is. In a normal dispersion treatment using a ball mill or the like, the carbon nanofibers may be damaged and the desired characteristics cannot be expressed in the composite material, and the electrical conductivity and thermal conductivity of the composite material may not be sufficiently improved. is there.
  • a dispersion process that can provide a cavitation effect or a crushing effect will be described.
  • the dispersion treatment that provides a cavitation effect is a dispersion method that uses shock waves generated by bursting of vacuum bubbles generated in water when high energy is applied to a liquid. And by using the said dispersion
  • dispersion treatment examples include dispersion treatment using ultrasonic waves, dispersion treatment using a jet mill, and dispersion treatment using high shear stirring. These distributed processes may be performed only one, or may be performed in combination. More specifically, for example, an ultrasonic homogenizer, a jet mill, and a high shear stirrer are suitably used for the dispersion treatment. These devices may be conventionally known devices.
  • the output is preferably 100 W or more and 500 W or less, and the temperature is preferably 15 ° C. or more and 50 ° C. or less.
  • the number of treatments may be appropriately set depending on the amount of carbon nanofibers, and is preferably 2 times or more, more preferably 5 times or more, preferably 100 times or less, and 50 times or less. More preferred.
  • the pressure is preferably 20 MPa to 250 MPa, and the temperature is preferably 15 ° C. to 50 ° C.
  • the coarse dispersion may be treated with a high shear stirring device.
  • the operation time (the time during which the machine is rotating) is preferably 3 minutes to 4 hours
  • the peripheral speed is 5 m / s to 50 m / s
  • the temperature is preferably 15 ° C. to 50 ° C.
  • the dispersion treatment for obtaining the above cavitation effect it is more preferable to perform the dispersion treatment for obtaining the above cavitation effect at a temperature of 50 ° C. or lower. This is because a change in concentration due to the volatilization of the solvent is suppressed.
  • Dispersion treatment that can produce a crushing effect Moreover, in the manufacturing method of the plating solution of this invention, the dispersion process from which the crushing effect shown below is acquired can also be applied. Dispersion treatment that provides this crushing effect allows carbon nanofibers to be uniformly dispersed in the solvent, as well as damage to carbon nanofibers caused by shock waves when bubbles disappear, compared to the dispersion treatment that provides the cavitation effect described above. This is more advantageous in this respect.
  • the above-mentioned coarse dispersion is subjected to shearing force to crush and disperse the aggregates of carbon nanofibers in the coarse dispersion, and a back pressure is applied to the obtained dispersion.
  • a back pressure is applied to the dispersion, the back pressure applied to the dispersion may be reduced to atmospheric pressure at a stretch, but it is preferable to reduce the pressure in multiple stages.
  • a dispersion system having a disperser having the following structure may be used.
  • the disperser has a disperser orifice having an inner diameter d1, a dispersion space having an inner diameter d2, and a terminal portion having an inner diameter d3 from the inflow side to the outflow side of the coarse dispersion liquid (where d2>d3> d1)).
  • an inflowing high-pressure (usually 10 to 400 MPa, preferably 50 to 250 MPa) coarse dispersion passes through the disperser orifice, thereby reducing the pressure and increasing the flow rate of the fluid. And flows into the dispersion space. Thereafter, the high-velocity coarse dispersion liquid flowing into the dispersion space flows at high speed in the dispersion space and receives a shearing force at that time. As a result, the flow rate of the coarse dispersion decreases, and the carbon nanofibers in the coarse dispersion are well dispersed. Then, a fluid having a pressure (back pressure) lower than the pressure of the inflowing coarse dispersion liquid flows out from the terminal portion as the dispersion liquid.
  • a pressure back pressure
  • the back pressure of the dispersion can be applied by applying a load to the flow of the dispersion.
  • a multistage step-down device described later can be provided on the downstream side of the disperser to provide a desired dispersion. Back pressure can be applied. By reducing the back pressure of the dispersion in multiple stages using this multistage pressure reducer, it is possible to suppress the generation of bubbles in the dispersion when the dispersion is finally released to atmospheric pressure.
