WO2023163083A1 - 銅粉及び銅粉の製造方法 - Google Patents

銅粉及び銅粉の製造方法 Download PDF

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WO2023163083A1
WO2023163083A1 PCT/JP2023/006620 JP2023006620W WO2023163083A1 WO 2023163083 A1 WO2023163083 A1 WO 2023163083A1 JP 2023006620 W JP2023006620 W JP 2023006620W WO 2023163083 A1 WO2023163083 A1 WO 2023163083A1
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Prior art keywords
copper powder
less
copper
boiling point
temperature
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English (en)
French (fr)
Japanese (ja)
Inventor
尚樹 山岡
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Priority to KR1020247032322A priority Critical patent/KR20240157058A/ko
Priority to JP2024503244A priority patent/JPWO2023163083A1/ja
Priority to CN202380023999.9A priority patent/CN118804807A/zh
Priority to US18/841,855 priority patent/US20250170640A1/en
Publication of WO2023163083A1 publication Critical patent/WO2023163083A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/10—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles
    • B22F2304/056—Particle size above 100 nm up to 300 nm

Definitions

  • the present invention relates to a copper powder obtained by heating copper oxide powder or copper powder in a polyol solvent and a method for producing the copper powder.
  • Copper powder is also used as a material for the conductive paste used to form the internal and external electrodes of multilayer ceramic capacitors (MLCCs), which are electronic components, and the electrodes of multilayer ceramic substrates.
  • MLCCs multilayer ceramic capacitors
  • multilayer ceramic capacitors have become smaller and have larger capacities, and the internal electrodes have become thinner. Desired.
  • fine metal particles with an average particle size of 250 nm or less have a low firing temperature, unlike normal particles of submicrons or larger, and are being considered for application to low-temperature firing pastes and the like.
  • metal powders that are sintered at low temperatures not only require less heat load during sintering and less residual stress during cooling, but also have the advantage of being able to exist stably without melting up to the bulk metal melting point once sintered. be. Therefore, low-temperature sintered metal powders are attracting attention in the fields of printed electronics, which dislike thermal damage to substrates, and die attach of power modules, which are compatible with high-temperature operation.
  • nano-sized silver powder is widely used as low-temperature sintered metal powder, but it has the drawback of being expensive and having ion migration properties. Therefore, in recent years, many efforts have been made to develop low-temperature sintering using copper powder, which is inexpensive and has excellent ion migration resistance.
  • oxidation-resistant film oxidation-resistant film
  • Patent Document 1 by physically adsorbing an aliphatic carboxylic acid having an aliphatic group having 5 or more carbon atoms on the surface of the copper particles, the particle size and particle size distribution are adjusted within a certain range, and A copper powder having both oxidation resistance and low-temperature sintering is disclosed. According to this, even if the SEM primary particle size of the copper powder is 100 nm or less, oxidation after standing in the air for a long period of time is not confirmed by XRD, and it is possible to sinter at 300 ° C in a nitrogen atmosphere. and
  • Patent Document 2 discloses a copper powder that can be fired at a low temperature under high vacuum conditions of 0.01 Pa or less by having a cuprous oxide film controlled at a constant ratio or average coating thickness on the copper powder surface.
  • the copper powder in which the cuprous oxide layer covering the copper powder was further protected with caproic acid achieved sintering at 100° C. under vacuum conditions of 3 ⁇ 10 ⁇ 6 Pa.
  • Patent Document 3 discloses a method of heating copper oxide powder (raw material) in a polyol solvent to reduce it (polyol method).
  • the copper powder produced by this method is characterized by excellent oxidation resistance due to the organic film formed during reduction.
  • a silver salt for nucleation is added, and polyvinylpyrrolidone is added as a dispersant to obtain fine copper particles having silver as nuclei and a particle size of 100 nm or less.
  • the copper powder described in Patent Document 1 contains a large amount of organic components, and the aliphatic carboxylic acid is coated with a high density close to that of a liquid condensed film.
  • Such a large amount of organic components present on the copper surface volatilizes and generates gas as a result of thermal decomposition, which may cause problems caused by gas generation, such as blisters and short circuits in the formation of MLCC internal electrodes. be.
  • the copper powder described in Patent Document 3 contains polyvinylpyrrolidone, which is a high-molecular polymer, as a dispersant in an amount of 40% by mass relative to copper.
  • the oxide film formed on the surface of the copper powder can inhibit sintering even if it is an extremely thin layer of several nanometers. Therefore, for the copper powder described in Patent Document 1, it is said that no XRD peaks derived from oxides are detected immediately after synthesis and after storage at 25 ° C. in the atmosphere for 4 months, but considering the detection sensitivity of XRD, It is difficult to use XRD to determine the presence or absence of an oxide film that may hinder sintering.
  • the copper powder described in Patent Document 2 also forms an oxide film, so it is a factor of generation of water vapor accompanying reduction of the oxide film in a reducing atmosphere and inhibition of sintering in an inert atmosphere. may become. Furthermore, high vacuum or ultra-high vacuum conditions are required for low-temperature sintering as disclosed, which is difficult to apply to heating furnaces for mass production such as conveying continuous heating furnaces. .
  • the present invention has been made in view of such conventional circumstances, and provides a copper powder that has an organic film that prevents the formation of an oxide film that can inhibit sintering and has excellent low-temperature sinterability. for the purpose.
  • the present inventors have found that the surface of copper powder produced using a polyol is coated with an organic substance derived from the polyol solvent and a chain-like compound having an appropriate molecular weight and a functional group.
  • the inventors have found that a copper powder having both excellent oxidation resistance and low-temperature sinterability can be obtained by coating with a mixture of organic substances, and have completed the present invention. That is, the present invention provides the following.
  • An aspect of the present invention provides a copper powder having an average particle diameter of 250 nm or less, a surface coated with an organic substance, and satisfying all of the following conditions (1) to (4).
