TW201024004A - Silver particle containing copper, its manufacturing method and dispersion liquid using the same - Google Patents

Abstract

The present invention provides a manufacturing method for simple and mass production of nanoparticles having a unified particle diameter, and a silver particle produced by the manufacturing method thereof. In the reaction for reducing the silver particles, a silver compound solution, a protective agent and a reducing-agent solution were mixed, and one or more of the substance selected from the group consisting of copper, copper compound and copper ion were added before the reaction terminated. By using such reaction procedures, even the silver particles in the solution having an average particle diameter of 1 to 100 nm, a homogeneous particle diameter regardless of the reaction scales can still be obtained.

Description

[Technical Field] The present invention relates to silver particles, a silver-containing particle dispersion liquid, and a method for producing the silver particles, which are applicable to wirings, electrodes, and the like of an electronic device or the like. [Prior Art] It is generally known that particles having a nanometer-sized particle diameter are more specific than the micron-scale or lower particles, and are being used for the utilization of the property. For example, in the electrical and electronic equipment industry, for various types and miniaturizations, it has been reviewed to form fine wiring on a substrate for using nano particles or a low-temperature substrate. In addition to the examples, there are also particles which are reviewed for various uses, and the production method is known to be roughly classified into a gas phase method and a liquid phase method, etc., because the production by the vapor phase method is generally under vacuum conditions. In the first step, the initial investment cost of the device is increased, and it is not suitable for a large number of shortcomings. Further, in the case of the liquid phase method, although it is suitable for mass production, the liquidity at the initial stage of the reaction and the vicinity of the reaction is different, and the liquidity of the reaction vessel (10) is changed, resulting in fluctuations in the size and shape of the obtained particles. As a result, the problem that the particle size distribution is easily widened is caused. "Knowledge", the synthesis of liquid phase ruthenium, for example, the case of obtaining silver particles by liquid phase reaction, mostly by directly contacting the silver salt solution with the reducing agent solution to start the reaction using the reaction. Because the reaction occurs rapidly, the time until the end of the reaction is extremely short. There are seconds unit 098122526 201024004 $ It' This reaction will be partially reacted by the added liquid. This month, the brother-readable is difficult to make The obtained particles have a uniform morphology, and in order to obtain a relatively uniform particle, an attempt is made to perform a highly controlled reaction state, or a slower reduction is selected to lower the reaction rate to achieve a uniform sentence. The rice particles still have the problem of particle agglomeration. The interparticle cohesive force caused by the fineness of the characteristic particle size of the nanoparticle is larger than the known micron-scale or *micro-material and the reactivity of the particle is better. 'Therefore, there is a so-called condensed state in which the particles of the same (4) are condensed and combined with each other. If this kind of H is still unable to exhibit the properties of the nanoparticles that are expected, in order to solve this kind of situation, various kinds of things have existed. In particular, it is possible to change the reaction form itself or to perform a reduction under a slow condition as described above to make the reaction system more uniform. For example, the former example, for example, the patent document, changes from a conventional batch reaction to a continuous one. According to the technique of this document, the mixing state can be made constant by forming a continuous type. Therefore, the variation of the local concentration occurring in the conventional batch type reaction is small, regardless of any part of the reaction system. The reaction can be made uniform. Thus, silver fine particles having a uniform particle diameter can be obtained. Further, the latter example is as in Patent Document 2, and attempts have been made to mix a silver salt solution with a weak reducing agent in the presence of a protective agent. And the method of starting the reduction by slowly heating. In this case, since the reducing power of the reducing agent is relatively slow, it is impossible to start the reaction only by bringing the reducing agent into contact with the raw material solution. The reaction is started by applying heat externally. That is, 098122526 5 201024004 The solution in the reaction tank can also be used before the temperature at which the reduction starts. The result is adjusted to a uniform state. As a result, from the time when the reduction start temperature is reached, the entire reaction vessel is uniformly reduced in the entire region, and a powder having a small particle diameter variation can be obtained. Patent Document 1: Japanese Patent Laid-Open No. 2004-068072 2: 曰 专利 专利 〇〇 _ _ _ _ _ _ ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 因为 因为A related problem of homogenization. However, in the case of Patent Document 1, since it is characterized by a continuous reaction, a poor portion occurs at the production management level. Specifically, it is usually reviewed in the case of mass production, depending on various conditions. The cause causes an adverse situation. In this case, it is