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WO2010137080A1 - Procédé de production d'une nanoparticule métallique présentant une aptitude au frittage à basse température, nanoparticule métallique, et procédé de production d'une dispersion la contenant - Google Patents

Procédé de production d'une nanoparticule métallique présentant une aptitude au frittage à basse température, nanoparticule métallique, et procédé de production d'une dispersion la contenant Download PDF

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WO2010137080A1
WO2010137080A1 PCT/JP2009/002433 JP2009002433W WO2010137080A1 WO 2010137080 A1 WO2010137080 A1 WO 2010137080A1 JP 2009002433 W JP2009002433 W JP 2009002433W WO 2010137080 A1 WO2010137080 A1 WO 2010137080A1
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amine
particles
silver
primary amine
metal nanoparticles
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Japanese (ja)
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中野谷太郎
佐藤王高
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Dowa Electronics Materials Co Ltd
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Dowa Electronics Materials Co Ltd
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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
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/08—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of toothed articles, e.g. gear wheels; of cam discs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/0545—Dispersions or suspensions of 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver

Definitions

  • the present invention relates to a method for producing metal nanoparticles exhibiting properties excellent in low-temperature sintering properties, metal nanoparticles obtained by the method, and a dispersion in which the metal nanoparticles are dispersed in an organic solvent.
  • the “single nano class” refers to particles having an average particle size of 1 nm or more and 10 nm or less measured by a measurement method such as TEM measurement.
  • the surface of the single nano-class metal nanoparticles usually has a slight difference, but there is an organic coating.
  • a thin film is to be formed with these metal nanoparticles, it is once applied in this form on the substrate, and then the organic material covering the surface is decomposed and evaporated to form a metal thin film by heating. Yes.
  • a suitable metal film can be obtained if the applied heat is high, but it cannot be applied to a substrate that is weak in heat resistance. Therefore, attempts have been made to lower the temperature during the formation of the metal thin film.
  • the method include a method of coating with an organic substance having a short carbon chain in advance, or converting an organic substance constituting the surface of particles prepared in advance into a substance that is more easily sinterable.
  • Patent Documents 1 to 3 disclose techniques for replacing a protective material covering the surface of metal particles with another protective material.
  • Patent Document 1 discloses an invention in which an organic substance formed on a surface is substituted in metal nanoparticles formed by dropping a reducing agent in a synthesis stage.
  • Patent Document 2 discloses a technique in which an organic solvent is added during a substitution reaction and used as a substitution driving force.
  • Patent Document 3 as a method for producing metal nanoparticles for ink jetting, after formation of a fatty acid metal salt, both amines having carbon chains 8 to 20 and fatty acids derived from raw materials are formed on the surface through two-stage substitution. A method for obtaining existing metal nanoparticles is disclosed.
  • JP 2006-089786 A (Claims and others)
  • JP 2008-095194 A (Claims) JP 2008-157071 (Claims and others)
  • Patent Document 1 In the case of the method described in Patent Document 1, no matter how much stirring is performed, it is difficult to cause a uniform reaction in the liquid, so it is not easy to obtain uniform particles.
  • Patent Document 2 it is essential to add a heterogeneous component as a component that promotes dispersion or reaction. Therefore, a heterogeneous system is used after the addition until the organic medium becomes uniform. Therefore, it is not easy to obtain particles having a uniform particle size distribution.
  • a surfactant component present on the particle surface is composed of at least two kinds, and heat generation occurs at least twice when forming a metal film, so that a substrate that is particularly weak in heat resistance is used. In such a case, it is not preferable.
  • the organic substance covering the surface often uses an organic substance having a relatively large molecular weight by utilizing the property of isolating metal particles.
  • an organic substance having a relatively large molecular weight by utilizing the property of isolating metal particles.
  • the inventors of the present application can obtain silver nanoparticles having extremely high dispersibility and independence by reducing silver salts such as silver nitrate in the presence of a primary amine having an unsaturated bond such as oleylamine.
  • a primary amine having an unsaturated bond such as oleylamine.
  • Silver nanoparticles obtained by this method are coated with a primary amine present around the reaction.
  • This primary amine has a relatively large molecular weight, has a function of keeping the distance between particles moderately, suppressing aggregation and sintering of silver nanoparticles in the liquid, and maintaining independence.
