WO2012176831A1 - Poussière d'argent et procédé de fabrication correspondant - Google Patents

Poussière d'argent et procédé de fabrication correspondant Download PDF

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Publication number
WO2012176831A1
WO2012176831A1 PCT/JP2012/065842 JP2012065842W WO2012176831A1 WO 2012176831 A1 WO2012176831 A1 WO 2012176831A1 JP 2012065842 W JP2012065842 W JP 2012065842W WO 2012176831 A1 WO2012176831 A1 WO 2012176831A1
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WIPO (PCT)
Prior art keywords
silver
silver powder
paste
particle size
size distribution
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PCT/JP2012/065842
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English (en)
Japanese (ja)
Inventor
美香 岡田
知倫 二瓶
川上　裕二
俊昭 寺尾
Original Assignee
住友金属鉱山株式会社
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Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to KR1020137005229A priority Critical patent/KR101883709B1/ko
Priority to CN201280002703.7A priority patent/CN103079729B/zh
Priority to JP2012548248A priority patent/JP5278627B2/ja
Publication of WO2012176831A1 publication Critical patent/WO2012176831A1/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
    • 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
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F1/12—Metallic powder containing non-metallic particles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form

Definitions

  • the present invention relates to silver powder and a method for producing the same, and more particularly to a silver powder that is a main component of a silver paste used for forming a wiring layer or an electrode of an electronic device and a method for producing the same.
  • This application claims priority on the basis of Japanese Patent Application No. 2011-137622 filed in Japan on June 21, 2011. By referring to these applications, the present application Incorporated.
  • silver pastes such as resin-type silver paste and fired-type silver paste are frequently used. That is, after applying or printing these silver pastes on various substrates, a conductive film to be a wiring layer, an electrode, or the like can be formed by heat curing or heat baking.
  • a resin-type silver paste is made of silver powder, resin, curing agent, solvent, etc., printed on a conductor circuit pattern or terminal, and cured by heating at 100 ° C. to 200 ° C. to form a conductive film.
  • the fired silver paste is made of silver powder, glass, solvent, etc., printed on a conductor circuit pattern or terminal, and heated and fired at 600 ° C. to 800 ° C. to form a conductive film to form wirings and electrodes.
  • electrically connected current paths are formed by continuous silver powder.
  • the silver powder used in the silver paste has a particle size of 0.1 ⁇ m to several ⁇ m, and the particle size of the silver powder used varies depending on the thickness of the wiring to be formed and the thickness of the electrode. Further, by uniformly dispersing silver powder in the paste, it is possible to form a wiring having a uniform thickness or an electrode having a uniform thickness.
  • silver powder is preliminarily kneaded with other components such as a solvent, and then kneaded while applying a predetermined pressure with a three-roll mill or the like.
  • a predetermined pressure with a three-roll mill or the like.
  • silver powder is required to be efficiently kneaded with a roll, that is, to have good kneading properties.
  • the silver powder has a viscosity that can be easily kneaded at the time of preparing the paste, has good dispersibility of the silver halide powder in the solvent, and does not generate coarse powder such as flakes.
  • Patent Document 1 discloses a conductive adhesive in which silver powder as a conductive powder is blended in a conductive adhesive in an amount of 30 to 98% by weight in a binder resin, and the primary particles are made from a flat silver powder.
  • a conductive adhesive containing 30% by weight or more of silver powder having a lump aggregate structure with a tap density of 1.5 g / cm 3 or less is proposed.
  • agglomerated silver powder can be easily deagglomerated into primary particles, so it is highly dispersible and can exhibit stable electrical conductivity without causing deterioration in conductivity due to poor dispersion of silver powder. It is said that a conductive adhesive that gives a cured product excellent in not only conductivity but also adhesiveness, heat resistance, moisture resistance, workability, thermal conductivity and the like is obtained.
  • Patent Document 2 a nonionic surfactant having an HLB value of 6 to 17 is added to a solution containing a silver complex, and when a reducing agent is added thereto, aggregation of reduced silver particles is prevented. Therefore, by setting the addition rate of the reducing agent-containing aqueous solution to 1 equivalent / min or more quickly, the tap density is 2.5 g / cm 3 or more, the average particle diameter is 1 to 6 ⁇ m, and the specific surface area is 5 m 2 / g or less. There has been proposed a method for producing a silver powder to obtain a silver powder having excellent dispersibility.
  • this proposal is to obtain a dispersed silver powder by preventing aggregation of the obtained silver powder, and does not take into consideration any dispersibility in the solvent and the generation of flakes during paste preparation.
  • conductive particles having an average particle diameter of 0.5 to 20 ⁇ m, a specific surface area of 0.07 to 1.7 m 2 / g, and having at least two or more peaks in the particle size distribution or
  • a conductive paste comprising conductive particles formed by mixing at least two conductive particles having different particle size distributions and a binder mainly composed of a thermosetting resin. According to this proposal, a conductive paste with good fluidity and dispersibility can be obtained, the filling property to the via and the contact between the conductive particles inside the via hole are stable, and the high-quality via-hole conductor is stable with little variation. Can be formed.
  • an object of the present invention is to provide a silver powder that has an appropriate viscosity range at the time of paste production, is easy to knead, and suppresses generation of flakes, and a method for producing the same.
  • the present inventor has an aggregate of silver particles and has a particle size distribution having two or more peaks or peaks and shoulders.
  • the present inventors have found that it has a viscosity range, can be easily kneaded at the time of paste production, can suppress a change in viscosity, and can improve kneadability.
  • the silver powder according to the present invention has a volume-based particle size distribution of 0.3 ⁇ m to 14.0 ⁇ m in a paste obtained by kneading at least silver powder, terpineol, and resin with a centrifugal force of 420 G using a self-revolving stirrer.
  • P 1 > P 2 P 1 is in the range of 2.0 ⁇ m to 5.0 ⁇ m, and P 2 is 0.5 ⁇ m to 3 It is characterized by being in the range of 0.0 ⁇ m.
  • the manufacturing method of the silver powder which concerns on this invention obtains silver powder through each process of washing
  • a method for producing silver powder wherein 1.0 to 15.0% by mass of a water-soluble polymer is added to the reducing agent solution for reduction, and the dried silver particles are rotated at a peripheral speed using a rolling stirrer. The crushing process is performed at 5 to 40 m / sec.
  • the silver powder of the present invention it is possible to control the aggregation state of silver particles, to have an appropriate viscosity range at the time of paste production, to prevent kneading by suppressing the viscosity change, and to suppress the occurrence of flakes. Thus, kneadability and printability can be improved.
  • the silver powder according to the present invention not only the dispersibility in the paste is excellent, but also the wiring layer and the electrode formed by the resin-type silver paste and the fired-type silver paste using the paste are uniform and It has excellent electrical conductivity, and has extremely high industrial value as a silver paste used for forming wiring layers and electrodes of electronic devices.
