TWI304003B - - Google Patents

Description

[Technical Field] The present invention relates to a fine silver particle-attached silver-copper composite powder excellent in low-temperature sinterability and a method for producing the same. In particular, a method for producing fine silver particles by a specific method in the silver-copper complex powder of the core material. [Prior Art] In addition to silver ink (paste), simultaneous calcination with a ceramic substrate for circuit formation, etc., at a relatively high temperature for calcination, there is a printed circuit 2 = wiring circuit, via filling, and component mounting Use of an adhesive or the like in combination with various resin components for curing. In the case of the latter, the conductive filler generally does not cause the silver powder particles to sinter each other, and only the powder particles are electrically connected to each other. However, in recent years, it has been required to use a low-resistance diode of a conductor formed of silver powder and a high connection reliability for realizing the low-resistance, and the silver powder itself which is hardened with the resin component is sintered to exhibit silver conductivity. The demand for ink or silver paste is increased. In general, in order to meet such requirements, it is necessary to reduce the sintering temperature, and it is of course considered necessary to atomize the powder of the silver powder of the conductive filler. From the previous production of silver powder, an organic solution of silver nitrate solution and: a silver-silver complex solution is described as described in the patent document (Japanese Patent No. Ltfff\2()() 2_334618). The wet type of the agent is processed into a silver paste. Then, in order to ensure the low-temperature sinterability of the previous silver powder, such as the special offer 2 (Japanese patent application ^

2213-8357-PF 1304003 Special opening 2 0 0 2 - 3 2 4 9 6 No. 6 bulletin). However, in the metal powder containing silver powder, it is considered that it is difficult to coexist the dispersibility of the micronization of the powder and the fact that the powder is closer to monodispersion. For example, in the case of the silver ink containing silver nanoparticles disclosed in the above Patent Document 2, in order to stabilize the dispersibility of the nanoparticles, it is generally necessary to add a large amount of a dispersant as a protective colloid. In this case, the decomposition temperature of the dispersant is generally higher than the sintering temperature of the silver nanoparticles, and the low temperature sinter of the nanoparticles itself cannot be fully exerted. The case of silver ink of silver nanoparticles is lower than the previous paste m. Therefore, although the solution forms a thin film, it is difficult to form: 'Difficult (4) to form a large circuit section that can be used for relatively large current levels. The purpose of the original circuit. Furthermore, the requirements for the use of the power / the low-resistance circuit are tightened, and it is indispensable to add - a quantitative amount of the resin which is stronger than the strength of the joint. Therefore, the upper part of the hunting is strongly strengthened. In the ink of silver nanoparticles, as described above, silver powder is often used as a filler for acid resistance or low electrical resistance. On the other hand, <br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br><br> Therefore, it is also possible to use silver-copper alloy powder as a filler. The characteristics of the weak point of the ink are not suitable for the low-temperature burning of the nanoparticle itself: the protective agent for decomposition, and the ink of the silver nanoparticle 2223-835 7 ~pf 1304003 cannot be applied to An adhesive for the assembly. Furthermore, the use of coarse silver powder alone can increase the content of the paste, but the degree of burning will become higher. Therefore, in order to realize low-temperature sintering in the form of a paste, it is necessary to have a powder having a high filling property (dispersibility) as a filler and a surface of a thermally active particle. On the other hand, as described above, the silver-copper alloy powder is a disadvantage of the silver powder and the copper powder, but is easily oxidized than the silver powder, and the manufacturing technique of the atomization and the homogenization is difficult and has not been established. Therefore, in the case of the silver-copper alloy powder, it is difficult to atomize the particles, and it is not possible to produce a product having excellent low-temperature sinterability. Therefore, the object of the present invention is to exhibit oxidation resistance equivalent to that of silver, to have migration resistance equivalent to that of silver-copper alloy powder, and to have excellent low-temperature sinterability, and to attach silver-copper composite powder to fine-particle silver particles for a wide range of applications. Its method of making. SUMMARY OF THE INVENTION Therefore, in order to solve the above problems, it is thought that the migration resistance is the same as that of the silver-copper alloy powder, and the low-temperature burning property is excellent, and the silver particles adhered to the silver-copper particles having good powder characteristics. Composite powder. (Particle silver-attached silver-copper composite powder of the present invention) The silver-particle-attached silver-copper composite powder of the present invention is characterized in that it is a powder obtained by attaching fine particle silver powder to the surface of the powder of the core material powder. The powder body, the core material powder system silver-copper composite powder. Then, in the case where the silver-particle composite silver powder of the present invention is attached to the silver-copper composite powder, which has a substantially spherical shape, it is preferable to have any of the following powders: 2213-8357-PF 7 1304003: Α·with a laser Diffraction scattering particle octave knife cloth measurement method body accumulation 穑 垧 垧 particle size Dso is 〇. 3 micron ~ 6 〇 micron 疋 group 槚 槚 十 均 · B · with laser diffraction scattering particles ^ ^ ^ knife The volume cumulative maximum particle diameter D ma X of the cloth measurement method is 2 0 · 〇 micron or less, and the C · specific surface area is 0.2 pinger eight 00 / B tens of meters / g or more. Then, in the silver-copper composite powder to which the granulated silver particles of the present invention are attached, which has a flaky powder shape, it is preferable to have any of the following powder characteristics: a. Laser diffraction scattering teaching The volume cumulative average particle size D 5 〇 is 1 · 〇 micron~1 〇· q micron· b. Volume cumulative maximum particle diameter D ma by laser diffraction scattering particle size distribution method X is 4 0 · 0 μm or less; and the aspect ratio (thickness / [heart.]) of C·powder is 〇.02 to 〇.5. Further, the silver-silver composite powder of the present invention is adhered to the silver-copper composite powder, and the film resistance formed using the powder is in the range of 毫·01 milliohm·cm to 2.0 milliohm. centimeters. Further, the silver-silver composite powder to which the fine particle silver particles of the present invention are attached has a silver content of 22% by weight to 60% by weight. The composition of the residual copper and inevitable impurities. (Manufacturing Method of Silver-Powder Particle-Coated Silver-Copper Composite Powder According to the Present Invention) Basic Method for Producing Silver-Copper Composite Powder with Silver Particles Attached to the Invention: A method for producing a silver-silver composite powder with silver particles attached to the present invention, characterized in that it is characterized by 2213 -8357-PF 8 1304003 consists in contacting the silver-copper composite powder 'with a solution containing a mixture of dissolving silver nitrate and disproducing d and transferring the complex. This adds a reductant to make the silver particles in the powder of silver-copper powder. The surface of the grain precipitated. The method for producing silver-copper composite powder adhered to the fine silver particles, the silver-copper composite powder used as the core material is used on the surface of the copper powder to form a silver coating layer: 艮k coated copper knows '5 hai silver coated copper After the powder is wet-treated, it is filtered, washed with alcohol, and dried. ^The above-mentioned silver-coated copper powder is obtained by adding a chelate-forming agent to a dispersion of copper powder in water, adding a silver-containing solution, and further filtering the surface of the powder of copper powder to form silver. The applicator is preferred. Further, when the weight of the copper powder in the dispersion liquid when the silver-copper composite powder is obtained is 100 parts by weight, it is preferable to add a silver-containing solution to the dispersion liquid as the silver contains 20 parts by weight to 95 parts by weight. Further, the above chelating agent is preferably ethylene diamine tetraacetate. Then, the wet heat treatment is preferably carried out in a solution of 50 ° C to 20 (temperature of rc, heat treatment for 30 minutes to 120 minutes. The method for producing silver-copper composite powder adhered to the fine particle silver particles of the present invention) Preferably, the above-mentioned distorting agent is a sulfite or an ammonium salt. The method for producing a silver-copper composite powder adhered to the fine particle silver particles, and the silver-copper composite powder used as the core material is a silver content of 20% by weight to 55%. In the method of producing the silver-copper composite powder to which the fine-particle silver particles are attached, the silver-copper composite powder used as the core material is substantially spherical in shape using the following powder properties of I. to III. The powder is better: 2213-8357-PF 9 1304003 1 · The particle size I of the laser diffraction scattering particle size distribution is 0·3 μm~6·〇micron; 'volume cumulative average II' with laser diffraction scattering The particle size distribution has a large particle size of 20. 〇 micro-below; and the volumetric accumulation of the 疋 method is the most III. The specific surface area is 0.2 m ^ 2 / g 乂 after the silver-particle composite particles are attached to the silver-copper composite powder, and the silver-copper composite is used. Powder, use the following 丨, · ·The sleeve is used as the heart material. The flaky powder is better: ·~· The powder characteristics

The volumetric cumulative average of the method is the cumulative volume of the volume. The particle size distribution is determined by the laser diffraction scattering particle size distribution. a microparticle control Dmax of 40. 0 μm or less; and 1 〇 micron to 1 〇 · 〇 micron; i i · by laser diffraction scattering particle size distribution measurement

The aspect ratio (thickness / [d5g]) of Hi particles is 0 〇 2 ~ 〇.5. Further, in the method for producing a silver-copper composite powder in which fine silver particles are adhered, as the silver-copper composite powder used as the core material, two silver-copper composite powders composed of substantially spherical particles are used, and a particle diameter of 0 5 mm is used. The following grinding beads with a specific gravity of 3 〇g/cm 3 to 6.5 gram/cm 3 are preferably plastically deformed by high-energy ball milling, and are preferably thin and deformed. [Effect of the Invention] In the silver-silver composite powder to which the fine particle silver particles of the present invention are attached, since the structure of the silver powder (silver nanoparticle) of the fine particles is further adhered to the surface of the powder of the silver-copper composite powder, the prior silver-coated steel can be exhibited. Powder or silver-copper alloy powder / other level of low-temperature sinterability. Further, by using the silver-copper composite powder for the core material to which the silver particles are attached, the micronization and homogenization are used, 2213-8357-pf 10