  • the disperser may include a heat exchanger for cooling the dispersion and a coolant supply mechanism. This is because the generation of bubbles in the dispersion can be further suppressed by cooling the dispersion that has been heated to a high temperature by the shearing force applied by the distributor. In addition, it can suppress that a bubble generate
  • the effect of improving dispersibility by suppressing the adhesion of bubbles to the carbon nanofibers is very large in carbon nanofibers having a large BET specific surface area, particularly carbon nanofibers having a BET specific surface area of 600 m 2 / g or more. This is because the larger the specific surface area of the carbon nanofibers and the easier the carbon nanofibers to adhere to the surface, the more easily the dispersibility decreases when bubbles are generated and attached.
  • a distributed system having the above-described configuration for example, there is a distributed system in which a product name “BERYU SYSTEM PRO” (manufactured by Migrain Co., Ltd.) is combined with a multistage step-down device.
  • BERYU SYSTEM PRO manufactured by Migrain Co., Ltd.
  • the 1st composite material of this invention is obtained as a plating film by performing a plating process on the base-material surface using the plating solution mentioned above.
  • the carbon nanofibers are well dispersed, and the metal and the carbon nanofibers are well composited. Excellent in properties.
  • the plating method is not limited to electrolytic plating, and electroless plating can also be applied.
  • the method is not limited to the direct current plating method, and a current reversal plating method or a pulse plating method can also be employed.
  • the plating treatment conditions are not particularly limited, and may be according to a conventional method.
  • it does not specifically limit about the material of a base material The material used by normal electrolytic plating and electroless plating can be used.
  • the first composite material of the present invention is obtained by dispersing carbon nanofibers in a plating solution and performing a plating process. Therefore, in the first composite material of the present invention, for example, CNTs are formed on a base material, and then CNTs vertically aligned with the base material are collapsed and compressed to be horizontally aligned, and then the CNTs are made of copper or the like. It is different from a composite material obtained by a method of dipping in a plating solution and electrolytic plating.
  • the second composite material of the present invention is a copper composite material in which copper and carbon nanostructures are combined, and in the X-ray diffraction analysis, the diffraction intensity of the X-ray diffraction peak attributed to cuprous oxide is detected. It needs to be below the limit. That is, the copper composite material as the second composite material of the present invention does not substantially contain cuprous oxide and does not have a problem in practice due to the presence of cuprous oxide. Therefore, the copper composite material can exhibit excellent conductivity and thermal conductivity.
  • Carbon nanostructure is a general term for nano-sized substances composed of carbon atoms.
  • Specific examples of the carbon nanostructure include, for example, a single-walled or multi-walled carbon nanotube, a coiled carbon nanocoil, a carbon nanotwist obtained by twisting the carbon nanotube, and a beaded carbon in which beads are formed on the carbon nanotube.
  • Examples thereof include nanotubes, carbon nanoribbons having a width of several nanometers, carbon nanobrushes in which a large number of carbon nanotubes are erected, spherical fullerenes, and fine carbon fibers that are nano-sized carbon fibers.
  • These carbon nanostructures may be used alone or in combination of two or more.
  • These carbon nanostructures can be manufactured by, for example, a catalytic chemical vapor deposition method using a raw material gas disclosed in International Publication No. 2005/118473.
  • the proportion of the carbon nanostructures contained in the copper composite material is preferably 1% by mass or more, and more preferably 5% by mass or more from the viewpoint of sufficiently obtaining a desired effect. Further, from the viewpoint of suppressing deterioration of mechanical properties such as bending properties of the copper composite material, the proportion of the carbon nanostructure is preferably 60% by mass or less, and more preferably 50% by mass or less.
  • the copper composite material as the second composite material of the present invention preferably contains a single-walled carbon nanotube (hereinafter also referred to as “SWCNT”) as the carbon nanostructure.
  • SWCNT has a small diameter and a large specific surface area compared to other carbon nanostructures such as multi-walled carbon nanotubes, so it can reduce the amount required to form a composite with copper and make a uniform composite Can be realized. Thereby, it becomes possible to improve the electroconductivity and thermal conductivity of a copper composite material.
  • the SWCNT ratio in the carbon nanostructure is preferably 1% by mass or more, and more preferably 10% by mass or more.
  • the total amount of carbon nanostructures may be SWCNT.