  • intermetallic sintering can be caused by heating at a lower temperature than particles coated with a conventionally known polymer. This is not because the surfactants constituting the particle surface have an unsaturated bond, so that the reaction and decomposition of the surfactant are promoted, and the desorption from the metal nanoparticles easily proceeds. I think.
  • some highly versatile substrates may be decomposed or melted at 100 to 180 ° C. or 100 to 150 ° C. If metal nanoparticles having a low sintering temperature can be produced, it is expected that their use will be promoted in a wider range of applications. For example, if it can be applied to a transparent polycarbonate substrate used for CDs, DVDs, etc., fine wiring can be formed on the surface of the media and lens, and various additional functions can be provided. Become. Also, if wiring can be formed on a PET substrate or paper, an antenna or the like can be formed on the material, so that it can be used for RFID (IC tags) and the like. .
  • wiring can be formed on things that could not be used in the past, it can be estimated that electronic devices can be made smaller, lighter, and thinner. It can also be widely used in fields such as planar heating elements such as film heaters, electromagnetic wave shielding films, solar cells, transparent electrodes, and electromagnetic wave shielding films such as plasma display televisions.
  • planar heating elements such as film heaters, electromagnetic wave shielding films, solar cells, transparent electrodes, and electromagnetic wave shielding films such as plasma display televisions.
  • the present invention is intended to provide a method for producing metal nanoparticles that are simpler than conventional methods and have an extremely low sintering temperature, and metal nanoparticles obtained by such methods, in order to be applied to such a wide range of applications. It is.
  • the average particle diameter D TEM of the particles confirmed by a transmission electron microscope coated with a primary amine having a molecular weight of 200 to 400 having an unsaturated bond.
  • the primary amine having a molecular weight of 200 to 400 attached to the metal nanoparticles first is indicated as amine
  • an exothermic peak is independently confirmed at 200 ° C. or lower in a DTA curve measured under atmospheric conditions. This is achieved by the substituted amine B and has the property that it does not result from the previously coated material.
  • the dispersion of the obtained particles when the dispersion of the obtained particles is baked after being applied, it has a property that the specific resistance of the metal film obtained when held in the atmosphere at 120 ° C. for 1 hour is 25 ⁇ ⁇ cm or less.
  • the method for calculating the specific resistance is not particularly limited, but it is preferable to adopt a generally known method.
  • the condition that the specific resistance obtained when the sample to be measured is baked at 200 ° C. in the atmosphere is measured as 20 ⁇ ⁇ cm or less is applied to the evaluation condition in 120 ° C. baking. The fired film was evaluated. That is, the specific resistance of the 120 ° C.
  • fired film is measured by making the conditions of preparation, coating, firing and measurement of the dispersion the same as the conditions when the specific resistance shows a value of 20 ⁇ ⁇ cm or less at 200 ° C. firing. That's it. If the method can confirm whether or not the sintering is progressing in the 200 ° C. firing, the progress of the sintering can be objectively determined even if the conditions are applied to the 120 ° C. firing. In the first place, particles whose specific resistance does not show 20 ⁇ ⁇ cm or less during firing at 200 ° C. in the atmosphere cannot be said to have obtained low-temperature sinterability. Inevitably excluded.
  • coated with a surfactant means that the individual metal nanoparticles exist independently in a state where they are not bonded, and sufficient organic substances are sufficient to prevent the particles from contacting each other as a guarantee of their independence. A state in which a protective substance consisting of is coated on the surface of metal particles.
  • the surfactant constituting the surface can be replaced very easily as compared with the conventional method for replacing the surfactant on the particle surface.
  • a metal film having high conductivity at a low temperature can be formed, and metal nanoparticles that can be used for a wider range of applications and a dispersion liquid in which the metal nanoparticles are dispersed can be provided.
  • 4 is a TEM photograph of silver particles obtained by a substitution reaction in tetradecane in Example 1.
  • FIG. 4 is a TEM photograph of silver particles obtained by replacement reaction in decane in Example 2.
  • FIG. 4 is a TEM photograph of silver particles obtained by a substitution reaction in kerosene in Example 3.
  • FIG. 4 is a TEM photograph of silver particles obtained by a substitution reaction in the presence of tetradecane and isopropanol in Example 4.
