WO2017072970A1 - Pâte conductrice pour impression ainsi que procédé de préparation de celle-ci, et procédé de préparation de dispersion liquide de nanoparticules d'argent - Google Patents

Pâte conductrice pour impression ainsi que procédé de préparation de celle-ci, et procédé de préparation de dispersion liquide de nanoparticules d'argent Download PDF

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WO2017072970A1
WO2017072970A1 PCT/JP2015/080828 JP2015080828W WO2017072970A1 WO 2017072970 A1 WO2017072970 A1 WO 2017072970A1 JP 2015080828 W JP2015080828 W JP 2015080828W WO 2017072970 A1 WO2017072970 A1 WO 2017072970A1
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silver
hydrocarbon solvent
amine
nanoparticle dispersion
conductive paste
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PCT/JP2015/080828
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English (en)
Japanese (ja)
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上田　雅行
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ハリマ化成株式会社
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Priority to PCT/JP2015/080828 priority Critical patent/WO2017072970A1/fr
Priority to PCT/JP2016/080516 priority patent/WO2017073364A1/fr
Priority to JP2017547732A priority patent/JPWO2017073364A1/ja
Priority to TW105134221A priority patent/TWI707052B/zh
Publication of WO2017072970A1 publication Critical patent/WO2017072970A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • 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

Definitions

  • the present invention relates to a method for preparing a silver nanoparticle dispersion using silver oxide as a starting material.
  • the present invention also relates to a conductive paste for printing containing silver nanoparticles and a method for preparing the same.
  • the conductive paste using silver nanoparticles is used for forming a fine wiring layer, for example.
  • the surface of the silver nanoparticles Since silver atoms on the surface of silver nanoparticles have a remarkably large mobility on the surface, when silver nanoparticles contact each other, the silver atoms on the surface move to each other, and there is a strong tendency to cause fusion. This fusion proceeds even near room temperature. Therefore, in order to prevent the silver nanoparticles contained in the conductive paste from fusing together and forming aggregated particles, the surface of the silver nanoparticles is usually coated with a coating agent molecule, This prevents the metal surfaces from touching each other directly.
  • Patent Document 1 powdered silver oxide is dispersed in a nonpolar solvent, an excessive amount of formic acid is added, and formic acid is allowed to act on the powdered silver oxide to convert it into powdered silver formate (HCOAAg). Then, a primary amine is allowed to act on the powdered silver formate to form a primary amine addition salt of silver formate, and a decomposing reduction reaction of the primary amine addition salt of silver formate is performed at a liquid temperature of about 70 ° C., A method of preparing silver nanoparticles having a surface coating layer composed of a primary amine is described. As the primary amine, an alkylamine having 7 to 12 carbon atoms is used.
  • Patent Document 2 discloses a metal oxide nanoparticle having at least rod-shaped metal oxide nanoparticles by heating a mixture containing an amine compound containing a secondary amine, a metal precursor, and a nonpolar solvent to 60 to 300 ° C. Forming an intermediate; adding capping molecules and a reducing agent to the mixture; heating to 90-150 ° C. to form metal nanoparticles; and recovering the metal nanoparticles.
  • a method for producing metal nanoparticles comprising rod-shaped nanoparticles is described.
  • Patent Document 3 discloses a metal fine particle dispersion in which a metal fine particle dispersion in which nanometer-scale metal fine particles are dispersed in a solution is obtained by heating and reducing a metal compound in a solution containing a primary amine and a tertiary amine.
  • a method for producing a liquid, in which the tertiary amine contains an alkyl group having 2 or more carbon atoms is described.
  • Patent Document 4 discloses a metal nanoparticle obtained by dispersing coated metal nanoparticles in which a protective agent made of an organic compound having a carboxyl group is coated on a metal nanoparticle surface in a polar dispersion solvent containing a polyhydric alcohol ether. A particle dispersion is described.
  • Patent Document 5 silver cations contained in silver formate (I) are reduced to silver atoms by a reduction reaction with an amine compound, and when forming silver nanoparticles whose surface is coated with an amine compound, an amine is formed.
  • a method for preparing silver nanoparticles is described that uses both primary and secondary amines as compounds.
  • Patent Document 6 discloses a conductive ink substantially free of a binder component for forming a conductive pattern by a letterpress reverse printing method, and having a volume average particle size (Mv) of 10 to 700 nm, A release agent, a surface energy regulator, and a solvent component as essential components, the solvent component having a surface energy at 25 ° C. of 27 mN / m or more, and a volatile solvent having a boiling point of 120 ° C. or less at atmospheric pressure
  • the conductive ink is characterized in that the surface energy of the ink at 25 ° C. is 10 to 21 mN / m.
  • JP 2011-153362 A JP 2009-084777 A JP 2008-081828 A JP 2011-038128 A Japanese Patent Laying-Open No. 2015-161008 WO2008 / 11484A1
  • the conductive performance of the conductor film is reduced due to the difficulty in removing the coating from the conductive paste film during firing.
  • the conductor film may crack due to volume shrinkage during firing. Accordingly, the film thickness that can be formed when such a conductive paste is used is limited.
  • Patent Documents 2 to 6 do not teach a silver nanoparticle dispersion excellent in this respect.
  • An object of the present invention is to prepare a conductive paste that can be fired at a low temperature suitable for producing a conductor having good cracking and no cracking, with various viscosities. It is to provide a method for preparing a conductive paste for printing.
  • Another object of the present invention is to provide a method for preparing a silver nanoparticle dispersion which can be suitably used for producing the conductive paste as described above.
  • a further object of the present invention is to provide a conductive paste for printing that can be fired at a low temperature and that can have various viscosities, which is suitable for producing a conductor having no cracks and good conduction performance. That is.
  • a method for preparing a dispersion of silver nanoparticles having an average particle diameter of 5 to 20 nm having a coating layer made of coating molecules on the surface a) allowing formic acid to act on powdered silver oxide (I) in a hydrocarbon solvent to convert the powdered silver oxide (I) into silver formate (I); and b) In the hydrocarbon solvent, a silver cation contained in silver formate (I) is reduced to a silver atom by a reduction reaction with an amine compound in the presence of a monocarboxylic acid having 8 to 11 carbon atoms.