  • (1) When the organic matter present on the surface of the copper powder is detected by gas chromatography mass spectrometry (GC/MS), H(—O—CH 2 —CH 2 ) n —OH (where n is an integer of 1 or more and 4 or less), HOOC-CH 2 (-O-CH 2 -CH 2 ) m -OH (where m is an integer of 1 or more and 3 or less), HOOC—CH 2 (—O—CH 2 —CH 2 ) l —O—CH 2 —COOH (where l is 1 or 2), H(—C 3 H 6 O) s —OH (where s is an integer of 1 or more and 4 or less), HOOC—CH(CH 3 )(—C 3 H 6 O) t —OH (where t is an integer of 1 or more and
  • a copper oxide powder slurry obtained by mixing copper oxide powder in a polyol solvent having a boiling point of 230° C. or lower to which the chain organic substance is added is heated to 230° C. or lower.
  • a method for producing copper powder is provided.
  • the amount of the chain organic substance added is preferably 0.005% by mass or more and 10% by mass or less with respect to the total amount of copper contained in the copper oxide powder.
  • the polyol solvent having a boiling point of 230° C. or less includes ethylene glycol (boiling point: 196° C.), propylene glycol (boiling point: 188° C.), 1,3-propanediol (boiling point: 214° C.), 1,2-butanediol (boiling point: 194°C), 1,3-butanediol (boiling point: 207°C), 1,4-butanediol (boiling point: 228°C), 1,2-pentanediol (boiling point: 210°C), and 1,2-hexanediol (boiling point: 223°C).
  • the copper powder having an average particle size of 250 nm or less and not satisfying at least one of the conditions (3) and (4) is added with the chain organic substance and has a boiling point of
  • a method for producing copper powder which comprises heat-treating a copper powder slurry dispersed in a polyol solvent at 250° C. or higher at 230° C. or higher.
  • the polyol solvent having a boiling point of 250°C or higher includes triethylene glycol (boiling point: 287°C), tetraethylene glycol (boiling point: 327°C), and polyethylene glycol having an average molecular weight of 200 to 600 (boiling point: around 300°C). It is more preferable to have one or more selected from the group.
  • the temperature of the heat treatment is preferably 230°C or higher, more preferably 250°C or higher, and even more preferably 270°C or higher.
  • the amount of the chain organic substance added is preferably 0.005% by mass or more and 10% by mass or less with respect to the total amount of copper contained in the copper powder to be heat-treated.
  • the copper powder according to the present embodiment has an organic film that prevents the formation of an oxide film that can inhibit sintering, and is a copper powder that is excellent in low-temperature sinterability.
  • copper powder that has an organic film that prevents the formation of an oxide film that can inhibit sintering and that is excellent in low-temperature sinterability.
  • FIG. 10 is a diagram showing the results of gas chromatography-mass spectrometry in Example 17 and Conventional Example 3;
  • this embodiment A specific embodiment (hereinafter referred to as "this embodiment") according to the present invention will be described in detail below.
  • the present invention is not limited to the following embodiments, and various modifications are possible without changing the gist of the present invention.
  • the notation "X to Y" (X and Y are arbitrary numerical values) means "X or more and Y or less”.
  • washing a method is used in which the copper powder obtained by reduction (polyol copper powder) is settled and decanted, and then pure water or the like is supplied for washing with agitation.
  • filtration a method of dehydration by centrifugation or the like is used.
  • the copper powder in the present embodiment is a copper powder having an average particle size of 250 nm or less and a surface coated with an organic substance, and the surface of the copper powder is detected by gas chromatography mass spectrometry (GC / MS). and specific organics detected by liquid chromatography-mass spectrometry (LC/MS).
  • GC / MS gas chromatography mass spectrometry
  • LC/MS liquid chromatography-mass spectrometry
  • the thermal shrinkage rate in an inert atmosphere is The temperature difference between 3% and the temperature at which the thermal contraction rate in a reducing atmosphere is 3% is less than 10°C, and an oxide film that can inhibit sintering is not formed on the surface of the copper powder, or is not formed. Even if there is, it is thin enough not to hinder sintering.
  • the copper powder of the present embodiment has an organic film that prevents the formation of an oxide film that can inhibit sintering, and is a copper powder that is excellent in low-temperature sinterability.
  • the average particle size of the copper powder is preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 150 nm or less.
  • the average particle size of the copper powder can be, for example, as described in the Examples, and can be 110 nm or less, 100 nm or less, 90 nm or less, 70 nm or less, or 60 nm or less. Since it is such a fine copper powder, it can be suitably used for electronic parts such as electrodes of laminated ceramic capacitors.
  • the lower limit of the average particle size of the copper powder is not particularly limited, the lower limit is about 20 nm according to the manufacturing method described later.
  • the average particle size of the copper powder in this embodiment is a value measured by the method described in Examples.
  • the average particle size of the copper powder can be controlled by the production conditions, as will be explained later in the production method section.
  • the specific organic matter detected by gas chromatography/mass spectrometry is preferably one or more selected from the group consisting of the following organic matter.
  • HOOC—CH 2 (—O—CH 2 —CH 2 ) l —O—CH 2 —COOH where l is 1 or 2
  • H(—C 3 H 6 O) s —OH where s is an integer of 1 or more and 4 or less
  • organic substances represented by the following (Chem. 1) to (Chem. 8) are more preferable.
  • These organic substances are organic substances derived from the polyol solvent.
  • (Chemical Formula 1) triethylene glycol (H(—O—CH 2 —CH 2 ) 3 —OH) (molecular weight: 150),
  • (Chemical Formula 2) tetraethylene glycol (H(--O--CH 2 --CH 2 ) 4 --OH) (molecular weight: 194),
  • (Chem. 1) triethylene glycol (H(—O—CH 2 —CH 2 ) 3 —OH) (molecular weight: 150)
  • (Chemical Formula 2) tetraethylene glycol (H(--O--CH 2 --CH 2 ) 4 --OH) (molecular
  • the specific organic substance detected by liquid chromatography mass spectrometry is a chain organic substance having a molecular weight of 200 or more and 1000 or less, and the chain organic substance has a functional capable of coordinating with copper ions at each end of the molecule.