  • a feature of the production method disclosed in the present invention is that a surfactant composed of amine A formed on the surface of metal nanoparticles during production is a primary amine having a carbon chain shorter than that of amine A and having 6 to 12 carbon atoms. It is characterized by substitution with B.
  • an organic compound such as a surfactant is present on the surface of the metal nanoparticles in order to prevent the particles from being bonded to each other.
  • a general surfactant has an R—X structure having a hydrophobic group R and a hydrophilic group X.
  • the hydrophobic group R is typically an alkyl group in which hydrogen is bonded to the carbon skeleton, and there are various hydrophilic groups X, for example, “—COOH” for fatty acids and “—NH 2 ” for amines. Become.
  • the hydrophilic group X is bonded to the surface of the metal silver, and the hydrophobic group R is directed to the outside of the particle covered with the organic protective material.
  • the organic protective material are considered to be oriented. Since metal nanoparticles are extremely active, normally, the surface of the particles cannot be stably present unless they are covered with a protective material. As can be understood from this, in order to keep the metal nanoparticles in a long and stable state as they are, a surfactant having a relatively large molecular weight is used so that the particles do not contact each other as much as possible. It is preferable.
  • the boiling point of an organic compound increases as it becomes a long chain, and more energy is required to decompose the long chain organic compound. That is, when a long-chain organic compound is inevitably used, a large amount of energy is required, so that high-temperature heating is required to obtain a sintered film. Therefore, in order to obtain a sintered film at a low temperature, it is necessary to use, as the surfactant, a substance having a carbon chain as short as possible as the surfactant constituting the surface. For that purpose, it is one of the methods to adopt a short-chain surfactant from the beginning at the time of synthesis and attach it to the surface, but it is difficult to obtain silver fine powder with good dispersibility due to aggregation, etc. It has been found by the inventors that the operation of preparing a paint through a process such as washing is likely to be hindered.
  • a surfactant having a relatively long chain is preferred as a surface coating agent.
  • a surfactant having a relatively long chain is preferred as a surface coating agent.
  • the surface is composed of an amine-based surfactant (amine A) having a specific molecular structure, and an organic substance having a carbon number shorter than that of amine A initially formed in the substitution liquid, particularly an amine.
  • amine A an amine-based surfactant
  • organic substance having a carbon number shorter than that of amine A initially formed in the substitution liquid particularly an amine.
  • the organic substance existing on the surface of the nanoparticles can be replaced by a simple method.
  • the firing temperature it is possible to appropriately select the firing temperature while taking into consideration the balance with other properties.
  • octylamine and hexylamine are preferable because a fired film can be formed even at a heating temperature of around 120 ° C.
  • the remaining amount of amine A before substitution may be less than 1% of the total amount of the total amine.
  • a having the largest absorption among absorptions caused by amine A having a molecular weight of 200 to 400 and amine B having 6 to 12 carbon atoms after substitution are used. It can also be obtained by calculating the total amine amount by adding the B value having the largest absorption among the resulting absorptions, and calculating the proportion of A in the total amount.
  • primary amine A having a molecular weight of 200 to 400 having an unsaturated bond is preferable to employ as the amine coated at the time of metal nanoparticle production. It was found that the primary amine having an unsaturated bond is likely to be detached from the metal particles and removed by volatilization by heating during firing even if the molecular weight is somewhat large. In view of the stability of the particles, it can be said that it is effective to select an amine having a molecular weight of 200 or more. If the molecular weight is excessively large, it becomes difficult to desorb and volatilize when the coating film is fired at a low temperature.
  • the primary amine B having 6 to 12 carbon atoms is preferably selected as the amine to be substituted. These organic substances can obtain a remarkable reduction effect of the sintering temperature due to the low molecular weight.
  • the particle size of the coated surfactant-protected metal nanoparticles can be represented by the average particle diameter D TEM or X-ray crystal particle diameter D X is measured from the image of the TEM (transmission electron microscope). Since X-rays have different diffractive surfaces depending on the type of metal, silver will be described in detail below for convenience.
  • particle size is measured by TEM: D TEM is 3 silver particles is ⁇ 20 nm or (111) X-ray was calculated from the half value width in the surface crystal grain size,: D x is 1 to Silver particles that are 20 nm are preferred targets. Further, D TEM is 3 ⁇ 7 nm, D X is very fine silver particles of about 1 ⁇ 5 nm, for example may be synthesized by such method of reducing the direct silver compound oleylamine as a reaction solvent. Since impurities are easily mixed into the crystal grain boundary of the synthesized metallic silver, it is preferable that one grain corresponds to one crystal as a structure in which no grain boundary is formed.