  • Forming silver nanoparticles having an average particle size of 5 to 20 nm, the surface of which is coated with a compound and a monocarboxylic acid There is provided a method for preparing a silver nanoparticle dispersion, wherein both a primary amine having 9 to 11 carbon atoms and a secondary amine are used as the amine compound.
  • the hydrocarbon solvent is a linear or cyclic alkane having 6 to 9 carbon atoms and having a boiling point of 65 ° C. to 155 ° C., In step a, it is preferable to use 400 to 700 parts by mass of the hydrocarbon solvent per 100 parts by mass of the powdered silver oxide (I).
  • the primary amine has a molecular weight of 120 to 200; It is preferable that the primary amine has an aliphatic hydrocarbon chain having affinity for the hydrocarbon solvent.
  • the secondary amine has a molecular weight of 100 to 150; It is preferable that the secondary amine has an aliphatic hydrocarbon chain having affinity for the hydrocarbon solvent.
  • step b per 1 mol of silver cation contained in silver formate (I), 0.05 mol-0.3 mol of the monocarboxylic acid is used, 0.05 mol-0.3 mol amount of the primary amine is used,
  • the secondary amine is preferably used so that the total molar amount of the primary amine and the secondary amine is in the range of 1.1 to 1.5 mol.
  • the silver nanoparticle dispersion is prepared by the following steps c to e. c) a step of recovering the residue containing the silver nanoparticles by removing the hydrocarbon solvent by evaporation under reduced pressure from the reaction solution obtained from step b; d) washing the residue with alcohol; and e) It is preferable to further include a step of obtaining a silver nanoparticle dispersion by dispersing the residue after washing in step d in the same or different hydrocarbon solvent as the hydrocarbon solvent.
  • a method for preparing a conductive paste for printing wherein the conductive paste for printing is prepared using the silver nanoparticle dispersion prepared by the above method.
  • a conductive paste for printing comprising silver nanoparticles having an average particle diameter of 5 to 20 nm having a coating layer composed of coating molecules on the surface,
  • the coating layer includes a monocarboxylic acid having 8 to 11 carbon atoms and a primary amine having 9 to 11 carbon atoms.
  • a conductive paste for printing is provided.
  • a method for preparing a conductive paste, particularly a conductive paste capable of being fired at a low temperature suitable for producing a conductor having good cracking performance without cracks, with various viscosities particularly A method for preparing a conductive paste for printing is provided.
  • a method for preparing a silver nanoparticle dispersion liquid that can be suitably used for producing the conductive paste as described above.
  • a conductive paste for printing which can be fired at a low temperature and is suitable for producing a conductor having good cracking performance without cracks, and can have various viscosities.
  • the inventors of the present invention made silver formate (I) by reacting powdered silver oxide (I) and formic acid in a hydrocarbon solvent, and then converting the silver cation contained in the silver formate (I) with an amine compound.
  • an amine compound In producing silver nanoparticles whose surface is coated with an amine compound after being reduced to silver atoms, by using a primary amine (carbon number 9 to 11) and a secondary amine as the amine compound, It has been found that silver nanoparticles with a small amount of coating agent covering silver can be prepared by reduction with an amine compound in the presence of a monocarboxylic acid having 8 to 11 carbon atoms.
  • the present invention has been made based on such knowledge.
  • the present invention relates to a method for preparing silver nanoparticles having a coating layer composed of coating molecules on the surface, and more particularly to a method for preparing a silver nanoparticle dispersion in which silver nanoparticles are dispersed in a liquid.
  • silver nanoparticles having an average particle diameter of the order of nanometers, particularly having an average particle diameter of 5 nm to 20 nm can be produced.
  • the presence of a primary amine is essential when silver formate is reduced.
  • silver formate When silver formate is reduced, it is coordinated to the nanoparticles produced by the presence of a primary amine, and the enlargement of the particles is suppressed.
  • silver formate When silver formate is reduced without the addition of primary amine, it enlarges and settles after passing through nanoparticles. The larger the amount of primary amine, the smaller the particle size.
  • the average particle diameter can be adjusted by increasing or decreasing the amount of primary amine used.
  • the dispersibility stability can be improved by coordinating with the nanoparticle in which the monocarboxylic acid is generated.
  • the average particle size refers to a particle size having an integrated value of 50% in a particle size distribution (volume basis) measured by a laser diffraction method.
  • the term “boiling point” means the boiling point at 1 atmosphere.
  • the term “ink” means a paste that is particularly suitable for printing.
  • the quantity (mass and content) of a silver nanoparticle unless there is particular notice, it means the quantity of only a silver nanoparticle (thus not including a coating material).
  • the particle size of the silver nanoparticles when referring to the particle size of the silver nanoparticles, unless otherwise specified, it means the particle size including the coating agent attached to the surface of the silver nanoparticles.
  • primary amine means a compound having only one primary amino group in the molecule. Even if it has a secondary amino group and / or a tertiary amino group, it is a primary amine as long as it is a compound having one primary amino group.
  • secondary amine means a compound having only one amino group in the molecule and the amino group is a secondary amino group.
  • steps a and b are performed.
  • both a primary amine (R a —NH 2 ) and a secondary amine (R b R c —NH) are used.
  • the addition time of monocarboxylic acid may be any time of steps a and b.
  • a monocarboxylic acid can be mixed with a hydrocarbon solvent, and then formic acid can be added.
  • monocarboxylic acid may not be used in step a, and monocarboxylic acid may be added together with the amine compound in step b.
  • step b silver nanoparticles in which a monocarboxylic acid and an amine compound (particularly a primary amine) are bonded to the surface via a coordinate bond to form a coating layer can be obtained.