1304003 is a very good low temperature sinter. [Embodiment] Hereinafter, the best mode for carrying out the silver-particle-attached silver-copper composite powder of the present invention and a method for producing the same will be described. <Silver-silver particle-attached silver-copper composite powder according to the present invention> The silver-particle-attached silver-copper composite powder of the present invention is characterized in that "the powder of the fine particle silver powder adhered to the surface of the powder of the core material powder" Powder 'this core powder is silver-copper composite powder'. That is, finer fine silver particles (primary particle diameter of 100 nm or less) adhere to the surface of the silver-copper composite powder of the core material. By the presence of the fine silver particles on the surface of the silver-copper composite powder, the fine silver particles having a small particle diameter exhibit low-temperature sinterability regardless of the shape and size of the particles of the core material, so that the silver particles adhere to the silver particles. Adjacent powder particles of the copper composite powder are easily sintered to each other. The so-called silver-copper composite powder is a powder composed of a silver-T alloy produced by an atomization method; a silver layer of 01 micronose to 30 micrometers thick is formed on the surface of the copper powder to obtain a silver-coated copper powder, which is made of silver. The layer is a powder composed of a slanted alloy in which silver is diffused into the copper particles, and the like, which means that silver and copper are contained as a powder composition: a powder. Therefore, in the present invention, these are collectively referred to as silver-copper composite powders. Hunting uses such a silver-copper composite powder, which is more economical than silver powder, and: mention: migration resistance. Further, in the case of using copper powder, the film resistance of the formed conductor can be lowered. Then, the particle size is 'microparticle silver particles' attached to the silver nanoparticles of the silver-copper composite powder below 1 nanometer, 'the silver only exists in the core material 2213-8357-pf 11 钃1304003 copper Mix the surface of the powder. As described above, when the silver nanoparticle itself is used as the silver ink, in order to stabilize the dispersibility of the nanoparticles, it is generally possible to add a dispersing agent having a high decomposition temperature to the sintering temperature of the rice particles. The low-temperature sinterability of the silver nanoparticle itself is fully utilized. However, by attaching finer fine silver particles to the surface of the powder of the silver-steel composite powder of the core material, the size and shape of the silver-copper composite powder of the core material are not sufficient, and the silver nanoparticle can be sufficiently extracted. Low temperature sinterability. Therefore, even if the silver-copper of the core material is 1024, the powder particle shape &amp; is substantially spherical, and the particle size of the powder is several tens of micrometers &lt; _ sheet powder, and can be used as a core material. Then, the silver-copper complex powder to which the fine-particle silver particles of the present invention are attached is not particularly limited, and the powder shape (4) of the powder is substantially spherical or flaky. Then, it is preferable to have any powder characteristics of the following A·C. _Knife body characteristic A· is the volume average particle diameter D5 of the body f of the laser diffraction scattering particle size distribution measurement method. For 〇 · 3 microns ~ 6 · 〇 micron. Laser diffraction: The volumetric cumulative particle size of the particle size measurement method, even if it is agglomerated particles, is also considered as a secondary particle. Therefore, the powder constituting the micro-adhered silver-copper composite powder of the invention of the present invention can be obtained by averaging the volume average cumulative particle diameter D5 at a certain level even if the primary particles are at a certain level: within the range of: 3 micrometers to 6 meters: On the volume, the cumulative average particle size ... 3 microns ~ 6 〇 shovel, (4) * powder, using a scanning electron microscope, by its observation image to measure one of the only hungry 〇 · 2 microns ~ "" because: observable The average primary particle size is now wide. Therefore, the filling of the gates for turning on the printed circuit board is less than 100 micrometers, and the filling of the V-vias between the layers of the layers is not

2213-8357-PF 12 1304003 The level of the problem. In addition, it is based on the specific powder of the present invention, the Θ Θ & \ &quot; sterling silver particles attached to the silver-copper complex, although not included in the powder characteristics, the two measurements / field diffraction diffraction particle size The volume cumulative particle diameter Dw of the distribution J 疋 method is also an element of the goodness of the particle size distribution of the powder. As described above, the half-size R &quot;&quot; 4 baskets accumulate an average particle diameter D5. 〇·3 "~U is a volume cumulative silver 偟D9 attached to the silver-silver composite powder by the silver particles of the particles. It is in the range of 0.5 μm to 10. 〇 microns. ...,, : Body ^ B. is a laser diffraction The particle size distribution measurement method (4) The large particle size L is 2°.μm or less. There is no special regulation of the 'lower limit'. If it is required to be specified, the industrially stable production range is 1: Micron. From the characteristics of the powder, the large-diameter particle diameter including the condensed state of the powder can be read. As long as the coarse particle is such a level, the via hole for turning on the layer of the printed circuit board having a diameter of 100 μm or less is used. The filling property will become the level of any problem. The powder property C· is about 0.2 square meter/gram or more of the specific surface material of the silver-silver composite powder adhered to the fine particle silver particles of the present invention. It indicates the uneven state of the surface of the powder, and the higher the specific surface area is processed into a paste: the viscosity is increased and it is difficult to handle, but on the other hand, the specific surface area is the same, the powder particles are easily sintered to each other, and it is related to low-temperature sintering. Therefore, in reality,微粒About the particle silver particles of the invention The specific surface area of the silver-copper composite powder is generally 0.2 square meters / gram ~ 3 〇 square meters / gram, and now, the upper limit to which limit is not specified. Consider the silver silver particles attached to the invention The specific surface area of the composite powder should be in the range of 〇·2 m ^ 2 / gram ~ 3 · 〇 m ^ 2 / gram, then processed into 2213-8357-PF 13 1304003 conductive paste when the side will lead (four) degrees (4) The grounding rise can be said to be a range of the sintering characteristics of the powder particles which are coexisting. Then, the silver-particle-attached silver-copper composite powder of the present invention has a thin powder shape, and may have the following a. Any of the powder characteristics. The flaky silver-copper composite powder has a flat shape, and can be used for reducing the processing into a conductive paste by using a flaky powder alone or a mixture of flaky powder and substantially spherical powder. The purpose of the conductor resistance of the formed conductor. The narrative property a. is the volume cumulative average particle diameter D5 of the laser diffraction scattering particle size distribution method. It is U micron, · 〇 micron. As described above, laser diffraction Scattering particle size The volume-accumulated particle size of the distribution measurement method is considered to be a primary particle even if it is agglomerated particles. Therefore, it is considered that the flaky particles of the silver-silver composite powder to which the fine-particle silver particles of the present invention are attached are considered to cause the primary particles to agglomerate at a certain level. , even if agglomeration occurs, the volume average cumulative particle control D5 can be collected in the above range. In reality, (4) accumulation product + (4) diameter D5. For the above-mentioned particles of silver particles adhered to the silver-copper composite powder, using scanning In the electron microscope, the average-secondary particle diameter of the sub-particle diameter (long diameter) measured by the observed image is observed to be u micrometers to 7 G micrometers. Therefore, the diameter between the layers for conducting the printed circuit board is less than 1 μm. The filling in the via holes becomes a level without any problem.