  • an index indicating how many crystallites a particle visible by a TEM or the like is composed of is expressed by dividing the particle size measured in a TEM photograph by the X-ray particle size. That it is desirable single crystallinity (D TEM / D X) is 2.5 or less, it is more preferably 2.0 or less, it is more preferable and more preferably 1 in the absence of grain boundaries.
  • This fine silver (hereinafter also referred to as “Ag”) fine powder having excellent low-temperature sinterability can be obtained as follows.
  • the silver nanoparticle raw material used in the present invention has a stable particle property such as a particle size distribution and has a property of being difficult to aggregate and settle in a liquid medium.
  • a synthesis method that has been conventionally studied will be briefly described. That is, in this synthesis method, silver particles are precipitated by reducing the silver compound in alcohol or polyol using alcohol or polyol as a reducing agent.
  • alcohol or polyol is a solvent and a reducing agent.
  • the reduction reaction can proceed by raising the temperature of the solvent solution, preferably by bringing it to a reflux state.
  • an organic compound functioning as a protective substance coexists by enclosing particles in a solvent.
  • the organic compound primary amine A having an unsaturated bond and having a molecular weight of 200 to 400 is used here.
  • the number of unsaturated bonds at this time is at least one per molecule.
  • the amount of primary amine A coexisting in the solvent during the reduction reaction can be 0.1 to 20 equivalents relative to silver, more preferably 1 to 15 equivalents, and even more preferably 2 to 10 equivalents.
  • 1 equivalent refers to the presence of 1 mole of the corresponding amine per mole of silver. If the amount of primary amine used is too small, the amount of protective material on the surface of the silver particles is insufficient, and monodispersion in the liquid cannot be realized. If the amount is too large, there is a possibility that the reaction of replacing amine A with amine B in the subsequent step cannot be performed efficiently.
  • the reducing agent As the reducing agent, alcohol or polyol as a solvent is used. In the reaction, it is efficient to perform a reflux operation. Therefore, the boiling point of the alcohol or polyol is preferably low, specifically 80 to 300 ° C., preferably 80 to 200 ° C., more preferably 80 to 150 ° C. In particular, isobutanol and n-butanol are preferred.
  • a reduction auxiliary agent may be added.
  • a reduction adjuvant should just select 1 or more types from what is indicated by patent documents 4, it is especially preferred to use diethanolamine and triethanolamine among these.
  • the silver compound which is a supply source of silver various compounds can be applied as long as they can be dissolved in the above solvent, and examples thereof include silver chloride, silver nitrate, silver oxide, and silver carbonate. preferable.
  • the concentration of Ag ions in the liquid during the reduction reaction can be 0.05 mol / L or more, preferably 0.05 to 5.0 mol / L.
  • the amine A / Ag molar ratio can be in the range of 0.05 to 5.0.
  • the molar ratio of reducing aid / Ag can be in the range of 0.1-20.
  • the temperature of the reduction reaction is preferably in the range of 50 to 200 ° C.
  • a temperature of 50 to 150 ° C. is more preferable, and a range of 60 to 140 ° C. is more preferable.
  • Silver particles covered with amine A (synthesized by the above reduction) have an amine A content ratio (hereinafter simply referred to as “amine A ratio”) of 0.05 to 25 mass with respect to the total of silver particles and amine A. It is desirable to adjust to%. If the amine A ratio is too low, particles are likely to aggregate. Conversely, when the amine A ratio is high, there is a possibility that the reaction of replacing amine A with amine B in the subsequent step cannot be performed efficiently.
  • the silver particles covered with amine A are synthesized, for example, by a reduction reaction in a wet process as described above, and then subjected to solid-liquid separation and washing. Then, it mixes with a liquid organic medium and makes a dispersion liquid.
  • a liquid organic medium a substance in which silver particles covered with amine A are well dispersed is selected.
  • a hydrocarbon system can be suitably used.
  • aliphatic hydrocarbons such as isooctane, n-decane, isododecane, isohexane, n-undecane, n-tetradecane, n-dodecane, tridecane, hexane, and heptane can be used.
  • Petroleum solvents such as kerosene may be used.