  • FIG. 1 is a diagram schematically showing the form of silver particles.
  • FIG. 2 is a diagram showing a volume-integrated particle size distribution of silver powder in Example 1.
  • FIG. 3 is a diagram showing a volume-integrated particle size distribution of silver powder in the evaluation paste in Example 1.
  • FIG. 4 is a diagram showing a volume-integrated particle size distribution of silver powder in Example 2.
  • FIG. 5 is a diagram showing a volume-integrated particle size distribution of silver powder in the evaluation paste in Example 2.
  • FIG. 6 is a diagram showing a volume-integrated particle size distribution of silver powder in Example 3.
  • FIG. 7 is a diagram showing a volume-integrated particle size distribution of silver powder in the evaluation paste in Example 3.
  • FIG. 8 is a diagram showing a volume-integrated particle size distribution of silver powder in Comparative Example 1.
  • FIG. 9 is a diagram showing a volume-integrated particle size distribution of silver powder in the evaluation paste in Comparative Example 1.
  • FIG. 10 is a diagram showing a volume-integrated particle size
  • the name for the silver particle form is defined as shown in FIG. That is, as shown in FIG. 1 (A), silver particles are judged from the apparent geometric form, and those considered as unit particles are called primary particles. Further, as shown in FIG. 1B, particles in which two to three or more primary particles are connected by necking are called secondary particles. Further, as shown in FIG. 1C, an aggregate of primary particles and secondary particles is called an aggregate.
  • the primary particles, secondary particles, and aggregates may be collectively referred to as silver particles.
  • the silver powder according to this embodiment has a volume-based particle size distribution of 0.3 ⁇ m in a paste obtained by kneading at least the silver powder, tarpioneel, and resin with a centrifugal force of 420 G using a self-revolving stirrer.
  • P 1 > P 2 P 1 > P 2
  • P 1 is in the range of 2.0 ⁇ m to 5.0 ⁇ m. 2 exists in the range of 0.5 ⁇ m to 3.0 ⁇ m.
  • the present inventor has found that it is important that the silver powder has a specific particle size distribution at least in the initial stage of the paste production in order to have an appropriate viscosity and good kneadability in the silver powder paste. That is, as the presence state of silver powder in the paste at the initial stage of paste production, silver powder composed of primary particles, secondary particles in which a plurality of the primary particles are connected, and aggregates (hereinafter referred to as aggregates) in which they are aggregated are: The silver powder and the organic solvent in the paste are difficult to separate, the formation of coarse aggregates excessively aggregated in the paste is suppressed, the viscosity of the paste is easily adjusted, and the kneadability is improved.
  • the paste solvent component penetrates into the gaps between the aggregates during paste production, and the paste The apparent amount of solvent that flows freely through the inside is reduced. Then, since the viscosity of the paste becomes high, it becomes difficult to mix and blend silver powder and other components such as a solvent. At this time, for example, when kneading is performed by a three-roll mill generally used in the manufacture of paste, the agglomerated lump in the paste enters the roll as it is, and as a result, coarse powder of mm order such as flakes is formed. I found out.
  • the amount of the solvent component that freely flows in the paste is appropriate at the time of manufacturing the paste, so that it has an appropriate viscosity range Therefore, it was confirmed that kneading of silver powder with other constituents such as a solvent and kneading with a three-roll mill were facilitated and coarse flakes were not generated.
  • the above-mentioned aggregate has, for example, a bunch of grapes and is approximately 5 to 10 ⁇ m in size.
  • Silver powder in which particles containing such aggregates are mixed is a general paste production stage in which paste is mixed, that is, a stage in which silver powder and a solvent component are mixed, for example, preliminary kneading with a kneader or the like and main kneading with a three-roll mill or the like.
  • the solvent component wraps around each particle constituting the silver powder and has an appropriate viscosity (hereinafter, distinguished from the finally obtained paste) Therefore, it may be called a kneaded product).
  • the viscosity of the paste is too high or too low, good paste printability cannot be obtained, but silver powder in which aggregates, primary particles and secondary particles are mixed, that is, two or more peaks as described above Alternatively, it can be adjusted to an appropriate viscosity by being a silver powder having a particle size distribution having a peak and a shoulder. And the paste which has the outstanding printability can be obtained by using such silver powder.
  • the particle size distribution of the silver powder described above is in the paste prepared as an evaluation test, but in order to further improve the kneadability of the silver powder, the particle size distribution in the state of the silver powder before the paste preparation is also described above. It is preferable to have a form similar to that of the particle size distribution in the paste after kneading.
  • a paste prepared as an evaluation test is, for example, a vehicle in which the weight ratio of epoxy resin (viscosity 2 to 6 Pa ⁇ s, for example, JER819 manufactured by Mitsubishi Chemical Corporation) and terpineol is 1: 7.
  • the silver powder can be produced by kneading the vehicle with 8.0% by mass and 92.0% by mass of silver powder with respect to the paste, and using a self-revolving stirrer with a centrifugal force of 420 G.
  • the silver powder in the paste has a volume-based particle size distribution in the range of 0.3 ⁇ m to 14.0 ⁇ m.
  • the volume-based particle size distribution can be obtained, for example, by measuring using a laser diffraction scattering method or the like.
  • the range of the volume-based particle size distribution means that 95% or more of silver particles are included in the particle size range by volume accumulation, but it is preferable that all the silver particles are included in the above range.
  • the cumulative volume is less than 95%, and when the volume-based particle size distribution is present up to an area of less than 0.3 ⁇ m, fine particles are present in the silver powder, and the silver particles are contained in the paste. Dispersibility is reduced, resulting in a non-uniform paste.
  • the particle size distribution is present up to a region exceeding 14.0 ⁇ m, coarse particles exist in the silver powder, and the conductive film becomes non-uniform when fine wiring or electrodes are formed.
  • the silver powder in the paste has P 1 > P 2 in the relationship between the particle sizes of P 1 and P 2 , P 1 is in the range of 2.0 ⁇ m to 5.0 ⁇ m, and P 2 is in the range of 0.5 ⁇ m to 3 ⁇ m. It exists in the range of 0.0 ⁇ m.
  • the peak or shoulder P 1 (hereinafter sometimes simply referred to as P 1 ) is a secondary particle formed by connecting primary particles, and a plurality of primary particles are further connected to the secondary particles.
  • the peak or shoulder P 2 (hereinafter sometimes simply referred to as P 2 ) is considered to be derived from the primary particles or the secondary particles.
  • P 1 and P 2 When a plurality of peaks or shoulders appear in the particle size range where P 1 and P 2 exist, the highest peaks may be P 1 and P 2 , respectively.