The human and the 疋 疋 疋 疋 疋 疋 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒It can also be used as an element to predict the particle size of the powder. The volume cumulative average particle diameter D5 is as described above. It is u 2213-8357-PF 14 1304003 D; the volume cumulative particle diameter of the flaky silver-copper composite powder of ~3 μm is in the range of ~2 〇·0 μm in the object. The ball produced by the atomization method is generally used to process a conventional thin film, and there is usually more than three times the thickness between the volume cumulative particle L value and the volume cumulative average particle diameter ^: the volume cumulative particle diameter D9 . The value and volume cumulative average particle size 1. There is no significant difference between the two. As a particle size distribution, it can be imagined that it is extremely sharp. The limb characteristics are b. The laser diffraction scattering particle size is divided into four. The maximum particle size U is less than retanning. From the powder characteristics ^ = the maximum particle size of the agglomerated state of the powder. Regarding the largest volume accumulation, Ί 'considering the use of a spherical shape made of a ball-shaped method, which is obtained by physical processing, is 8 μm or more, and depending on the case, it is more than 1 μm. When the flaky fine silver particles are adhered to the silver-copper composite powder, the volume cumulative maximum particle diameter U is 4 〇·〇 micrometer or less, and as long as it is at this level, the via hole for turning on the interlayer (10) micrometers between the layers of the printed circuit board is used. The filling property inside does not cause a big problem. Powder characteristics c. The aspect ratio (thickness / [I]) of the powder particles is 〇.〇2 to 0.5. Here, the aspect ratio is the cumulative average particle diameter D5 of the volume constituting the sheet and the volume. Indicates the aspect ratio ([thickness] / [^ value is 0.02~0.5. This aspect ratio can be said to indicate the processing of the sheet powder. Therefore, the aspect ratio is not full. 〇2, The thickness of the granules becomes thin, the dislocations inside the granules are dense, and the θ 山 mountain level rises and the micronization of the crystal grains occurs violently, causing an increase in electrical resistance and a significant change in the generation of coarse particles. When the value of the aspect ratio exceeds 〇· 5 ', the degree of processing is low and the flatness is low. Therefore, it is impossible to carry out 2 2213-8357-PF 15 1304003. The improvement of the contact area of the formed particles and the resistance of the body can not be reduced. The above-mentioned powder characteristics are considered to be related to the basic powder characteristics of the silver-copper powder used as the core material in the following production method, but the particle aggregation occurs in the manufacturing process of the silver-silver composite powder adhered to the fine-particle silver particles. Then, the characteristics of the powder are deteriorated, so that it is possible to find a product which can be manufactured by the manufacturing process as much as possible to avoid particle agglomeration. The characteristics of the silver-particle-attached silver-copper composite powder of the present invention are excellent in low-temperature sintering characteristics. Make (four) powder The film resistance is 0.01 nm ohm. centimeters to 2. 〇 milliohms. The low resistance of the range of centimeters. Therefore, the paste can be made and inked. (4) The conductor of the silver particles of the invention is adhered to the silver-copper composite powder. In addition, the silver-copper composite powder to which the fine-particle silver particles of the present invention are attached has a composition containing a silver content of 20% by weight to 90% by weight, a residual copper, and an unavoidable impurity, and is contained in a good electrical conductor. The amount of silver is relatively high and is evenly distributed, so that the low resistance of the formed conductor is promoted. Here, the amount of silver is less than 20%, and the silver-copper composite powder of the product is not improved. The conductor resistance of the conductor formed by the conductive paste loses the silver-containing meaning. When the amount of silver exceeds 90% by weight, the total amount of silver is too large, and the effect of preventing migration is not obtained, and uneven silver is easily obtained on the composition. The copper bismuth powder is used to ensure a good balance of economics, and the silver content of the silver-silver composite powder adhered to the silver particles is preferably 4% by weight to 6% by weight. Further, the measurement is carried out as silver particles attached to the particles. When the silver content of the copper composite powder is used, the silver-copper composite powder to which the fine particle silver particles are attached is completely dissolved, and the ion plasma luminescence is used to analyze the optical analysis device (ICP) of 2213-8357-PF 16 1304003. The silver particles are adhered to the silver-copper composite powder, and the sintering temperature is 1 70 ° C or less, which shows extremely good sinterability. As a result, the silver paste is adhered to the silver-copper composite powder to prepare a silver paste (ink), which is used for formation. In the case of a circuit or the like, a circuit that can be used with a large current to ensure a large current can be used, and since the particles are easily sintered to each other, the resistance of the conductor can be greatly improved and the reliability of conduction can be greatly improved. As the powder, a flat shape such as a substantially spherical shape or a flat shape can be used, and a sharp particle size distribution and dispersibility can be ensured by considering the manufacturing conditions from the previously existing manufacturing method. As a result, even if the silver nanoparticles which are regarded as lacking in dispersibility by the monomer are used, the silver-silver composite powder which adheres the silver nanoparticles to the surface of the silver-copper composite powder of the core material can be attached to the silver-copper composite powder, and the operability can be obtained. Preferably, a large amount of protective colloid is not required for the paste processing, and the silver particle content equivalent to that of the prior silver paste can be achieved, and the coating film thickness can be made in the shape of a circuit or the like. (Manufacturing Method of Silver-Grain Composite Powder Attached to the Invention of the Invention) The method for producing the silver-copper composite powder of the present invention is characterized in that silver-copper composite powder is used. It is contacted with a solution containing a complex compound obtained by mixing and dissolving silver nitrate and a distoring agent, and a reductant is added thereto to precipitate fine silver particles on the surface of the silver-copper powder. Silver-copper composite powder. Among the silver-copper composite powders used in the production method of the silver-particle-attached silver-copper-filled ruthenium of the present invention, it is particularly preferable to use the silver-copper composite powder of the following description: 2213-8357-pf 17 1304003. That is, a silver-copper-copper composite powder containing silver and copper is used to form a silver coating layer on the surface of the powder of the copper powder, and the silver-coated copper powder is heated in a solvent to cause the silver and the copper to thermally disperse each other. good. The silver-copper composite powder obtained by this production method has a gradient concentration gradient in which the concentration of the surface layer silver is higher toward the internal silver concentration in the powder particles. In this regard, the silver-copper composite powder prepared by the atomization method is uniformly mixed with silver and copper in the powder particles in the inner portion of the powder and the outer silver concentration distribution. Here, the formation of the silver coating on the surface of the powder of the copper powder is preferably a silver layer formed by an electrochemical method. The technique of electrochemistry refers to the method of replacing the precipitation method, the electroless shovel method, and the electrolysis method. In other words, it can be easily diffused by wet processing which will be described later, compared with a method in which a mixed copper powder and a silver powder are fixed to a surface of a powder of copper powder by a mechanochemical method. Then, the silver-copper composite powder as the core material is preferably a composition having a silver content of from 5% to 55% by weight, residual copper, and unavoidable impurities. Because: Death: The composition of silver-silver composite particles adhered to the silver particles, the composition of the core material, copper complex S powder should be included in the above range. The silver core material, the silver-copper composite powder is used as the surface layer of the powder. The ingredients of the surface of the powder are as follows: 银 'silver is 10% by weight '% by weight, and the residual copper is only inevitable impurities. . The sound of copper in such a particle is difficult to measure using chemical analysis. Because the second M = 2 ' uses the energy dispersion type of the surface layer of the grease, the accelerating voltage of the (4) beam is 15 仟 electronic fruit - 〇〇〇 〇〇〇 times, the simple quantitative analysis of the knot, ° ' lies in the powder When the silver content of the surface layer portion exceeds 60% by weight, -pp 2213-8357 18 1304003 tends to cause migration, and expensive silver is wasted. Then, if the silver content is not more than 1% by weight, the good conductivity of silver cannot be utilized. Therefore, it is preferable to use a simple quantitative analysis of the surface layer portion of the powder of the energy-dispersible EPMA, and the silver content is preferably in the range of from 1% by weight to 60% by weight. The above-mentioned resin silver-copper composite powder is not particularly limited as the copper powder used for the core material, and it is preferable to use a copper powder particle having a substantially spherical shape or a sheet shape. The silver-copper composite powder used in the present invention is a copper powder having good particle dispersibility by using copper powder having a fine particle size distribution by using fine particles'. Then, the silver-copper composite powder is used, which is suitable for the production of the silver-particle-attached silver-copper composite powder of the present invention. Among the silver-copper composite powders of the present invention, the silver-copper composite powder composed of substantially spherical powder particles may be one having the following powder properties of 丨.~m. The powder characteristics I· are measured by the laser diffraction scattering particle size distribution method. The cumulative average particle size is 微米.2 μm to 6. Gm. When the addition of the fine silver particles to the silver-copper composite powder, the volume average cumulative particle diameter D5 required to satisfy the above-mentioned powder characteristics A• is satisfied. The scope. Therefore, in the silver-copper composite powder specifically used in the present invention, although not included in the powder characteristics, the volumetric cumulative particle # of the laser diffraction scattering particle size distribution method can also be used as the particle size distribution of the powder. Elements. The volume cumulative particle diameter of the silver-copper composite powder having a volume cumulative average particle size of 0.2 μm to 6.0 μm as described above is in the range of 5 μm to 10 μm. 9°... Powder characteristics II. The volume of the laser diffraction scattering particle size distribution method is the largest particle size of 2〇.〇micron. When the silver-copper composite powder is added, the volume accumulation 2213-8357-PF 19 1304003 of the maximum particle diameter Dmax required to satisfy the above powder property β is satisfied. The particle size of the silver-copper composite powder used in the present invention is 0. 2 square meters / gram or more. When the silver-silver composite powder is adhered to the fine silver particles, the range of the specific surface area required for the above-mentioned powder characteristics c• is satisfied. Further, there is a powder property of a silver-copper composite powder which can be composed of a substantially spherical powder. In the case of a solid-filled density, the silver-copper composite powder having the above-mentioned powder characteristics is in the range of 10 g/cm 3 to 5.0 g/cm. Then, as the silver-copper composite powder used in the present invention, the silver-copper composite powder composed of the flaky particles is used as the powder having the following i. to iii. Life knife body characteristics 1 · Based on the laser diffraction scattering particle size distribution method, the accumulated average particle size is 1)5. For micrometers ~1〇 〇 micron. When the silver-copper composite powder is processed into fine silver particles, the volume average cumulative particle diameter D5 required to satisfy the above-mentioned powder characteristics a• is satisfied. The scope. Further, it is specifically used in the silver-copper composite powder of the invention of the present invention, and the volume cumulative particle diameter D9 of the laser diffraction scattering particle size distribution method is not included in the powder property. Further, as an element for predicting the goodness of the particle size distribution of the powder, the volume cumulative average particle diameter 1 is as described above. $ L 〇 micron ~ W 〇 The volume of the silver-copper composite powder of the micron accumulation of particles # D ... · 〇 micron ~ 20 · 0 by the range of meters. There is also no difference between the value of the volume cumulative particle # and the volume cumulative average particle diameter Dso, and it is used as a core material as a particle size distribution.

2213-8357-PF 20 1304003 接 尹 又 又 又 又 I I I I I I I I I I I I I I I I I I I I I I Processing into fine silver particles: When the silver-copper composite powder is used, the volume maximum particle diameter Dmax of the above-mentioned powder characteristics b•f is satisfied.尔, 尔, powder characteristics iU. The aspect ratio of the powder particles (thickness / [D5.]) is 〇· 〇2 〇. 5. When the silver-copper composite powder is adhered to the fine particle silver particles, the range of the aspect ratio (thickness / [D5.]) required for the powder property b. This ancient office system indicates that the thickness of the sheet powder is not sufficient. 〇2: The thickness of the two particles is too thin, and the adhesion of the particle silver powder to the surface of the powder is likely to be uneven and uneven. The value of this 'aspect ratio' is exceeded. 5, since the degree of processing is low and the flatness ratio is low, it is impossible to improve the sufficient contact interface area between the particles, and the resistance of the formed conductor is spherical copper or the like. - Man: The manufacture of the silver-copper composite powder of the present invention: the manufacture of the silver-copper double-mouth powder used in the present invention, characterized in that the surface of the powder of the copper powder is 4PIn h ^ ^ ^ of the silver coating layer The silver powder is coated with silver, and the silver coated copper powder is subjected to wet heat treatment, filtered, washed with alcohol, and dried. Zhu Ming's copper powder used as an anger material when making silver-copper composite powder. The steel powder is not particularly limited in its shape by a usual electrolysis method, a reductive method, or an atomization method: a copper powder obtained by adding 7 knives, and the shape is preferably a shape or a sheet shape. Further, in the case of the former copper powder, the treatment may be classified, the cleaning with dilute sulfuric acid, and the degreasing of the test solution. You 丨 ' 1 ώ double 丨 king / combined / night, can be used well in pure water to add copper powder, stir = after 'adding dilute sulfuric acid' to disturb, before processing and cleaning, copper 2213-8357-ρρ 21 In particular, in the silver-copper composite powder of the present invention, when a silver-copper composite powder composed of a substantially spherical powder is produced, the following powder properties of A • to C • are used, and the shape is substantially spherical. Copper powder is preferably used as the core material. As the powder characteristic A of the core copper powder, the volume cumulative average particle diameter of the laser diffraction scattering particle size is 〇·2 μm~5· 〇 micrometer. If it is not in this range, it is difficult to produce a silver-coated copper powder having a silver content in the range of (2 (% by weight to 55 weight %), and a volume cumulative average of the powder characteristics of the silver-copper composite powder after further wet heat treatment. Particle size Ds. Closed in the range of 微米·3 μm ~6 · 〇 microns. As the powder characteristic of the anger copper powder, β is the volume cumulative maximum particle size of the laser diffraction scattering particle size distribution method. If it is not in this range, it is difficult to produce a silver-coated copper powder having a silver content (in the range of 2% by weight to 555% by weight), and the volume-accumulation of the powder characteristics of the silver-copper composite powder after the wet-process heat treatment is the largest. The diameter u is less than or equal to 20 μm. Then, the powder characteristic of the core copper powder is c, · 0·1 m ^ 2 /g or more. If it is not "&quot;, ... (20% by weight to 555% by weight) The scope of the 泠 泠 r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r r 2 a or more. Also as 'the core steel powder is not full 〇 尺 尺 / 克 ' when silver coated copper powder coating ·:: uniform tendency, there are powder after the wet heat treatment of silver and copper The tendency to disperse the organization.