  • the SWCNT specific surface area improves the conductivity and thermal conductivity of the copper composite material, and improves the dispersibility of the SWCNTs during the dispersion treatment to obtain the crushing effect described below. From the viewpoint of sufficiently preventing SWCNT damage, it is preferably 600 m 2 / g or more, more preferably 800 m 2 / g or more, and preferably 1200 m 2 / g or less in the unopened state. .
  • SWCNT preferably has a peak of Radial Breathing Mode (RBM) when evaluated using Raman spectroscopy. Note that there is no RBM in the Raman spectrum of multi-walled carbon nanotubes of three or more layers.
  • RBM Radial Breathing Mode
  • the ratio of the G band peak intensity to the D band peak intensity (G / D ratio) in the Raman spectrum of SWCNT is the viewpoint of the dispersibility of SWCNT and the conductivity of the copper composite material even when the amount of SWCNT is small. From the viewpoint of sufficiently improving the property and thermal conductivity, it is preferably 1 or more and 20 or less.
  • the ratio (3 ⁇ / Av) of the diameter distribution (3 ⁇ ) to the average diameter (Av) of SWCNT is from the viewpoint of sufficiently improving the conductivity and thermal conductivity of the copper composite material even when the amount of SWCNT is small. , More than 0.20, more preferably more than 0.25, particularly preferably more than 0.50, and preferably less than 0.60. That is, in SWCNT, the average diameter (Av) and the diameter distribution (3 ⁇ ) preferably satisfy the relational expression: 0.20 ⁇ (3 ⁇ / Av) ⁇ 0.60.
  • SWCNTs those having a normal distribution when the measured diameter is plotted on the horizontal axis and the frequency is plotted on the vertical axis and approximated by Gaussian are usually used.
  • the average diameter (Av) of SWCNT is preferably 0.5 nm or more, and more preferably 1 nm or more, from the viewpoint of suppressing SWCNT aggregation and improving dispersibility in the plating solution. . From the viewpoint of improving the conductivity and thermal conductivity of the copper composite material, the average diameter (Av) of SWCNT is preferably 15 nm or less, and more preferably 10 nm or less.
  • the average length of SWCNT is preferably 50 ⁇ m to 2000 ⁇ m, and more preferably 100 ⁇ m to 1000 ⁇ m, from the viewpoint of improving the conductivity and thermal conductivity of the copper composite material.
  • SWCNTs preferably have a plurality of micropores, and preferably have micropores having a pore diameter smaller than 2 nm.
  • the amount of micropores is the micropore volume (Vp) determined by the following method, and the lower limit is preferably 0.4 mL / g or more, more preferably 0.43 mL / g or more, and particularly preferably 0. It is 45 mL / g or more, and an upper limit can be 0.65 mL / g or less. If SWCNT has the above-mentioned micropores, the dispersibility of SWCNT can be improved.
  • the micropore volume can be adjusted, for example, by appropriately changing the SWCNT preparation method and preparation conditions.
  • Vp micropore volume (Vp)
  • Vp (V / 22414) ⁇ (M / ⁇ ).
  • P is a measurement pressure at the time of adsorption equilibrium
  • P0 is a saturated vapor pressure of liquid nitrogen at the time of measurement
  • M is an adsorbate (nitrogen) molecular weight of 28.010
  • ⁇ is an adsorbate ( Density) at 77K of 0.808 g / cm 3 .
  • the SWCNT is not subjected to opening treatment (that is, is not open), and the t-plot obtained from the adsorption isotherm shows an upwardly convex shape.
  • the t-plot is obtained by converting the relative pressure to the average thickness t (nm) of the nitrogen gas adsorption layer in the adsorption isotherm measured by the nitrogen gas adsorption method for SWCNT (t-plot by de Boer et al. Law).
  • the convex shape of the t-plot indicates that the ratio of the internal specific surface area to the total specific surface area of SWCNT is large, and a large number of openings are formed on the sidewalls of SWCNT.
  • the SWCNT preferably has an inflection point in the range of 0.2 ⁇ t (nm) ⁇ 1.5 in the above-described t-plot, and 0.45 ⁇ t (nm) ⁇ 1.5. More preferably, it is in the range of 0.55 ⁇ t (nm) ⁇ 1.0.