  • P 1 or P 2 appears as a shoulder, the position where the increase rate of the differential value of the change rate of the appearance frequency indicating the particle size distribution in the vicinity of P 1 or P 2 is the lowest as P 1 or P 2 do it.
  • P 1 and P 2 can also be specified by performing peak separation using, for example, peak separation software, Origin 8.5 (manufactured by Lightstone).
  • the relationship between the heights (appearance frequencies) of P 1 and P 2 is not particularly limited, but it is more preferable that P 2 has a height of 25% or more of P 1 .
  • P 2 is less than 25% of P 1 , the above-described aggregates are large, and the solvent component that enters the voids of the aggregates increases, which may make it difficult to form a paste.
  • P 2 is preferably 150% or less of P 1 in height.
  • P 2 is more than 150% of P 1, will exist many fine particles in the silver powder, the dispersibility of the silver particles may become uneven paste decreases in the paste. Also, flakes are likely to occur.
  • the height of the relationship between P 2 and P 1 is within the range described above, with silver powder has excellent kneading properties, can be those obtained paste also have good printability, low Resistance wiring, electrodes, and the like can be formed.
  • the silver powder according to the present embodiment is primary in a paste obtained by kneading at least silver powder, tarpioneel and resin with a centrifugal force of 420 G using a self-revolving stirrer. It has a particle size distribution having two or more peaks or peaks and shoulders derived from particles and aggregates. According to the silver powder having such a particle size distribution, the formation of coarse aggregates excessively aggregated in the paste is suppressed, the viscosity of the paste is easily adjusted, and the occurrence of flakes during paste production is suppressed, which is excellent. A paste having printability can be produced.
  • the silver powder according to the present embodiment not only is it excellent in dispersibility in the paste, but the wiring layer and the electrode formed by the resin-type silver paste and the fired-type silver paste using the same are uniform. It is excellent in properties and conductivity.
  • the particle diameter D 50 of the point where the cumulative curve becomes 50% is 2.0 .mu.m ⁇ 5.0 .mu.m
  • D 84 represents the particle diameter of the point where the cumulative volume curve becomes 84%
  • D 16 represents the particle diameter of the point where the cumulative volume curve becomes 16%.
  • the silver powder according to the present embodiment preferably has two or more peaks or peaks and shoulders as described above, and has a broad particle size distribution.
  • the particle diameter D 50 and the standard deviation SD shows the degree of broad particle size distribution absolute value.
  • the particle diameter D 50 is less than 2.0 ⁇ m, a sufficient amount of aggregates is not formed, and the paste viscosity is lowered, so that the shearing force during kneading is reduced and the aggregates are coarsened by reaggregation in the paste. Agglomerates are likely to be generated, and flake generation may not be sufficiently suppressed.
  • D 50 exceeds 5.0 ⁇ m, a large amount of coarse aggregates are present, the apparent amount of solvent is reduced, and paste formation may be difficult.
  • coarse silver particles remain after pasting, and the conductive film may be non-uniform when fine wiring or electrodes are formed.
  • the conductive film may be non-uniform.
  • the silver powder in the paste described above has a variation coefficient CV of the volume-based particle size distribution represented by the following formula (2) of 40 to 70. preferable.
  • CV (SD / D 50 ) ⁇ 100 (2)
  • the coefficient of variation CV indicates the degree of broadness with respect to the particle size. If the coefficient of variation CV is less than 40, the formation of aggregates is not sufficient, and reaggregation in the paste tends to generate coarse aggregates. On the other hand, when the coefficient of variation CV exceeds 70, fine silver particles and coarse agglomerates are relatively increased, and the apparent amount of solvent is reduced. When formed, the conductive film may be non-uniform.
  • the silver powder according to the present embodiment preferably has the following relationship when viewed in terms of the particle content in a predetermined particle size range. That is, the silver powder in the paste described above preferably contains 40 to 80% of particles in a particle size range of 1.5 ⁇ m to 5.0 ⁇ m of the volume-based particle size distribution.
  • P 1 is a secondary particle formed by connecting primary particles, and an aggregate formed by connecting a plurality of primary particles to the secondary particles.
  • P 1 exists in the range of 2.0 ⁇ m to 5.0 ⁇ m. Therefore, the content of particles present in the particle size range of 1.5 ⁇ m to 5.0 ⁇ m indicates the formation ratio of moderately sized aggregates.
  • the particle content is less than 40%, the formation of aggregates is not sufficient.
  • the particle content exceeds 80%, it indicates that coarse aggregates are excessively present, and flakes in which the aggregates are crushed when kneaded by a three-roll mill are easily generated. Become.
  • the silver powder according to the present embodiment is, as a test evaluation, in a kneaded material obtained by kneading at least silver powder, tarpioneel, and resin with a centrifugal force of 420 G using a self-revolving stirrer.
  • the volume-based particle size distribution of the silver powder is in the range of 0.3 ⁇ m to 14.0 ⁇ m, and in the relationship between the particle sizes of the peak or shoulder P 1 and the peak or shoulder P 2 , P 1 > P 2 and P 1 is P 2 exists in the range of 2.0 ⁇ m to 5.0 ⁇ m, and P 2 exists in the range of 0.5 ⁇ m to 3.0 ⁇ m.
  • the silver powder having such a particle size distribution when the silver paste is produced using this silver powder, it becomes difficult to separate the silver powder from the organic solvent in the paste, and the coarse agglomeration excessively aggregated in the paste. Generation of lumps is suppressed, and generation of flakes is suppressed. Moreover, the viscosity change during paste manufacture is small, and the viscosity adjustment of the paste becomes easy.
  • the silver powder according to the present embodiment is not limited to the above-described silver paste for evaluation tests, but is applied to all commonly used silver pastes.
  • the viscosity of the paste at a shear rate of 4.0 (1 / sec) is 50 to 150 Pa ⁇ s. Can do.
  • the viscosity at a shear rate of 20.0 (1 / sec) can be 20 to 50 Pa ⁇ s.
  • Silver paste with a paste viscosity lower than the above-mentioned range may cause bleeding or dripping in the wiring formed by paste printing, and the shape may not be maintained.
  • the viscosity of the paste is higher than the above-described range, it may be difficult to print the paste.
  • the silver powder which concerns on this Embodiment which has the outstanding paste characteristic as mentioned above formation of the coarse aggregate by excessive aggregation can be effectively suppressed also in the silver paste generally used. It can be said. That is, in the silver powder in which excessive agglomeration occurs in the paste and coarse agglomerates are formed, flakes in which the agglomerates are crushed are generated. In addition, when the silver powder has excessive aggregates, the viscosity at the time of paste production becomes too large, and kneading becomes difficult, resulting in a problem in paste production. In addition, the manufactured paste has poor paste characteristics such as printability. Since the silver powder according to the present embodiment can produce the paste having an appropriate viscosity as described above, it effectively suppresses the occurrence of defects due to the formation of coarse aggregates by suppressing excessive aggregation. It can be said that it can be done.