2213-8357-PF 22 1304003 Further, when the silver-copper composite powder composed of flaky powder particles is produced in the silver-copper composite powder of the present invention, a sheet having the following characteristics of ~c, powder characteristics is used. Copper powder is preferred as the core material. &amp; c The powder characteristic a' of the core copper powder is the volume cumulative average particle diameter D5 of the laser diffraction scattering particle size distribution method. For 1 〇 micron ~ 8. Micrometer. If it is not in this range, it is difficult to produce a silver-coated copper powder having a silver content of (2% by weight), and a volume cumulative average particle diameter Ds of the powder characteristics of the silver-copper composite powder after the wet heat treatment. . Closed in the range of 1 〇 micron ~ 10 · 0 micron. As the powder characteristic b of the core copper powder, the volume cumulative maximum particle #H 30 () micrometer is measured by the laser diffraction scattering particle size distribution method. If it is not in this range, it is difficult to produce a silver-coated copper powder having a silver content of (2% by weight to 55% by weight), and a volume cumulative maximum particle diameter of the powder characteristics of the silver-copper composite powder after further wet heat treatment. Dnax closed below 40 microns. Then, as the powder characteristic C of the core copper powder, the aspect ratio (thickness / [D5.]) of the powder is 0.02 to 0.5. If it is not in this range, it is difficult to produce a silver-coated copper powder in the range of (3 weight 3; % to 55 weight %) in the silver 3, and powder characteristics of the silver-copper composite powder after the wet heat treatment. The aspect ratio i thickness / [L]) is 〇.〇2~0.5. Further, the aspect ratio of the powder of the core material copper powder is the relative relationship of the particle size of the underfill 〇 02, and if it is made thin, it is not preferable that the dispersion becomes large and the coarse particles are likely to be generated. The copper powder of the above-mentioned type is a substantially spherical copper powder which cannot be obtained by the prior method, and is directly applied to a pulverizer such as a spheroidal bead mill by means of a medium 2213-8357-PF 23 1304003 ball or bead. The plastic deformation of the powder is flattened into a thin sheet. Even if the compression deformation of the particles in a certain agglomerated state is not inhibited, the aggregation state of the particles is compressed and deformed, and the copper powder is obtained in a state of aggregation. The powder particles cannot be dispersed. Therefore, it is preferable to firstly destroy the agglomerated state of the copper powder, perform a granulation treatment for dispersing the agglomerated molecules, and then compress the particles into a flaky shape. For example, the dried copper powder in agglomerated state is blown up using a centrifugal force 2 wind cycle machine to draw a circular orbit, and the agglomerated knives collide with each other during the flight. X, the copper powder in agglomerated state is dispersed in a solvent, and a fluid mill using a centrifugal force is used to cause a high-speed flow in a circumferential manner, and the centrifugal force generated thereby causes the agglomerated powder particles to collide with each other in the solvent. Degranulation work. Then, a method of compressing and deforming the powder of the copper powder by using a high-energy ball milling treatment to form a substantially spherical copper powder to complete the granulation operation is preferred. The so-called high-energy ball milling is used as, for example, a bead mill, an attriter, whether the copper powder is dried or in the state of a steel powder slurry, and the medium is used to compress the copper powder. A general term for a device that plastically deforms it. It is preferable to use a steel powder coated copper powder using the steel powder as described above as the core material, and the silver-coated copper powder used therefor, which is preferably produced by a wet method. When the silver coating layer is formed on the surface of the copper powder by the wet method, the silver coating layer is not a pure silver I' and tends to have a composition of a copper component which is dissolved by the copper powder containing the core material. Then, by forming a silver coating layer containing such a copper component, the silver and copper contents of the H-type heat treatment described later can be mutually diffused in the low temperature region. ,

2213-8357-PF 24 1304003 Adding an integrator ingredient to the silver coating by the generic method Μ &quot;10 knives loose steel powder in the water of the drug into a cow μ zhenzheng liquid 'to add silver solution to make it The reaction '-and the silver coating of the clothing surface is preferred. That is, since the valley is easy to control the thickness of the silver coating layer, the film thickness of the uniform sentence can be formed. , = Γ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ As such a nutrient, the use of ethylene-monoamine tetraacetate, triethyl----------------------------- Suspect - a φ - Weng 雔 ^ ^ ~ fe, an ethylene diamine, morphine, ethylene milk and (ethylamine) - Nn M, X4, - Tian deficiency u, N ~ tetraacetic acid, nitro triacetic acid,呪口疋甲酉夂 and combinations of these. (E), because of the superiority of the copper dimerization complex, the use of the ethylene diamine tetraacetate is preferred, and the use of the copper chelate chelating agent Add 1 to the 涞 剤 , , , , 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜 铜(5) What is the amount of the above added amount =, the copper hydroxide or oxide on the surface of the copper powder becomes &amp; complex, so that the silver coating can quickly and effectively carry out the surface of the copper powder. When the amount of the chelating agent added is less than 1 part by weight, the subsequent coating may not be performed satisfactorily. On the other hand, the chelation of the scorpion sputum is added to the surface of the copper powder even if it exceeds 5 parts. The coating speed is not straightforward to ensure the profitability of the industry. Then, the preferred 2 is the result of the stability of the step. Considering the mass productivity, the manufacturing method of the present invention, together with the chelation agent It is necessary to add various additives. As the additive, it is possible to increase the ductility by combining the gloss 2213-8357-PF 25 1304003. Chlorine (tetra), potassium ferricyanide or lauric acid is divided into the ig of the present invention, etc. &amp; method, a copper chelating agent is added to the skin, and a chelating agent is added to the dispersion, The addition of the silver-containing solution used herein is not particularly limited, but when the weight of the copper powder is 100 parts by weight, the weight of the silver knife solution is preferably added. The content of silver for the weight of the copper powder is not two. When the amount is 5, the amount of silver applied to the surface of the powder of copper powder is less than 20%. The minimum silver content required for the silver-copper composite powder used in the present invention is the surface, and the content of silver to copper powder exceeds 95. In the case of the weight portion, the silver coating amount on one of the grain surfaces has a high tendency to have a range of the silver content of each of the powders of the steel, and the thickness of the silver coating layer of the mouth is also uneven. The tendency of the surface, then, as a silver containing solution, the cheapest and good step stability of the silver nitrate solution. Here, the use of silver acetate is gram / liter ~ 300 grams / liter ❹ ^ degree 'such as adjusting brother / Soaring use. Silver nitrate solution, 锢敕 =, _41 () points ~ 6 () points added as good. For the _second reset portion, it is preferable to add about 30 parts by weight to 15 parts by weight of silver nitrate. The above range tends to deviate from the range of the silver content. '', soil. detachment due to the addition of silver by the dispersion The solution, immediately began to take the 'silver precipitated on the surface of the copper powder. By adding the silver-containing solution and after the Jaga, the dispersion can be promoted to promote the reaction' and prevent the uneven reaction. The silver-coated copper powder is prepared by filtering and washing the mixed solution of the mixed dispersion and the silver ion solution. 2213-8357-PF 26 1304003 Here, the wet heat treatment is described. After being dispersed in pure water, a wet heat treatment is performed. The wet heat treatment is carried out at 50 C to 20 (temperature of TC) by stirring for 3 minutes to 12 minutes. By performing such a wet treatment, the silver of the silver coating layer is scattered in the copper, silver and copper. Uniformly dispersed. Strictly speaking, it can be considered that the concentration of silver changes from a high gradient to a low silver concentration from the surface of the particle to the center. Generally, when interdiffusion between dissimilar metals is required, it is necessary to At the high temperature, the metal layer which is precipitated by the reductive reaction of the electrochemical reaction is in a state of activation, and has a crystal structure in which relocation of the crystal structure is easily caused by heating at a low temperature. There is a case where copper is contained in the silver coating layer - it is considered that it can be easily diffused at a low temperature. Then, it is carried out in such a heating solvent to prevent contact with the atmosphere and prevent the surface of the powder from being useless. Oxidation and pollution. After the above-mentioned wet heat treatment, filtration, followed by (4) clearing and drying to produce a silver-copper composite powder. At this time, alcohol cleaning is used to make the water easy to volatize, not special. Ingredients: alcohol cleaning, general (4) methanol, ethanol. Here, another method for obtaining a flake-shaped silver-copper composite powder is described. The manufacture of the flake-shaped silver-copper composite powder described above is described. In the case where a flaky copper powder is used for the core material, the silver steel composite powder composed of the substantially spherical powder obtained here may be used in a particle size of 55 mm or less and a specific gravity of 3.0 gram/ The grinding beads of cubic centimeters to 6.5 g/cm3 are compressed and plastically deformed by high-energy ball milling. The so-called high-energy ball milling is used as a bead mill, polisher 2213-8357-PF 27 • 1304003 (attri Ter ) 'Whether the copper powder is dried or in the state of copper powder, the medium is used to compress the copper powder to make it plastically deformed. Then, according to the invention, the grinding The choice of the particle size and material of the beads is very important.

First, 'grinding beads having a particle diameter of 0. 5 mm or less are used. The particle size of the beads is defined by the following reasons. When the particle size of the grinding beads exceeds 〇·5 mm, the particles of the silver-copper composite powder are easily agglomerated when the ball is compressed and plastically deformed by the grinding ball, and as a result, the agglomerated particles are compressed and deformed. When coarse grain flakes are produced and the particle size distribution is broadened, it is not possible to obtain a flake-shaped silver-copper composite powder having a high particle size distribution and high dispersibility. Μg/cm^6 Further, the beads are preferably used at a specific gravity of 3 g/cm3. The specific gravity of the grinding ball is less than 3. When the weight is gram/cm ^ 3, the weight of the grinding ball becomes too light, and the powder of the compression-deformed silver-copper composite powder takes a long time. Considering the productivity, it is not an industrially applicable condition. . When the specific gravity of the 'grinding beads exceeds 6.5 gram/cm 3 , the weight of the grinding balls becomes heavier'. The compressive deformation force of the powder of the silver-copper composite powder becomes larger: the granules condense each other' and the deformed thin silver copper The composite powder is easy to produce unevenness when it is 7 degrees. The flaky silver-copper composite powder thus obtained, the granules of the granules and the powdery granules required for the core material of the present invention are produced by the silvery-copper composite powder with the flaky fine-particle silver particles. The production of silver-copper-copper composite powder composed of silver-copper 扒 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 In the following, the back mouth 1k is evil, which is indicated in 1 liter of pure water.

