WO2024095698A1 - 溶剤組成物、及び焼結体の製造方法 - Google Patents

溶剤組成物、及び焼結体の製造方法 Download PDF

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WO2024095698A1
WO2024095698A1 PCT/JP2023/036559 JP2023036559W WO2024095698A1 WO 2024095698 A1 WO2024095698 A1 WO 2024095698A1 JP 2023036559 W JP2023036559 W JP 2023036559W WO 2024095698 A1 WO2024095698 A1 WO 2024095698A1
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solvent
group
solvent composition
metal
compound
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PCT/JP2023/036559
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English (en)
French (fr)
Japanese (ja)
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貴慎 小畑
基治 芳我
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株式会社ダイセル
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Priority to KR1020257017246A priority Critical patent/KR20250103672A/ko
Priority to EP23885461.6A priority patent/EP4613403A1/en
Priority to CN202380075723.5A priority patent/CN120129581A/zh
Priority to JP2024554343A priority patent/JPWO2024095698A1/ja
Publication of WO2024095698A1 publication Critical patent/WO2024095698A1/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
    • B22F1/10—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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • 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
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/68—Temporary coatings or embedding materials applied before or during heat treatment
    • C21D1/70—Temporary coatings or embedding materials applied before or during heat treatment while heating or quenching

Definitions

  • the invention disclosed herein relates to a solvent composition and a method for producing a sintered body.
  • heat sinks are attached to the metal housing of rotating electrical machines to promote heat dissipation.
  • lead solder is used to attach the heat sink, but joining using lead solder has problems such as the base being prone to distortion due to heat.
  • Patent Document 1 discloses a joining method using sintered copper, in which copper nanoparticles are formed into a sheet shape, sintered, laminated with the object to be joined, and then joined by applying pressure and heat to create a laminate.
  • Patent Document 2 discloses a conductive paste used to form a metal sintered body, which contains a mixture of formic acid and a basic compound in a specific molar ratio as a dispersion medium, thereby generating formic acid gas, enabling good firing even without a reducing atmosphere, and suppressing corrosion of metal particles by formic acid.
  • the bonding method using the copper sintered body of Patent Document 1 has problems such as the need to quickly remove the sintered precursor (copper nanoparticle aggregate) from the copper sintered body in a reducing atmosphere and then sinter it to prevent it from being oxidized again before bonding with the object to be bonded, and the need to remove the surface oxide film using a reducing agent (formic acid) or an etching solution (sulfuric acid aqueous solution) before bonding to avoid corrosion, making the operation complicated.
  • a reducing agent formic acid
  • an etching solution sulfuric acid aqueous solution
  • the sintered precursor metal particle aggregate
  • the sintered precursor metal particle aggregate
  • the sintered precursor can be sintered without removing the dispersion medium containing formic acid, even if it is not in a reducing atmosphere, but the generation of voids due to the decomposition gas of formic acid is not sufficiently suppressed when the metal particle aggregate is formed, and the generation of voids may reduce the bonding property.
  • the object of this disclosure is therefore to provide a solvent composition that does not require removal after application and that facilitates the production of sintered bodies that have excellent electrical conductivity and bondability.
  • the inventors conducted extensive research to solve the above problems and found that when a solvent composition containing a reducing organic substance and a basic compound is applied to a metal component, the metal oxide film on the surface of the metal component can be dissolved, and that a sintered body with excellent electrical conductivity can be easily obtained from the resulting solvent-treated metal component without removing the solvent after treatment.
  • the inventors found that when a solvent composition containing a reducing organic substance, a basic compound, and a coordinating organic substance is applied to a metal component, the metal oxide film on the surface of the metal component can be dissolved and metal fine particles can be precipitated on the surface of the metal component, and that a sintered body with excellent electrical conductivity and bondability can be easily obtained from such a solvent-treated metal component without removing the solvent after treatment.
  • the invention disclosed herein was completed based on these findings.
  • the present disclosure provides a solvent composition for assisting sintering, which contains a reducing organic substance and a basic compound.
  • the present disclosure also provides a solvent composition that contains a reducing organic substance, a basic compound, and a coordinating organic compound other than the compounds contained in the basic compound, and the coordinating organic compound has a higher boiling point than the reducing organic substance.
  • the reducing organic substance is preferably formic acid.
  • the above solvent composition preferably further contains a reducing organic substance other than formic acid.
  • R a to R c are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent.
  • the substituent is the same or different and represents at least one group selected from an amino group, an N-substituted amino group, an N,N-substituted amino group, an imino group, an N-substituted imino group and a hydroxyl group.
  • R a to R c cannot simultaneously be a hydrogen atom.
  • a double line including a dashed line represents a single bond or a double bond, and when it represents a double bond, R c does not exist. Any two of R a to R c may be bonded to each other to form a ring together with the adjacent nitrogen atom.) It is preferable that the nitrogen-containing compound is represented by the following formula:
  • the basic compound preferably has an ethylenediamine structure or an ethanolamine structure in its molecular structure, and the amino group in the structure is a tertiary amino group.
  • the ratio of the total number of moles of basic groups contained in the basic compound to the total number of moles of acidic groups contained in the reducing organic substance is preferably 0.40 to 2.50.
  • the coordinating organic compound is preferably a compound having a carboxyl group.
  • the above solvent composition preferably further contains a solvent.
  • the present disclosure also provides a method for producing a solvent-treated metal component, which comprises applying the above-mentioned solvent composition to a metal component.
  • the metal component before coating is an aggregate of metal particles having a number average particle diameter of 600 nm or more.
  • the present disclosure also provides a method for producing a solvent-treated metal component, which comprises dissolving a metal compound in the above-mentioned solvent composition and then applying the composition to the metal component.
  • the metal member preferably contains copper.
  • the metal compound is preferably at least one selected from cuprous oxide (I), copper oxide (II), and copper hydroxide (II).