  • SWCNTs whose t-plot has an upwardly convex shape have a large ratio of the internal specific surface area to the total specific surface area.
  • the ratio of the internal specific surface area S2 to the total specific surface area S1 (S2 / S1) preferably satisfies 0.05 ⁇ S2 / S1 ⁇ 0.30.
  • the total specific surface area S1 is preferably 600 to 1800 m 2 / g, and more preferably 800 to 1500 m 2 / g.
  • the internal specific surface area S2 is preferably 30 to 540 m 2 / g.
  • the total specific surface area S1 and the internal specific surface area S2 can be obtained from the above-described t-plot.
  • the SWCNT production method is not particularly limited, and includes a chemical vapor deposition method (CVD method), an arc discharge method, a laser ablation method, and the like, and the super growth method described above is particularly preferable.
  • CVD method chemical vapor deposition method
  • arc discharge method arc discharge method
  • laser ablation method a laser ablation method
  • super growth method described above is particularly preferable.
  • the copper composite material as the second composite material of the present invention is a carbon nanostructure, the single-walled carbon nanotube (SWCNT), and a fibrous carbon nanostructure having an average diameter larger than the average diameter of SWCNT.
  • SWCNT single-walled carbon nanotube
  • fibrous carbon nanostructure having an average diameter larger than the average diameter of SWCNT.
  • the ratio of the large-diameter carbon nanostructure in the carbon nanostructure is preferably 1% by mass or more, and more preferably 5% by mass or more from the viewpoint of sufficiently obtaining a desired effect. Further, from the viewpoint of suppressing deterioration of mechanical properties such as bending properties of the copper composite material, the ratio of the large-diameter carbon nanostructure is preferably 60% by mass or less, and more preferably 50% by mass or less. preferable.
  • Large-diameter carbon nanostructures are nano-sized carbon fibers.
  • Examples of the large-diameter carbon nanostructure include multi-walled carbon nanotubes and fine carbon fibers.
  • the average diameter of the large-diameter carbon nanostructure is not particularly limited as long as it is larger than the average diameter of SWCNT, and can be, for example, 10 nm or more and 200 nm or less.
  • the large-diameter carbon nanostructure is not particularly limited and can be produced, for example, according to the method described in the above-mentioned International Publication No. 2005/118473.
  • the copper composite material as the second composite material of the present invention for example, by subjecting the carbon nanostructure to a dispersion treatment in which a cavitation effect or a crushing effect is obtained in a dispersion medium in the presence of a dispersant, Dispersing the carbon nanostructure in a dispersion medium to obtain a carbon nanostructure dispersion liquid (A), and mixing the carbon nanostructure dispersion liquid and the copper plating solution material, the carbon nanostructure
  • the manufacturing method of the copper composite material of this invention including the mixing process (B) which obtains a dispersion
  • an ionic surfactant and a polymer surfactant are used in combination as a dispersant. You don't have to.
  • a carbon nanostructure is first dispersed to prepare a dispersion (carbon nanostructure dispersion), and then the carbon nanostructure dispersion and the plating solution are used. Since they are mixed, contact between oxygen contained in the carbon nanostructure and the copper component in the plating solution can be effectively suppressed. Therefore, cuprous oxide generated in the copper composite material can be significantly reduced, and thereby a copper composite material containing no cuprous oxide can be obtained.
  • Dispersion step (A) In the method for producing a copper composite material of the present invention, first, the carbon nanostructure is subjected to a dispersion treatment in which a cavitation effect or a crushing effect is obtained in a dispersion medium in the presence of a dispersing agent, whereby a carbon nanostructure is obtained. Is dispersed in a dispersion medium to obtain a carbon nanostructure dispersion liquid (dispersion step (A)).
  • the dispersant used in the dispersion step (A) is not particularly limited, and a known dispersant that can assist the dispersion of the carbon nanostructure can be used.
  • the dispersant include ionic surfactants, nonionic surfactants, polysaccharides, and the like, and surfactants are particularly preferable.
  • anionic surfactants are particularly preferable from the viewpoint of ensuring sufficient dispersibility of the carbon nanostructure.