2213-8357-PF 28 13〇4〇〇3 t: a solution of the complex compound, dispersing 50 grams of silver-copper composite powder of silver-copper j-diqin slurry on the surface of the silver-copper composite powder to make silver Nanoparticles are attached to the method of attaching silver-copper composite powder to the silver particles. First, the description will be directed to "a solution containing a mixed silver nitrate and a dissolving agent to dissolve a ruthenium/silver complex." For the silver-copper composite powder which is subjected to the above conditions, 8 g to 2 6 g of silver nitrate is used. In the case of less than 8 grams of acidity, it is impossible to obtain a practically adequate coverage of the fine silver. Even if a silver nitrate of 26 g is used, the coverage rate above the period will not increase. After the =, the stabilizing agent used herein is a sulfite or an ammonium salt. When using sulfite potassium, it is used in the range of 50 gram to 15 gram gram. When the amount of potassium sulfite added is less than 50 g, the misalignment of silver cannot be completely performed, and the silver complex cannot be completely formed. Even if the amount of the sulphurous acid slag is more than (four) gram, the amount of the miscruding amount which is sufficient to form the silver complex is exceeded, and it is uneconomical that the reaction rate of the dextran compound does not become fast. The above nitrate was dissolved in 1 liter of pure water, and a distoring agent was added thereto, and the mixture was sufficiently stirred to obtain a solution containing a silver-containing compound. The 50 g of the silver-copper composite powder was mixed with the solution containing the silver complex obtained as above. Then, the reductant is added thereto to carry out the antimony reaction, and the fine particle silver powder having a nanometer-scale particle size is uniformly deposited on the surface of the silver-copper composite powder. The reductant used at this time may, for example, be a hydrazine, DMAB, SBH, fumarin, or sub-frinic acid. For example, when using hydrazine, dissolve 5 gram to 50 gram of hydrazine in 2 liters of pure water (containing 〇ml), and add it within 60 minutes (including the case of one breath addition) . If the amount of the hydrazine is less than 5 gram, then the merging can not be effectively carried out without the 2213-8357-PF 29 1304003 method, and the fine silver powder is uniformly deposited on the surface of the silver-copper composite powder. Then, even if the hydrazine I exceeds 50 gram, the speed of repayment does not become extremely fast, but it is detrimental to economics. Then, the liquid temperature at the time of the reductive reaction was carried out at a temperature ranging from room temperature to 45 °C. When the liquid/m exceeds 45 C, the reaction is too fast, and the precipitation of the fine silver powder on the surface of the silver-copper composite powder is liable to be uneven, and the particle size distribution of the obtained fine silver particles adhered to the silver alloy powder is deteriorated. Then, the range of the above-mentioned reductant concentration == addition time is preferably in the range of 5 minutes to 4 minutes. When the reaction % is less than 5 minutes, the aggregation of the resulting powder tends to become stronger. On the other hand, the addition time of 4 〇 is used to make a sufficiently uniform coating. For example, the fine silver is precipitated on the surface of the silver-copper composite powder as described above, and then filtered, washed, dehydrated, and dried to obtain a silver-copper composite powder of the U-particle silver particles attached to the present invention. Here, the so-called filtration, washing, and dehydration drying can be used in various methods, and the method and conditions are not particularly limited. The silver fine particle-attached silver alloy powder of the present invention can be used for various purposes. In particular, it can be used as an ink (paste). Further, the resin component can be freely selected, and can also be used as an adhesive for constitution. Hereinafter, the present invention will be specifically described based on examples and comparative examples. Further, in the following examples, the silver-copper composite powder of the core material and the fine particle silver particles adhered to the surface of the silver-copper composite powder tend to have a smaller specific surface area. Since the silver ruthenium before the adhesion of the fine silver particles to the surface of the powder is oxidized to have extremely fine unevenness, and the fine silver particles are adhered, even if the appearance unevenness is increased, the fine uneven shape is reduced.

2213-8357~pF 30 1304003 [Example 1] &lt;Manufacture of silver-copper composite powder of core material> Sulfuric acid cleaning for producing copper-copper composite copper powder···················· The powder consisting of copper powder 2 2 7 1) 50 by 50 micrograms of roughly spherical acid solution, given a mixture of grams, after 5 minutes of mixing, 'add 20% sulfur to wash 3 times, as a pre-treated steel powder to 1 The liter of pure water is then clarified by the preparation of silver-coated copper powder. 2πη /V, 袅. Add 200 grams of the above-mentioned pretreated copper in 1 liter of pure water, and stir to obtain a dispersion. Next, the nitrate (tetra) _· 6 gram 'stirring for 5 minutes, the ancients will dissolve 94.4 grams of niobium silver in pure water 9 〇〇 pen liters to keep the silver nitrate solution in the ^ L u 琼 stir the above dispersion to spend 30 knives to replace reaction. After stirring for 5 minutes, the slurry was filtered and silver coated with steel powder. The powder characteristics of the silver-coated copper powder and the like are not shown in Table 1. Production of silver-copper composite powder: 1.3 liters of pure water, adding the above-mentioned silver-coated copper powder, and dropping 6 ( of the liquid temperature of TC, and performing wet treatment, then smashing, followed by methanol washing and drying. A silver-copper composite powder was produced. The silver-copper composite powder at this stage was used as Comparative Example i, and the powder characteristics and the like were disclosed in the table in comparison with the silver-copper composite powder to which the fine silver particles of the final product were attached. Manufacture of silver-copper composite powder> Add 541 grams of silver sulphate and 3 parts of sulfuric acid to the sulphuric acid (3 gram of dissolving agent egg, dissolved in 4 (rc). Add 240 ml of pure water to dissolve the above silver in the solution. A mixture of 160 g of copper composite powder and a polytheneimide solution of 4 d 3 of polytheneimide was added. The mixture was added to 2213-8357-PF 31 1304003 ', and the water was dissolved in 320 ml. Amine (returning agent) 32 grams of hydrazine solution, for reversing ruthenium, ~ 'filtration, cleaning, manufacturing silver particles adhered to the silver particles of particles, the particle size of silver particles adhered to the silver alloy powder D9. Dmax), specific surface area and solid packing density The measurement, the chemical conversion, and the film evaluation (specific resistance) are shown in Table 1 as the first embodiment. Table 1. :--- Samples of the makeup residue &gt; Evaluation Chemical Analysis (%) EDX (8) Membrane ratio Resistance 71 people do not knife--'^--- Deo 1) 90 IU SSA TD Ag Cu Ag Cu (milliohms · cm) Silver coated copper powder 1.42 2. 98 11.8 0.72 3.5 23.3 76.8 55.8 44.2 Comparative Example 1 Composite powder 1.39 2.91 12.0 1.39 3.5 23.3 76.8 33.9 66.1 10 1 Example 1 Silver alloy particles adhered to silver alloy powder --- 1.61 3.33 13.0 0.81 3.3 31.2 70.1 40.2 59.8 XV/· 1 1.5 Example 1 and Comparative Example 1 Contrast

The results of the measurement of the particle size distribution (D5m), the specific surface area and the solid packing density of the silver-coated copper powder, the silver-copper composite powder and the silver-particle-attached silver alloy powder, and the chemical analysis of the composition are shown. In Table 1. In addition, in Table 1, it is shown that: powder characteristics, specific surface area (like), shake packing density (td), and chemical powder quantitative analysis results of dissolved powder particles using an ICP analyzer (in the table Chemical "Jinzhi 1"), using energy dispersive brain A in the surface layer of the powder: easy quantitative analysis results (in the table, "the amount of the component in the surface layer of the leg" film ratio f resistance from silver coated copper The powder is changed to a state in which silver-copper composite powder and fine-particle silver particles are attached to the silver alloy powder. Knowledge of powder characteristics: It can be seen from Table 1 that even silver is coated

2213-8357-PF 32 1304003, '° u , , , , and treated as silver-copper composite powder, among the powder characteristics. ,

There is no change in Dfflax padding density (T·D). However, the value of the surface and the surface of the composite has changed. The ratio of the surface area of the silver-copper composite powder to the wet heat treatment is larger than that of the silver coating layer. In this regard, it will be silver and copper.微粒 粕 表面 表面 表面 表面 表面 表面 表面 表面 表面 表面 表面 表面 表面 表面 表面 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒 微粒, 'X, shake packing density (T\D) / what changes. However, the value of specific surface area (SSA), the ruthenium of the example γ AI is smaller. Then, see the example i and compare In the case of the specific resistance of the example i, it is understood that the first embodiment exhibits a smaller electrical resistance than that of the comparative example 1, and can be sintered at a low temperature to exhibit good electrical conductivity. The knowledge of the formation of the knives is as follows: The chemical quantitative analysis of the content of silver and copper in the silver-coated copper powder and the silver-copper composite powder is not affected by the wet heat treatment. For this, the energy-dispersed EPMA powder is used. For the simple quantitative analysis of the surface layer, the amount of silver in the surface layer of the silver-coated copper powder is 55.8% by weight, and the amount of silver in the surface layer of the silver-copper composite powder after the wet heat treatment is reduced to 339 % by weight. It can be understood that it is surely diffused into the copper powder of the core material. After cooling, in the wet heat treatment The silver-copper composite powder (comparative example) adhered to the silver particles of the fine particles, and the silver-silver composite powder was adhered to the fine silver particles (Example 1). It was found that the results of the chemical analysis and the results of the EDX analysis increased the silver content. For the measurement of the distribution, silver-copper composite powder 丨. 丨 gram is mixed with SN·1% aqueous solution of SN dispersant 5468 (manufactured by St. Nopco Co., Ltd.), and ultrasonic homogenizer (us_3〇〇T made by Nippon Seiki Co., Ltd.) After dispersing for 5 minutes 2213-8357-PF 33 1304003, use laser diffraction scattering particle size distribution丨彳

〇, 9π γιηπ^, τ 邛州疋裴 Micro Trac HRA 9320-X1 00 (M ^ , J made by Leeds + Northrup) performs 0 averaging particle size D5 〇 is obtained by s-ray diffraction scattering method The size of the body and the basket at 50% of the 10 points (by the meter), 仏. According to the laser diffraction scattering method, / &amp; passed the cumulative volume of 90%

Particle size (micron), the finest diameter of the fine laser diffraction scattering method to determine the largest cumulative particle size (micron). The specific surface area is the value obtained by the penetration method using the island ratio: the ratio measuring device ss_10. In addition, the cradle filling degree is based on the fine barrel silver-copper composite powder _ gram, put into the (four) cubic a knife barrel, and fall down by 40 house meters! The method of measuring the volume of the silver-copper composite powder after the shaking is repeated. In the measurement of the membrane specific resistance, a conductive lake material was produced using powder, and the circuit was pulled at 180 on the ceramic substrate. The temperature range of the 25th generation is calcined into a 1 mm wide circuit measuring device that can measure the resistance of the spoon. Further, the composition of the conductive paste was 85% by weight of the powder, 75 % by weight of ethyl cellulose, and 14.5% by weight of terpineol. The measurement methods are the same in the following examples.