  • Process b can be performed in the hydrocarbon solvent used in process a following process a. Therefore, the step b can be performed by adding the monocarboxylic acid and the amine compound (primary amine and secondary amine) to the reaction solution obtained from the step a and stirring as necessary.
  • step b the same hydrocarbon solvent used in step a may be added.
  • an amine compound can be diluted with a hydrocarbon solvent and the density
  • concentration of an amine compound can be adjusted.
  • concentration of the amine compound can be adjusted (diluted) by adding a hydrocarbon solvent of 50 to 150 parts by mass per 100 parts by mass of powdered silver oxide (I).
  • Silver nanoparticles can be prepared in a hydrocarbon solvent by performing steps a and b.
  • silver nanoparticles can be separated from the hydrocarbon solvent.
  • An appropriate method can be used for the separation.
  • the hydrocarbon solvent can be removed by evaporation under reduced pressure to obtain silver nanoparticles (a state not included in the hydrocarbon solvent) (see step c).
  • Hydrocarbon solvents are generally nonpolar solvents that have no polarity or very low polarity.
  • the hydrocarbon solvent is used as a dispersion medium for powdered silver oxide (I), and is also used as a solvent for dissolving monocarboxylic acid and amine compounds (primary amine and secondary amine).
  • silver nanoparticles may be separated and recovered from the reaction solution (the solution containing silver nanoparticles obtained in step b).
  • the hydrocarbon solvent contained in the reaction solution is distilled off under reduced pressure. Can be removed. Therefore, a hydrocarbon solvent showing transpiration that can be distilled off under reduced pressure is preferred.
  • the secondary amine can also be removed by distilling off under reduced pressure.
  • the hydrocarbon solvent is preferably a straight chain alkane having 6 to 9 carbon atoms or a cycloalkane having 6 to 9 carbon atoms.
  • the boiling point of the hydrocarbon solvent is preferably 65 ° C to 155 ° C, more preferably 80 ° C to 130 ° C, and further preferably 80 ° C to 101 ° C.
  • hydrocarbon solvents examples include methylcyclohexane (boiling point 101 ° C.) and heptane (boiling point 98.42 ° C.).
  • the hydrocarbon solvent is used in an amount of 400 parts by mass or more and 700 parts by mass or less per 100 parts by mass of the powdered silver oxide (I). It is preferable.
  • powdered silver oxide (I) As starting material, powdered silver oxide (I) (Ag 2 O, formula weight 231.74, density 7.22 g / cm 3 ) is used.
  • the particle diameter of the powdered silver oxide (I) can be appropriately selected. From the viewpoint of uniform dispersion in a hydrocarbon solvent, the particle diameter distribution of the powdered silver oxide (I) is in the range of 200 mesh or less (75 ⁇ m or less). Those that fall within the range are preferably used.
  • step a formic acid (HCOOH) is allowed to act on powdered silver oxide (I) in a hydrocarbon solvent to convert the powdered silver oxide (I) into silver formate (I).
  • powdered silver (I) oxide can be added and dispersed in a hydrocarbon solvent, and formic acid can be added to the dispersion. In the reaction, stirring can be appropriately performed.
  • Formic acid associates by hydrogen bonding to form a dimer (HCOOH: HOOCH).
  • dimer Most hydrocarbon solvents disperse in the form of dimers. Therefore, the dimer of formic acid acts on the powdery silver oxide (I) in the dispersion, and silver formate (HCOOAg) is produced by the reaction represented by the following formula i.
  • the reaction represented by the above formula i corresponds to a “neutralization reaction” between silver (I), which is a basic metal oxide, and a dimer of formic acid, and is an exothermic reaction.
  • the temperature of the reaction solution It is easy to suppress the rise to around 40 ° C. That is, it is easy to suppress the side reaction by suppressing the liquid temperature from rising.
  • the side reaction include a reduction reaction that can be expressed by the following formula A1, and a degradative reduction reaction of the generated silver formate (I) itself that can be expressed by the following formula (A2).
  • Formula A1 2 [(HCOO ⁇ ) (Ag I ) + ] + HCOOH ⁇ 2Ag + 2HCOOH + CO 2 ⁇
  • Formula A2 2 [(HCOO ⁇ ) (Ag I ) + ] ⁇ 2Ag + HCOOH + CO 2 ⁇ .
  • formic acid is preferably 1.02 mol to 1.4 mol, more preferably 1.05 mol per mol of silver cation contained in the raw powdered silver oxide (I). It is preferably used in the range of -1.2 mol. By adding an excessive amount of formic acid, the total amount of the raw material powdered silver oxide (I) can be converted into silver formate (I).
  • step a the silver cation contained in the silver (I) formate is converted to an amine compound (primary amine and secondary amine in the presence of a monocarboxylic acid having 8 to 11 carbon atoms in the hydrocarbon solvent. ) To a silver atom. As a result, silver nanoparticles whose surface is coated with a monocarboxylic acid and an amine compound are formed.
  • the solution obtained from step a is added to a monocarboxylic acid having 8 to 11 carbon atoms and an amine compound (primary amine ( NH 2 —R a ) and secondary amine (NH—R b R c )) can be added.
  • a monocarboxylic acid having 8 to 11 carbon atoms and an amine compound (primary amine ( NH 2 —R a ) and secondary amine (NH—R b R c )) can be added.
  • an amine complex of silver (I) formate that is, a primary amine complex (HCOOAg: NH 2 —R a ) and a secondary amine complex (HCOOAg: NH—R b R c ) are produced.
  • the silver (I) formate complex (primary amine complex and secondary amine complex) starts a degradative reduction reaction represented by the following formula ii or iii: To do.
  • the formic acid produced as a by-product once forms a dimer of formic acid, but may react with an amine compound dissolved in the reaction solution to form an amine addition salt of formic acid.
  • the metallic silver atoms [Ag: NH 2 —R a ] and [Ag: NH—R b R c ] generated by the decomposing reduction reaction aggregate to form an aggregate of metallic silver atoms.