  • the present disclosure also provides a method for producing a sintered body, in which a sintered body is obtained by heating the solvent-treated metal member obtained by the above-mentioned production method.
  • the present disclosure also provides a method for producing a joined body, in which the solvent-treated metal member obtained by the above-mentioned production method is brought into contact with the bodies to be joined and heated to obtain a joined body.
  • the present disclosure also provides a method for producing a bonded body, which comprises applying the above-mentioned solvent composition to an aggregate layer of metal particles formed on the surface of a substrate to form a treated aggregate layer, and then contacting a substrate and the treated aggregate layer and heating the substrate to bond the substrate and the treated aggregate layer.
  • the present disclosure also provides a method for producing a metal member having metal nanoparticles on its surface by applying a solvent composition to a metal member to dissolve at least a portion of the surface of the metal member to form a metal complex, and then subjecting the formed metal complex to thermal decomposition and/or reductive decomposition to precipitate metal nanoparticles on the surface of the metal member.
  • the solvent composition of the present disclosure is applied to a metal member (such as a metal particle aggregate) and used to aid in sintering, it is possible to produce a sintered body with excellent electrical conductivity and bondability without the need to remove the solvent composition after application.
  • a metal member such as a metal particle aggregate
  • Example 6 shows an electron microscope photograph of the solvent-treated copper foil surface of Example 6.
  • 1 shows an electron microscope photograph of the solvent-treated copper foil surface of Example 11.
  • 1 shows an electron microscope photograph of the solvent-treated copper foil surface of Comparative Example 3.
  • 1 shows an SAT image of the conjugate of Example 24.
  • 13 shows an electron microscope photograph of the arrangement pattern of Si chips with copper bumps used in Example 25.
  • 14 shows an electron microscope photograph of the surface of the copper bumps of a Si chip with copper bumps used in Example 25.
  • 13 shows an electron microscope photograph of the surface of the copper bump portion of the solvent-treated Si chip of Example 25.
  • the solvent composition of the first aspect of the present disclosure is a sintering-aid solvent composition containing a reducible organic substance and a basic compound. Since the solvent composition contains a reducible organic substance, by applying it to the surface of a metal member, oxidation of the metal member surface can be suppressed even in a reducing atmosphere during firing. In addition, since the solvent composition contains a basic compound, it can dissolve the metal member surface to remove the metal oxide film, and even if it is not removed after being applied to the surface of the metal member, corrosion of the metal member surface caused by the reducible organic substance can be suppressed. From the above, the solvent composition is suitable as a sintering-aid solvent composition for sintering a metal member.
  • the solvent composition of the second aspect of the present disclosure contains a reducing organic substance, a basic compound, and a coordinating organic compound excluding compounds contained in the basic compound, and the coordinating organic compound has a higher boiling point than the reducing organic substance.
  • the solvent composition contains a coordinating organic compound, which makes it easier for a metal complex to be formed when the surface of the metal member is dissolved, and the metal complex that is formed is easily converted into metal nanoparticles when it is thermally or reductively decomposed and precipitates on the surface of the metal member.
  • a coordinating organic compound which makes it easier for a metal complex to be formed when the surface of the metal member is dissolved, and the metal complex that is formed is easily converted into metal nanoparticles when it is thermally or reductively decomposed and precipitates on the surface of the metal member.
  • Examples of the reducing organic substances contained in the solvent compositions of the first and second aspects of the present disclosure include alcohols (lower alcohols such as ethanol, higher alcohols such as palmitol, and aminoalkanols such as ethanolamines), amino acids, organic acids (carboxylic acids, etc.), and aromatic compounds (polyphenols, phenolic acid compounds, etc.).
  • alcohols lower alcohols such as ethanol, higher alcohols such as palmitol, and aminoalkanols such as ethanolamines
  • amino acids amino acids
  • organic acids (carboxylic acids, etc.) amino acids
  • aromatic acids polyphenols, phenolic acid compounds, etc.
  • organic acids (carboxylic acids, etc.) and aromatic compounds are preferred because they are acidic
  • carboxylic acids are more preferred because they are liquid at room temperature, easy to handle, and not highly toxic. These may be used alone or in combination of two or more.
  • carboxylic acid examples include formic acid, acetic acid, lactic acid, propionic acid, acrylic acid, malic acid, n-hexanoic acid, succinic acid, n-octanoic acid, tartaric acid, and oxalic acid.
  • formic acid and oxalic acid are preferred because they are more likely to produce sintered bodies that have excellent reducing properties and electrical conductivity.
  • the reducing organic substance used in the solvent composition of the second aspect of the present disclosure is preferably formic acid, since it has a low boiling point and can be easily used in combination with a coordinating organic substance having a boiling point higher than that of the reducing organic substance.
  • the content of reducing organic substances other than formic acid is 1 molar part or less per 1 molar part of formic acid.
  • the basic compound contained in the solvent composition of the first and second aspects of the present disclosure is not particularly limited as long as it acts as a base and realizes the effects of the present disclosure, but specific examples include hydroxides of alkali metals, alkaline earth metals, etc., nitrogen-containing compounds such as ammonia and amine compounds, phosphorus-containing compounds such as phosphines and phosphites, etc. Among them, the nitrogen-containing compound represented by the following formula (1) is preferred because it is easy to obtain a sintered body with excellent electrical conductivity.
  • R a to R c are the same or different and represent a hydrogen atom or a hydrocarbon group which may have a substituent.
  • the substituent is the same or different and represents at least one group selected from an amino group, an N-substituted amino group, an N,N-substituted amino group, an imino group, an N-substituted imino group and a hydroxyl group.
  • R a to R c cannot simultaneously be a hydrogen atom.
  • a double line including a dashed line represents a single bond or a double bond, and when it is a double bond, R c does not exist. Any two of R a to R c may be bonded to each other to form a ring together with the adjacent nitrogen atom.
  • Examples of the hydrocarbon group for R a to R c include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these, an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are preferred, and an aliphatic hydrocarbon group is more preferred.