  • carboxy group (-COOH), hydroxy group (-OH), amino group (-NH 2 ), aldehyde group (-CHO), nitro group (-NO 2 ), thiol group (-SH), sulfo group ( —SO 3 HHH), phosphate group (—PO 4 H 2 ), cyanide group (—CN), chloro group (—Cl), bromo group (—Br), and iodo group (—I) It is preferably a chain organic substance having one kind of
  • chain organic substances having a molecular weight of 200 or more and 700 or less are more preferable.
  • the chain organic substance more preferably has a carboxy group or a hydroxy group at each end of the molecule, and more preferably has a carboxy group or a hydroxy group at both ends.
  • chain organic substances include (Chem. 9) sebacic acid (molecular weight: 202), (Chem. 10) dodecanedioic acid (molecular weight: 230), (Chem. 11) tetradecanedioic acid (molecular weight: 258). , (Chem. 12) hexadecanedioic acid (molecular weight: 286), (Chem.
  • the mechanism of having low-temperature sinterability as described above has not been elucidated in detail, but the specific organic substances detected by the GC / MS and the LC / MS A specific organic substance has a small proportion of functional groups that can be coordinated with copper ions in long chain molecules, so even if the copper powder surface is evenly coated with organic substances, It is possible that the density of the bonds became lower and detachment from the copper powder surface by heat became easier.
  • the organic substances detected by the GC/MS may be detected by the LC/MS, and the organic substances detected by the LC/MS may be detected by the GC/MS.
  • the copper powder in the present embodiment is press-molded at 100 MPa to form a green compact, and when heated from 25 ° C. at a temperature rising rate of 10 ° C./min in an inert atmosphere, the green compact at 25 ° C.
  • the temperature at which the thermal shrinkage rate becomes 1% is 230° C. or lower.
  • the temperature at which the thermal contraction rate of the compact is 1% is the temperature at which the copper powder begins to shrink in volume due to the sintering phenomenon, and can also be expressed as the temperature at which sintering starts.
  • the temperature at which the heat shrinkage rate is 1% is 220° C. or less, 215° C. or less, 210° C. or less, 205° C. or less, and 200° C. or less, as described in the Examples. , 195° C. or less, and the like.
  • the copper powder in the present embodiment is pressure-molded at 100 MPa to form a green compact, and when heated from 25 ° C. at a temperature increase rate of 10 ° C./min in an inert atmosphere and a reducing atmosphere,
  • the thermal shrinkage rate is measured based on the thickness of the green compact at ° C.
  • the temperature at which the thermal shrinkage rate is 3% in an inert atmosphere and the temperature at which the thermal shrinkage rate is 3% in a reducing atmosphere is less than 10°C.
  • the sintering behavior does not change greatly depending on whether the firing (heating) atmosphere is an inert atmosphere or a reducing atmosphere, restrictions due to the difficulty of sintering copper powder in selecting the firing atmosphere are relaxed. be.
  • the temperature at which the thermal shrinkage of the green compact is 3% is the temperature at which volumetric shrinkage due to the sintering phenomenon of the copper powder has progressed to some extent.
  • the presence or absence of an oxide film that inhibits sintering can be estimated by comparing the conditions under an inert atmosphere and under a reducing atmosphere. That is, if the temperature difference between the temperatures at which the thermal contraction rate of the green compact is 3% in an inert atmosphere and in a reducing atmosphere is less than 10°C, the surface of the copper powder is oxidized to inhibit sintering. It means that no film is formed.
  • the temperature difference between the temperature at which the thermal shrinkage rate is 3% in the inert atmosphere and the temperature at which the thermal shrinkage rate is 3% in the reducing atmosphere is described in Examples. 8° C. or less, 6° C. or less, 5° C. or less, and the like.
  • the temperature at which the thermal shrinkage of the compact under a reducing atmosphere is 3% is lower than the temperature at which the thermal shrinkage of the compact under an inert atmosphere is 3% by 10°C or more
  • the surface of the copper powder used for measuring the thermal shrinkage rate was covered with a thin oxide film, so the oxide film was reduced by the reducing gas, making it easier to sinter. inhibited).
  • the thermal shrinkage rate is measured in a reducing atmosphere under conditions where there are more oxides present on the surface of the copper powder subjected to thermomechanical analysis, a large amount of water vapor is generated by the reduction, and the copper powder is sintered.
  • the mechanism by which the copper powder in the present embodiment has the effect of preventing the formation of an oxide film as described above has not been elucidated in detail, but the specific organic substances detected by the GC / MS and the LC / MS
  • the specific organic substance used is a combination of organic substances with different molecular lengths, and can coat the surface of the copper powder efficiently and evenly.
  • the organic substances present on the surface of the copper powder of the present embodiment, the organic substances detected by the GC / MS, and the organic substances detected by the LC / MS are all within the scope of the present invention. It may also contain other substances such as other organics and compounds.
  • the copper powder of the present embodiment has an average particle size of 250 nm or less, is a copper powder whose surface is coated with an organic substance, and is a copper powder that satisfies all of the following conditions (1) to (4). be.
  • (1) When the organic matter present on the surface of the copper powder is detected by gas chromatography mass spectrometry, H(—O—CH 2 —CH 2 ) n —OH (where n is an integer of 1 or more and 4 or less), HOOC-CH 2 (-O-CH 2 -CH 2 ) m -OH (where m is an integer of 1 or more and 3 or less), HOOC—CH 2 (—O—CH 2 —CH 2 ) l —O—CH 2 —COOH (where l is 1 or 2), H(—C 3 H 6 O) s —OH (where s is an integer of 1 or more and 4 or less), HOOC—CH(CH 3 )(—C 3 H 6 O) t —OH (
  • the copper powder of the present embodiment has an organic film that prevents the formation of an oxide film that can inhibit sintering, and is a copper powder that is excellent in low-temperature sinterability.