  • the formed aggregate of metallic silver atoms is a coating molecule layer composed of a spherical nucleus composed of metal atoms and an amine compound (primary amine (R a —NH 2 )) covering the surface of the nucleus. Composed silver nanoparticles.
  • Thermally dissociated amines (R a —NH 2 and R b R c —NH) produce amine complexes of silver formate (HCOOAg: NH 2 —R a and HCOOAg: NH—R b R c ). It may be involved in the reaction as well as the reaction of formic acid to form an amine addition salt.
  • the temperature of the reaction solution in step b is 70 ° C. or higher. Can be prevented from rising.
  • step b if an excessive amount of amine compound is present in the reaction solution, the amine addition salt formation reaction of formic acid proceeds, so that the concentration of dissolved formic acid is maintained at a low level. Accordingly, it is possible to prevent the formic acid having the function of a reducing agent from acting and the reduction reaction (side reaction) represented by the above formula A1 from proceeding.
  • step b if the liquid temperature of the reaction solution is prevented from rising to 70 ° C. or higher in step b, it is easy to preferentially advance the formation reaction of the silver formate amine complex, which is a side reaction. It is easy to suppress the progress of decomposing reaction of silver formate (I) itself.
  • the molecular weight of the primary amine is preferably 120 or more and 200 or less.
  • the primary amine can be easily detached and decomposed from the silver during the firing process when the particles are used as a conductive paste. Yes, from the viewpoint of conduction characteristics.
  • silver nanoparticles are prepared using a primary amine having a molecular weight of 120 or more, stable silver nanoparticles can be easily prepared. Specifically, it is easy to avoid the phenomenon that the side surface of the reaction vessel is mirror-finished (silver deposition) during particle production.
  • the primary amine preferably has an aliphatic hydrocarbon chain having an affinity for the hydrocarbon solvent. That is, a primary amine (R a -NH 2) constituting the atomic group (other than hydrogen, atom group bonded to the nitrogen atom) R a is an aliphatic hydrocarbon chain having affinity for the hydrocarbon solvent It is preferable to contain.
  • Ra contains an aliphatic hydrocarbon chain having affinity for the hydrocarbon solvent
  • the prepared silver nanoparticles are easily dispersed stably in the hydrocarbon solvent.
  • a primary amine (R a —NH 2 ) having 9 to 11 carbon atoms in the molecule can be used. From the viewpoint of the conductivity of the sintered body when the conductive paste is sintered at a low temperature of about 120 ° C., it is desirable to use a primary amine having 11 or less carbon atoms in the molecule.
  • preferred primary amines include 3- (2-ethylhexyloxy) propylamine, dibutylaminopropylamine, decylamine and the like (these primary amines have an affinity for hydrocarbon solvents. Have).
  • the molecular weight of the secondary amine is preferably 100 or more and 150 or less.
  • a secondary amine having a molecular weight of 150 or less is preferable in terms of reducing power, and it is easy to proceed the reaction.
  • An amine having a molecular weight of 100 or more is preferable from the viewpoint of boiling point, and it is easy to prevent rapid evaporation during the reaction.
  • the secondary amine has an aliphatic hydrocarbon chain having affinity for the hydrocarbon solvent. That is, atomic group forming a secondary amine (R b R c -NH) (other than a hydrogen, atom group bonded to the nitrogen atom) one or both of R b and R c, relative to the hydrocarbon solvent It is preferable to include an aliphatic hydrocarbon chain having high affinity. When one or both of R b and R c contain an aliphatic hydrocarbon chain having affinity for the hydrocarbon solvent, the prepared silver nanoparticles are stably dispersed in the hydrocarbon solvent. Is easy. Specifically, it is preferable to use a secondary amine (R b R c —NH) having 6 to 12 carbon atoms in the molecule.
  • Examples of such secondary amines include dipropylamine, diisopropylamine, methylhexylamine, dibutylamine, diisobutylamine and the like.
  • step b it is preferable to use the following amounts of monocarboxylic acid having 8 to 11 carbon atoms, primary amine and secondary amine, respectively.
  • Monocarboxylic acid having 8 to 11 carbon atoms 0.05 mol to 0.3 mol per mol of silver cation contained in silver formate (I).
  • Primary amine 0.05 to 0.3 mol per mol of silver cation contained in silver formate (I).
  • Secondary amine 2 so that the total molar amount of primary amine and secondary amine is in the range of 1.1 to 1.5 moles per mole of silver cation contained in silver formate (I).
  • Use a tertiary amine Use a tertiary amine.
  • steps c to e Subsequent to steps a and b, steps c to e can be performed in this order. Thereby, a dispersion liquid in which silver nanoparticles are dispersed in a certain hydrocarbon solvent (hydrocarbon solvent used in step e) can be obtained.
  • washing the residue with alcohol e) A step of obtaining a silver nanoparticle dispersion by dispersing the residue after washing in the step d in the same or different hydrocarbon solvent as the hydrocarbon solvent.
  • step c the hydrocarbon solvent used in steps a and b is removed by vaporization under reduced pressure.
  • the secondary amine can be vaporized and removed.
  • This operation can be appropriately performed by a known method such as a method using an evaporator. For example, the pressure in the container is lowered to about 50 hPa or less by an evaporator at a liquid temperature of 40 ° C., and the hydrocarbon solvent and the secondary amine are removed.
  • step d examples of the alcohol used in step d include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 2-methyl-1-propanol.
  • methanol can be suitably used from the viewpoint of particularly high polarity and ease of removal in a subsequent process.
  • methanol is described as an example of alcohol.
  • step d a known method of washing fine particles with methanol can be employed.
  • methanol can be substantially removed from the residue by adding methanol to the residue obtained from step c and stirring, and then removing the methanol by decantation.
  • silver nanoparticles are washed by dissolving a considerable amount of components such as excess formic acid, amine compound, or a salt containing them in methanol.
  • the hydrocarbon solvent used in step e may be the same as or different from the hydrocarbon solvent used in steps a and b.