  • the cationic surfactant include quaternary ammonium salts such as dodecyltrimethylammonium bromide, cetyltrimethylammonium bromide, distearyldimethylammonium chloride; tetrabutylphosphonium chloride, tetrapentylphosphonium chloride, trioctylmethylphosphonium chloride, Quaternary phosphonium salts such as pentyltriphenylphosphonium; and the like.
  • anionic surfactant examples include sodium dodecyl sulfate, sodium deoxycholate, sodium cholate, sodium dodecylbenzenesulfonate, sodium dodecyldiphenyloxide disulfonate, and the like.
  • nonionic surfactants include ether type nonionic surfactants such as polyoxyethylene alkyl ether; ether ester type nonionic surfactants such as polyoxyethylene ether of glycerin ester; polyethylene glycol fatty acid ester Glycerin ester; and the like.
  • polysaccharide examples include hydroxypropylcellulose, gum arabic, carboxymethylcellulose sodium salt, carboxymethylcellulose ammonium salt, hydroxyethylcellulose and the like.
  • Dispersion medium As the dispersion medium used in the dispersion step (A), water is usually used from the viewpoint of forming micelles with a dispersant.
  • a dispersant for example, an ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, and the like can be used in combination with water as long as micelle formation is not inhibited.
  • the concentration of the dispersant in the dispersion medium is not particularly limited as long as it is equal to or higher than the critical micelle concentration.
  • the amount of carbon nanostructures to be dispersed in the dispersion medium is preferably 0.01 g / L or more, more preferably 0.1 g / L or more, from the viewpoint of obtaining a copper composite material having sufficient characteristics. . Further, from the viewpoint of improving the dispersibility in the dispersion medium, the amount of the carbon nanostructure dispersed in the dispersion medium is preferably 20 g / L or less, and more preferably 10 g / L or less.
  • the dispersion treatment used in the dispersion step (A) (dispersion treatment for obtaining a cavitation effect or a crushing effect) is performed on the coarse dispersion obtained by adding the above-described dispersant and carbon nanostructure to the above-described dispersion medium. Except for carrying out, it can be carried out in the same manner as the “dispersion treatment that provides a cavitation effect or a crushing effect” that can be used in the method for producing the plating solution used for the preparation of the first composite material described above.
  • the dispersion treatment that can obtain the cavitation effect in the dispersion step (A) is the same as that described in the item [Dispersion treatment that can obtain the cavitation effect], with “solvent” as “dispersion medium” and “ionic properties”. “Surfactant and polymeric surfactant” can be read as “dispersing agent”, and “carbon nanofiber” can be read as “carbon nanostructure”.
  • the dispersion treatment in which the crushing effect in the dispersion step (A) is obtained is the content described in the above item [Dispersion treatment in which the crushing effect is obtained], “solvent” as “dispersion medium”, “ It can be carried out by replacing “ionic surfactant and polymeric surfactant” with “dispersing agent” and “carbon nanofiber” with “carbon nanostructure”.
  • a surfactant ionic interface
  • an activator or a nonionic surfactant it is preferable to use an activator or a nonionic surfactant.
  • the dispersant does not freeze or falls below the cloud point of the nonionic surfactant in order to make the function of the dispersant better. It is preferable to perform the dispersion treatment at a low temperature.
  • the carbon nanostructure dispersion liquid and the copper plating liquid material are mixed to obtain a carbon nanostructure dispersion copper plating liquid (mixing step (B)).
  • the carbon nanostructure dispersion liquid and the copper plating liquid material if a desired carbon nanostructure dispersion copper plating liquid is obtained, (i) the carbon nanostructure dispersion liquid and It may be performed by mixing with a copper plating solution (solution containing a material of the copper plating solution), or (ii) the material of the copper plating solution is added individually or simultaneously to the carbon nanostructure dispersion liquid. Then, it may be carried out by mixing these, or (iii) the above (i) and (ii) may be used in combination.
  • Examples of the material for the copper plating solution include those commonly used in plating solutions such as a copper ion source, a chelating agent, and a pH adjusting agent.
  • examples of the copper ion source include copper sulfate pentahydrate.