  • the copper powder manufacturing method (copper powder manufacturing method 1, copper powder manufacturing method 2) according to the present embodiment will be described.
  • the above-mentioned matters may be omitted or simplified.
  • the items described in the copper powder according to the present embodiment can be appropriately applied.
  • the items described in the method for producing the copper powder according to the present embodiment can also be appropriately applied to the copper powder according to the present embodiment.
  • Method 1 for producing copper powder In the method for producing copper powder in the present embodiment, copper oxide powder (raw material) is placed in a polyol solvent with a boiling point of 230 ° C. or lower (hereinafter, the polyol solvent with a boiling point of 230 ° C. or lower may be referred to as polyol solvent A).
  • polyol solvent A in which copper oxide powder is suspended
  • the desired copper powder is obtained by adding the above-described specific chain-like organic substance to the reaction liquid, and heating and reducing the mixture.
  • the added organic matter including the chain organic matter can be applied to the surface of the copper powder, and the copper powder of the present embodiment described above can be obtained.
  • the chain organic substance to be added may be in the form of a salt or the like, as long as the chain organic substance is in the form of the chain organic substance in the reaction solution.
  • Both copper oxide (CuO) and cuprous oxide (Cu 2 O) can be used as the copper oxide powder used as a raw material in the reduction step.
  • the copper oxide powder may be pulverized in advance and subjected to the reduction reaction.
  • Polyol solvent A used in the reduction step is a polyol solvent having a boiling point of 230° C. or less, and includes ethylene glycol (boiling point: 196° C.), propylene glycol (boiling point: 188° C.), and 1,3-propanediol (boiling point: 214° C.).
  • 1,2-butanediol (boiling point: 194 ° C.), 1,3-butanediol (boiling point: 207 ° C.), 1,4-butanediol (boiling point: 228 ° C.), 1,2-pentanediol (boiling point: 210 ° C.), and 1,2-hexanediol (boiling point: 223° C.).
  • the amount of the chain organic substance added to the polyol solvent A is preferably 0.005% by mass or more and 10% by mass or less with respect to the total amount of copper contained in the copper oxide powder.
  • the reaction temperature in the reduction step is preferably ⁇ 50° C. or higher relative to the boiling point of the polyol solvent A, and more preferably ⁇ 40° C. or higher relative to the boiling point of the polyol solvent A.
  • the reaction temperature is preferably ⁇ 0° C. or lower with respect to the boiling point of the polyol solvent A, and more preferably ⁇ 5 or lower with respect to the boiling point of the polyol solvent A.
  • the reaction temperature is preferably ⁇ 50° C. or higher with respect to the boiling point of polyol solvent A, ⁇ 0° C. or lower with respect to the boiling point of polyol solvent A, ⁇ 40° C.
  • the boiling point of the polyol solvent A is ⁇ 5° C. or lower.
  • the reaction temperature is lower than ⁇ 50° C. with respect to the boiling point of the polyol solvent A, the copper powder (polyol The oxygen content in the copper powder) is sometimes increased, and the reaction time is greatly extended, resulting in deterioration of productivity.
  • the heating temperature is higher than the boiling point of the polyol solvent A, the decrease (consumption) due to decomposition and volatilization of the polyol solvent becomes significant, and there is a possibility that sufficient reduction cannot be achieved.
  • the copper powder according to the present embodiment is obtained by heat-reducing the copper oxide powder with the polyol solvent A to which the chain organic substance is added.
  • heating is started after the chain organic substance is added to the reaction solution.
  • the chain organic substance may be added later to the reaction solution during heating.
  • a chain organic substance that does not become neutral (pH of about 6.5 to 7.5) when used as an aqueous solution, neutralize with an alkali or acid to neutralize the chain organic substance added to the reaction solution. It is preferable to add them together as agents.
  • an alkali is used as the neutralizing agent, an alkali metal hydroxide is preferable, and specifically sodium hydroxide or potassium hydroxide can be used.
  • an acid is used as the neutralizing agent, an inorganic acid is preferred, and specifically sulfuric acid or hydrochloric acid can be used.
  • adding the neutralizing agent to the reaction solution it may be added in advance in the form of an aqueous solution.
  • the particle size (average particle size) of the obtained copper powder becomes finer as the amount of the chain organic substance in the reaction solution increases. That is, the average particle size of the copper powder can be controlled by the amount of chain organic matter. Furthermore, the sinterability is improved by incorporating the chain-like organic substance into the organic film formed on the surface of the copper powder.
  • the amount of the chain organic substance in the reaction solution is set according to conditions such as the particle size of the copper powder obtained after the reduction reaction.
  • the amount of the chain organic substance in the reaction solution can be set by preliminary experiments.
  • the amount of the chain organic substance in the reaction liquid is preferably 10% by mass or less with respect to the total amount of copper contained in the raw material copper oxide.
  • the amount of the chain organic substance in the reaction solution (the amount of the chain organic substance added to the polyol solvent A) is 0.005% by mass or more with respect to the total amount of copper contained in the raw material copper oxide. is preferred. Moreover, the amount of the chain organic substance in the reaction liquid is preferably 0.005% by mass or more and 10% by mass or less with respect to the total amount of copper contained in the raw material copper oxide. The addition of the chain organic material in an amount of less than 0.005% by mass relative to the total amount of copper contained in the raw material copper oxide may not be sufficient to exhibit the particle size control effect and the sinterability improvement effect. be.
  • the amount of the chain organic substance in the reaction solution (the amount of the chain organic substance added to the polyol solvent A is 0.001 mol% or more with respect to the total amount of copper contained in the raw material copper oxide. Preferably, for example, it may be 0.01 mol % or more, or 0.1 mol % or more.
  • the amount of the chain organic substance in the reaction solution is 1 mol with respect to the total amount of copper contained in the raw material copper oxide.