  • Aliphatic hydrocarbon groups include linear or branched alkyl groups, linear or branched alkenyl groups, linear or branched alkynyl groups, linear or branched alkylidene groups, etc., with linear or branched alkyl groups being preferred.
  • the linear or branched alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, or a branched alkyl group having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and 2-ethylhexyl groups.
  • the linear or branched alkenyl group is preferably a linear alkenyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms, or a branched alkenyl group having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, and examples thereof include vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 3-hexenyl group, 5-hexenyl group, 1-heptenyl group, 1-octenyl group, 1-nonenyl group, 1-decenyl group, isopropenyl group, 2-methyl-1-propenyl group, methallyl group, 3-methyl-2-but
  • the linear or branched alkynyl group is preferably a linear alkynyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms, or a branched alkynyl group having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, and examples thereof include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-heptynyl, 1-octynyl, 1-nonynyl, 1-decynyl,
  • the linear or branched alkylidene group is preferably a linear alkylidene group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 2 to 4 carbon atoms, or a branched alkylidene group having 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, and examples thereof include a methylidene group, a propylidene group, an isopropylidene group, a butylidene group, an isobutylidene group, a sec-butylidene group, a pentylidene group, an isopentylidene group, an octylidene group, and an isooctylidene group.
  • Alicyclic hydrocarbon groups include cycloalkyl groups and cycloalkenyl groups.
  • the cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 5 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group.
  • the cycloalkenyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 5 to 8 carbon atoms, and examples of such groups include cyclopentenyl and cyclohexenyl groups.
  • the aromatic hydrocarbon group is preferably an aryl group having 6 to 18 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms, such as a phenyl group or naphthyl group.
  • the double line including the dashed line in formula (1) represents a single bond or a double bond.
  • Rc does not exist, and the nitrogen atom to which Ra and Rb in formula (1) are bonded represents an imino group or an N-substituted imino group.
  • the total number of amino groups, N-substituted amino groups and N,N-substituted amino groups which R a to R c may have is preferably 0 to 6, more preferably 1 to 4, and even more preferably 1 or 2.
  • the total number of imino groups and N-substituted imino groups which R a to R c may have is preferably 0 to 4, more preferably 1 to 3, and even more preferably 1 or 2.
  • the total number of hydroxyl groups which R a to R c may have is preferably 0 to 6, more preferably 1 to 4, and even more preferably 1 or 2.
  • N-substituted amino group N,N-substituted amino group and N-substituted imino group are the same as those of the hydrocarbon groups related to R a to R c above.
  • any two of R to R may be bonded to each other to form a ring together with the adjacent nitrogen atom.
  • the ring formed include a pyrrolidine ring, a pyrroline ring, a piperidine ring, a pyrrole ring, an imidazolidine ring, an imidazole ring, a piperazine ring, an imidazolidine ring, a pyridine ring, a diazine ring, and a triazine ring.
  • the hydrocarbon groups represented by R a to R c may have a substituent other than an amino group, an N-substituted amino group, an N,N-substituted amino group, an imino group, an N-substituted imino group, or a hydroxyl group.
  • Examples of such a substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxo group, a substituted oxy group (an alkoxy group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyloxy group having 7 to 16 carbon atoms, an acyloxy group having 1 to 4 carbon atoms, etc.), a carboxyl group, a substituted oxycarbonyl group (an alkoxycarbonyl group having 1 to 4 carbon atoms, an aryloxycarbonyl group having 6 to 10 carbon atoms, an aralkyloxycarbonyl group having 7 to 16 carbon atoms, etc.), a cyano group, a nitro group, a sulfo group, a mercapto group, a heterocyclic group, etc.
  • the basic compound represented by formula (1) include alkylamines in which at least one of R a to R c in formula (1) is a linear or branched alkyl group; monoalkanolamines in which R a and R b in formula (1) are hydrogen atoms and R c is a linear or branched alkyl group having one hydroxyl group; dialkanolamines in which R a in formula (1) is a hydrogen atom and R b and R c are the same or different and are linear or branched alkyl groups having one hydroxyl group; trialkanolamines in which R a to R c in formula (1) are the same or different and are linear or branched alkyl groups having one hydroxyl group; aminoalkanediols in which R a and R b in formula (1) are the same or different and are hydrogen atoms or linear or branched alkyl groups and R c is a linear or branched alkyl group having two hydroxyl groups; diamines in which R a
  • alkylamines examples include methylamine, ethylamine, propylamine, butylamine, pentylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, piperidine, trimethylamine, triethylamine, dimethyldodecylamine, 4-dimethylaminopyridine, 2-aminopyrazine, 2-aminopyrimidine, 3-aminopyridazine, 2-aminotriazine, diazabicyclononene, and diazabicycloundecene.
  • Examples of the monoalkanolamines include 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 1-amino-2-methyl-2-propanol, 2-amino-2-methyl-1-propanol, 4-amino-1-butanol, 6-amino-1-hexanol, 10-amino-1-decanol, 12-amino-1-dodecanol, N-methyl-2-aminoethanol, N-ethyl-2-aminoethanol, 1-dimethylamino-2-propanol, N-propyl-2-aminoethanol, 2-dimethylaminoethanol, 6-diethylaminohexanol, 1-(2-hydroxyethyl)pyrrolidine, 2-(hydroxymethyl)pyrrolidine, 2-(2-hydroxyethyl)-1-methylpyrrolidine, 1-piperidineethanol, and 1-ethanol-4-propanolpiperidine.
  • dialkanolamine examples include diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, N-methyl-diethanolamine, and N-ethyl-diethanolamine.
  • trialkanolamines examples include triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, and triisobutanolamine.
  • aminoalkanediol examples include 1-amino-2,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, 1-methylamino-2,3-propanediol, 1-ethylamino-2,3-propanediol, 1-propylamino-2,3-propanediol, 1-butylamino-2,3-propanediol, 3-dimethylamino-1,2-propanediol, and 2-diethylamino-1,3-propanediol.