  • a well-known method can be used.
  • a vehicle to be used a solution in which various celluloses, phenol resins, acrylic resins, etc. are dissolved in alcohol-based, ether-based, ester-based solvents or the like can be used.
  • the silver powder production method uses, for example, silver chloride or silver nitrate as a starting material. Basically, silver obtained by dissolving a starting material such as silver chloride with a complexing agent is used. A solution containing the complex and a reducing agent solution are mixed, the silver complex is reduced to precipitate silver particles, a silver particle slurry is obtained, and silver powder is obtained through the washing, drying, and crushing steps.
  • 1.0 to 15.0% by mass more preferably 1.0 to 10.0, based on silver with respect to the reducing agent solution for reducing the silver complex.
  • the water-soluble polymer is added in an amount of mass%, particularly preferably more than 3.0 mass% and 10.0 mass% or less.
  • Aggregation state of silver particles can be controlled by adding a functional polymer to the reducing agent solution to reduce the silver complex and crushing the resulting silver particle slurry with weak agitation after drying.
  • Silver powder can be obtained by the same method when starting materials other than silver chloride.
  • the above-described nitrite gas recovery device and the treatment device for nitrate nitrogen in wastewater are used. Necessary.
  • a silver chloride starting material is dissolved using a complexing agent to prepare a solution containing a silver complex.
  • a complexing agent it does not specifically limit as a complexing agent, It is preferable to use the ammonia water which is easy to form a complex with silver chloride and does not contain the component which remains as an impurity. Moreover, it is preferable to use a high purity silver chloride.
  • a slurry such as silver chloride may be prepared and ammonia water may be added.
  • ammonia water may be added in order to increase the complex concentration and increase the productivity. It is preferable to add and dissolve silver chloride in ammonia water.
  • the aqueous ammonia used for the dissolution may be a normal one used industrially, but preferably has a purity as high as possible in order to prevent contamination with impurities.
  • a reducing agent solution to be mixed with the silver complex solution is prepared.
  • the reducing agent it is preferable to use a strong reducing power such as ascorbic acid, hydrazine, formalin and the like.
  • Ascorbic acid is particularly preferred because the crystal grains in the silver particles are easy to grow. Since hydrazine or formalin has a reducing power stronger than ascorbic acid, crystals in silver particles can be reduced.
  • it in order to control the uniformity of reaction or reaction rate, it can also be used as an aqueous solution whose concentration is adjusted by dissolving or diluting a reducing agent with pure water or the like.
  • the reducing agent solution is 1.0 to 15.0 mass%, more preferably 1.0 to 10.0 mass%, based on silver. Particularly preferably, more than 3.0% by mass and 10.0% by mass or less of the water-soluble polymer is added.
  • silver particles (primary particles) produced by reduction with a reducing agent solution have an active surface, and are easily connected to other silver particles to form secondary particles. Further, the secondary particles aggregate to form an aggregate.
  • an anti-aggregation agent having a high anti-aggregation effect for example, a surfactant or a fatty acid is used, secondary particles and aggregates are not sufficiently formed, primary particles increase, and appropriate aggregates are not formed.
  • the formation of secondary particles and aggregates becomes excessive, resulting in a silver powder containing excessively aggregated coarse aggregates.
  • the water-soluble polymer has an appropriate anti-aggregation effect, so it is possible to easily control the formation of secondary particles and aggregates by adjusting the addition amount, and the silver complex containing after the addition of the reducing agent solution Aggregates of an appropriate size can be formed in the solution.
  • the water-soluble polymer to be added is not particularly limited, but is preferably at least one of polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin and the like, and at least one of polyethylene glycol, polyvinyl alcohol, and polyvinyl pyrrolidone. It is more preferable that According to these water-soluble polymers, in particular, excessive aggregation is prevented and aggregation of the grown nuclei is insufficient to prevent the silver particles (primary particles) from becoming fine. Silver powder having aggregates can be easily formed.
  • the mechanism by which silver particles are connected to a predetermined size and aggregates are formed by adding a water-soluble polymer is as follows. That is, by adding a water-soluble polymer, the water-soluble polymer is adsorbed on the surface of silver particles. At this time, when almost all of the surface of the silver particles is covered with the water-soluble polymer, the silver particles will be present alone, but by adding the water-soluble polymer at a predetermined ratio to the silver, It is considered that a surface where no partly water-soluble polymer exists remains, and silver particles are connected to each other through the surface to form an aggregate.
  • the amount of water-soluble polymer added is 1.0 to 15.0 mass% with respect to silver.
  • the addition amount of the water-soluble polymer is less than 1.0% by mass with respect to silver, the dispersibility in the silver particle slurry is deteriorated, the silver powder is excessively aggregated, and many coarse aggregates Will be generated.
  • the addition amount with respect to silver is more than 15.0% by mass, almost all silver particle surfaces are covered with the water-soluble polymer, the silver particles cannot be connected to each other, and the aggregate It cannot be formed. As a result, silver powder composed of primary particles is formed, and even in this case, flakes are generated during paste production.
  • the silver particles are appropriately connected through the surface where no water-soluble polymer exists, and the structure Stable aggregates can be formed, the dispersibility during paste production can be improved, and the occurrence of flakes can be effectively suppressed.
  • this water-soluble polymer is added to the reducing agent solution.
  • the water-soluble polymer By adding the water-soluble polymer to the reducing agent solution, the water-soluble polymer is present at the nucleation or growth stage, and the water-soluble polymer is quickly adsorbed on the surface of the generated nucleus or silver particle.
  • the aggregation of silver particles can be controlled efficiently. Therefore, in addition to the adjustment of the concentration of the water-soluble polymer described above, by adding the water-soluble polymer to the reducing agent solution in advance, the formation of coarse aggregates due to excessive aggregation of silver particles is suppressed.
  • the silver particles can be more appropriately connected to a predetermined size to form a highly stable aggregate.
  • the water-soluble polymer can be added to the silver complex-containing solution, but in this case, it is difficult to supply the water-soluble polymer to the site of nucleation or growth. There is a possibility that the water-soluble polymer cannot be adsorbed to the surface of the particles appropriately. Therefore, when adding to a silver complex containing solution previously, it is preferable to make the addition amount of a water-soluble polymer into the quantity exceeding 3.0 mass% with respect to silver. Accordingly, when the water-soluble polymer can be added to any of the reducing agent solution and the silver complex-containing solution, the amount is more than 3.0% by mass and not more than 10.0% by mass with respect to silver. It is particularly preferable to do this.