[Example 2] <Production of silver-copper composite powder of core material>;,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Gram, stir for 5 minutes] knife to discharge liquid. Then, silver nitrate was dissolved in pure water at a temperature of 9 〇. The silver nitrate solution was kept at 40 ° C, and the dispersion was added for 30 minutes under stirring to carry out a substitution reaction. Further, after stirring for 5 minutes, silver coated copper powder was prepared by 遽'α washing. The powder characteristics of the silver-coated copper powder and the like are shown in Table 2. 2213-8357-ρρ 34 1304003 The obtained silver-coated copper powder was subjected to a wet treatment in the same manner as in the Example, and filtered, and the methanol was first cleaned to make a silver-copper composite powder. The silver-copper composite powder of the stage was used as Comparative Example 2, and the powder characteristics and the like were shown in Table 2 in comparison with the silver-silver composite powder to which the fine silver particles of the final product were attached. <Manufacture of Fine Silver Particle-Coated Silver-Copper Composite Powder> A silver-particle-attached silver-copper composite powder was produced by the same procedure as in Example 1. The particle size distribution (m), the specific surface area, and the solid packing density, the chemical analysis, and the film evaluation (specific resistance) of the fine silver particles adhered to the silver alloy powder produced in this manner were shown in Table 2 as Example 2. . Table 2. Chemical analysis of sample spherical powder 〇〇 EDX (%) Membrane specific resistance D50 D90 SSA TD Ag Cu Ag Cu (milliohm ohms) - Silver coated copper powder 1.44 3.33 12.4 0.77 3.3 39.6 59.9 59.4 40.6 Comparative example 2 Silver-copper composite powder 1.41 3.11 11.9 1.45 3.2 39.6 59.9 47.0 53.0 8, 9 Example 2 Silver-particle-attached silver alloy powder 1.57 4.01 13.1 0.83 3.0 46.1 55 55.1 44.9 1.1 Comparison of Example 2 and Comparative Example 2 The silver-coated copper powder, the silver-copper composite powder and the silver-silver particles adhered to the silver alloy powder, the particle size distribution (Dse, Ds, D_), the specific surface area and the solid packing density, and the chemical analysis of the composition The result is compared. As to the knowledge of the powder characteristics, it can be seen from Table 2 that even if the silver-coated copper powder is subjected to the wet heat treatment to the silver-copper composite powder, the powder characteristics are poor. , h. , D„ax, shake packing density (TD) has no change, but the specific surface

2213 — 8357 — PF 35 1304003 , ▲ The value varies, the ratio of the silver-copper composite powder of the wet heat treatment, and the specific surface area of the ferritic silver-coated copper powder of the person: large. In this regard, it will be silver and copper. The particles on the surface of the granules are adhered to the particles of silver particles, and the silver particles are attached to the silver = 稷 mouth powder (Case 2), and the silver-copper composite powder with the wet heat treatment is related to the powder characteristics. What sharks. However, the value of the specific surface area (SSA), Example ★ The rutting of Comparative Example 2 is small. Then, it can be seen that the target example 2 shows a smaller resistance than that of the comparative example 2, and can be sintered at a low temperature to exhibit good electrical conductivity. This tendency is the same as the embodiment &quot; The knowledge of the change in the amount of the component: The results of the chemical quantitative analysis of the contents of the silver-coated copper powder and the silver-copper composite powder before and after the wet heat treatment are 'not affected by the wet heat treatment. In this regard, the simple quantitative analysis result of the surface layer portion of the powder using the energy-dispersible EPMA is 59.4% by weight of the surface layer of the silver-coated copper powder, and the surface of the silver-copper composite powder after the thirst-type heat treatment is The amount of silver is reduced to 重量% by weight, and it is understood that it is surely diffused into the copper powder of the core material. Then, the silver-copper particles in the wet heat treatment (Comparative Example 2) were adhered to the silver particles, and the silver-copper particles were adhered to the silver-silver composite powder (Example 2). The results of chemical analysis and EDX analysis showed silver content. This tendency is the same as in the first embodiment. [Example 3] <Manufacture of silver-copper composite powder of core material> Add 1 liter of pure water to the same pretreated copper 2213-8357-pf 36 1304003 as used in Example 1 After adding the mixture, add 62.2 After mixing for 5 minutes, the silver nitrate 22G.4g was dissolved in pure water _:= the silver acid solution was kept in the grasping liquid 3 on the above dispersion. Minutes See the 入 substitution reaction. After stirring for 5 minutes, the mixture was washed twice to prepare a silver-coated copper powder. The powder characteristics of the silver-coated copper powder and the like are disclosed in Table 3.

The obtained silver-coated copper powder was subjected to a wet treatment in the same manner as in Example j, and the mixture was washed with a decyl alcohol and dried to prepare a silver-copper composite powder. The silver-copper cut at this stage was used as Comparative Example 3, and the particle size cloth (1) 5〇, D9 was carried out in the same manner as in Example 丨. The measurement of the specific surface area and the tamping density, and the chemical analysis were described in Table 3 in comparison with the silver-copper composite powder to which the fine silver particles of the final product were attached. <Production of silver-copper composite powder adhered to silver particles> A silver-particle-attached silver-copper composite powder was produced by the same procedure as in Example 1. Performing the silver particle particles thus attached to the silver alloy powder

The particle size distribution (Dw, Dm, Draax), specific surface area and measured solid packing density, chemical analysis and film evaluation (specific resistance) were shown in Table 3 as Example 3. Table 3. Experimental analysis of spherical powder for evaluation (%) EDX (°/〇) Membrane specific resistance D50 D90 Dmax SSA TD Ag Cu Ag Cu (milliohms·cm) - Silver coated copper powder 1.14 2.68 11.9 0.82 3.3 49.9 51.2 69.3 30.7 Comparative Example 3 Silver-copper composite powder 1.25 2.80 11.9 1.51 3.2 49.9 51.2 51.6 48.4 8.1 Example 3 Silver-particle-attached silver alloy powder 1.71 3. 33 13.1 0. 99 3.0 56.9 44.1 59.9 40.1 0.8 2213-8357-PF 37 1304003 <Comparative Example 3 and Comparative Example 3> Silver-coated copper powder, silver-copper composite powder and fine-particle silver particles thus produced: particle size distribution of attached silver alloy powder (I., D9q, Dma〇, ratio The measurement of the surface area and the shake filling degree is compared with the results of chemical analysis indicating the composition. - Knowledge of the powder characteristics: It can be seen from Table 3 that even if the silver-coated copper ruthenium is heat-treated into a silver-copper composite powder, Regarding the powder characteristics, there is no change in the 仏〇, D9, D„ax, and the tangling density (TD). However, the value of the surface, ★) varies, and the ratio of the silver-copper composite powder of the wet heat treatment is shown. : The specific surface area of Ai's rut silver coated copper powder In this case, the silver-copper-... particles on the surface of the granules are attached with silver particles of silver particles attached to silver II:, (""column 3)" and wet-heat treated silver-copper composite powder (Comparative Example 2 on powder The body characteristics of "1", D_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ According to Example 3 and Comparative Example 3, only Example 3 showed a smaller electrical resistance than Comparative Example 3, and it was only temperature-sintered to exhibit good electrical conductivity. This is the same as in Example 2. And the results of the analysis of the wet silver coated copper powder and the silver-copper composite powder, it can be seen that the difference is not due to the chemical quantification of the various chemical processes. The gentleman throws the energy-dispersed EPMA m. In view of this, for the silver-coated copper powder, the amount of silver in the surface layer of the silver-copper composite powder after the heat treatment is reduced to: /, In the case of wet %', it can be understood that the copper powder which is surely diffused into the core material is the inner core.

2213-8357-PF 38 1304003 Then, in the wet-heat-treated silver-copper composite powder (Comparative Example 3), the silver particles were adhered to the silver-silver composite powder (Example 3), and the chemical analysis results were obtained. The results of EDX analysis increased the silver content. This tendency is the same as in the first embodiment and the second embodiment. [Example 4] <Manufacture of silver-copper composite powder of core material>

As the raw material copper powder, three kinds of silver coatings having a varying amount of silver coating were prepared in the same manner as in Example 1 except that the flaky copper powder having a volume cumulative average particle diameter D 5 3 of 32 μm and an enthalpy ratio of 〇·1 was used. Copper powder (flake powder). The powder characteristics of the three coated copper powders are separately disclosed in Tables 4 to 6. The obtained three kinds of silver-coated copper powders were subjected to a wet treatment in the same manner as in Example ,, and filtered, and washed with methanol and dried to produce a silver-steel composite powder (10) powder. The silver-copper composite powder at this stage was used as a comparative example 4-b comparative example, and the particle size distribution (Ds., D9, Dj, specific surface area, and the solid packing density) and chemical analysis were carried out in the same manner as in Example 1. * Finally, purple mouth = silver: sub-attached silver-copper composite powder (flake powder) will be contrasted with: body;; sex # is not shown in Table 4 to Table 6. <Particle silver particles adhere to silver-copper composite powder (flake powder) 〉 Three types of silver-copper composite powders were prepared, and three kinds of silver-copper composite powders were adhered to the three kinds of fine-particle silver particles by the same procedure as in Example 1. The particle size distribution of the silver-particle powder adhered to the same fine particle silver particles produced by the same method.仃The measurement of U, the specific surface area, and the solid packing density, the chemical code /50, ^, the valence (specific resistance), the result is taken as the small implementation of Example 4 = analysis and film evaluation 4 to Table 6. 4~3 Table 2213-8357-pp 39 1304003 Table 4.

Table 6.