more difficult to find the cause of the abnormality in the case of continuous reaction. In addition, when the particles belong to the level of the meter, it is difficult to confirm the inconvenience on the spot (in_situ). As a result, continuous manufacturing is carried out under unfavorable conditions, and a large number of manufactured products become a month of disposing, etc., and it is known from the above, and it is preferable to perform a batch reaction by minimizing the viewpoint of occurrence of a problem. Further, according to the method of Patent Document 1, even if it is simply a batch type reaction, it is known from the comparison of the document = that the particle size unevenness is formed because the method of the grain size is not formed. The result of the particle size uniformity improvement effect. Therefore, it is quite difficult to use this method to satisfy both the raw and the particle size uniformity. 098122526 201024004 Furthermore, in the case of Patent Document 2, because of the special eyebrow agent, the temperature is raised to a predetermined value, and "the reducing agent with a weak reducing power is used to raise the fox to the temperature of the ruthenium and gradually reduce it, so that it takes several hours to cause a production reaction. Time is prosperous. In addition, since it is a reaction to reduce the reaction, the reaction tank _ temperature fluctuation becomes large when the reaction tank has a hundred-fold common phase, and there is a large valley such as _

=' is: the solvent is changed to a desired substance, so-called solvent replacement work must be performed and because the silver concentration of the obtained solvent is Μ% thin matter', therefore, in order to form a concentration suitable for utilization, it is necessary to carry out a thickening

There is a problem that the concentration step consumes time due to the ultrafiltration. Therefore, from the viewpoint of mass production, there is a need for further improvement. Μ I In view of the problems in the prior art, the purpose of this (4) is to provide a simple and escaping method for the integration of the size of the nano-greens, and the silver particles and aggregates thereof obtained by the method. Powder. (Means for Solving the Problem) The present inventors have intensively studied in order to achieve the above object, and as a result, have found that the above object can be attained by carrying out a reduction reaction in the presence of a trace amount of a copper component in the reaction liquid, and the present invention has been completed. That is, the method for producing silver particles of the present invention is a method for producing silver particles which are obtained by mixing a silver compound solution, a protective agent and a reducing agent solution in a reaction vessel, and is characterized in that copper is added before the completion of the reduction reaction. A substance (copper component) selected from the group consisting of a copper compound and a copper ion. Further, in a preferred embodiment of the method for producing silver particles of the present invention, the copper 098122526 7 201024004 2 is added to a mixed solution of a Wei compound solution, a protective agent, a reducing agent solution, a protective agent, and a reducing agent solution and a protective agent. Mix: At least one of the selected groups of fluids. In a preferred embodiment of the method for producing the above-mentioned silver particles, the amount of the above-mentioned copper compound and the constitutive group of the above-mentioned copper compound and the genus Implementation. ^ 2 〇〇〇 ppm form, which is the above-mentioned reducing form, which is the protective agent form, and is the above protective agent. Further, the method for producing the silver particles is preferably carried out according to 40 to 8 (Tc. Further, the above silver The method for producing the particles preferably contains at least one of carbon, nitrogen and oxygen. Further, the method for producing the silver particles preferably has a boiling point of 250. (The following is the same. Further, the method for producing the silver particles described above In a preferred embodiment, the functional group of the protective agent is selected from the group consisting of an amine group and m. "In addition, the towel of the present invention is composed of silver particles (the so-called "powder" in this book - The term used is the value provided in the measurement of physical properties ^ According to the average declination of the plural (4), the copper containing the w-face lion contains the arithmetic mean of the particle size measured from the TEM image. It is a copper having a surface of 1 to 100 Å and a powder having a surface ratio of 5 to 4 Å. 098122526 8 201024004 Further, the coefficient of variation of the particle diameter measurement value of the preferred silver particles is less than 30%. Furthermore, the preferred form of the silver particles is the above The boiling point of the agent is not more than 25 ° C. Further, a preferred form of the silver particles is a protective agent containing at least one of carbon, nitrogen and oxygen. Further, the protective agent is derived from an organic carboxylic acid or a derivative thereof. The composition of the present invention is Φ 3 to 8. Further, the dispersion of the present invention contains the above-described silver particles of the present invention. (Effect of the Invention) By using the method disclosed in the present specification, even if the average particle size in the solution is 1~ In the reaction operation of silver particles of 〇〇nm, the particle size uniformity can be obtained regardless of the reaction standard. [Embodiment] The following description of the preferred embodiments of the present