  • the amount of the chain organic substance in the reaction solution is preferably 0.001 mol % or more and 1 mol or less with respect to the total amount of copper contained in the raw material copper oxide. 01 mol % or more and 1 mol % or less, or 0.1 mol % or more and 1 mol % or less.
  • the average particle diameter of the copper powder obtained by the copper powder production method 1 according to the present embodiment is preferably 250 nm or less.
  • the copper powder (polyol copper powder) obtained by the production method described so far is controlled to have an average particle diameter equal to or less than the above average particle size by using the chain organic substance during the reduction reaction. Since it is a fine copper powder, it can be used for electronic parts such as electrodes of laminated ceramic capacitors.
  • copper powder having an average particle size of 200 nm or less, 150 nm or less, 110 nm or less, 100 nm or less, 90 nm or less, 70 nm or less, and 60 nm or less, as described in Examples, can be obtained by the copper powder production method 1. can.
  • a copper oxide powder slurry obtained by mixing a copper oxide powder with a polyol solvent having a boiling point of 230° C. or less to which the chain organic substance is added is prepared at 230°C.
  • the copper powder production method 1 of the present embodiment is a method capable of producing the copper powder of the present embodiment.
  • the structures other than the above are arbitrary structures.
  • the copper powder production method 1 of the present embodiment it is possible to obtain a copper powder that has an organic film that prevents the formation of an oxide film that can inhibit sintering and that is excellent in low-temperature sinterability.
  • substances other than those described above may be added to the reaction solution within the scope of the present invention.
  • the copper powder production method of another aspect of the present embodiment has an average particle size of 250 nm or less, and satisfies at least one of the conditions (3) and (4) of the copper powder in the above-described embodiment.
  • the copper powder that does not contain the chain organic substance is dispersed in a polyol solvent having a boiling point of 250 ° C. or higher (hereinafter, the polyol solvent having a boiling point of 250 ° C. or higher may be referred to as a polyol solvent B) (hereinafter, this polyol
  • the liquid in which the solvent B and the copper powder are mixed and suspended may be collectively referred to as "treatment liquid"), and a heat treatment step is provided to obtain the desired copper powder by heating.
  • the heat treatment step it is possible to modify the organic matter on the surface of the copper powder, including applying the chain organic compound added to the surface of the copper powder.
  • the copper powder of the present embodiment described above can be obtained.
  • copper powder having an average particle size of 200 nm or less, 150 nm or less, 110 nm or less, 100 nm or less, 90 nm or less, 70 nm or less, or 60 nm or less, as described in Examples can be obtained by the copper powder production method 2. can.
  • the copper powder having an average particle size of 250 nm or less and not satisfying at least one of the conditions (3) and (4) of the copper powder in the present embodiment described above is, for example, JP-A-2022- It is a copper powder produced by the method for producing copper powder described in 128445. Of course, it is not limited to this, and if it is a copper powder that does not satisfy at least one of the conditions (3) and (4) of the copper powder in the above-described embodiment, other wet methods and vapor phase methods can be used. It may be a copper powder produced by.
  • the polyol solvent B used in the heat treatment step is a polyol having a boiling point of 250° C. or higher, and includes triethylene glycol (boiling point: 287° C.), tetraethylene glycol (boiling point: 327° C.), and polyethylene glycol having an average molecular weight of 200 to 600. (boiling point: around 300°C).
  • the amount of the chain organic substance to be added is preferably 10% by mass or less with respect to the total amount of copper contained in the copper powder to be treated.
  • the amount of the chain organic substance to be added is preferably 0.005% by mass or more with respect to the total amount of copper contained in the copper powder to be treated.
  • the amount of the chain organic substance to be added is preferably 0.005% by mass or more and 10% by mass or less with respect to the total amount of copper contained in the copper powder to be treated.
  • the heat treatment temperature in the heat treatment step is preferably 230°C or higher.
  • the heat treatment temperature can be set, for example, according to the conditions described in Examples, and can be 240° C. or higher, 250° C. or higher, 260° C. or higher, or 270° C. or higher.
  • the heat treatment temperature is preferably ⁇ 0° C. or lower with respect to the boiling point of the polyol solvent B, and more preferably ⁇ 5° C. or lower with respect to the boiling point of the polyol solvent B.
  • the heat treatment temperature is preferably 230° C. or higher and ⁇ 0° C. or lower with respect to the boiling point of polyol solvent B, more preferably 250° C. or higher and ⁇ 5° C.
  • the heat treatment time is preferably 1 hour or less, more preferably 30 minutes or less, and still more preferably 15 minutes or less.
  • the copper powder that does not satisfy at least one of the conditions (3) and (4) of the copper powder in the above-described embodiment is heated in the polyol solvent B to which the chain organic substance is added.
  • a copper powder according to the present embodiment is obtained.
  • heating is started after the chain organic substance is added to the treatment liquid.
  • the chain organic substance may be added later to the reaction solution during heating.
  • the chain organic substance that does not become neutral (pH of about 6.5 to 7.5) when used as an aqueous solution, neutralize with an alkali or acid to neutralize the chain organic substance added to the treatment liquid. It is preferable to add them together as agents.
  • an alkali is used as the neutralizing agent, an alkali metal hydroxide is preferable, and specifically sodium hydroxide or potassium hydroxide can be used.
  • an acid is used as the neutralizing agent, an inorganic acid is preferred, and specifically sulfuric acid or hydrochloric acid can be used.
  • adding the neutralizing agent to the reaction solution it may be added in advance in the form of an aqueous solution.
  • the chain organic matter in the treatment liquid also functions as an anticoupling agent for the copper powder.
  • the amount of the chain organic substance in the treatment liquid is set according to conditions such as the particle size of the copper powder to be treated.
  • the amount of the chain organic substance in the treatment liquid can be set by preliminary experiments.
  • the amount of the chain organic substance in the treatment liquid is preferably 10% by mass or less with respect to the total amount of copper contained in the copper powder to be treated.