  • examples of the chelating agent include ethylenediaminetetraacetic acid disodium salt, ethylenediamine, triethanolamine, thiourea, Rochelle salt, and tartaric acid.
  • Examples of the pH adjuster include potassium hydroxide.
  • the copper plating solution of said (i) can be obtained by dissolving the materials of these copper plating solutions in solvents, such as water.
  • the concentration of the copper ion source in the carbon nanostructure-dispersed copper plating solution is preferably 0.01 mol / L or more, and 0.05 mol / L or more. More preferably.
  • the concentration of the copper ion source is preferably 1.0 mol / L or less, and more preferably 0.5 mol / L or less, from the viewpoint of ensuring sufficient dispersibility of the carbon nanostructure.
  • the mixing of the carbon nanostructure dispersion liquid and the copper plating solution is such that the temperature of the obtained carbon nanostructure-dispersed copper plating solution is 90 ° C. or less from the viewpoint of ensuring sufficient dispersibility of the carbon nanostructure. It is preferable to carry out the temperature adjustment as appropriate.
  • the pH of the carbon nanostructure-dispersed copper plating solution is preferably 8 or more from the viewpoint of efficiently obtaining a desired copper composite material.
  • plating treatment examples of the plating method include electrolytic plating and electroless plating, and electrolytic plating is particularly preferable from the viewpoint of suppressing the generation of cuprous oxide.
  • electrolytic plating it is not limited to direct current plating, and current reversal plating or pulse plating can also be used.
  • the plating treatment conditions are not particularly limited, and may be in accordance with ordinary methods.
  • current density from the viewpoint of producing a copper composite material efficiently, it is preferably 0.1Adm -2 or more, is 0.5Adm -2 or More preferably.
  • the current density is preferably 6 Adm ⁇ 2 or less, and more preferably 4 Adm ⁇ 2 or less, from the viewpoint of obtaining a copper composite material having sufficient characteristics.
  • SGCNT-1 Synthesis of carbon nanotubes CNT
  • the catalyst layer was formed on the surface of the substrate by a wet process, and a raw material gas mainly composed of acetylene was used.
  • the obtained SGCNT-1 has a BET specific surface area of 1050 m 2 / g (unopened) and a micropore volume of 0.44 mL / g, and is characteristic of single-walled CNT in measurement with a Raman spectrophotometer.
  • a spectrum of radial breathing mode (RBM) was observed in the low wavenumber region of ⁇ 300 cm ⁇ 1 .
  • the average diameter (Av) was 3.3 nm
  • the standard deviation ( ⁇ ) of the diameter was multiplied by 3 (3 ⁇ ) was 1.9 nm
  • the ratio (3 ⁇ / Av) was 0.58.
  • the obtained plating solution was stirred using a stirrer under the condition of a temperature of 60 ° C. for 1 week. Thereafter, the plating solution is treated with an ultracentrifuge (centrifugation conditions: 8000 G, 20 ° C., 4 hours), and the presence or absence of CNT aggregates in the treated plating solution is visually observed to determine the dispersibility of CNTs. evaluated.
  • an ultracentrifuge centrifugation conditions: 8000 G, 20 ° C., 4 hours
  • Example 1-1 The concentration of SGCNT-1 as the carbon nanofiber is 0.2 g / L, the concentration of sodium dodecyl sulfate (SDS) as the ionic surfactant and the concentration of hydroxypropyl cellulose as the polymeric surfactant is 1 g / L, respectively.
  • An aqueous solution was prepared and stirred with a stirrer for 30 minutes to obtain a crude dispersion.
  • This coarse dispersion is subjected to a dispersion process 20 times under the condition of 50 MPa using a jet mill (product name: “JN-20”, manufactured by Joko Co., Ltd.), which is a dispersion apparatus utilizing the cavitation effect. A dispersion containing -1 was obtained.
  • FIG. 1 shows a state when 1 mL of the obtained copper plating solution 1 is taken and dropped on a slide glass. And when the dispersibility of CNT in the copper plating solution 1 was evaluated according to the method described above, no CNT aggregates were observed, and it was confirmed that the dispersion stability was excellent.