  • the above diamines include, for example, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,5-diamino-2-methylpentane, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N,N'-dimethyl-1,4-butanediamine, and N,N'-diethyl-1,4-butanediamine.
  • N,N'-dimethyl-1,6-hexanediamine N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dimethyl-1,6-hexanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, piperazine, N-methylpiperazine, N-ethylpiperazine, N,N'-dimethylpiperazine, homopiperazine, etc.
  • triamines examples include diethylenetriamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentakis(2-hydroxypropyl)diethylenetriamine, 3,3'-diaminodipropylamine, N-(3-aminopropyl)-N-methyl-1,3-propanediamine, N'-[3-(dimethylamino)propyl]-N,N-dimethyl-1,3-propanediamine, 2,6,10-trimethyl-2,6,10-triazaundecane, N-(2-aminoethyl)piperazine, 1,4,7-triazacyclononane, N,N,N',N",N"-pentakis(2-hydroxypropyl)diethylenetriamine, 1-(2-aminoethyl)-4-methylpiperazine, 1-(2-dimethylaminoethyl)-4-methylpiperazine, etc.
  • diaminoalkanols examples include 1,3-diaminopropan-2-ol, 2-(2-aminoethylamino)ethanol, 2-(2-aminopropylamino)ethanol, 2-(2-aminoethylmethylamino)ethanol, 1-(2-hydroxyethyl)piperazine, 4-methylpiperazine-1-ethanol, and 1,4-bis(2-hydroxyethyl)piperazine.
  • imidazole compounds include imidazole, 2-methylimidazole, 2-propylimidazole, N-methylimidazole, N-propylimidazole, N-butylimidazole, 1-(2-hydroxyethyl)imidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole, and 2-hydroxybenzimidazole.
  • nitrogen-containing aromatic compounds examples include pyridine, ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2,6-lutidine, 2,3-lutidine, pyrazine, 2-hydroxypyrazine, pyrimidine, 2-hydroxypyrimidine, 4-hydroxypyrimidine, pyridazine, 3-hydroxypyridazine, 4-hydroxypyridazine, triazine, and 2-hydroxytriazine.
  • the basic compound contained in the solvent composition of the first and second aspects of the present disclosure is preferably a chelating basic compound having an ethylenediamine structure or an ethanolamine structure in its molecular structure, since it is easy to stabilize the metal ions that have dissolved the metal oxide on the surface of the metal member by chelating coordination.
  • the amino group in the above structure may be any of primary to tertiary amino groups, but is preferably a tertiary amino group, since side reactions such as amidation are unlikely to occur between the reducing organic substance and the basic compound.
  • the content of the basic compound is preferably 0.25 to 10.0 parts by weight, more preferably 0.50 to 5.0 parts by weight, and even more preferably 0.75 to 3.0 parts by weight, per part by weight of the reducing organic substance, in order to facilitate adjustment of the molar ratio (basic group/acidic group) described below.
  • the basic compound has a relatively low polarity, which makes it easier to adjust the viscosity and wettability of the solvent composition. Therefore, it is preferable that the basic compound contains an alkylamine having at least one linear alkyl group having 1 to 20 carbon atoms (preferably 1 to 15 carbon atoms) together with the chelating basic compound.
  • the content of the alkylamine is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.75 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per part by weight of the reducing organic substance.
  • the above basic compounds may be used alone or in combination of two or more.
  • the ratio of the total number of moles of the basic groups contained in the basic compound to the total number of moles of the acidic groups contained in the reducing organic substance is preferably 0.40 to 2.50, more preferably 0.45 to 2.40, and even more preferably 0.50 to 2.30. If the molar ratio is 0.40 or more, the reducing agent is thermally stabilized, and the reduction is likely to proceed during the heating process, and the metal ions eluted from the surface of the metal member are likely to be stabilized. Furthermore, if it is 2.50 or less, the influence of the organic residue present after drying the solvent on sintering is reduced.
  • the total number of moles of the acidic groups contained in the reducing organic substance is the number of moles of the reducing organic substance multiplied by the number of acidic groups contained in the reducing organic substance
  • the total number of moles of the basic groups contained in the basic compound is the number of moles of the basic compound multiplied by the number of basic groups contained in the basic compound.
  • the coordinating organic compound contained in the solution composition of the second aspect of the present disclosure is a coordinating organic compound other than the compound contained in the basic compound.
  • the coordinating organic compound has a higher boiling point than the reducing organic compound, so that it is more likely to remain than the reducing organic compound during firing, and it is easier to suppress contact between the reducing organic compound and the active metal surface, so that decomposition of the reducing organic compound is more easily suppressed.
  • Examples of the coordinating organic compound include compounds having a carboxyl group (such as carboxylic acid), compounds having a ketone group (such as diketones such as acetylacetone and ⁇ -ketoesters), and compounds having a hydroxyl group, sulfo group, and thiol group.
  • compounds having a carboxyl group such as carboxylic acid
  • compounds having a ketone group are preferred because they facilitate the precipitation of dissolved metal oxides as metal nanoparticles.
  • the compound having a carboxyl group is preferably a monovalent or divalent carboxylic acid, and more preferably a monovalent carboxylic acid, since the precipitated metal nanoparticles are easily sintered.
  • carboxylic acids examples include acetic acid (boiling point 118°C), lactic acid (boiling point 122°C), propionic acid (boiling point 141°C), acrylic acid (boiling point 141°C), malic acid (boiling point 167°C), n-hexanoic acid (boiling point 205°C), succinic acid (boiling point 235°C), n-octanoic acid (boiling point 237°C), tartaric acid (boiling point 275°C), and oxalic acid (boiling point 365°C).