  • the amount of the chain organic substance in the treatment liquid (the amount of the chain organic substance added to the polyol solvent B) is 0.005% by mass or more with respect to the total amount of copper contained in the copper powder to be treated. preferable. Also.
  • the amount of the chain organic substance in the treatment liquid is preferably 0.005% by mass or more and 10% by mass or less with respect to the total amount of copper contained in the copper powder to be treated. Addition of the chain organic material less than 0.005% by mass relative to the total amount of copper contained in the copper powder to be treated is not sufficient to exhibit the effect of copper powder as an anticoupling agent. In addition, since the effect of adding the chain organic substance gradually decreases as the amount added increases, the addition of the chain organic substance exceeding 10% by mass relative to the total amount of copper contained in the copper powder to be processed increases the production cost. Therefore, it is not economical.
  • the amount of the chain organic substance in the treatment liquid (the amount of the chain organic substance added to the polyol solvent B) is 0.001 mol% or more with respect to the total amount of copper contained in the copper powder to be treated. is preferable, and may be, for example, 0.01 mol % or more, or 0.1 mol % or more. Moreover, the amount of the chain organic substance in the treatment liquid is preferably 1 mol % or less with respect to the total amount of copper contained in the copper powder to be treated. The amount of the chain organic substance in the treatment liquid is preferably 0.001 mol% or more and 1 mol or less, or even 0.01 mol% or more and 1 mol% or less, relative to the total amount of copper contained in the copper powder to be treated. Alternatively, it may be 0.1 mol % or more and 1 mol % or less.
  • the copper powder production method 2 of the present embodiment has an average particle size of 250 nm or less, and at least one of the conditions (3) and (4) described in the copper powder of the present embodiment.
  • a method for producing a copper powder wherein a copper powder slurry obtained by mixing a copper powder that does not satisfy the above with a polyol solvent having a boiling point of 250 ° C. or higher to which the chain organic substance is added is heat-treated at 230 ° C. or higher. is.
  • the copper powder manufacturing method 2 of the present embodiment is a method capable of manufacturing the copper powder of the present embodiment.
  • the structures other than the above are arbitrary structures.
  • the copper powder production method 2 of the present embodiment it is possible to obtain a copper powder that has an organic film that prevents the formation of an oxide film that can inhibit sintering and that is excellent in low-temperature sinterability.
  • substances other than those described above may be added to the reaction solution within the scope of the present invention.
  • the polyol solvent used in the reduction step is the first polyol solvent
  • the polyol solvent used in the heat treatment step is the second polyol solvent.
  • the method for measuring physical properties is as follows.
  • the average particle size of the obtained copper powder is the number-average particle size obtained from image analysis of 200 or more particles observed with a SEM (scanning electron microscope). diameter.
  • (2) Analysis of Organic Substances on the Surface of the Copper Powder Regarding the organic components on the surface of the copper powder, 10 mg of the copper powder was immersed in 70 ⁇ l of a 1% by weight tetramethylammonium hydroxide-methanol solution to extract the organic substances on the surface. After drying under the conditions of minutes, the organic component is gasified under the conditions of 300 ° C.
  • ⁇ Temperature increase rate 10°C/min ⁇ Temperature range: Room temperature to 800°C ⁇ Applied load: 98 mN Atmosphere: pure nitrogen (inert atmosphere) or 2% by volume-H 2 +98% by volume-N 2 (reducing atmosphere)
  • Example 1 [Reduction step] 3.6 g of cuprous oxide (Cu 2 O) powder (manufactured by Chemet, product number: Ultrafine) as copper oxide powder was placed in a 50 ml tall beaker, and propylene glycol (abbreviation: PG, boiling point: 188 ° C.) was used as the first polyol solvent.
  • cuprous oxide (Cu 2 O) powder manufactured by Chemet, product number: Ultrafine
  • PG propylene glycol
  • molecular weight 76 13.5 g was added, and then poly(ethylene glycol) bis(carboxymethyl) ether (average molecular weight 600) (abbreviation: PEG600 dibasic acid, manufactured by Sigma-Aldrich) was added 0.302 g (suboxidation 9.44% by mass (1 mol%) relative to the total amount of copper in the copper) and 162 ⁇ l of a 25% by mass sodium hydroxide aqueous solution for neutralization were added and mixed to form a uniform slurry. This slurry was heated to 185° C. and maintained at that temperature with stirring for 45 minutes to effect a reduction reaction. After cooling the reaction solution, the polyol copper powder produced was centrifuged, washed and dried.
  • PEG600 dibasic acid average molecular weight 600
  • Example 2 A polyol copper powder was obtained in the same manner as in Example 1 except that 1,3-propanediol (abbreviation: 1,3-PDO, boiling point: 214° C., molecular weight: 76) was used as the first polyol solvent.
  • 1,3-propanediol abbreviation: 1,3-PDO, boiling point: 214° C., molecular weight: 76
  • Example 3 A polyol copper powder was obtained in the same manner as in Example 1, except that 1,2-butanediol (abbreviation: 1,2-BDO, boiling point: 194° C., molecular weight: 90) was used as the first polyol solvent.
  • 1,2-butanediol abbreviation: 1,2-BDO, boiling point: 194° C., molecular weight: 90
  • Example 4 A polyol copper powder was obtained in the same manner as in Example 1 except that 1,3-butanediol (abbreviation: 1,3-BDO, boiling point: 207° C., molecular weight: 90) was used as the first polyol solvent.
  • 1,3-butanediol abbreviation: 1,3-BDO, boiling point: 207° C., molecular weight: 90
  • Example 5 The amount of PEG600 dibasic acid added was 0.0302 g (0.94% by mass (0.1 mol%) with respect to the total amount of copper in the cuprous oxide), and a 25% by mass sodium hydroxide aqueous solution was added for neutralization.
  • a polyol copper powder was obtained in the same manner as in Example 3, except that 16 ⁇ l of the solution was added.