  • an antifoaming agent can be added to the silver complex-containing solution or the reducing agent mixed solution.
  • the antifoaming agent is not particularly limited, and may be one usually used during reduction. However, in order not to inhibit the reduction reaction, the addition amount of the antifoaming agent is preferably set to a minimum level at which an antifoaming effect can be obtained.
  • the water used when preparing a silver complex containing solution and a reducing agent solution in order to prevent mixing of an impurity, it is preferable to use the water from which the impurity was removed, and it is especially preferable to use a pure water.
  • the silver complex-containing solution prepared as described above and a reducing agent solution are mixed, and the silver complex is reduced to precipitate silver particles.
  • This reduction reaction may be performed by a batch method or a continuous reduction method such as a tube reactor method or an overflow method.
  • a tube reactor method in which the grain growth time can be easily controlled.
  • the particle size of the silver particles can be controlled by the mixing rate of the silver complex-containing solution and the reducing agent solution and the reduction rate of the silver complex, and can be easily controlled to the target particle size.
  • the washing step may be performed after the surface treatment step on the silver particles. preferable.
  • the washing method is not particularly limited, but the silver particles solid-liquid separated from the slurry by a filter press or the like are put into the washing liquid, stirred using an agitator or an ultrasonic washing machine, and then again solid-liquid.
  • a method of separating and collecting silver particles is generally used. Further, in order to sufficiently remove the surface adsorbate, it is preferable to repeat the operations consisting of charging into the cleaning liquid, stirring cleaning, and solid-liquid separation several times.
  • the cleaning liquid water may be used, but an alkaline aqueous solution may be used in order to efficiently remove chlorine. Although it does not specifically limit as an alkaline solution, It is preferable to use the sodium hydroxide aqueous solution with few remaining impurities and cheap. In the case of using a sodium hydroxide aqueous solution as the cleaning liquid, it is desirable to further wash the silver particles or the slurry thereof with water in order to remove sodium after washing with the sodium hydroxide aqueous solution.
  • the concentration of the sodium hydroxide aqueous solution is preferably 0.01 to 1.00 mol / l.
  • concentration is less than 0.01 mol / l, the cleaning effect is insufficient.
  • concentration exceeds 1.00 mol / l, sodium may remain in silver particles more than allowable.
  • the water used for the cleaning liquid is preferably water that does not contain an impurity element harmful to silver particles, and pure water is particularly preferable.
  • the surface of the formed aggregate is aggregated before the aggregate formed by reduction in the silver complex-containing solution further aggregates to form a coarse aggregate. It is more preferable to perform surface treatment with a treatment agent having a high prevention effect to prevent excessive aggregation. That is, after the above-described aggregates are formed and before excessive aggregation proceeds, the silver particles are treated with a surfactant, or more preferably a surface treatment on silver particles treated with a surfactant and a dispersant. Perform the process. Thereby, it can prevent that excessive aggregation arises, maintains the structural stability of the desired aggregate, and can suppress effectively that a coarse aggregate is formed.
  • the effect of surface treatment can be obtained at any stage before the silver particles are dried. For example, it can be performed after the reduction process, before the above-described cleaning process, simultaneously with the cleaning process, or after the cleaning process.
  • a water-soluble polymer is added to the reducing agent solution at a predetermined ratio with respect to silver to reduce the amount, and the water-soluble polymer is appropriately added to the surface of the silver particles.
  • Aggregates in which silver particles are linked to a predetermined size are formed by adsorption.
  • the water-soluble polymer adsorbed on the surface of the silver particles is relatively easily washed by the washing treatment, the water-soluble polymer on the surface of the silver particles is removed when the washing step is performed prior to the surface treatment.
  • the silver particles are excessively aggregated with each other, and a coarse aggregate larger than the formed aggregate may be formed. Further, when such a coarse aggregate is formed, uniform surface treatment on the surface of the silver particles becomes difficult.
  • the silver particles including the desired aggregate can be efficiently subjected to surface treatment, and a silver powder having no coarse aggregate and good dispersibility can be produced.
  • the surface treatment after the reduction treatment and before the washing step is preferably performed after solid-liquid separation of the slurry containing silver particles with a filter press or the like after the reduction step.
  • this surface treatment step it is more preferable to treat the surface with both a surfactant and a dispersant.
  • a strong surface treatment layer can be formed on the surface of the silver particles due to the interaction. It is effective to maintain the aggregate.
  • the silver particles are put into water added with a surfactant and a dispersant and stirred, or put into water added with a surfactant. After stirring, a dispersant may be further added and stirred.
  • a surfactant and a dispersing agent should be added simultaneously to a washing
  • the silver particles are added to the water or the cleaning liquid to which the surfactant is added and stirred, and then the dispersant is further added and stirred. It is preferable.
  • a surfactant may be added to a reducing agent solution, and a dispersing agent may be added to a slurry of silver particles obtained by mixing a silver complex-containing solution and a reducing agent solution, followed by stirring.
  • a surface active agent is present in the nucleation or growth stage, and the surface is rapidly adsorbed on the surface of the generated nucleus or silver particle, and then a dispersant is adsorbed to provide a stable and uniform surface treatment. be able to.
  • the surfactant is not particularly limited, but a cationic surfactant is preferably used. Since the cationic surfactant is ionized into positive ions without being affected by pH, for example, an effect of improving the adsorptivity to silver powder using silver chloride as a starting material can be obtained.
  • the cationic surfactant is not particularly limited, but is an alkyl monoamine salt type represented by a monoalkylamine salt, an alkyl diamine represented by N-alkyl (C14 to C18) propylene diamine dioleate.
  • Salt type alkyltrimethylammonium salt type represented by alkyltrimethylammonium chloride, alkyldimethylbenzylammonium salt type represented by alkyldimethylbenzylammonium chloride, quaternary ammonium salt type represented by alkyldipolyoxyethylenemethylammonium chloride , Alkylpyridinium salt type, tertiary amine type typified by dimethylstearylamine, polyoxyethylene alkylamine typified by polyoxypropylene / polyoxyethylene alkylamine N, N ′, N′-tris (2-hydroxyethyl) -N-alkyl (C14-18) 1,3-diaminopropane is preferably at least one selected from oxy
  • the surfactant preferably has at least one alkyl group having a C4 to C36 carbon number represented by methyl group, butyl group, cetyl group, stearyl group, beef tallow, hard beef tallow, and plant stearyl.
  • the alkyl group is preferably a group to which at least one selected from polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene, polyacrylic acid, and polycarboxylic acid is added. Since these alkyl groups are strongly adsorbed with a fatty acid used as a dispersant described later, the fatty acid can be strongly adsorbed when the dispersant is adsorbed to the silver particles via the surfactant.