invention will be described. A method for producing a recording medium in which a silver compound solution, a protective agent, and a (4) money are mixed and reduced in a reaction tank, characterized in that copper is present in the reaction system towel, and the "stomach copper component" in the present specification is In the present invention, in the case where the copper, the copper compound, and the copper ion towel are present in a plurality of cases, in the period in which the silver in the solution is reduced to silver by the reaction with the reducing agent, the copper is formed. The step of being present in the mixed solution is called 098122526 201024004: "copper addition step". The copper addition step may also include the operation of raising the copper in, for example, the reaction, and the reaction of the reaction (4) after the reaction. The manufacturing method of the present invention is intended to provide a reaction in the form of a reverse-sewed towel: a reduction reaction is carried out, and the effect is obtained. Therefore, the period of addition may be before the completion of the reduction reaction, but the reaction can be ensured. The uniformity is preferably present in the period before the reduction reaction. The addition form is not particularly limited, and it is preferred that the copper which acts in the solution is in an ionic state. The addition of the copper component may also be in, for example, silver. One or more of the raw material solutions are added to the compound solution, the protective agent, the reducing agent solution, the silver compound solution, the lysate (mixed), and the reducing agent solution and the protective solution-mixing solution. It may be added during the period from the start of the mixing of the raw material solution to the start of the reduction reaction. However, since the reduction reaction is completed in a short time in a few minutes depending on the situation, it is recommended to select a case where the reduction reaction is weak. In addition, in the present emission, when the reducing agent is added to the solution sampled from the reaction solution in the "end of reaction" county, the time at which the unreduced silver reaction is not caused is not caused. The final raw silk t, from the fact that there is almost no photo in the presence of copper, is not necessary for the copper to be absorbed into the particles. Namely, although the reaction mechanism is not known, in the present invention, it is sufficient that copper is present in the reaction liquid at the time of the reaction. Therefore, the form of copper added is not subject to any restrictions. For example, if it is added in the form of a block of 098122526 201024004, it may be in the form of powder, foil, or block in the case where copper is eluted in the form of ions. However, in this case, it is preferable to consider the method of separating the powder, the foil, the block, and the like after the reaction is completed, from the viewpoint of suppressing the incorporation of impurities. In the present invention, the amount of the copper component added varies depending on the reaction standard, and if it is a certain amount or more, the effect is saturated. Therefore, the upper limit of the amount of copper component added is not particularly determined. Therefore, the presence of more than the required copper is not required, and the maximum is less than 2000 ppm, preferably less than 1 ppm, relative to the total of the / liquid mixture. Since the copper system is a metal that is more inferior to silver, the ion form in the solution in which copper and silver coexist is relatively stable. Therefore, in the silver particles of the final product, the copper added in the solution is hardly contained. Further, the silver particles of the present invention and the main drying step may be provided in the form of a powder. Therefore, the so-called "silver particles" of this (4) book towel also covers the powder in the form of a dry form.银 The silver powder towel formed in accordance with the method of the present invention contains copper in the range of 1000 ppm. If it is not full of lions, it can be said that according to the invention, the filth is in accordance with the invention. Another: Aspects' When more than 1000ρρηι Temple, it will show the copper and g-shaped silk material in the solution, there is still the possibility of affecting the conductivity, so it is best to avoid. In order to form pure silver, it is necessary to have: = generation and thus the residual steel content is preferably from 1 to 500 ppm, more preferably from 1 to 3 ppm. . The above silver compound solution is described below with respect to the raw material solution of the present invention. 098122526 201024004 means a compound in which a silver compound is dissolved in a solvent. The type of the above-mentioned silver compound may be appropriately selected by using a solvent, and for example, if the solvent is water, silver nitrate is preferably used. The functional group constituting the particles according to the present invention is preferably one which can be easily incorporated into the surface of the silver particles and has a property of so-called high affinity. Specific examples thereof include a mercapto group, an amine group and the like. The use form of the silver particles of the present invention is used in the form of a conductive dispersion or a paste, for example, in a solvent or the like. At this time, in order to form a highly conductive material, it is preferable to form a high-purity substance having as few impurities as possible. In order to form a high-purity metal film, it is necessary to minimize the incorporation of impurities. Therefore, it is preferable that the protective agent in the conductive film composition after