Evaluation Chemical Analysis (3⁄4) EDXC%: ) Membrane Specific Resistance Sample Wafer Powder D50 D90 Dmax SSA TD Ag Cu Ag Cu (Milliohms·cm) - Silver Coated Copper Powder 5.55 8. 99 23.2 0.53 3.2 47.3 52.1 66.3 33.7 - Compare Example 4-2 Silver-copper composite powder 6.01 9.83 26.2 1.52 3.1 47.3 52.1 52.5 47.5 4.2 Example 4-2 Silver-particle-attached silver alloy powder 6.97 11.6 26.2 0.58 3.0 55.6 45.9 59.9 40.1 0.6 Evaluation Chemical Analysis (%) EDX (%&gt ; _-r--- 丨 film specific resistance sample sheet powder D50 D90 Dam SSA TD Ag Cu Ag Cu (milliohm ohms) a silver coated copper powder 5.55 8.92 23.2 0.43 3.3 24.4 77.7 55.1 44.9 - Comparative Example 4-1 Silver-copper composite powder 5.74 9.66 26.2 0. 99 3.2 24.4 77.7 34.5 65. 5 6.9 Example 4-1 Silver-particle-attached silver alloy powder 5. 63 9.22 26.2 0. 54 3.0 32.3 68.0 42.8 57.2 1.2 Table 5 · Evaluation of chemical analysis (%) EDX (%: ) Membrane specific resistance sample flakes ϋδΟ D90 Dmx SSA TD Ag Cu Ag Cu (milliohms·cm) - Silver coated copper powder 5.55 9.62 26.2 0.49 3.3 38.5 61.0 57.8 42.2 - Comparative Example 4-2 Silver-copper composite powder 6.09 10.3 26.2 1.21 3.1 39.5 61.0 48.0 52.0 5.3 Example 4-2 Silver-particle-attached silver alloy powder 5. 95 9.68 26.2 0.51 3.0 47.2 53.2 56.0 44.0 1.0 &lt;Example 4-1 to Example 4-3 and Comparative Example 4-1 to Comparative Example 4 -3 comparison> Determination of particle size distribution (Dm, Dg(i, Dnax), specific surface area and shake packing density of silver-coated copper powder, silver-copper composite powder and fine-particle silver-attached silver alloy powder And the result of chemical analysis such as composition, etc. 40

2213-8357-PF ‘1304003 ratio. Here, the comparative object of Example 4-1 is Comparative Example 4-1, and the comparative object of Example 4-2 is Comparative Example 4-2, Comparative Example 4-3 of Comparative Example 4-3. 4

_ I in the characteristics of the corpus callosum: From Table 4 to Table 6, it can be seen that the silver-coated copper powder is heat-treated into a silver-copper composite powder (Comparative Example 4_丨~Comparative Example 3), regarding the characteristics of the powder The towel m- and the solid packing density (TD) tend to become larger. X. Regarding the value of the specific surface area (SSA), the specific surface area of the silver-copper composite powder of the thirst-heat treatment is changed to that of the silver-coated copper powder: the specific surface area is slightly larger, and there is no significant increase as the spherical powder. In this case, silver-particle composite silver-copper composite powder with silver particles attached to the surface of the powder of silver-copper composite powder (Example 4 - Example 4_3), and wet heat treatment Comparative Example 4 + Comparative Example &quot; In contrast, there is no change in the powder D9° and the actual filling density (u). =: two surface area (10): the value of the embodiment is smaller than the comparative example. = The film specific resistance of the fine example and the comparative example shows that the examples show a resistance lower than =, and can be sintered at a low temperature to exhibit good electrical conductivity. The tendency is the same as that of the spherical powder of Example 3. Knowledge of the change in the amount of components: about the silver-coated copper powder and the silver-copper composite powder before and after the wet heat treatment, and the chemical quantification of each of the inclusions It changes with heat treatment. In this regard, when the surface layer and the fruit of the energy-dispersed enamel are used, the amount of silver in the surface layer of the silver-copper composite powder is easily quantitatively analyzed for the surface layer of the silver-coated copper powder; Copper powder inside. The solution was surely diffused to the core material 2213-8357-PF 41 1304003. Then, the silver-copper particles were adhered to the wet-heat-treated silver-copper composite powder (Comparative Example 4-1 to Comparative Example 4-3) to form fine particle silver particles. In the silver-copper composite powder (Example 4-1 to Example 4-3), it was found that the results of chemical analysis and the results of EDX analysis increased the silver content. This tendency is the same as that of the spherical powders of Examples 1 to 3. [Example 5] <Production of silver-copper composite powder of core material> A spherical silver-copper composite powder was produced by a conventional atomization method using the silver-copper alloy smelting method in the above Example 5'. The silver-copper composite powder at this stage was Comparative Example 5, and the particle size distribution (D5, Dg(), Draax), the specific surface area, and the measurement of the filling density, and the chemical analysis were carried out in the same manner as in Example 1, and the particles of the final product were obtained. Silver particles adhered to the silver-copper composite powder, and the powder properties and the like are shown in Table 7. <Manufacture of Fine Silver Particle-Coated Silver-Copper Composite Powder> A silver-particle-attached silver-copper composite powder was produced by the same procedure as in Example 1. The particle size distribution (Du, D9, Dmax) of the silver nanoparticle-attached silver alloy powder thus produced, the measurement of the specific surface area and the solid packing density, the chemical analysis and the film evaluation (specific resistance), and the result are as follows; Examples are shown in Table 7. Table sample spherical powder Comparative Example 5 Silver steel composite powder Example 5 Evaluation of particulate silver particle-attached silver alloy powder ϋδΟ D90 Dmax 5.52 10.9 33.0 6.09 10.3 33.0 Chemical analysis (%) Membrane specific resistance (milliohm·cm) 2213-8357- PF 42 m 1304003 <Comparative Example 5 with Comparative Example 5> The silver-coated copper powder, silver-copper composite powder and fine-particle silver particles adhered to the silver alloy powder have a particle size distribution (3) (1) ~ 汍 ^ 仏 "~ ratio The measurement of the surface area and the solid packing density is compared with the results of the chemical analysis of the composition. The knowledge of the powder characteristics. As can be seen from Table 7, the particles of the silver particles are adhered to the surface of the silver-copper composite umbrella knife. Silver particles adhered to silver-copper composite powder (Example 5), compared with wet heat-treated silver-copper composite powder (Comparative Example 5). 'About powder characteristics, Du, Dh, Dn^x, and shake packing density (τ·) D) There is no change in the scent. However, the value of the specific surface area (SSA) is different from that of the comparative example 5 in the fifth embodiment, and is different from the first to fourth embodiments. Then, the example 5 and the comparative example are seen. 5 film specific resistance, it can be known to implement Example 5 shows a resistance smaller than that of Comparative Example 5, and can be sintered at a low temperature to exhibit good electrical conductivity. The tendency of the film resistance is the same as in Examples 1 to 4. The change in the amount of the component is compared with The silver-copper composite powder (Comparative Example 5) and the silver in the surface layer were added to the silver-silver composite powder (Example 5), and the results of chemical analysis (analysis of the total amount of silver) were obtained. As a result of the analysis (simple analysis of the amount of surface silver), the silver content was increased. This tendency was similar to that of Examples 1 to 4, and it was understood that the fine silver particles were firmly adhered. [Example 6] <Silver copper of the core material Manufacture of Composite Powder In the sixth embodiment, a silver-copper composite powder of Example 5 in which a spherical silver-copper composite powder is produced by a known atomization method using a silver-copper alloy melt is known. The method of thinning. The thinned silver-copper composite powder at this stage is

2213-8357-PF 43 1304003 Compared with Example 6, the particle size distribution was carried out in the same manner as in Example i. , ", D_), specific surface area and the measurement of the solid packing density, chemical analysis, and the powder characteristics and the like can be disclosed in Table 8 in comparison with the silver-copper composite powder to which the fine silver particles of the final product are attached. Manufacture of copper composite powder> The silver-copper composite powder was adhered to the fine silver particles by the same process as in Example 1. The particle size distribution (D5, D90, Dmax) and ratio of the silver alloy particles adhered to the fine particle silver particles thus produced were obtained. Measurement of surface area and tamping density, chemical analysis, and film evaluation (specific resistance), the results are shown in Table 8 as Example 6. Table 8 · Evaluation of chemical powder of sample spherical powder 00 EDX (%) Membrane specific resistance ϋ δ 〇D90 Dmax SSA TD Ag Cu Ag Cu (milliohm ohm·cm) Comparative Example 6 Silver-copper composite powder (silver-copper alloy powder) 5.68 12.5 37.0 0.53 4.3 71.8 29.2 62.1 37.9 6.7 Example 6 Silver-particle-attached silver alloy powder 6.97 12.5 37.0 0.54 4.1 80.1 19.8 70.8 29.2 0.7 <Comparison of Example 6 and Comparative Example 6>

The particle size distribution (D5d, D9g, specific surface area, and the filling density) of the flaky silver-coated copper powder, the silver-copper composite powder, and the silver-particle-attached silver alloy powder thus produced are determined by chemical analysis such as composition and composition. Comparison of the results. Knowledge of the characteristics of the powder: It can be seen from Table 8 that the silver particles of the silver particles adhered to the surface of the silver-copper composite powder are adhered to the silver-copper composite powder (Example 6), and the wet type The heat-treated silver-copper composite powder (Comparative Example 6) was compared, and there was no change in the powder characteristics among Ds., Dm, Dmax, and shake packing density (T.D.) 2213-8357-PF 44 1304003. However, the specific surface area The value of (SSA) was not significantly different between Example 6 and Comparative Example 6. However, considering the specific resistance of the film of Example 6 and Comparative Example 6, it was found that Example 6 showed much lower resistance than that of Comparative Example 6. It can be sintered low and exhibits good electrical conductivity. The tendency of the film resistance is the same as in the first to fifth embodiments. The knowledge of the change in the component amount is compared with the silver-copper composite powder (Comparative Example 6). ^ Body and surface silver*, making it into particles When the particles were attached to the silver-steel composite powder (Example 6), it was found that the silver content of the chemical analysis (analysis of the total amount of silver) and the EDx knife analysis (simple analysis of the amount of surface silver) increased. In the same manner as in the case of Example 1 to Example 5, it can be understood that the fine silver particles are firmly adhered. 'Dry another dry application Example 7> <Manufacture of silver-copper composite powder of core material> Copper powder for producing silver-copper composite powder Sulfuric acid cleaning: In pure water, μ liter, adding copper powder composed of 穑芈····································· After that, the mixture was washed three times, and the copper powder was treated by re-pulping with 1 liter of pure water as a clock. The preparation of the silver-coated copper powder was repeated, and the description was omitted. In Table 9, the powder is coated with copper powder to reveal the copper powder, and 8 〇iUt: 1,3 liters in pure water, and the above silver is added to concentrate, followed by methanol ', !&quot; , and mix 60 minutes 'after the wet treatment, after &quot;H, dry, make silver-copper composite powder.