  • the hydrocarbon solvent the hydrocarbon solvents described above in [Hydrocarbon solvent used in steps a and b] can be used. It is preferable to disperse silver nanoparticles in 100 to 300 parts by mass of a hydrocarbon solvent per 100 parts by mass of powdered silver oxide (I) used as a raw material. Since the obtained silver nanoparticles are silver nanoparticles coated with a monocarboxylic acid and an amine compound having a hydrocarbon chain, by using a hydrocarbon solvent in step e, silver nanoparticles uniformly dispersed in the hydrocarbon solvent are used. Particles can be obtained.
  • the dispersion obtained from step e can be used as it is as a raw material for ink or the like.
  • a conductive paste particularly a conductive paste for printing, can be prepared according to the following procedure.
  • the hydrocarbon solvent of the dispersion obtained in step e is preferably a high boiling point hydrocarbon solvent with a boiling point in the range of 180 ° C. to 355 ° C., more preferably a boiling point of 200 ° C. to 310 ° C.
  • the conductive paste can be prepared by substituting with a high boiling point hydrocarbon solvent having a boiling point of 220 ° C. to 310 ° C.
  • the high-boiling hydrocarbon solvent can be used as a dispersion solvent for dispersing the residue (after methanol washing) in step e.
  • a conductive paste can be obtained directly from step e.
  • JX Nippon Oil is a mixed solvent of alkanes having 12 to 16 carbon atoms such as tetradecane (boiling point 253.6 ° C.) or naphthene / paraffin hydrocarbons.
  • alkanes having 12 to 16 carbon atoms such as tetradecane (boiling point 253.6 ° C.) or naphthene / paraffin hydrocarbons.
  • Examples include AF Solvent (trade name) and Naphthezol (trade name) manufactured by Energy.
  • IP solvent trade name manufactured by Idemitsu Kosan Co., Ltd. is also included.
  • a mixture of a plurality of high boiling hydrocarbon solvents can also be used.
  • Conductive paste can be used for printing ink.
  • printing methods include inkjet printing, gravure offset printing, screen printing, and the like.
  • Known components used in the conductive paste for printing can be appropriately added.
  • the coating agent is preferably 10 parts by mass or more per 100 parts by mass of silver from the viewpoint of dispersion stability. Further, from the viewpoint of forming a film having a thickness of several microns or more after firing by low-temperature firing, the coating agent is preferably 22 parts by weight or less per 100 parts by weight of silver.
  • Example 1 ⁇ Process a Disperse 100 parts by mass (0.43 mol part) of powdered silver (I) oxide (Ag 2 O, formula 231.735) in 550 parts by mass of methylcyclohexane (boiling point 100.9 ° C., density 0.7737). It was. While stirring at room temperature (25 ° C.), 41.3 parts by mass (0.90 mol part) of formic acid (HCOOH, formula weight 46.03, boiling point 100.75 ° C.) was added to the resulting dispersion for 3 to 5 minutes. It was dripped over. This means that 1.04 mol of formic acid is added per 1 mol of Ag of silver (I) oxide.
  • HCOOH formic acid
  • silver nanoparticles whose surface is coated with neodecanoic acid and 2-ethylhexyloxypropylamine, diisopropylamine addition salt of formic acid or neodecanoic acid, 2-ethylhexyloxypropyl of formic acid or neodecanoic acid Contains amine addition salts, residual methylcyclohexane.
  • a diisopropylamine addition salt of formic acid or neodecanoic acid, a 2-ethylhexyloxypropylamine addition salt of formic acid or neodecanoic acid, and methylcyclohexane are dissolved in a mixed solvent consisting of methanol and distilled water.
  • silver nanoparticles settle without being dispersed in hydrous methanol.
  • the supernatant phase of the mixed solvent (hydrous methanol) was removed by decantation.
  • Step e (redispersion in solvent) To the precipitated phase obtained from decantation, 120 parts by mass of methylcyclohexane was added. The precipitated silver nanoparticles were dispersed in methylcyclohexane. Methanol remaining in the precipitated silver particles was phase-separated due to poor compatibility with methylcyclohexane. The phase portion of methanol phase separated was removed.
  • the methylcyclohexane solution in which the obtained silver nanoparticles were dispersed was filtered through a 0.2 ⁇ m membrane filter to remove aggregates.
  • a silver nanoparticle dispersion was obtained as the filtrate obtained from the filtration.
  • the method for measuring the total amount of metallic silver is as follows.
  • the obtained silver nanoparticle dispersion liquid was weighed in a crucible, and methylcyclohexane contained in a hot air dryer was removed by drying to obtain a solid.
  • the crucible was placed in a muffle furnace and baked at 700 ° C. for 30 minutes. Since only the metal remains after firing, the amount of metal was weighed, and the total amount of metallic silver was calculated from the concentration of the dispersion.
  • the obtained silver nanoparticle dispersion was allowed to stand at room temperature for 1 week, and then the presence or absence of particle sedimentation was visually observed. No settling of particles was observed.
  • the particle size of silver nanoparticles dispersed in the obtained silver nanoparticle dispersion is measured using a light scattering particle size distribution analyzer (trade name: Nanotrac UPA150, manufactured by Microtrack Bell Co., Ltd.). did. From the measurement results, it was found that the average particle diameter of the silver nanoparticles uniformly dispersed in the filtrate was 9 nm.
  • neodecanoic acid per 100 parts by mass of silver nanoparticles coated with neodecanoic acid and 2-ethylhexyloxypropylamine (100 parts by mass as the only mass without silver). 14.0 parts by mass in total of 2-ethylhexyloxypropylamine covered the surface of the silver nanoparticles.
  • the method for measuring the amount of the coating agent covering the silver nanoparticles is as follows. That is, about 0.1 g of a dispersion in which silver nanoparticles were dispersed in methylcyclohexane was weighed into a glass bottle, and the solvent was dried with a dryer (cold air) to form powder. About 10 mg of the dried powder was measured by raising the temperature to 500 ° C. with a thermal analyzer (trade name: TG / DTA6200, manufactured by SII Nanotechnology Co., Ltd.), and the amount of coating agent was calculated from the weight reduction rate.