  • Carboxylic acids may function as reducing organic substances or coordinating organic compounds, so when a carboxylic acid is used as a reducing organic substance, another carboxylic acid having a boiling point higher than that of the carboxylic acid can be used in combination as a coordinating organic compound.
  • the boiling point of the above carboxylic acid at normal pressure is preferably above 110°C, more preferably 150°C or higher, and even more preferably 200°C or higher, because it is less volatile than formic acid (boiling point 101°C).
  • the content of the coordinating organic compound in the solution composition of the second aspect of the present disclosure is preferably 0.05 to 1.00 parts by weight, more preferably 0.10 to 0.75 parts by weight, and even more preferably 0.15 to 0.50 parts by weight, per 1 part by weight of the reducing organic substance. If the content is 0.05 parts by weight or more, precipitation of metal nanoparticles is easily obtained, and if it is 1.00 parts by weight or less, the solution composition is less likely to remain when calcined.
  • the molar ratio of the coordinating organic compound to the basic compound is preferably 0.01 to 1.00, more preferably 0.05 to 0.50, and even more preferably 0.10 to 0.40. If the molar ratio is 0.01 or more, metal nanoparticles are likely to precipitate, and if it is 1.00 or less, the solution composition is unlikely to remain after firing.
  • the solvent composition of the first and second aspects of the present disclosure may contain, in addition to the above-mentioned reducing organic substance, basic compound, and coordinating organic compound, a solvent such as water or an organic solvent in order to adjust the fluidity (viscosity) and operability.
  • organic solvent examples include ester-based solvents such as acetates (ethyl acetate, butyl acetate, etc.), ester oils (butyl stearate, hexyl laurate, triethyl citrate, etc.); ether-based solvents such as dioxane and tetrahydrofuran; ketone-based solvents such as acetone; aromatic solvents such as toluene and xylene; halogen-based solvents such as dichloromethane and chloroform; alcohol-based solvents such as methanol, ethanol, isopropanol, and butanol; and nitrile-based solvents such as acetonitrile and benzonitrile. These may be used alone or in combination of two or more.
  • ester-based solvents such as acetates (ethyl acetate, butyl acetate, etc.), ester oils (butyl stearate, hexyl laur
  • the content of the solvent is preferably 0 to 200 parts by weight, more preferably 0.10 to 100 parts by weight, even more preferably 0.20 to 40 parts by weight, particularly preferably 0.50 to 10 parts by weight, and most preferably 1 to 5 parts by weight, per 1 part by weight of the reducing organic substance.
  • the solvent compositions of the first and second aspects of the present disclosure may contain other components, such as resin components (e.g., polymeric compounds having a number average molecular weight of 10,000 or more, such as ethyl cellulose resin, alkyl cellulose resin, polyvinyl acetal resin, and acrylic resin), additives (surface conditioners, leveling agents, defoamers, dispersants, thixotropic agents, etc.), within the range that does not impair the effects of the present disclosure.
  • the content of the other components in the solvent composition is, for example, 1% by weight or less (preferably 0.5% by weight or less).
  • the solvent compositions of the first and second aspects of the present disclosure can be produced through a process of mixing the reducing organic substance and basic compound, as well as the coordinating organic compound, with the solvent and other components.
  • the temperature during mixing does not exceed 100°C.
  • the mixture can be cooled to room temperature (e.g., 25°C) or below, and may be cooled gradually at room temperature or rapidly by cooling on ice, etc.
  • room temperature e.g. 25°C
  • the mixture may be cooled gradually at room temperature or rapidly by cooling on ice, etc.
  • a solvent-treated metal member can be produced by applying the solvent composition of the first and second aspects of the present disclosure to a metal member.
  • the metal oxide film on the surface is dissolved and removed by the solvent composition.
  • the solvent-treated metal member is used, a sintered body and a bonded body having excellent electrical conductivity can be produced even without a reducing atmosphere by the solvent composition remaining on the surface during firing.
  • the solvent composition of the second aspect of the present disclosure to a metal member, the metal oxide film on the surface is dissolved and removed, and a solvent-treated metal member having a metal member surface on which metal nanoparticles having a number average particle size of less than 600 nm (1 nm or more and less than 600 nm, 5 nm or more and less than 100 nm, or 10 nm or more and less than 60 nm) are precipitated can be produced.
  • a metal member having metal nanoparticles on its surface can be produced by applying the solvent composition to a metal member, dissolving at least a part of the surface of the metal member to form a metal complex, and then thermally and/or reductively decomposing the formed metal complex to precipitate it on the surface of the metal member as metal nanoparticles.
  • the thermal decomposition and/or reductive decomposition is achieved by heating in the presence of the reductive organic substance. Since the metal member has nanometal particles on its surface, it can be fired at a lower temperature.
  • the number average particle size of the metal nanoparticles can be calculated on a number basis, for example, by observation with an electron microscope.
  • the metal member may be any metal member of various forms and shapes, so long as it is a member used to form a conductive film, a conductive circuit, or a conductive joint and is the target for coating with the solvent composition.
  • metal members include aggregates of metal particles and semi-sintered bodies thereof, woven and non-woven metal fiber fabrics, and metal members with a dense internal structure that have a surface that bonds with the object to be joined.
  • metals that form the metal members include gold, silver, copper, nickel, palladium, tin, aluminum, and alloys of these.
  • copper and silver are prone to forming metal oxide films on their surfaces, so when the solvent composition is used, the improvement effect of obtaining sintered bodies and joined bodies with excellent electrical conductivity is remarkable.
  • the shape of the metal particles contained in the aggregate which is the metal member, may be various shapes such as spherical, ellipsoidal flake (flat), short fiber, etc., or may be irregular. These may be used alone or in combination of two or more types.
  • the volume average particle size (median size, D50 ) of the metal particles used to form the aggregate, which is the metal member may be, for example, 1 nm to 100 ⁇ m, and may be 600 nm or more (600 nm to 100 ⁇ m, or 1 to 10 ⁇ m) when the second solvent composition is applied, since the metal nanoparticles precipitate.