  • Example 6 The amount of PEG600 dibasic acid added was 0.0030 g (0.094% by mass (0.01 mol%) relative to the total amount of copper in the cuprous oxide), and a 25% by mass sodium hydroxide aqueous solution was added for neutralization.
  • a polyol copper powder was obtained in the same manner as in Example 3, except that 16 ⁇ l of the solution was added.
  • Example 7 The amount of PEG600 dibasic acid added was 0.0003 g (0.0094% by mass (0.001 mol%) relative to the total amount of copper in the cuprous oxide), and a 25% by mass sodium hydroxide aqueous solution was added for neutralization.
  • a polyol copper powder was obtained in the same manner as in Example 3, except that 16 ⁇ l of the solution was added.
  • Example 8 [Reduction step] Copper powder was produced by the method of Example 5 described in JP-A-2022-128445. Specifically, 27 g of cuprous oxide powder as copper oxide powder is placed in a 200 ml separable flask, and 100 g of ethylene glycol (abbreviation: EG, boiling point: 197 ° C., molecular weight 62) is added as a first polyol solvent.
  • EG ethylene glycol
  • Example 9 A heat-treated polyol copper powder was obtained in the same manner as in Example 8, except that the temperature of the reduction reaction was changed to 180°C.
  • Example 10 Copper powder was produced by the method of Example 24 described in JP-A-2022-128445. Specifically, 27 g of cuprous oxide powder as copper oxide powder was placed in a 200 ml separable flask, and 100 g of propylene glycol (abbreviation: PG, boiling point: 188 ° C., molecular weight 76) was added as a first polyol solvent.
  • PG propylene glycol
  • Example 11 In the heat treatment step, the amount of PEG600 diacid added was 0.0302 g (0.94% by weight (0.1 mol%) relative to the total amount of copper in the copper to be treated) and 25% by weight for neutralization. % sodium hydroxide aqueous solution was added in the same manner as in Example 10 to obtain a polyol copper powder.
  • Example 12 In the heat treatment step, the amount of PEG600 diacid added was 0.0030 g (0.094% by weight (0.01 mol%) relative to the total amount of copper in the copper to be treated), and 25% by weight for neutralization. % sodium hydroxide aqueous solution was added in the same manner as in Example 10 to obtain a polyol copper powder.
  • Example 13 In the heat treatment step, the amount of PEG600 diacid added was 0.0003 g (0.0094% by weight (0.001 mol%) relative to the total amount of copper in the copper to be treated), and 25% by weight for neutralization. % sodium hydroxide aqueous solution was added in the same manner as in Example 10 to obtain a polyol copper powder.
  • Example 14 A heat-treated polyol copper powder was obtained in the same manner as in Example 10, except that the slurry was heated to 260° C. in the heat treatment step.
  • Example 15 A heat-treated polyol copper powder was obtained in the same manner as in Example 10, except that the slurry was heated to 240° C. in the heat treatment step.
  • Example 16 A heat-treated polyol copper powder was obtained in the same manner as in Example 10, except that the slurry was heated to 230° C. in the heat treatment step.
  • Example 17 Poly(ethylene glycol) bis(carboxymethyl) ether (average molecular weight 600) (PEG 600 diacid) was replaced with 0.1724 g of eicosanedioic acid (5.0 g relative to the total amount of copper in the treated copper) in the heat treatment step. 39 mass % (1 mol %)) was added in the same manner as in Example 10 to obtain a polyol copper powder after heat treatment.
  • Example 18 Poly(ethylene glycol) bis(carboxymethyl) ether (average molecular weight 600) (PEG 600 dibasic acid) was replaced with 0.1018 g of sebacic acid (3.18 g of total copper in treated copper) in the heat treatment step. % (1 mol %)) was added in the same manner as in Example 10 to obtain a polyol copper powder after heat treatment.
  • Example 19 Poly(ethylene glycol) bis(carboxymethyl) ether (average molecular weight 600) (PEG 600 diacid) was replaced with 0.1159 g of dodecanedioic acid (3.0 g relative to the total amount of copper in the treated copper) in the heat treatment step. 63% by mass (1 mol%)) was added, and a heat-treated polyol copper powder was obtained in the same manner as in Example 10.
  • Example 2 A polyol copper powder was obtained in the same manner as in Example 2 except that the PEG600 dibasic acid and the 25% by mass sodium hydroxide aqueous solution for neutralization were not added in the reduction step.
  • Example 3 Polyol copper powder was obtained in the same manner as in Example 3 except that PEG600 dibasic acid and 25% by mass sodium hydroxide aqueous solution for neutralization were not added in the reduction step.
  • Example 4 A polyol copper powder was obtained in the same manner as in Example 4 except that the PEG600 dibasic acid and the 25% by mass sodium hydroxide aqueous solution for neutralization were not added in the reduction step.
  • a copper powder was produced by the method of Example 24 described in JP-A-2022-128445. After cooling the reaction solution, the polyol copper powder produced was centrifuged, washed and dried. Unlike Examples 10 to 19, this polyol copper powder was not heat-treated.
  • Example 6 A polyol copper powder was obtained in the same manner as in Example 10 except that the PEG600 dibasic acid and the 25% by mass sodium hydroxide aqueous solution were not added in the heat treatment step.
  • Table 1 shows the manufacturing conditions of Examples 1 to 19, Comparative Examples 1 to 6, and Conventional Examples 1 to 3.
  • GC/MS and LC/MS detected organic substances that satisfied the conditions (1) and (2) described above.
  • the temperature at which TMA reaches 1% in an inert atmosphere is 230° C. or less in any of the examples, and the temperature difference between the temperatures at which TMA reaches 3% in an inert atmosphere and in a reducing atmosphere is , was less than 10°C.
  • the sintering (thermal shrinkage) behavior hardly changed under an inert atmosphere and under a reducing atmosphere, and sintering occurred on the surface of the copper powder. It can be seen that an oxide film that inhibits sintering is not formed, or that the oxide film is thin enough not to inhibit sintering.