  • the addition amount of the surfactant is preferably in the range of 0.002 to 1.000% by mass with respect to the silver particles. Since almost the entire amount of the surfactant is adsorbed on the silver particles, the addition amount of the surfactant and the adsorption amount are almost equal. When the addition amount of the surfactant is less than 0.002% by mass, the effect of suppressing aggregation of silver particles or improving the adsorptivity of the dispersant may not be obtained. On the other hand, when the addition amount exceeds 1.000% by mass, the conductivity of the wiring layer or electrode formed using the silver paste is not preferable.
  • the dispersant for example, protective colloids such as fatty acids, organometallics, and gelatins can be used.
  • fatty acids or salts thereof in view of adsorbability with a surfactant without the possibility of contamination with impurities, it is preferable to use fatty acids or salts thereof. .
  • the fatty acid used as the dispersant is not particularly limited, but is preferably at least one selected from stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, and linolenic acid. This is because these fatty acids have a relatively low boiling point and thus have little adverse effect on the wiring layer and electrodes formed using the silver paste.
  • the addition amount of the dispersant is preferably in the range of 0.01 to 3.00% by mass with respect to the silver particles.
  • the amount of adsorption on the silver particles varies depending on the type of the dispersant, but when the added amount is less than 0.01% by mass, the amount of the dispersant is sufficient to sufficiently suppress the aggregation of the silver particles or improve the adsorptivity of the dispersant. May not be adsorbed by silver powder.
  • the added amount of the dispersant exceeds 3.00% by mass, the dispersant adsorbed on the silver particles increases, and the conductivity of the wiring layer and the electrode formed using the silver paste cannot be sufficiently obtained. Sometimes.
  • cleaning and surface treatment may be used normally,
  • the reaction tank with a stirrer etc. can be used.
  • the apparatus used for solid-liquid separation may also be a normally used apparatus, for example, a centrifuge, a suction filter, a filter press, etc. can be used.
  • the silver particles that have been washed and surface-treated are dried by evaporating moisture in the drying step.
  • a drying method for example, silver powder recovered after completion of cleaning and surface treatment is placed on a stainless steel pad and heated at a temperature of 40 to 80 ° C. using a commercially available drying apparatus such as an atmospheric oven or a vacuum dryer. Good.
  • the manufacturing method of the silver powder which concerns on this Embodiment controls the aggregation of silver particle by a reduction process
  • it is weak crushing conditions with respect to the silver powder after drying which stabilized the degree of aggregation by surface treatment.
  • the crushing process is performed under control. Even if the silver powder after the surface treatment described above is further aggregated between the aggregates by subsequent drying or the like, since the binding force is weak, it is easily separated into aggregates of a predetermined size at the time of preparing the paste. However, in order to stabilize the paste, it is preferable to crush and classify.
  • the silver particles after drying are stirred at a peripheral speed of 5 to 40 m / s of a stirring blade, for example, using a device having a weak crushing force such as a vacuum reduced pressure atmosphere rolling stirrer. While disintegrating.
  • a device having a weak crushing force such as a vacuum reduced pressure atmosphere rolling stirrer.
  • the pulverization energy is weak, so that a large amount of aggregate remains.
  • the peripheral speed is higher than 40 m / s, the pulverization energy becomes strong and the aggregate becomes too small. Even in this case, the silver powder having the above-mentioned particle size distribution cannot be obtained.
  • a silver powder having a particle size equal to or smaller than a desired particle size can be obtained by performing a classification treatment.
  • the classifying apparatus used in the classification process is not particularly limited, and an airflow classifier, a sieve, or the like can be used.
  • Example 1 A silver complex solution was prepared by adding, while stirring, 36 L of 25% aqueous ammonia and 2492 g of silver chloride (manufactured by Sumitomo Metal Mining Co., Ltd.) maintained in a 38 ° C. warm bath at a liquid temperature of 36 ° C.
  • Antifoaming agent manufactured by Adeka Co., Ltd., Adecanol LG-126
  • the prepared silver complex solution and the reducing agent solution are fed into the basket with a silver complex solution of 2.7 L / min and a reducing agent solution of 0.9 L / min using a MONO pump (manufactured by Hyojin Equipment Co., Ltd.).
  • the silver complex was reduced.
  • the reduction rate at this time is 127 g / min in terms of silver.
  • the ratio of the reducing agent supply rate to the silver supply rate was 1.4. Note that a PVC pipe having an inner diameter of 25 mm and a length of 725 mm was used for the rod.
  • the slurry containing silver particles obtained by reduction of the silver complex was received in a receiving tank with stirring.
  • the silver particle slurry obtained by reduction is subjected to solid-liquid separation, and the recovered silver particles before drying and 0.75 g of a polyoxyethylene-added quaternary ammonium salt which is a commercially available cationic surfactant as a surface treatment agent.
  • a polyoxyethylene-added quaternary ammonium salt which is a commercially available cationic surfactant as a surface treatment agent.
  • a polyoxyethylene-added quaternary ammonium salt which is a commercially available cationic surfactant as a surface treatment agent.
  • 14.08 g of stearic acid emulsion as a dispersant manufactured by Chukyo Yushi Co., Ltd., cellosol 920, and 0.08% based on silver particles.
  • 76 mass% was put into 15.4 L of pure water and stirred for 60 minutes for surface treatment.
  • the silver particle slurry was filtered using a filter press, and the silver particles were solid-liquid separated.
  • the silver particles are put into 15.4 L of a 0.05 mol / L aqueous sodium hydroxide (NaOH) solution, stirred for 15 minutes, washed, and then filtered with a filter press. The silver particles were recovered.
  • NaOH sodium hydroxide
  • the collected silver particles were put into 23 L of pure water maintained at 40 ° C., stirred and filtered, then the silver particles were transferred to a stainless steel pad and dried at 60 ° C. for 10 hours in a vacuum dryer. 1.75 kg of dried silver powder was taken and charged into a 5 L Henschel mixer (manufactured by Nippon Coke Industries, Ltd., FM5C). In a Henschel mixer, silver powder was obtained by reducing the pressure with a vacuum pump while stirring at 2000 rpm for 30 minutes (the peripheral speed of the stirring blade was 18.2 m / s).
  • the particle size distribution of the obtained silver powder was measured using a laser diffraction / scattering particle size distribution measuring apparatus (MICROTRAC® HRA 9320X-100, manufactured by Nikkiso Co., Ltd.). Note that isopropyl alcohol was used as a dispersion medium, and the measurement was performed by adding silver powder in a state where the dispersion medium was circulated.
  • FIG. 2 shows the measured volume-integrated particle size distribution
  • Table 1 below shows the obtained values.