  • the average particle size of the metal particles can be measured, for example, by a laser diffraction/scattering method.
  • the amount of metal nanoparticles that precipitate can be adjusted by dissolving a metal compound separately in the solvent composition of the first and second aspects of the present disclosure and then applying the composition.
  • the metal compound to be dissolved is preferably a metal compound containing copper, since it precipitates copper nanoparticles that are easily sintered, and more preferably copper oxide (II), cuprous oxide (I), or copper hydroxide (II), since they are easy to store. These may be used alone or in combination of two or more.
  • a sintered body can be obtained by heating the solvent-treated metal member obtained by the above manufacturing method, and a joined body can be obtained by contacting the solvent-treated metal member with the objects to be joined and heating them.
  • the above-mentioned bonded body may be formed by applying a solvent composition according to the first or second aspect of the present disclosure to an aggregate layer of metal particles formed on the surface of a substrate to form a treated aggregate layer, and then contacting the substrate and the treated aggregate layer and heating the substrate to bond the substrate and the treated aggregate layer.
  • the substrate is not particularly limited as long as it can be bonded by the treated aggregate layer, but examples include substrates made of metals (including alloys), ceramics (metal oxides, metal nitrides, silicon, silicon nitride, aluminum nitride, etc.), glass, polymeric materials, etc., substrates made of the above materials that have been surface-treated by metal plating, and multilayer boards made of a combination of the above materials.
  • the above-mentioned bonded object is not particularly limited as long as it can be bonded by the above-mentioned solvent-treated metal member or the above-mentioned treated aggregate layer, but examples include semiconductor chips (discrete semiconductors such as capacitors, transistors, diodes, MOS FETs, IGBTs, etc., integrated circuits such as ICs and LSIs), compound semiconductor chips (GaN, SiC, etc.), electric and electronic parts such as heat sinks, bus bars for automotive parts, connectors, harnesses, etc.
  • semiconductor chips discrete semiconductors such as capacitors, transistors, diodes, MOS FETs, IGBTs, etc., integrated circuits such as ICs and LSIs
  • compound semiconductor chips GaN, SiC, etc.
  • electric and electronic parts such as heat sinks, bus bars for automotive parts, connectors, harnesses, etc.
  • the heating can be performed within a temperature range of, for example, 100 to 400°C (120 to 300°C, or 150 to 250°C).
  • the heating time can be, for example, 1 to 120 minutes (or 5 to 60 minutes).
  • the bonded body (laminate) can be pressurized on the bonding surfaces with a pressure of, for example, 10 MPa or less.
  • the above-mentioned solvent-treated metal members and the above-mentioned treated aggregate layers can be used for semiconductor bonding, wire bonding, clip bonding, forming wiring on wiring boards, forming multilayer printed wiring boards, forming bumps, bonding between bumps, etc., and can be suitably used in the manufacture of electronic devices (printed wiring boards, capacitors, inductors, varistors, thermistors, transistors, speakers, actuators, antennas, solid oxide fuel cells, hybrid ICs, etc.) and rotating electrical machines, etc.
  • the reducing organic substances, basic compounds, coordinating organic compounds, solvents, and metal particles (copper particles) used are as follows:
  • MDETA N-methyldiethanolamine, a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • PMDTA pentamethyldiethylenetriamine, a reagent manufactured by Tokyo Chemical Industry Co., Ltd.
  • DAMPZ 1-(2-dimethylaminoethyl)-4-methylpiperazine, a reagent manufactured by Tokyo Chemical Industry Co., Ltd.
  • DMDA N,N-dimethyldodecylamine, a reagent manufactured by Tokyo Chemical Industry Co., Ltd.
  • TEC Triethyl citrate, a reagent manufactured by Tokyo Chemical Industry Co., Ltd.
  • EtOH Ethanol, a reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • CH-0200L1 Product name "CH-0200L1", volume average particle size 200 nm, manufactured by Mitsui Mining & Smelting Co., Ltd.
  • CT-0500 Product name "CT-0500”, volume average particle size 800 nm, manufactured by Mitsui Mining & Smelting Co., Ltd.
  • a copper foil (product name "C1020P") having a thickness of 100 ⁇ m was cut into a square shape (5 cm ⁇ 5 cm) and heated at 200° C. for 10 minutes in air using a hot plate to prepare a test piece of oxidation-treated copper foil having an oxide film on the surface.
  • the above-mentioned oxidation-treated copper foil test piece was placed on a hot plate in a glove box with a nitrogen atmosphere (oxygen concentration 100 ppm or less) on which two drops (approximately 40 mg) of the above-mentioned solvent sample were dropped using a dropper, and the above-mentioned oxidation-treated copper foil test piece was placed on a hot plate in a glove box with a nitrogen atmosphere (oxygen concentration 100 ppm or less), and the temperature was increased from room temperature (25°C) to 150°C at a heating rate of 10°C/min and held for 5 minutes, and then the temperature was increased further to 200°C at a heating rate of 10°C/min and held for 10 minutes, and then the sample was allowed to cool naturally to room temperature (25°C), and after cooling, it was washed with methanol to produce a solvent-treated copper foil.
  • a nitrogen atmosphere oxygen concentration 100 ppm or less
  • the oxide film thickness of the oxide film on the surface of the treated copper foil was measured by a continuous electrochemical method using an oxide film/metal film thickness measuring device (product name "QC-100", manufactured by ECI Technology). The measurement conditions were as follows. The total value of the thicknesses of the cuprous oxide (I), copper oxide (II), and copper sulfide obtained from the measurement results was taken as the oxide film thickness. The measurement was performed on the part where the droplets remained until the end when the solvent evaporated. If the measurement could not be performed within the measurement time of 10 minutes, the thickness was taken as 100 ⁇ or more. The solvent samples used and the evaluation results are shown in Table 3. The copper oxide thickness of the copper foil before the oxidation treatment was 35 ⁇ . Measurement range (gasket size): ⁇ 3.2mm Current value: 30 ⁇ A/ cm2 Measurement time: Maximum 10 minutes
  • Examples 8 to 14 showed that copper nanoparticles precipitated, and Examples 5 to 7, in which no coordinating organic compound was added, showed that copper particles over 1000 nm precipitated. On the other hand, Comparative Example 3, in which no basic compound was added, showed that copper particles did not precipitate.