  • One or more of these substances may be used to form a liquid organic medium.
  • a silver particle dispersion in which silver particles coated with amine A are monodispersed.
  • “monodispersed” means that individual silver particles exist in a liquid medium in a state where they can move independently without aggregating with each other.
  • a liquid containing silver particles is subjected to a solid-liquid separation operation by centrifugation, a liquid (supernatant) in which the particles remain dispersed can be adopted as the silver particle dispersion here. it can.
  • the appropriate temperature of the reaction varies depending on the type of amine B, but if the temperature of the liquid is generally less than 10 ° C., part of amine A Often remain adsorbed and do not become completely substituted, and tend to be particles covered with “a composite organic protective material composed of amine A and amine B”. In this case, the dispersibility in the aromatic organic compound is lowered, which is disadvantageous in producing an inexpensive liquid ink using the aromatic organic compound as a dispersion medium. Therefore, in this specification, replacement with amine B is performed at a temperature of 50 ° C. or higher, preferably 55 ° C. or higher. However, if the temperature is increased too much, unnecessary fusion of particles may occur, so that the temperature is preferably 80 ° C. or lower, and more preferably 70 ° C. or lower.
  • the amount of substitution with amine B increases with time, but it is desirable to secure a substitution reaction time of 1 hour or more. However, even if it exceeds 24 hours, the further substitution reaction does not proceed so much, so it is practical to terminate the substitution reaction within 24 hours. Actually, it may be adjusted in the range of 1 to 7 hours.
  • the amount of amine B to be mixed is sufficient to realize the “enclosed state by amine B”. It is desirable to add at least an amount greater than equimolar to the amount of amine A present as a protective material prior to mixing. Preferably, the amount of amine B is at least twice that of amine A.
  • Solid-liquid separation As described above, since the particles after the substitution are settled, the particles obtained after the reaction can be easily recovered as a solid content by solid-liquid separation of the liquid after completion of the reaction.
  • the solid-liquid separation can be performed by decantation, but centrifugal separation is preferably used for more efficient separation and recovery in a short time.
  • the obtained solid content is mostly silver nanoparticles coated with an organic substance composed of amine B.
  • the solid content is desirably washed using a solvent such as alcohol.
  • the solid content obtained after the solid-liquid separation after one or more washing operations is used for the paint.
  • the silver paint of the present invention can be obtained by mixing the solid content after washing (silver nanoparticles with the protective material replaced with amine B) and an appropriate organic medium so that they can be applied. It is important that the organic medium to be mixed here is one that is easy to volatilize and remove at a temperature of about 120 ° C. When an ink in which the silver nanoparticles are dispersed in a liquid medium is prepared, an aromatic organic compound or aliphatic hydrocarbon that is liquid at room temperature can be used as the medium.
  • Comparative Example 1 a coating material was prepared using silver nanoparticles synthesized by the alcohol reduction method shown below, and the specific resistance of a fired film fired at a firing temperature of 200 ° C. and 120 ° C. was examined.
  • the silver fine powder is such that the surface of each particle is covered with an organic protective material made of amine A (here, oleylamine). Specifically, the experiment was conducted as follows.
  • Tetradecane was prepared as a liquid organic medium. The solid component after washing was mixed and dispersed therein, and solid-liquid separation was performed with a centrifuge for 30 minutes, and the separated liquid was recovered. In this liquid, silver particles covered with amine A are monodispersed.
  • This silver particle dispersion was observed with a transmission electron microscope (TEM) to obtain an average particle diameter DTEM . That is, among the particles observed at a magnification of 600,000 by TEM (JEM-2010 manufactured by JEOL Ltd.), the particle diameters of 300 independent silver particles that did not overlap were measured, and the average particle diameter was calculated. . As a result, D TEM was 8.5 nm. In this example, as described later, Since this silver particle dispersion is used for silver paint, Table 1 shows the DTEM values.
  • amine A coating amount the ratio of amine A to the total of silver particles and amine A (oleylamine) covering the surface thereof (hereinafter referred to as “amine A coating amount”) was determined.
  • the heat pattern shown in FIG. 2 is adopted.
  • the shaded portion represents temperature retention
  • the dotted line portion represents temperature rise (specifically, 10 ° C./min as shown below).