  • Example 1-2 A copper plating solution 2 containing SGCNT-1 was obtained in the same manner as in Example 1-1 except that sodium deoxycholate (DOC) was used instead of sodium dodecyl sulfate (SDS) as the ionic surfactant.
  • DOC sodium deoxycholate
  • SDS sodium dodecyl sulfate
  • Example 1-3 A copper plating solution 3 containing SGCNT-1 was obtained in the same manner as in Example 1-1 except that polyvinylpyrrolidone was used in place of hydroxypropylcellulose as the polymeric surfactant. When the dispersibility of CNT in the obtained copper plating solution 3 was evaluated, no CNT aggregates were observed, and it was confirmed that the dispersion stability was excellent.
  • the single-walled carbon nanotubes used in the following Examples 2-1 to 2-3 were synthesized by the following method.
  • SWCNT-1 Single-walled carbon nanotubes (SWCNT-1) as carbon nanostructures were prepared by the super-growth method according to the description in WO 2006/011655.
  • the thickness of the iron thin film layer as a catalyst layer was 2 nm.
  • the obtained SWCNT-1 had a BET specific surface area of 1050 m 2 / g (unopened state) and a micropore volume of 0.45 mL / g.
  • the t-plot in the unopened state shows an upwardly convex shape
  • the inflection point is in the range of 0.55 ⁇ t (nm) ⁇ 1.0
  • the total specific surface area S1 and the internal specific surface area S2 The ratio satisfied 0.05 ⁇ S2 / S1 ⁇ 0.30.
  • Single-walled carbon nanotubes were prepared in the same manner as in SWCNT-1, except that the thickness of the iron thin film layer as the catalyst layer was changed to 4 nm.
  • the obtained SWCNT-2 had a BET specific surface area of 820 m 2 / g (unopened state) and a micropore volume of 0.41 mL / g.
  • a spectrum of radial breathing mode (RBM) was observed in a low wavenumber region of 100 to 300 cm ⁇ 1 characteristic of single-walled CNT.
  • the average diameter (Av) was 5.9 nm
  • the diameter distribution (3 ⁇ ) was 3.2 nm
  • (3 ⁇ / Av ) was 0.54.
  • the t-plot in the unopened state shows an upwardly convex shape
  • the inflection point is in the range of 0.55 ⁇ t (nm) ⁇ 1.0
  • the total specific surface area S1 and the internal specific surface area S2 The ratio satisfied 0.05 ⁇ S2 / S1 ⁇ 0.30.
  • Example 2-1 A solution was prepared so that the concentration of SWCNT-1 as a carbon nanostructure was 0.2 g / L, and the concentration of sodium dodecyl sulfate (SDS) and hydroxypropyl cellulose as a dispersant was 1 g / L. The solution was stirred for 30 minutes using a stirrer. By subjecting this solution (crude dispersion) to 20 times of dispersion treatment at 50 MPa using a jet mill (manufactured by Joko, manufactured by JN-20) which is a dispersion device capable of obtaining a cavitation effect.
  • SDS sodium dodecyl sulfate
  • hydroxypropyl cellulose hydroxypropyl cellulose
  • distribution copper plating solution was about 50 degreeC.
  • the copper substrate whose surface was activated was attached to the anode side of the plating tank, maintained at 50 ° C., and immersed in a carbon nanostructure-dispersed copper plating solution stirred at a stirring speed of 450 rpm using a stirrer. And the electroplating process was performed so that it might become the energization amount 136.4C on the conditions of current density 1Adm- 2 (plating process (C)).
  • a copper composite material 1 composed of copper and SWCNT-1 was obtained.
  • FIG. 2 (A) shows a photograph of the surface of the copper composite material 1
  • FIG. 2 (B) shows an enlarged photograph. From the results of observation with a scanning electron microscope, it was observed that in the produced copper composite material 1, the matrix copper and SWCNT-1 were composited at the nano level. Further, surface elemental analysis of the obtained copper composite material 1 was performed using an X-ray diffraction apparatus (manufactured by Shimadzu Corporation, product name: XRD-6000). FIG. 3 shows the results. In the analysis using an X-ray diffraction apparatus, no peak derived from cuprous oxide was observed. From this result, it was confirmed that the copper composite material 1 does not contain cuprous oxide.