  • the copper paste was molded and heated in a nitrogen atmosphere at 200°C for 5 minutes to produce copper particle aggregates (rectangle-shaped, 50 mm long, 10 mm wide, 20 ⁇ m thick). Sintering had not progressed in these copper particle aggregates, and they did not exhibit electrical conductivity.
  • the above solvent sample was applied to the prepared copper particle aggregate, and the resulting sintered body was fired at 200°C for 30 minutes in a nitrogen atmosphere.
  • the volume resistivity of the resulting sintered body was measured using a resistivity meter (product name "Loresta GP MCP-T610", manufactured by Mitsubishi Chemical Analytech Co., Ltd.). The smaller the volume resistivity value, the better the "conductivity”.
  • the solvent samples used and the evaluation results are shown in Table 5.
  • the electrical conductivity was evaluated according to the following criteria. ⁇ (good): The volume resistivity is less than 20 ⁇ cm ⁇ (passable): The volume resistivity is 20 ⁇ cm or more and less than 100 ⁇ cm ⁇ (poor): The volume resistivity is 100 ⁇ cm or more
  • a "-" in the particle size column indicates that no current flowed and no measurement was obtained.
  • Example 23 Cu-Cu bonding (length 10 mm, width 10 mm)
  • the copper paste was printed on a copper plate of 30 mm x 30 mm and 1 mm thick using a metal mask with an opening size of 10 mm x 10 mm and a thickness of 100 ⁇ m.
  • the copper paste was heated at 200 ° C. for 5 minutes under a nitrogen atmosphere to obtain a copper particle aggregate.
  • Solvent sample 19 was dropped onto the copper particle aggregate so that the solvent penetrated the entire aggregate, and a copper plate of 10 mm x 10 mm and 1 mm thick was placed on the copper particle aggregate to which the solvent was applied. Thereafter, a bonded body in which the copper plate and the copper plate were bonded was obtained by heating at 200 ° C. for 30 minutes under a nitrogen atmosphere while applying pressure of 10 MPa from above.
  • the bonded body was divided into four parts, and the bond strength was measured using a universal bond tester (product name: Die Shear Tester SERIES 4000, manufactured by Nordson DAGE). The bond strength was over 40 MPa, indicating sufficiently excellent bondability.
  • the void ratio of the above bonded body was measured using an ultrasonic imaging device (SAT, Scanning Acoustic Tomograph) (product name "FineSAT FS300II", manufactured by Hitachi High-Tech Corporation), and the void ratio was found to be less than 1%, indicating excellent bondability.
  • SAT Scanning Acoustic Tomograph
  • Example 24 Cu-Cu bonding (length 20 mm, width 20 mm))
  • a metal mask with an opening size of 20 mm x 20 mm and a thickness of 150 ⁇ m
  • the above copper paste was printed on a copper plate with a size of 30 mm x 30 mm and a thickness of 1 mm, and a bonded body was obtained in the same manner as in Example 23.
  • the void ratio of this bonded body was also 1% or less.
  • An SAT image of the bonded body is shown in Figure 4 (white areas in the figure indicate voids).
  • a copper bumped Si chip (product name "WALTS-TEG CC40", 10 mm x 10 mm, manufactured by Waltz Corporation) with a pattern of 28224 (168 x 168) copper bumps (height 15 ⁇ m, ⁇ 22 ⁇ m) arranged at 40 ⁇ m intervals within an area of 10 mm x 10 mm, and a Si interposer (product name "WALTS-TEG IP40", manufactured by Waltz Corporation) with copper pads corresponding to the above pattern were used.
  • Figure 5 shows an electron microscope photograph of the arrangement pattern of the copper bumps
  • Figure 6 shows an electron microscope photograph of the surface of the copper bumps (bottom right bar in Figure 5: 10 ⁇ m, bottom right bar in Figure 6: 100 nm).
  • the copper bumped Si chip was heated on a hot plate in air at 200°C for 5 minutes to oxidize the surface of the copper bumps.
  • the chip was placed on a hot plate in a glove box with a nitrogen atmosphere (oxygen concentration 100 ppm or less), and the chip was heated from room temperature (25°C) to 150°C at a heating rate of 10°C/min, held for 5 minutes, further heated to 200°C at a heating rate of 10°C/min, held for 10 minutes, and then naturally cooled to room temperature (25°C). After cooling, the chip was washed with methanol to obtain a solvent-treated Si chip.
  • Figure 7 shows an electron microscope photograph of the surface of the copper bumps of the solvent-treated Si chip (bottom right bar in Figure 7: 100 nm). Copper nanoparticles were precipitated on the surface of the copper bumps.
  • a solvent-coated Si interposer was obtained by applying 5 ⁇ L of the above-mentioned solvent sample 19 onto the Si interposer using a micropipette.
  • the above-mentioned solvent-coated Si interposer and the above-mentioned solvent-treated Si chip were stacked together in such a way that the positions of the copper pads and copper bumps corresponded, and the two were bonded by heating at 200°C for 10 minutes under a nitrogen atmosphere and a load of 5 kgf using a flip chip bonder (product name "T-3000-PRO-HF", manufactured by Dr. TRESKY).
  • the bond strength of the above bonded structure was measured using a universal bond tester (product name: Die Shear Tester SERIES 4000, manufactured by Nordson DAGE). The bond strength was 25 MPa, which was sufficient and indicated excellent bondability.
  • [Appendix 1] A solvent composition for assisting sintering, comprising a reducing organic substance and a basic compound.