  • the temperature is raised from room temperature to 200 ° C. at 10 ° C./min (Stage I) and maintained at 200 ° C. for 60 minutes (Stage II).
  • the organic medium here, tetradecane contained in is volatilized.
  • the temperature is raised from 200 ° C. to 700 ° C. at 10 ° C./min (Stage III), and maintained again at 700 ° C. for 60 minutes (Stage IV). It can be considered that all of the organic medium is volatilized in stages I to II and amine A as a protective material remains, and in stages III to IV, all of amine A is volatilized.
  • the weight change measured by the TG-DTA apparatus is monitored with the heat pattern of FIG. 2, and the weight change becomes almost zero by the end of stage II. Therefore, the weight W 1 reduced up to this point is reduced to the organic medium ( The weight of the dispersion medium. Then, after the start of stage III, the weight decrease occurs again, and the change in weight becomes substantially zero by the end of stage IV. Therefore, the newly reduced weight W 2 between stages III to IV is used as the weight of amine A. To do. Let the remaining weight W 3 be the net weight of silver. The amine A coating amount (%) is calculated by W 2 / (W 2 + W 3 ) ⁇ 100. As a result, the amine A coating amount of the particles in this silver particle dispersion was 8.0% by mass.
  • FT-IR measurement of protective material Using FT-IR (Fourier transform infrared spectrophotometer), the spectrum of the organic compound was measured for the reagent oleylamine and the particles in the silver particle dispersion. As a result, it was confirmed that the organic protective film was oleylamine alone.
  • Cu-K ⁇ was used for X-rays.
  • D X K ⁇ ⁇ / ( ⁇ ⁇ cos ⁇ ) (1)
  • K is a Scherrer constant and 0.94 is adopted.
  • ⁇ is the X-ray wavelength of the Cu—K ⁇ ray
  • ⁇ is the half width of the diffraction peak
  • ⁇ is the Bragg angle of the diffraction line. The results are shown in Table 1 (same in the following examples).
  • a silver paint using silver particles coated with a protective material made of amine A was prepared.
  • the viscosity of the silver paint dispersion was measured with a rotary viscometer (RE550L manufactured by Toki Sangyo Co., Ltd.), the viscosity was 5.8 mPa ⁇ s.
  • the silver concentration in this silver particle dispersion was 60% by mass as measured using the above-described TG-DTA apparatus. Since this silver particle dispersion was judged to have properties that can be applied as an ink, it was decided to use this as it is as a silver paint.
  • a coating film was formed by coating the silver paint on a glass substrate by spin coating.
  • Examples 1 to 4 Silver nanoparticles were synthesized according to “Synthesis of Silver Particles” described in Comparative Example 1. However, decane and kerosene were further prepared in addition to tetradecane as a liquid organic medium in “production of silver particle dispersion” as the next step. In the same manner as in Comparative Example 1, the washed solid components were mixed and dispersed in tetradecane (Examples 1 and 4), decane (Example 2) and kerosene (Example 3), respectively. Solid-liquid separation was performed for a minute, and the separated liquid (silver particle dispersion) was recovered. In these liquids, silver particles covered with amine A are monodispersed.
  • amine B a reagent octylamine (C 8 H 17 —NH 2 , a special grade manufactured by Wako Pure Chemical Industries, Ltd.) was prepared. Moreover, isopropanol (special grade made by Wako Pure Chemical Industries, Ltd.) was prepared.
  • octylamine in an amount corresponding to 10 equivalents to Ag was added to each of the above silver particle dispersions.
  • octylamine in an amount corresponding to 10 equivalents with respect to Ag and isopropanol in an amount corresponding to 20 equivalents with respect to Ag were added.
  • the liquid temperature was kept at 60 ° C. and the stirring state shown in Table 1 was maintained for the time shown in Table 1. It was observed that precipitated particles were formed when stirring was stopped.
  • Example 2 In Example 1, particles were formed in the same manner except that no stirring was performed.
  • Example 3 Comparative Example 3 >> In Example 1, particles were formed in the same manner except that the reaction temperature was 40 ° C.
  • Solid-liquid separation and washing The liquid in which the precipitated particles were generated was subjected to solid-liquid separation by centrifugation for 5 minutes. The obtained solid content is recovered, methanol is further added to this solid content, ultrasonic dispersion is performed for 30 minutes, and then a washing operation is performed once to recover the solid content by solid-liquid separation by centrifugation for 5 minutes. went.