  • the obtained silver powder has a particle size distribution in the region of 0.3 ⁇ m to 14.0 ⁇ m, and P 1 > P 2 in the relationship between the peak P 1 and the shoulder P 2.
  • 1 was in the range of 2.0 ⁇ m to 5.0 ⁇ m
  • P 2 was in the range of 0.5 ⁇ m to 3.0 ⁇ m.
  • the particle size (D 50 ) of the volume-based particle size distribution obtained by the laser diffraction scattering method is 2.3 ⁇ m
  • the standard deviation (SD) of the volume-based particle size distribution is 1.
  • the coefficient of variation (CV) was 49.7%, and the proportion of particles in the particle size range of 1.5 ⁇ m to 5.0 ⁇ m in the volume-based particle size distribution was 68.9%.
  • SD (D 84 ⁇ D 16 ) / 2
  • CV (SD / D 50 ) ⁇ 100, and so on.
  • a paste was prepared using the obtained silver powder, the particle size distribution of the silver powder in the paste was measured, and the viscosity of the paste was measured to evaluate the paste characteristics.
  • silver powder was dispersed in isopropyl alcohol, and the particle size distribution of the silver powder in the paste was measured using a laser diffraction scattering method.
  • FIG. 3 shows the measured particle size distribution of the silver powder in the paste, and Table 1 below shows the obtained values.
  • the silver powder in the kneaded product has a particle size distribution in the region of 0.3 ⁇ m to 14.0 ⁇ m, and P 1 > P 2 in the relationship between the peak P 1 and the shoulder P 2 .
  • P 1 was in the range of 2.0 ⁇ m to 5.0 ⁇ m
  • P 2 was in the range of 0.5 ⁇ m to 3.0 ⁇ m.
  • the particle size (D 50 ) of the volume-based particle size distribution obtained by the laser diffraction scattering method is 2.3 ⁇ m
  • the standard deviation (SD) of the volume-based particle size distribution is 1.
  • the coefficient of variation (CV) was 49.7%, and the proportion of particles in the particle size range of 1.5 ⁇ m to 5.0 ⁇ m in the volume-based particle size distribution was 68.7%.
  • the obtained silver powder was used to evaluate the paste. After weighing 9.2 g of silver powder, 0.8 g of a 1: 7 weight ratio of epoxy resin (Mitsubishi Chemical Co., Ltd. JER819) and terpineol in a stainless steel dish and mixing with a metal spatula Further, the evaluation was carried out by kneading using a three-roll mill (manufactured by Kodaira Seisakusho Co., Ltd., table type three-roll mill, RIII-1CR-2 type). During the kneading by the three roll mill, the occurrence of flakes by visual observation was not recognized, and the kneading property was good.
  • a three-roll mill manufactured by Kodaira Seisakusho Co., Ltd., table type three-roll mill, RIII-1CR-2 type
  • the obtained paste had a viscosity of 93.0 Pa ⁇ s at a shear rate of 4 (1 / sec) and a viscosity of 39.1 Pa ⁇ s at a shear rate of 20 (1 / sec). s.
  • the viscosity ratio was 2.4. From this result, it was confirmed that it has a good paste characteristic. That is, by using the silver powder obtained in Example 1, it is possible to produce a paste having an appropriate viscosity and to suppress the occurrence of bleeding or dripping at the time of application to a wiring or the like and have good printability. It was found that a paste could be made.
  • Example 2 Silver powder was prepared in the same manner as in Example 1 except that the amount of water-soluble polymer polyvinyl alcohol used was 65.7 g (manufactured by Kuraray Co., Ltd., PVA205, 3.5% by mass with respect to silver particles). Manufactured.
  • Example 2 a uniform kneaded material produced by a self-revolving kneading machine (ARE-250 type manufactured by Sinky Corporation) was evaluated in the same manner as in Example 1 to obtain a particle size distribution obtained.
  • the values shown in FIG. 5 are shown in Table 1 below.
  • the particle size (D 50 ) of the volume-based particle size distribution obtained by the laser diffraction scattering method of the obtained silver powder is 2.5 ⁇ m
  • the standard deviation (SD) of the volume-based particle size distribution was 1.32 ⁇ m
  • the coefficient of variation (CV) was 52.4%
  • the ratio of particles having a particle size range of 1.5 ⁇ m to 5.0 ⁇ m in the volume-based particle size distribution was 71.4%.
  • the particle diameter (D 50 ) of the volume-based particle size distribution obtained by the laser diffraction scattering method of the obtained kneaded product is 2.4 ⁇ m
  • the standard deviation of the volume-based particle size distribution (SD) is 1.20 ⁇ m
  • coefficient of variation (CV) is 50.9%
  • the proportion of particles in the particle size range of 1.5 ⁇ m to 5.0 ⁇ m in the volume-based particle size distribution is 69.7%. there were.
  • the paste obtained by kneading the obtained silver powder with a three roll mill (manufactured by Kodaira Manufacturing Co., Ltd., desktop type three roll mill, RIII-1CR-2 type) was also used to measure viscoelasticity (Anton Paar, MCR). -301), the viscosity at a shear rate of 4 (1 / sec) and 20 (1 / sec) and the viscosity at a shear rate of 4 (1 / sec) at a shear rate of 2.0 (1 / sec) The viscosity ratio divided by the viscosity was measured.
  • the viscosity at a shear rate of 4 (1 / sec) is 97.2 Pa ⁇ s
  • the viscosity at a shear rate of 20 (1 / sec) is 37.4 Pa ⁇ s
  • the viscosity ratio was 2.6 and the viscosity was in the preferred range. From this result, it was confirmed that the paste characteristics were also good. Further, during the kneading by the three-roll mill, the occurrence of flakes by visual observation was not recognized, and the kneadability was good.
  • Example 3 The amount of water-soluble polymer polyvinyl alcohol used was 262.8 g (manufactured by Kuraray Co., Ltd., PVA205, 14.0% by mass with respect to silver particles), and the pulverization condition was a 5 L high-speed stirrer (Nippon Coke Industries, Ltd.) Silver powder was produced in the same manner as in Example 1 except that the powder was decompressed with a vacuum pump while being stirred for 30 minutes at a peripheral speed of 33 m / s.
  • Example 2 a uniform kneaded material produced by a self-revolving kneading machine (ARE-250 type manufactured by Sinky Corporation) was evaluated in the same manner as in Example 1 to obtain a particle size distribution obtained.
  • the values shown in FIG. 7 are shown in Table 1 below.
  • the particle size (D 50 ) of the volume-based particle size distribution obtained by the laser diffraction scattering method of the obtained silver powder is 2.5 ⁇ m
  • the standard deviation (SD) of the volume-based particle size distribution was 1.15 ⁇ m
  • the coefficient of variation (CV) was 45.6%
  • the proportion of particles in the particle size range of 1.5 ⁇ m to 5.0 ⁇ m in the volume-based particle size distribution was 75.7%.