  • [Appendix 2] A solvent composition comprising a reducing organic substance, a basic compound, and a coordinating organic compound excluding compounds contained in the basic compound, wherein the coordinating organic compound has a higher boiling point than the reducing organic substance.
  • [Appendix 3] The solvent composition according to appendix 1 or 2, wherein the reducing organic substance is formic acid.
  • Appendix 4 The solvent composition according to Appendix 3, further comprising a reducing organic substance other than formic acid.
  • the substituent is the same or different and represents at least one group selected from an amino group, an N-substituted amino group, an N,N-substituted amino group, an imino group, an N-substituted imino group and a hydroxyl group.
  • R a to R c cannot simultaneously be a hydrogen atom.
  • a double line including a dashed line represents a single bond or a double bond, and when it represents a double bond, R c does not exist.
  • any two of R a to R c may be bonded to each other to form a ring together with the adjacent nitrogen atom.
  • [Appendix 10] The solvent composition according to appendix 9, wherein the basic compound is at least one selected from the group consisting of N-methyldiethanolamine, pentamethyldiethylenetriamine, and 1-(2-dimethylaminoethyl)-4-methylpiperazine.
  • Appendix 11 The solvent composition according to any one of Appendices 1 to 10, wherein the basic compound includes an alkylamine having at least one linear alkyl group having 1 to 20 carbon atoms (preferably 1 to 15 carbon atoms) together with a chelating basic compound.
  • [Appendix 12] The solvent composition according to appendix 11, wherein the alkylamine is N,N-dimethyldodecylamine.
  • the content of the alkylamine is 0.01 to 1 part by weight (preferably 0.05 to 0.75 parts by weight, more preferably 0.1 to 0.5 parts by weight) per 1 part by weight of the reducing organic substance.
  • the content of the basic compound is 0.25 to 10.0 parts by weight (preferably 0.50 to 5.0 parts by weight, more preferably 0.75 to 3.0 parts by weight) per 1 part by weight of the reducing organic substance.
  • [Appendix 15] The solvent composition according to any one of Appendices 1 to 14, wherein the ratio of the total number of moles of basic groups contained in the basic compound to the total number of moles of acidic groups contained in the reducing organic substance (basic groups/acidic groups) is 0.40 to 2.50 (preferably 0.45 to 2.40, more preferably 0.50 to 2.30).
  • [Appendix 16] The solvent composition according to any one of Appendices 2 to 15, wherein the coordinating organic compound is a compound having a carboxyl group.
  • [Appendix 17] The solvent composition according to appendix 16, wherein the compound having a carboxyl group is a monovalent or divalent (preferably monovalent) carboxylic acid.
  • [Appendix 20] The solvent composition according to any one of Appendices 2 to 19, wherein the molar ratio of the coordinating organic compound to the basic compound (coordinating organic compound/basic compound) is 0.01 to 1.00 (preferably 0.05 to 0.50, more preferably 0.10 to 0.40).
  • [Appendix 21] The solvent composition according to any one of appendices 1 to 20, further comprising a solvent.
  • Appendix 22] The solvent composition according to appendix 21, wherein the solvent is at least one selected from an ester-based solvent and an alcohol-based solvent.
  • [Appendix 23] The solvent composition according to appendix 21, wherein the solvent is at least one selected from triethyl citrate and ethanol.
  • the content of the solvent is 0 to 200 parts by weight (preferably 0.10 to 100 parts by weight, more preferably 0.20 to 40 parts by weight, even more preferably 0.50 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight) relative to 1 part by weight of the reducing organic substance.
  • Appendix 27 A method for producing a solvent-treated metal component, comprising applying the solvent composition according to any one of appendices 2 and 16 to 24 to a metal component, wherein the solvent-treated metal component has a surface on which metal nanoparticles having a number average particle size of less than 600 nm (1 nm or more and less than 600 nm, 5 nm or more and less than 100 nm, or 10 nm or more and less than 60 nm) are precipitated.
  • [Appendix 28] The method for producing a solvent-treated metal component described in Appendix 27, wherein the metal component before coating is an aggregate of metal particles having a volume average particle diameter of 600 nm or more (600 nm to 100 ⁇ m, or 1 to 10 ⁇ m).
  • [Appendix 29] A method for producing a solvent-treated metal component according to any one of Appendices 25 to 28, comprising dissolving a metal compound in the solvent composition according to any one of Appendices 1 to 24 and then applying the solvent composition to a metal component.
  • [Appendix 30] The method for producing a solvent-treated metal component according to any one of Appendices 25 to 29, wherein the metal component contains copper.
  • [Appendix 31] The method for producing a solvent-treated metal component according to appendix 29 or 30, wherein the metal compound is at least one selected from the group consisting of cuprous oxide (I), copper oxide (II), and copper hydroxide (II).
  • [Appendix 32] A method for producing a sintered body, comprising heating a solvent-treated metal member obtained by the method according to any one of appendices 25 to 31 to obtain a sintered body.
  • [Appendix 33] A method for producing a joined body, comprising contacting a solvent-treated metal member obtained by the method according to any one of appendices 25 to 31 with objects to be joined and heating the resulting joint.
  • [Appendix 34] A method for producing a bonded body, comprising applying a solvent composition according to any one of Appendices 1 to 24 to an aggregate layer of metal particles formed on a surface of a substrate to form a treated aggregate layer, and then contacting a substrate with the treated aggregate layer and heating the substrate to bond the substrate and the treated aggregate layer.
  • [Appendix 35] A method for producing a metal component having metal nanoparticles on its surface, comprising applying a solvent composition to a metal component to dissolve at least a portion of the surface of the metal component to form a metal complex, and then subjecting the formed metal complex to thermal decomposition and/or reductive decomposition to precipitate as metal nanoparticles on the surface of the metal component.

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JP2020025765A (ja) 2018-08-13 2020-02-20 株式会社高尾 遊技機
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