  • FIGS. 9 to 12 illustrate TEM photographs of silver particles (coated with amine B protective material) obtained in Examples 1 to 4, respectively.
  • the coating film was formed by apply

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Abstract

L'invention concerne une poudre fine d'argent enduite d'un matériau protecteur et pouvant subir un frittage à une température considérablement plus basse que les poudres conventionnelles. La poudre fine d'argent comprend des particules d'argent qui possèdent un diamètre de particule moyen (DTEM) comprise entre 3 et 20 nm ou un diamètre de grain cristallin aux rayons X (Dx) comprise entre 1 et 20 nm et qui ont été enduites d'un matériau protecteur organique constitué d'une amine primaire en C6-C12 (B). Cette poudre fine d'argent possède une propriété telle que lorsque la poudre est mélangée à un milieu organique pour préparer un matériau de revêtement en argent et que ce matériau de revêtement est appliqué, alors le chauffage du film de revêtement résultant dans l'air à 120 °C donne un film conducteur possédant une résistivité inférieure ou égale à 25 µΩ cm. Cette poudre fine d'argent peut être produite par : mélange d'une amine primaire en C6-C12 (B) avec une dispersion de particules d'argent qui comprend un milieu organique et, dispersées dans celui-ci en tant que particules principales, des particules d'argent enduites d'une amine primaire (A) possédant une liaison insaturée et un poids moléculaire de 200 à 400 ; et maintien du mélange à une température comprise entre 50 et 80 °C avec agitation, pour donner des particules sédimentaires.
PCT/JP2009/002433 2009-05-27 2009-06-01 Procédé de production d'une nanoparticule métallique présentant une aptitude au frittage à basse température, nanoparticule métallique, et procédé de production d'une dispersion la contenant Ceased WO2010137080A1 (fr)

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JP2009-128325 2009-05-27
JP2009128325A JP2010275580A (ja) 2009-05-27 2009-05-27 低温焼結性金属ナノ粒子の製造方法および金属ナノ粒子およびそれを用いた分散液の製造方法

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JP2012119132A (ja) * 2010-11-30 2012-06-21 Harima Chemicals Inc 導電性金属ペースト
CN106128543A (zh) * 2016-07-18 2016-11-16 贵州大学 一种防沉降效果好的导电银浆及其制备方法
CN116532653A (zh) * 2023-07-07 2023-08-04 长春黄金研究院有限公司 Slm铺粉打印成型用银粉及其制备方法

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JP5976684B2 (ja) 2012-01-20 2016-08-24 Ｄｏｗａエレクトロニクス株式会社 接合材およびそれを用いた接合方法
JP6962321B2 (ja) * 2016-05-26 2021-11-05 株式会社大阪ソーダ 導電性接着剤
JP6574746B2 (ja) * 2016-09-21 2019-09-11 矢崎総業株式会社 導電性ペースト及びそれを用いた配線板

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JP2006169613A (ja) * 2004-12-20 2006-06-29 Ulvac Japan Ltd 金属薄膜の形成方法及び金属薄膜
JP2009068035A (ja) * 2007-09-11 2009-04-02 Dowa Electronics Materials Co Ltd 低温焼結性銀微粉および銀塗料ならびにそれらの製造法

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JP2006169613A (ja) * 2004-12-20 2006-06-29 Ulvac Japan Ltd 金属薄膜の形成方法及び金属薄膜
JP2009068035A (ja) * 2007-09-11 2009-04-02 Dowa Electronics Materials Co Ltd 低温焼結性銀微粉および銀塗料ならびにそれらの製造法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012119132A (ja) * 2010-11-30 2012-06-21 Harima Chemicals Inc 導電性金属ペースト
CN106128543A (zh) * 2016-07-18 2016-11-16 贵州大学 一种防沉降效果好的导电银浆及其制备方法
CN106128543B (zh) * 2016-07-18 2021-02-02 贵州大学 一种防沉降效果好的导电银浆及其制备方法
CN116532653A (zh) * 2023-07-07 2023-08-04 长春黄金研究院有限公司 Slm铺粉打印成型用银粉及其制备方法
CN116532653B (zh) * 2023-07-07 2023-09-05 长春黄金研究院有限公司 Slm铺粉打印成型用银粉及其制备方法

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