  • the particle size (D 50 ) of the volume-based particle size distribution obtained by the laser diffraction scattering method of the obtained kneaded product is 2.5 ⁇ m
  • the standard deviation of the volume-based particle size distribution (SD) is 1.11 ⁇ m
  • coefficient of variation (CV) is 44.6%
  • the proportion of particles in the particle size range of 1.5 ⁇ m to 5.0 ⁇ m in the volume-based particle size distribution is 75.9%. there were.
  • the paste obtained by kneading the obtained silver powder with a three roll mill (manufactured by Kodaira Manufacturing Co., Ltd., desktop type three roll mill, RIII-1CR-2 type) was also used to measure viscoelasticity (Anton Paar, MCR). -301), the viscosity at a shear rate of 4 (1 / sec) and 20 (1 / sec) and the viscosity at a shear rate of 4 (1 / sec) at a shear rate of 2.0 (1 / sec) The viscosity ratio divided by the viscosity was measured.
  • the viscosity at a shear rate of 4 (1 / sec) was 73.1 Pa ⁇ s
  • the viscosity at a shear rate of 20 (1 / sec) was 28.7 Pa ⁇ s
  • the viscosity ratio was 2.5 and the viscosity was in the preferred range. From this result, it was confirmed that the paste characteristics were also good. Further, during the kneading with the three roll mill, no flakes were visually observed, and the kneadability was good.
  • Comparative Example 1 In Comparative Example 1, as a crushing condition, except that the crushing was performed by reducing the pressure with a vacuum pump while stirring at 4600 rpm for 30 minutes (the peripheral speed of the stirring blade was 42 m / s) using a Henschel mixer. Produced silver powder in the same manner as in Example 1. That is, crushing was performed under a stronger crushing condition than in Example 1.
  • the particle size distribution of the obtained silver powder was measured in the same manner as in Example 1.
  • FIG. 8 shows the measured volume-integrated particle size distribution, and Table 1 below shows the obtained values.
  • Example 2 the obtained silver powder was used to measure the particle size distribution of the silver powder in a uniform kneaded material produced by a self-revolving kneading machine (ARE-250 type manufactured by Sinky Co., Ltd.).
  • FIG. 9 shows the measured particle size distribution of the silver powder in the kneaded material, and Table 1 below shows the obtained values.
  • the particle size distribution of the obtained silver powder and the particle size distribution of the silver powder in the kneaded material prepared using the silver powder have only one peak, and two or more peaks. Or it was not a particle size distribution with peaks and shoulders.
  • the silver powder in the kneaded product has a volume-based particle size distribution particle size (D 50 ) obtained by a laser diffraction scattering method not in the range of 2.0 ⁇ m to 5.0 ⁇ m.
  • the standard deviation (SD) of the volume-based particle size distribution was 0.57 ⁇ m which was not in the range of 0.8 ⁇ m to 3.0 ⁇ m.
  • the ratio of the particles in the particle size range of 1.5 ⁇ m to 5.0 ⁇ m in the volume basis particle size distribution was 33.8% which is not in the range of 40 to 80%.
  • the silver powder before the preparation of the uniform kneaded product also has only one peak in the particle size distribution, and D 50 , SD, and grains of 1.5 ⁇ m to 5.0 ⁇ m.
  • the ratio of the particles in the diameter range was not in the above-described range, and was 1.4 ⁇ m, 0.55 ⁇ m, and 32.9%, respectively.
  • Example 2 The silver powder was prepared in the same manner as in Example 1 except that the amount of the water-soluble polymer polyvinyl alcohol used was 1.9 g (manufactured by Kuraray Co., Ltd., PVA205, 0.1% by mass based on silver particles). Manufactured.
  • the particle size distribution of the obtained silver powder had only one peak and was not a particle size distribution with two peaks or shoulders.
  • the particle diameter (D 50 ) of the volume-based particle size distribution obtained by the laser diffraction scattering method is 7.7 ⁇ m which is not in the range of 2.0 ⁇ m to 5.0 ⁇ m
  • the standard deviation (SD) of the particle size distribution was 6.84 ⁇ m which is not in the range of 0.8 ⁇ m to 3.0 ⁇ m.
  • the coefficient of variation (CV) is 88.5% which is not in the range of 40 to 70%, and the proportion of particles in the particle size range of 1.5 ⁇ m to 5.0 ⁇ m in the volume-based particle size distribution is 50 to 80%. It was 33.1% which was not in the range.
  • a uniform kneaded product with a self-revolving kneading machine (ARE-250 type, manufactured by Shinky Co., Ltd.), a silver powder three roll mill (manufactured by Kodaira Seisakusho Co., Ltd., desktop type three roll mill, RIII-1CR-2 type) was used to produce pastes.
  • ARE-250 type manufactured by Shinky Co., Ltd.
  • a silver powder three roll mill manufactured by Kodaira Seisakusho Co., Ltd., desktop type three roll mill, RIII-1CR-2 type

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Abstract

L'invention porte sur une poussière d'argent qui présente une plage de viscosités appropriée pour faciliter le corroyage et pour supprimer l'apparition de flocons au moment de la fabrication d'une pâte, et sur un procédé de fabrication de celle-ci. Selon la présente invention, dans une pâte dans laquelle au moins une poussière d'argent, du terpinéol, et une résine sont corroyés à l'aide d'un agitateur du type à auto-révolution à force centrifuge de 420 G, la distribution de taille de particules sur la base du volume est dans la région de 0,3 μm à 14,0 μm, et dans la relation entre un pic ou un épaulement (P1) et un pic ou un épaulement (P2), P1 > P2, P1 est dans la plage de 2,0 μm à 5,0 μm, et P2 est dans la plage de 0,5 μm à 3,0 μm.
PCT/JP2012/065842 2011-06-21 2012-06-21 Poussière d'argent et procédé de fabrication correspondant WO2012176831A1 (fr)

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WO2014087728A1 (fr) * 2012-12-05 2014-06-12 住友金属鉱山株式会社 Poudre d'argent
WO2016129686A1 (fr) * 2015-02-13 2016-08-18 株式会社カネカ Cellule solaire, procédé de fabrication correspondant, et module solaire
WO2020262115A1 (fr) * 2019-06-27 2020-12-30 Ｄｏｗａエレクトロニクス株式会社 Poudre d'argent et son procédé de production
JP2021006661A (ja) * 2019-06-27 2021-01-21 Ｄｏｗａエレクトロニクス株式会社 銀粉およびその製造方法

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JP6282616B2 (ja) * 2014-07-30 2018-02-21 Ｄｏｗａエレクトロニクス株式会社 銀粉およびその製造方法
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