  • Example 2 The silver nanoparticle dispersion obtained in Example 1 was used in such an amount that the amount of silver contained in this dispersion was 70 parts by mass, and IP solvent 2028 (trade name, manufactured by Idemitsu Kosan Co., Ltd., boiling points 213 to 262) was used. 30 parts by mass at a temperature of 0.789 g / cm 3 ).
  • the methylcyclohexane contained in the obtained liquid mixture was distilled off under reduced pressure to prepare an ink (printing conductive paste) using IP solvent 2028 as a dispersion solvent.
  • the viscosity of the produced ink was 11 mPa ⁇ s (20 ° C.), and the metal content was 63% by mass. This viscosity is a viscosity that can be printed by inkjet.
  • a pattern having a width of 250 ⁇ m and a length of 15 mm was applied on a slide glass having a width of 25 mm and a length of 75 mm by inkjet printing.
  • the average film thickness of this coating film was 7 ⁇ m.
  • the obtained coating film was heat-treated at 120 ° C. in the atmosphere for 60 minutes, and the silver nanoparticles contained therein were sintered at a low temperature.
  • the resistivity of the produced silver nanoparticle fired film was measured.
  • the film thickness after firing was 1.0 ⁇ m, and the resistivity of the low-temperature fired film was 3.5 ⁇ ⁇ cm.
  • the distillation of methylcyclohexane under reduced pressure was carried out at a temperature of 35 to 40 ° C. and a reduced pressure of 50 hPa.
  • the degree of vacuum was increased to 35 hPa, the temperature was 60 ° C., and the pressure was reduced for about 30 minutes.
  • the viscosity of the obtained ink was measured at 20 ° C. and 60 rpm using an E-type rotational viscometer (trade name: Viscometer TV-25, Type L, manufactured by Toki Sangyo Co., Ltd.).
  • the metal content was calculated from the value obtained by weighing about 0.8 g of ink in a crucible, baking it at 700 ° C. for 30 minutes in a muffle furnace, weighing the metal amount.
  • Example 3 The silver nanoparticle dispersion obtained in Example 1 was used in such an amount that the amount of silver contained in this dispersion was 87 parts by mass, and IP solvent 2835 (trade name, manufactured by Idemitsu Kosan Co., Ltd., boiling point 277 to 353) was used. 13 parts by mass of [C, density 0.82 g / cm 3] were mixed.
  • a paste using IP solvent 2835 as a dispersion solvent was prepared by distilling off methylcyclohexane contained in the obtained mixed liquid under reduced pressure.
  • the viscosity of the prepared conductive paste was measured at 25 ° C. and 60 rpm using an E-type rotational viscometer (trade name: Viscometer TV-25 Type H, manufactured by Toki Sangyo Co., Ltd.). The viscosity was 30 Pa ⁇ s (25 ° C.), and the metal content was 79% by mass. This viscosity is a viscosity that can be printed by gravure offset printing or screen printing.
  • a pattern having a width of 5 mm and a length of 30 mm was printed on a slide glass having a width of 25 mm and a length of 75 mm by screen printing.
  • the average film thickness of this coating film was 20 ⁇ m.
  • the obtained coating film was heat-treated at 120 ° C. in the atmosphere for 60 minutes, and the silver nanoparticles contained therein were sintered at a low temperature.
  • the resistivity of the produced silver nanoparticle fired film was measured.
  • the film thickness after firing was 3.5 ⁇ m, and the resistivity of the low-temperature fired film was 6.5 ⁇ ⁇ cm.
  • Example 4 The conductive paste obtained in Example 3 was used in such an amount that the amount of silver contained in this paste was 50 parts by mass, and silver powder Ag-SHA-224 (trade name, manufactured by Dowa Electronics, average particle size) 50 parts by mass of 0.5 ⁇ m in diameter) and 2.0 parts by mass of IP solvent 2835 (boiling point 277 to 353 ° C., density 0.82 g / cm 3 , Idemitsu Kosan Co., Ltd.) Dispersed to obtain a conductive paste.
  • the viscosity of the prepared paste was 50 Pa ⁇ s (25 ° C.), and the metal content was 87% by mass. This viscosity is a viscosity that can be printed by gravure offset printing or screen printing.
  • Example 3 Using the prepared paste, screen printing and low-temperature baking were performed in the same manner as in Example 3.
  • the average film thickness of the coating film formed by screen printing was 25 ⁇ m.
  • the film thickness after firing was 7 ⁇ m, and the resistivity of the low-temperature fired film was 8.5 ⁇ ⁇ cm.
  • Example 5 A silver nanoparticle dispersion was prepared in the same manner as in Example 1 except that the amount of neodecanoic acid (monocarboxylic acid) added was changed from 18.4 parts by mass to 10 parts by mass. Although the yield of silver nanoparticles decreased, the dispersion stability was good.
  • neodecanoic acid monocarboxylic acid
  • Example 6 A conductive paste for printing was prepared and printed in the same manner as in Example 3 except that the silver nanoparticle dispersion obtained in Example 5 was used instead of the silver nanoparticle dispersion obtained in Example 1. And firing. The conductive paste was finished uniformly, and a conductivity of 7 ⁇ ⁇ cm (film thickness after firing: 4 ⁇ m) was obtained after firing at 120 ° C. for 60 minutes.
  • Example 7 A silver nanoparticle dispersion was prepared in the same manner as in Example 1 except that the amount of neodecanoic acid (monocarboxylic acid) added was changed from 18.4 parts by mass to 25 parts by mass. Although silver nanoparticles with good dispersion stability were obtained, the amount of coating was slightly increased.
  • neodecanoic acid monocarboxylic acid
  • Example 8 A conductive paste for printing was prepared and printed in the same manner as in Example 3 except that the silver nanoparticle dispersion obtained in Example 7 was used instead of the silver nanoparticle dispersion obtained in Example 1. And firing. The conductive paste was uniformly finished, and a conductivity of 9.5 ⁇ ⁇ cm (film thickness after firing: 5 ⁇ m) was obtained after firing at 120 ° C. for 60 minutes.