2213-8357-PF 45 1304003 Next, the silver-copper composite powder was dispersed in a medium by DISGMAT D-5226 manufactured by VMG-GETZMANN Co., Ltd., and a 0.3 mm diameter yttrium oxide bead having a specific gravity of 5 gg/cm 3 was used. 600 g is used as the grinding beads, and 1 20 g of methanol and 5 g of citric acid are mixed in a solvent, and treated at a rotation of 2000 rpm for 3 hours. By compressing and plastically deforming the powder of the elemental powder, the ball is substantially spherical. The shape of the powder becomes a flake. The silver-copper composite powder of this stage was used as Comparative Example 9, and the particle size distribution (Ds〇, _D9, Dmax), specific surface area, and the silver-copper composite powder (flake powder) adhered to the fine silver particles of the final product. The measurement of the solid packing density, the chemical analysis, the powder characteristics and the like are disclosed in Table 9. <Production of the silver-silver composite powder (flake powder) to which the fine silver particles are adhered> The silver-copper composite powder was adhered to the silver-copper composite powder (flake powder) by the same procedure as in the first embodiment. The particle size distribution (^, U, specific surface area) of the silver-coated copper powder (approximately spherical powder), the silver-copper composite powder (flake powder), and the silver-particle-attached silver alloy powder (flake powder) produced as described above And the chemical analysis of the measurement and composition of the shake packing density. The results are shown in Table 9. Table 9· Evaluation of the spherical powder/sheet powder chemical analysis (%) EDX(8) Membrane specific resistance D50 ΰθ〇Dmax SSA TD Ag Cu Ag Cu (Milliohm ohm·cm) - Silver coated copper powder (spherical powder) 6.19 8. 95 14.3 1.79 3.2 46.9 50.3 69.1 30.9 Comparative Example 7 Silver-copper composite powder (flake powder) 7.19 13.8 31.3 2.04 3.2 47.0 50.8 60.0 40.0 4.1 Implementation Example 7 Silver Particles Attached to Silver Particles _ (Flake Powder) 7. 46 14.9 32.0 0.69 3.4 55.2 43.9 73.9 26.1 0.7 2213-8357-pf 46 1304003 &lt;Comparative Example 7 vs. Comparative Example 7 Powder characteristics (^, D9,, specific surface area (SSA), shaking filling density (τ·D), chemical quantitative analysis results, simple sizing results, film specific resistance to understand the coating of copper powder by silver To silver-copper composite powder, silver particles attached to silver The change of the copper composite powder is shown in the state of the powder. It can be seen from the table g that the silver-coated copper powder is composed of substantially spherical particles. For this, the silver-copper composite Yang after the wet heat treatment It is composed of flaky particles, so the comparison of Du, D9, Dmax, specific surface area (SSA), and solid packing density (7)) among these powder characteristics is serious; Therefore, the only ones that can be compared are the results of chemical quantitative analysis and the results of simple quantitative analysis. This will be described later. The particles of silver particles attached to the surface of the silver-copper complex a silver particles adhere to the silver-copper composite powder. (Example 7), compared with the wet heat-treated silver-copper composite powder (Comparative Example 7), there was no change in D5Q, D9G, Dmax, and shake packing density (TD) among the powder characteristics. However, the specific surface area ( The value of SSA) was smaller than that of Comparative Example 7 in Example 7. Then, referring to the specific resistance of the film of Example 7 and Comparative Example 7, it was found that Example 7 showed a smaller electric resistance than Comparative Example 7, and it was able to be sintered at a low temperature. Good electrical conductivity. Insight into changes in composition: The results of chemical quantitative analysis of the respective contents of silver and copper of the silver-coated copper powder and the silver-copper composite powder before the wet heat treatment were found to be not changed by the wet heat treatment, and the total amount did not change. In this regard, the results of the simple quantitative analysis of the surface layer of the powder-dispersed EPMA are 69_1% by weight for the surface layer of the silver-coated copper powder, and the surface of the silver-copper composite powder after the wet heat treatment. Silver 2213-8357-PF 47 • 1304003 The amount is reduced to 60 〇 番 g g / γ β 乂 乂 重 重 重 , , , , , , , , , , , , , , , , , 确实 确实 确实 确实 确实 确实 确实 确实 确实Then, after the wet-heat-treated silver-copper composite powder (Comparative Example 7) adhered to the fine-particle silver particles 'to make the fine-particle silver particles adhered to the silver-copper composite powder (Example 7), the chemical analysis results were obtained, Ε])χ As a result of the analysis, the silver content increased. [Industrial Applicability] The silver-silver composite powder of the fine-particle silver particles of the present invention has a structure in which fine particles of silver powder (silver nanoparticle) are adhered to the surface of the silver-copper composite powder. Use the previous silver powder, silver coated copper powder or ♦ silver copper: the low-temperature sinterability of the level not seen in the powder. Then, since the stable low-temperature sinterability which has never been seen before is expected, it is expected that the utilization field can be greatly expanded, and the energy cost of the sintering step can be greatly reduced. In addition, since the silver-copper composite powder to which the core material of the silver-copper composite powder is adhered to the fine particle silver particles is used, it is a fine-grained, homogenized one. σ On the other hand, the method for producing the silver-silver composite powder of the fine particle silver particles of the present invention is a method for producing the silver-silver composite powder by attaching the silver particles to the fine particles because the operation stability of the step is good. Therefore, it is possible to supply the silver-copper composite powder to the low-cost and high-quality fine silver particles in the market. [Simple description of the diagram] None [Key component symbol description] Μ 2213-8357-PF 48

Claims (1)

1304003 X. Patent application scope: 1 · A powder composed of fine silver particles adhered to silver-copper composite powder, which is composed of powder particles adhered to the surface of the powder particles of the core material powder, characterized in that: the core powder System silver-copper composite powder. 2. The silver-particle-attached silver-copper composite powder as described in claim 1 wherein the volume cumulative average particle diameter D5 is determined by a laser diffraction scattering particle size distribution measurement method. It is composed of approximately spherical powder particles of 粉·3 μm to 6.0 μm. 3. The silver-particle composite silver-copper composite powder as described in claim 2, wherein the volume-accumulated maximum particle diameter Dmax of the laser diffraction scattering particle size distribution method is less than 20 μm. It consists of roughly spherical powder. The fine particle silver-attached silver-copper composite powder described in the second aspect of the invention is composed of substantially spherical particles having a powder characteristic having a specific surface area of 0.2 m 2 /g or more. 5. The micro as described in item 1 of the patent application scope Also, the silver particles of the particles are attached to the silver and copper. 2213-8357-PF 49 1304003 7. The silver-particle composite silver-copper composite powder according to claim 5, wherein the powder has an aspect ratio (thickness of 〇, 0 2 〜 0 · 5) The flaky powder of the body characteristics is composed of a powder. The silver-particle-attached silver steel according to the first aspect of the patent application, wherein the film resistance formed by using the powder is 〇1 亳 ohm = cm ～2·0 milli ohm·cm. 、9. The silver-particle composite silver-copper composite powder as described in the third paragraph of the patent scope, wherein the silver content is 2〇% by weight to 9〇% by weight, residual steel And avoiding impurities. 10. A method for producing a silver-copper composite powder with silver particles attached thereto, characterized in that the silver-copper composite powder is brought into contact with a solution containing a mixture of a silver nitrate and a distorting agent. The addition of the reductant causes the particulate silver particles to precipitate on the surface of the powder of the silver-copper powder. 11. The method for producing the silver-silver composite powder of the particulate silver particles according to claim 10, in the bean, A + ^ T 1 silver-copper composite powder used in Hummer heartwood For copper powder surface, # Aha a, silver coated copper powder coated with silver coating, the silver coated copper powder wet processing, you, M, Fen..., after treatment, filtered, washed with alcohol, dried The invention relates to a method for manufacturing a silver-particle composite silver-copper composite powder according to the invention, wherein the silver-coated copper powder is added to the slurry of the dispersed copper powder in water. The chelate is treated with a silver-containing solution, and the one-half, a^ A ^ is used to form a silver coating on the surface of the powder of the copper powder. The weight of the copper powder in the dispersion is 1 00 weight 13. The fine particle silver particles adhered to the silver 2213-8357-PF 50 1304003 as described in the manufacturing method of the 12th copper composite powder of the patent application, and 20 parts by weight to 95 parts by weight of silver are contained in the above dispersion. The silver-containing solution is added to the liquid. 14. The method for adding the silver-silver composite powder to the silver-silver composite powder according to claim 12, wherein the above-mentioned chelating agent is ethylene diamine tetraacetate. — The particle silver described in Section 11 of the patent scope Sub-attached silver _ Fukoutai manufacturing method, wherein the above-mentioned wet heat treatment is carried out in a solution of temperature of ~200 C, and heat treatment for 3 〇 minutes to 12 〇 minutes. 16 · For example, the scope of the patent application scope of the application The method for producing a silver-copper double-coated cup of the fine-particle silver particles, wherein the above-mentioned error-solving agent is a sulfite or an ammonium salt. 17. The silver-silver composite powder adhered to the fine-particle silver particles according to claim 10 In the production method, the silver-copper composite powder used as the core material is made of silver; strontium is 20% by weight to 55% by weight, residual copper and inevitable impurities. The method for producing a fine silver particle-attached silver-copper composite powder according to the first aspect of the invention, wherein the silver-copper composite powder used as the core material has a powder characteristic having the following I · to III Approximate spherical powder: I · Volumetric cumulative average particle size D50 by laser diffraction scattering particle size distribution method is 0·2 μm~6. 〇micron; Π·volume accumulation by laser diffraction scattering particle size distribution method The maximum particle diameter Dmax is 20. 〇 micron or less; and the III· specific surface area is 0.2 m 2 /g or less. 1 9. The method for producing a copper composite powder according to the silver particle-attached silver 2213-8357-PF 51 1304003 #1, wherein the silver-copper composite powder used as the core material has the following i· ~ iii · The flaky particles of the powder characteristics: 1 · The volume cumulative average particle diameter D5Q of the laser diffraction scattering particle size distribution method is 〇·5 μm~1 〇· 〇micron; 11 ·Rolling around the laser The volume cumulative maximum particle diameter Dmax of the scattering particle size distribution measurement method is 4 〇·〇 micron or less; and the aspect ratio of the in·fine particles (thickness 〇·〇2~〇·5. 2 0 · (1) The method for producing a silver-copper composite according to the above-mentioned silver-particle composite, wherein the silver-copper composite powder used as the core material is a silver-copper composite powder composed of substantially spherical particles, and the particles are used. The position is G·5 pens or less and the specific gravity is &amp; 〇 gram / cubic centimeter ~ 6 · 5 gram / square boring abrasive beads are compressed and plastically deformed by high energy ball milling, and the gas is changed. 2213-8357-PF 52