firing disappears almost to the reading which is not recognized by the ball. Therefore, the interface _ point of the surface constituting the surface is preferably lower. Specifically, it is below 250 ° C, preferably 200X: below, and the skill is 15 feet. The protective agent of the present invention is not particularly limited as long as it has the above characteristics, and examples thereof include butyric acid, valeric acid, caproic acid, heptanoic acid, octanoic acid, ° 1X1 acid, lactic acid, succinic acid, hexylamine, and octylamine. , hexamethylene diamine, etc. In addition, the molar ratio of silver is protected (the molar number of the protective agent molecule/the number of silver moles is 1, and the amount is 0.1 to 4.0. If it is less than G1, it occurs because the protective dose relative to silver is too good. The possibility of condensation between most particles. V. In addition, in the case of more than 4.0, there is a large amount of protective agent around the coated silver. This phenomenon indicates that the silver composition in the final formation has the concern of the residual impurity compared with 098122526 201024004. South 'has not easy to obtain a high-purity silver film, so it is best to avoid it. Therefore, the ratio of the amount of the protective agent added / silver is preferably in the range of 0.5 to 3.0, more preferably 1.0 to 2.0. Under the premise of reducing silver ions to silver, the rest is not particularly limited. Hydrogenated sodium, strontium, L-ascorbic acid, hydroquinone, gallic acid, formalin, phosphine, and glucosamine, which have been widely used since the beginning of the study, can be used. a sugar acid, or a derivative of the filial acid, etc. The amount of the reducing agent added is preferably in the range of 1.0 to 9.0 in terms of the equivalent of silver. If less than 1 〇, the possibility of non-reduction may occur, and vice versa. If it exceeds 9.0, because there is too much reducing dose Therefore, the reaction is too fast, resulting in an increase in the number of condensed particles. "There is a possibility that the particle size variation becomes large, and thus it is preferable to avoid it. Further, in the above-mentioned reducing agent solution, a solvent containing a protective agent can be further contained. The protective agent which can be used in the production method of the present invention is used for dissolving the above protective agent when it lacks solubility in a solvent. When the protective agent is not uniformly present in the reducing agent solution, it is unevenly present because the reaction is uneven. It is preferable to add a protective agent solubilizing agent to dissolve the protective agent. The type of the protective agent solubilizing agent is changed depending on the kind of the protective agent, and when the protective agent is an acid, ammonia or the like is used. The amount of the protective agent required to dissolve is sufficient. Further, the method for producing the above silver particles is preferably carried out in the range of 40 to 。. If it is less than 40 (:: because of the supersaturation of silver) Increase, and thus excessive nuclear generation occurs, and excess particulates of the primary particles are carried out. Generally, when the primary particle diameter is small, since the cohesive force becomes strong, the particles are formed. Condensation between 098122526 13 and 201024004 causes particle size variation. In addition, according to other reaction conditions, it is insufficient in terms of reduction, and thus unreduced. In addition, if it exceeds 80C, 'because the reaction is too fast', it is utilized. The protective agent is fully protected, and the particles are dissolved to cause an increase in the number of coagulated particles. This phenomenon causes a change in the particle size. The so-called reduction reaction is 40 to 80. (: Implementation), the solution introduced into the reaction tank may be separately added or subtracted. 4 〇 ~ 8 (Π:, can also be taken in the initial reaction in the reaction to heat the solution to 40 ~ 8 (TC, and then add 4 〇 ~ thief other solution method. The second, for the manufacturing method according to the invention can be made The silver particles are described in detail. According to the production method of the present invention, nano-sized silver particles having an integrated particle size can be obtained regardless of the reaction specifications. Here, the "silver particle diameter" means a particle diameter measured by a measurement method described later from a TEM image. The silver particles of the present invention are preferably such that the average value of the primary particle diameter is in the range of iMOOnm. If the average value of i of the i-th particle diameter is less than 1 nm, since the cohesive force of the particles is too strong, it is difficult to prevent the occurrence of particle coagulation. Further, when it exceeds 1 〇〇 nm, since the low-temperature sinterability is deteriorated, it is considered to be unsuitable for use in metal wiring applications and the like intended for the silver particles of the present invention. Further, the specific surface area measured by the bet method of the silver particle powder of the present invention is 5 to 4 m 2 /g, preferably 15 to 40 m 2 /g, more preferably 20 to 30 m 2 /g. The silver particles produced by the method of the present invention 4 are apparently increased by adding a copper component at the time of manufacture 098122526 _ 201024004. Although the reason for this is not known, it is found that the reaction rate of the former is remarkably faster when the steel is added and compared with the case of no addition. This phenomenon is considered to be a possibility of exerting a catalytic effect. Further, the specific surface area