  • Example 2-2 In the same manner as in Example 2-1, except that the carbon nanostructure to be used was replaced with SWCNT-2, and the dispersion of the carbon nanostructure was performed by a dispersion treatment capable of obtaining a crushing effect, copper and A copper composite material 2 composed of SWCNT-2 was obtained.
  • the dispersion treatment was performed 4 times under the condition of 100 MPa using a high-pressure homogenizer having a multi-stage step-down device (product name: BERYU SYSTEM PRO).
  • the obtained copper composite material 2 was observed and analyzed in the same manner as in Example 2-1. As a result of observation using a scanning electron microscope, the copper composite material 2 had a matrix of copper and SWCNT-2.
  • Example 2-3 As carbon nanostructure, in addition to SWCNT-1, VGCF-H (manufactured by Showa Denko, average diameter 150 nm) (fine carbon fiber) (fine carbon fiber) which is a large-diameter carbon nanostructure was used. Thus, a copper composite material 3 composed of copper and SWCNT-1 and VGCF-H was obtained. Here, the concentrations of SWCNT-1 and VGCF-H in the dispersion liquid (carbon nanostructure dispersion liquid) were 0.5 g / L and 0.5 g / L, respectively. The obtained copper composite material 3 was observed and analyzed in the same manner as in Example 1.
  • the matrix copper, SWCNT-1 and VGCF-H are compounded while forming an advanced network at the nano level. Observed. Moreover, from the result of the analysis using an X-ray diffraction apparatus, in the copper composite material 3, no peak derived from cuprous oxide was observed, and it was confirmed that the copper composite material 3 does not contain cuprous oxide.
  • a plating solution in which carbon nanofibers are well dispersed in the solution can be provided.
  • a composite material having excellent conductivity and thermal conductivity can be provided.

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Abstract

　La présente invention concerne une solution de placage dans laquelle des nanofibres de carbone sont bien dispersées dans un liquide. La présente invention concerne également des matériaux composites exceptionnels en termes de conductivité électrique et de conductivité thermique. Cette solution de placage comprend des ions métal à dépôt électrolytique, un chélateur, un tensioactif ionique, un tensioactif à base de polymère, et des nanofibres de carbone. Ce premier matériau composite est obtenu par la mise en œuvre d'un processus de dépôt électrolytique ou d'un processus de dépôt autocatalytique sur une surface d'un matériau de base, au moyen de la solution de placage. Ce second matériau composite est un matériau composite de cuivre dans lequel du cuivre et une structure de nanofibres de carbone ont été complexés, l'intensité de diffraction du pic de diffraction des rayons X attribué à l'oxyde de cuivre (I) dans le matériau composite de cuivre étant égale ou inférieure à la limite de détection dans une analyse de diffraction des rayons X.
PCT/JP2015/003679 2014-07-23 2015-07-22 Solution de placage et son procédé de production, matériau composite, matériau composite de cuivre, et procédé de production associé Ceased WO2016013219A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
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KR20190091010A (ko) * 2018-01-26 2019-08-05 삼성전자주식회사 도금액과 금속 복합 재료 및 그 제조 방법
JP2021102793A (ja) * 2019-12-24 2021-07-15 古河電気工業株式会社 複合めっき、めっき付き金属基材及び電気接点用端子
WO2021239722A3 (fr) * 2020-05-26 2022-02-10 University College Dublin, National University Of Ireland Électrodéposition améliorée
US11643328B2 (en) 2017-03-16 2023-05-09 Zeon Corporation Method of producing surface-treated carbon nanostructures
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KR102562279B1 (ko) * 2018-01-26 2023-07-31 삼성전자주식회사 도금액과 금속 복합 재료 및 그 제조 방법
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JPWO2023105747A1 (fr) * 2021-12-10 2023-06-15
JP7736811B2 (ja) 2021-12-10 2025-09-09 日本カニゼン株式会社 ニッケルめっき液、及び、ニッケルまたはニッケル合金めっき皮膜の製造方法
CN119242079A (zh) * 2024-09-11 2025-01-03 国网湖北省电力有限公司电力科学研究院 一种提升气体绝缘设备内金属与环保替代气体相容性的镀覆液及其制备方法

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