  • Comparative Example 1 Although the surface of the copper powder is coated with an organic substance that satisfies the above-described condition (1) detectable by GC/MS, the above-described condition (2) detectable by LC/MS is not satisfied. Since there was no filling organic matter on the surface of the copper powder, the surface coating with the organic matter was insufficient compared to Examples 1 to 4, and an oxide film that inhibited sintering was likely to be formed on the surface of the copper powder. . Therefore, it is considered that the sinterability in an inert atmosphere deteriorated and a difference from the sintering behavior in a reducing atmosphere occurred. (The condition (4) mentioned above is not satisfied.)
  • Examples 8 to 19 were obtained by heat-treating Conventional Examples 1 to 3, respectively, the organic matter satisfying the above-described conditions (1) and (2) by GC/MS and LC/MS due to the heat treatment was copper powder. As a result of the reconstruction on the surface of the copper powder, it is considered that the copper powder satisfying the above conditions (3) and (4) was obtained.
  • the copper powder in the present embodiment has an average particle size of 250 nm or less, and the surface is a specific organic substance detected by GC / MS and a specific organic substance detected by LC / MS
  • the green compact obtained by pressure molding the copper powder at 100 MPa is heated from 25 ° C. at a temperature rising rate of 10 ° C./min in an inert atmosphere, 25 ° C.
  • the temperature at which the thermal shrinkage rate is 1% is 230 ° C. or less
  • the copper powder is pressure-molded at 100 MPa.
  • the thermal shrinkage based on the thickness of the green compact at 25° C.
  • the temperature difference between the temperature at which the thermal shrinkage rate is 3% in the inert atmosphere and the temperature at which the thermal shrinkage rate is 3% in the reducing atmosphere is less than 10°C.
  • An embodiment of the present invention includes the following configurations.
  • Condition (1) When the organic matter present on the surface of the copper powder is detected by gas chromatography mass spectrometry, H(—O—CH 2 —CH 2 ) n —OH (where n is an integer of 1 or more and 4 or less), HOOC-CH 2 (-O-CH 2 -CH 2 ) m -OH (where m is an integer of 1 or more and 3 or less), HOOC—CH 2 (—O—CH 2 —CH 2 ) l —O—CH 2 —COOH (where l is 1 or 2), H(—C 3 H 6 O) s —OH (where s is an integer of 1 or more and 4 or less), HOOC—CH(CH 3 )(—C 3 H 6 O) t —OH (where t is an integer
  • Condition (3) Thermal shrinkage rate based on the thickness of the green compact at 25°C when the green compact obtained by pressure molding the copper powder is heated from 25°C in an inert atmosphere. , the temperature at which the heat shrinkage rate becomes 1% is 230°C or less.
  • Condition (4) The thickness of the green compact at 25°C when the green compact obtained by pressure-molding the copper powder is heated from 25°C in an inert atmosphere and a reducing atmosphere. In the measurement of the thermal shrinkage rate, the temperature difference between the temperature at which the thermal shrinkage rate is 3% in the inert atmosphere and the temperature at which the thermal shrinkage rate is 3% in the reducing atmosphere is less than 10°C.
  • the polyol solvent having a boiling point of 230°C or less includes ethylene glycol (boiling point: 196°C), propylene glycol (boiling point: 188°C), 1,3-propanediol (boiling point: 214°C), and 1,2-butanediol.
  • a method for producing a copper powder comprising heat-treating a copper powder slurry obtained by mixing with a polyol solvent at 230° C. or higher.
  • the amount of the chain organic substance added is 0.005% by mass or more and 10% by mass or less with respect to the total amount of copper contained in the copper powder to be heat-treated.
  • a method for producing copper powder is 0.005% by mass or more and 10% by mass or less with respect to the total amount of copper contained in the copper powder to be heat-treated.
  • the polyol solvent having a boiling point of 250°C or higher includes triethylene glycol (boiling point: 287°C), tetraethylene glycol (boiling point: 327°C), and polyethylene glycol having an average molecular weight of 200 to 600 (boiling point: around 300°C).

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US20110132144A1 (en) * 2008-07-23 2011-06-09 Jochen Mezger Method For Producing Metal Nanoparticles In Polyols
JP2013159830A (ja) * 2012-02-06 2013-08-19 Toyota Central R&D Labs Inc 表面被覆金属ナノ粒子、およびその製造方法
JP2014111800A (ja) * 2012-12-05 2014-06-19 Nippon Handa Kk ペースト状金属微粒子組成物、固形状金属または固形状金属合金の製造方法、金属製部材の接合方法、プリント配線板の製造方法および電気回路接続用バンプの製造方法
JP2020105359A (ja) * 2018-12-27 2020-07-09 日華化学株式会社 接合材料及びそれを用いた接合方法
JP2021134393A (ja) * 2020-02-27 2021-09-13 住友金属鉱山株式会社 銅粉の製造方法

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JP6033485B2 (ja) 2016-04-21 2016-11-30 協立化学産業株式会社 被覆銅粒子
JP7006872B2 (ja) 2017-11-29 2022-01-24 国立大学法人北海道大学 低温焼結性銅粒子とそれを用いた焼結体の製造方法

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US20110132144A1 (en) * 2008-07-23 2011-06-09 Jochen Mezger Method For Producing Metal Nanoparticles In Polyols
JP2013159830A (ja) * 2012-02-06 2013-08-19 Toyota Central R&D Labs Inc 表面被覆金属ナノ粒子、およびその製造方法
JP2014111800A (ja) * 2012-12-05 2014-06-19 Nippon Handa Kk ペースト状金属微粒子組成物、固形状金属または固形状金属合金の製造方法、金属製部材の接合方法、プリント配線板の製造方法および電気回路接続用バンプの製造方法
JP2020105359A (ja) * 2018-12-27 2020-07-09 日華化学株式会社 接合材料及びそれを用いた接合方法
JP2021134393A (ja) * 2020-02-27 2021-09-13 住友金属鉱山株式会社 銅粉の製造方法

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