of the silver particle powder can be adjusted by the amount of the copper component added at the time of production. When the silver particles are dispersed and liquefied, the viscosity is adjusted to suit the application and the printing method. The viscosity of the dispersion is greatly affected by the specific surface area of the particle powder. For example, when the specific surface area of the particle powder is large, since the amount of solvent which contacts the surface of the particle increases, the amount of the solvent which is not in contact with the surface of the particle decreases, resulting in an increase in viscosity. On the other hand, when the surface area of the particle powder is small, since the amount of solvent contacting the surface of the particle is reduced, the amount of solvent-free is increased, and the viscosity is lowered. In general, in addition to adjusting the surface area of the powder, the addition of the viscosity modifier and the adjustment of the amount of the solvent may be adjusted according to the viscosity of the dispersion, but the addition of the viscosity modifier is as described above, because the residual impurities may increase. As a result of suppressing the conductivity, the volume resistance value at the time of forming the metal film is increased. In order to eliminate this possibility, it is preferable to adjust the particle powder by the change in the surface area. From this point of view, the method for producing various specific surface area silver particle powders is easily obtained as in the present invention, and has an advantage that the viscosity of the dispersion liquid suitable for various uses can be easily adjusted. Further, regarding the specific surface area adjustment of the particle powder, a method which is not conventionally employed in the production method of the present invention, such as a reduction amount or a reaction temperature adjustment, may be considered, and the specific surface area of the particle powder may be adjusted, but according to the present invention Review of 098122526 15 201024004, 'It is still not possible to obtain dry silver particle powder having a specific surface area of 5 m 2 /g or more even if it is changed according to such reaction conditions. In addition, there are cases of poor silver particles such as changes in the shape of the job when each liquidity changes, or

Generally, the particle diameter changes from one of the TEM images. Regarding the variation of the particle size, - the standard deviation value of the average granule squatting' is obtained by dividing the average value; the coefficient of variation (4) of the ^ is an index. In the ft condition of the silver particles of the present invention, the above coefficient of variation is less than 35%. If the value is above, the particle size will vary greatly and it is best to avoid it. Preferably, it is less than 3%. The silver particles of the present invention have an I1 biomass which is excellent in low-temperature sinterability by adopting the above structure. The bulk resistance value of silver is 1.6 μΩ • cm, and by using the particles of the present invention, a resistance value similar to this value can be obtained even if the firing temperature is set to about 250 C. Further, in order to impart such a property, it is of course necessary to take into consideration the structure at the time of forming a dispersion described later, in particular, a dispersing medium, an additive decomposition point, and a boiling point. Further, according to the method for producing silver particles of the present invention, it is possible to easily produce silver particle powders having various specific surface areas, and thus it is possible to produce a dispersion liquid which can be used in various applications and printing methods. The "dispersion liquid" in the present invention means a liquid in which the silver particles of the present invention are dispersed in a solvent. Further, according to a preferred embodiment of the present invention, since the solidified liquid separation can be easily carried out by filtration after the reaction, the powder 098122526 16 201024004 can be further dispersed in various solvents. The dispersion solvent which can be used at this time may, for example, be water, an alcohol, a polyhydric alcohol, a glycol ether, a methylpyrrolidinedione, pyridyl oleyl alcohol, butyl carbitol, butyl carbitol acetate, 2,2,4_trimethyl 3_pentanediol monobutyrate (Texanol), phenoxypropanol, and the like. Further, in order to further improve the dispersibility of the dispersion liquid or the addition of a binder or a dispersant together with the dispersion solvent, it is also possible to form a preferred embodiment. The binder is an essential element for imparting dispersion independence to the particles, and therefore must have at least affinity with the solvent and the particles. In addition, regardless of the increase in the dispersibility, if it is not discharged outside the system during sintering, it does not meet the purpose of the invention of H. That is, the decomposition or vaporization temperature is selected at 25 (rc). If at least the above properties are present, the commercially available organic materials are not suitably used. Further, not only a single type but also a combination of specific types may be used. As the organic binder, for example, an acrylic resin, a polyester resin, an epoxy resin, a phenol resin, a phenoxy resin, a DAp resin, an amino phthalate resin, a fluororesin, a polyimide resin, a poly For example, a ruthenium resin, a polysiloxane resin, a polyolefin resin, an ethyl cellulose, a polyvinyl alcohol, or the like, as the inorganic binder, for example, a oxidized sol, an oxidized sol, a zirconia sol, a titania sol or the like can be used. .