  • Example 9 As monocarboxylic acid, it replaced with neodecanoic acid (carbon number 10) 18.4 parts by mass, and the same procedure as in Example 1 except that 1ethyl part of 2-ethylhexanoic acid (carbon number 8) was used. A silver nanoparticle dispersion was prepared. However, the molar amount of monocarboxylic acid is the same as in Example 1. Even if the type of monocarboxylic acid was changed, silver nanoparticles having high yield and good dispersion stability were obtained.
  • Example 10 The silver nanoparticle dispersion obtained in Example 9 was used in such an amount that the amount of silver contained in this dispersion was 65 parts by mass, and naphthesol 220 (trade name, manufactured by JX Nippon Mining & Energy, boiling point 221) was used. 35 parts by mass of ⁇ 240 ° C. and density 0.814 g / cm 3 ) were mixed. Except for this point, the same procedure as in Example 2 was carried out, and a conductive ink using naphthesol 220 as a dispersion solvent was prepared and evaluated. The conductive ink was uniformly finished, and a conductivity of 3.9 ⁇ ⁇ cm (film thickness after firing 1.1 ⁇ m) was obtained after firing at 120 ° C. for 60 minutes.
  • Example 11 A conductive paste for printing was produced in the same manner as in Example 3, except that the silver nanoparticle dispersion obtained in Example 9 was used instead of the silver nanoparticle dispersion obtained in Example 1. .
  • the conductive paste was finished uniformly, and a conductivity of 6.8 ⁇ ⁇ cm (film thickness after baking 5 ⁇ m) was obtained after baking at 120 ° C. for 60 minutes.
  • Example 12 A silver nanoparticle dispersion was prepared in the same manner as in Example 1, except that the addition amount of 2-ethylhexyloxypropylamine (primary amine) was changed from 23.1 parts by mass to 15 parts by mass. Although the yield of silver nanoparticles was slightly reduced, particles with good dispersion stability were obtained.
  • 2-ethylhexyloxypropylamine primary amine
  • Example 13 A conductive paste for printing was produced in the same manner as in Example 3 except that the silver nanoparticle dispersion liquid obtained in Example 12 was used instead of the silver nanoparticle dispersion liquid obtained in Example 1. .
  • the conductive paste was uniformly finished, and a conductivity of 6.7 ⁇ ⁇ cm (film thickness after firing: 3.2 ⁇ m) was obtained after firing at 120 ° C. for 60 minutes.
  • Example 14 Preparation of silver nanoparticle dispersion liquid As in Example 1, except that the primary amine was changed from 2-ethylhexyloxypropylamine (carbon number 11) to dibutylaminopropylamine (carbon number 11). A silver nanoparticle dispersion was prepared. Even if the kind of primary amine was changed, silver nanoparticles having high yield and good dispersion stability were obtained.
  • Example 15 A conductive paste for printing was prepared in the same manner as in Example 3 except that the nanoparticles obtained in Example 14 were used instead of the silver nanoparticle dispersion obtained in Example 1. The conductive paste was finished uniformly, and a conduction of 8.2 ⁇ ⁇ cm (film thickness after firing: 3 ⁇ m) was obtained after firing at 120 ° C. for 60 minutes.
  • Example 16 The silver nanoparticles were dispersed in the same manner as in Example 1 except that the primary amine was changed from 23.1 parts by mass of 2-ethylhexyloxypropylamine (carbon number 11) to 19.4 parts by mass of decylamine (carbon number 10). A liquid was prepared. Even if the kind of primary amine was changed, silver nanoparticles having high yield and good dispersion stability were obtained.
  • Example 17 The silver nanoparticle dispersion obtained in Example 16 was used in such an amount that the amount of silver contained in this dispersion was 65 parts by mass, and IP solvent 2028 (trade name, manufactured by Idemitsu Kosan Co., Ltd., boiling points 213 to 262) was used. 35 parts by mass at 0 ° C. and a density of 0.789 g / cm 3 ) were mixed. Except for this point, a conductive ink using the IP solvent 2028 as a dispersion solvent was prepared and evaluated in the same manner as in Example 2. The conductive ink was uniformly finished, and a conductivity of 4.2 ⁇ ⁇ cm (film thickness after firing 1.2 ⁇ m) was obtained after baking at 120 ° C. for 60 minutes.
  • IP solvent 2028 trade name, manufactured by Idemitsu Kosan Co., Ltd., boiling points 213 to 262
  • Example 18 A conductive paste for printing was produced in the same manner as in Example 3, except that the nanoparticles obtained in Example 16 were used instead of the silver nanoparticle dispersion obtained in Example 1. The conductive paste was uniformly finished, and a conductivity of 7 ⁇ ⁇ cm (film thickness after firing: 3.8 ⁇ m) was obtained after baking at 120 ° C. for 60 minutes.
  • Example 19 A silver nanoparticle dispersion was prepared in the same manner as in Example 1 except that the type of secondary amine was changed from diisopropylamine to dibutylamine. Even if the kind of secondary amine was changed, silver nanoparticles having high yield and good dispersion stability were obtained.
  • Example 20 A conductive paste for printing was produced in the same manner as in Example 3 except that the nanoparticles obtained in Example 19 were used in place of the silver nanoparticle dispersion obtained in Example 1.
  • the conductive paste was uniformly finished, and a conductivity of 7.5 ⁇ ⁇ cm (film thickness after baking 3.6 ⁇ m) was obtained after baking at 120 ° C. for 60 minutes.
  • Example 2 Evaluation similar to Example 1 was performed about the obtained silver nanoparticle dispersion liquid.
  • the silver yield was 98%.
  • the average particle diameter of the silver nanoparticles was 7 nm.
  • 28.2 parts by mass of 2-ethylhexyloxypropylamine covered the surface of the silver nanoparticles per 100 parts by mass of the silver nanoparticles.
  • Comparative Example 2 A conductive ink for printing was prepared in the same manner as in Example 2 except that the silver nanoparticle dispersion obtained in Comparative Example 1 was used instead of the silver nanoparticle dispersion obtained in Example 1. Inkjet printing and baking were performed.
  • the average film thickness of the coating film formed by inkjet printing was 7 ⁇ m.
  • the film thickness after firing was 0.7 ⁇ m, and the resistivity of the low-temperature fired film was 5 ⁇ ⁇ cm.
  • Example 3 A conductive paste was prepared in the same manner as in Example 3 except that the silver nanoparticle dispersion obtained in Comparative Example 1 was used instead of the silver nanoparticle dispersion obtained in Example 1.
  • the prepared conductive paste was highly sticky and did not flow at all, and the viscosity could not be measured.
  • the conductive paste was in an inappropriate state for printing.
  • the conductive paste was applied onto glass by hand with a metal spatula and fired at 120 ° C., but the film was severely cracked and the conductivity could not be measured.
  • Example 5 A conductive paste was produced in the same manner as in Example 3 except that the silver nanoparticle dispersion liquid obtained in Comparative Example 4 was used instead of the silver nanoparticle dispersion liquid obtained in Example 1.
  • the conductive paste was finished uniformly, but no conductivity was obtained after baking at 120 ° C. for 60 minutes. Conductivity of 6 ⁇ ⁇ cm (film thickness after firing 3 ⁇ m) was obtained after firing at 200 ° C. for 30 minutes.
  • Comparative Example 8 A silver nanoparticle dispersion was prepared without adding monocarboxylic acid. That is, the same operation as in Step a1 of Comparative Example 1 was performed, and then the same operations as in Steps b, c, d, and e of Example 1 were performed to prepare a silver nanoparticle dispersion. Although the yield decreased, a silver nanoparticle dispersion liquid in which silver nanoparticles were uniformly dispersed was obtained. However, when it was left at room temperature for about 1 day, sedimentation occurred, and the dispersion stability could not be maintained.
  • Example 9 A silver nanoparticle dispersion liquid was prepared in the same manner as in Example 1, except that the monocarboxylic acid was changed from 18.4 parts by mass of neodecanoic acid (carbon number 10) to 13.9 parts by mass of heptanoic acid (carbon number 7). Was prepared. Even if the kind of monocarboxylic acid was changed, particles with high yield and dispersion stability were obtained, but the amount of coating agent was increased.
  • Example 10 A conductive paste was prepared in the same manner as in Example 2 except that the silver nanoparticle dispersion obtained in Comparative Example 9 was used in place of the silver nanoparticle dispersion obtained in Example 1, and an inkjet was prepared. Printing and baking were performed. The conductive ink finished uniformly, but no conduction was obtained after baking at 120 ° C. for 60 minutes. In baking at 180 ° C. for 60 minutes, conductivity of 8 ⁇ ⁇ cm (film thickness after baking 0.8 ⁇ m) was obtained. This seems to be because the coordinating power to silver increases as the chain length of the carboxylic acid is shorter.
  • Table 1 shows the amounts of main components used (parts by mass) and evaluation results in the examples.
  • Table 2 the usage-amount (mass part) of the main component in a comparative example and an evaluation result are shown.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)

Abstract

Selon l'invention, il est possible de préparer selon des degrés de viscosité variés une pâte conductrice permettant une cuisson à basse température adaptée à l'élaboration d'un conducteur dont les performances de conduction sont satisfaisantes. L'invention concerne un procédé destiné à préparer une dispersion liquide de nanoparticules d'argent de diamètre particulaire moyen compris entre 5 et 20nm qui possèdent à leur surface une couche de revêtement constituée de molécules d'agent de revêtement. Le procédé de l'invention inclut : a) une étape au cours de laquelle dans un solvant hydrocarburé, un acide formique agit sur un oxyde d'argent en poudre (I) qui est converti en formiate d'argent (I) ; et b) une étape au cours de laquelle dans ledit solvant hydrocarburé, un cation d'argent contenu dans le formiate d'argent (I) est réduit en atome d'argent par réaction de réduction à l'aide d'un composé amine, en présence d'un acide monocarboxylique de 8 à 11 atomes de carbone, et les nanoparticules d'argent de diamètre particulaire moyen compris entre 5 et 20nm dont la surface est revêtue par le composé amine et l'acide monocarboxylique, sont ainsi formées. Une amine primaire et une amine secondaire de 9 à 11 atomes de carbone, sont mises en œuvre en tant que composé amine. L'invention concerne également un procédé de préparation de pâte conductrice pour impression mettant en œuvre cette dispersion liquide.
PCT/JP2015/080828 2015-10-30 2015-10-30 Pâte conductrice pour impression ainsi que procédé de préparation de celle-ci, et procédé de préparation de dispersion liquide de nanoparticules d'argent WO2017072970A1 (fr)

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PCT/JP2015/080828 WO2017072970A1 (fr) 2015-10-30 2015-10-30 Pâte conductrice pour impression ainsi que procédé de préparation de celle-ci, et procédé de préparation de dispersion liquide de nanoparticules d'argent
PCT/JP2016/080516 WO2017073364A1 (fr) 2015-10-30 2016-10-14 Pâte conductrice pour impression ainsi que procédé de fabrication de celle-ci, et procédé de préparation de dispersion liquide de nanoparticules d'argent
JP2017547732A JPWO2017073364A1 (ja) 2015-10-30 2016-10-14 印刷用導電性ペーストおよびその調製方法、ならびに銀ナノ粒子分散液の調製方法
TW105134221A TWI707052B (zh) 2015-10-30 2016-10-24 印刷用導電性糊劑及其調製方法與銀奈米粒子分散液之調製方法

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PCT/JP2016/080516 WO2017073364A1 (fr) 2015-10-30 2016-10-14 Pâte conductrice pour impression ainsi que procédé de fabrication de celle-ci, et procédé de préparation de dispersion liquide de nanoparticules d'argent

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