The following names are known from the specific names, but those having the above properties do not exclude substances other than those described in the column. Examples of the acrylic resin system include BR-102, BR-105, BR-117, BR-118, BR-1122, MB_3058 (manufactured by S. Ryokan Co., Ltd.), ARFLON UC-3000, and ARFLON 098122526 17 201024004 UG. -4010, ARFLON UG-4070, ARFLON UH-2041, ARFLON UP-1020, ARFLON UP-l (m, ARFLON UP-1061 (manufactured by Toagosei Co., Ltd.); as a polyester resin, for example, Vylon 220,

Vylon 500, Vylon UR1350 (manufactured by Toyobo Co., Ltd.), MALKYD® No. 1 (manufactured by Arakawa Chemical Industry Co., Ltd.); as epoxy resin, for example, ADEKA RESIN EP-4088S, ADEKA RESIN EP-49-23 (made by ADEKA Co., Ltd.), 871 (made by Japan Epoxy Resins Co., Ltd.); phenolic resin type: RESITOP ❿ PL-4348, RESITOP PL-6317 (made by Qunrong Chemical Industry Co., Ltd.); Examples of the oxy-resin may be, for example, 1256, 4275 (manufactured by Japan Epoxy Resins Co., Ltd.) or TAMANOL 340 (manufactured by Arakawa Chemical Industries Co., Ltd.); and as DAP resin, for example, DAP A, DAP K (DAISO Co., Ltd.) (A), for example, ETHOCEL © STAND ARD4, ETHOCEL STAND ARD7, ETHOCEL STANDARD20, ETHOCEL STANDARD100 (made by Nippon Evolution Co., Ltd.); as a polyvinyl alcohol, for example, RS-1713, RS-1717, and RS-2117 (KURARAY shares are available) Co., Ltd.). Further, the dispersant is also provided on the premise that it has a particle surface and affinity and has affinity for a dispersing medium. In addition, not only individual types but also combinations can be used. 098122526 18 201024004 Representatives of dispersing agents are: fatty acid salts (soap), α_continuous fatty acid vinegar (MES), benzoic acid (ABS), linear alkyl benzoate (las), alkyl Low molecular anionic (anionic) compounds such as sulfate (AS), alkyl ether sulfate (AES), alkyl triacetate, etc.; fatty acid ethanol decylamine, polyoxyethylene squaring (AE), polyoxygen Low-molecular nonionic compounds such as ace, sorbitol, sorbitol, etc.; succinyltrimethylammonium salt, dinonyldithiocarbamate, and base gas a low molecular cation (cationic) compound such as hydrazine or the like; a low molecular amphoteric compound such as an alkylcarboxy beet test, a sulfonic acid beet test, or an egg squama; or a formalin a polymer aqueous dispersant represented by a condensate, a polystyrene acid salt, a polyacrylic acid salt, a copolymer salt of an ethylene compound and a few acid monomers, a carboxymethyl cellulose, a polyvinyl alcohol, or the like; a polyacrylic acid Polymer non-aqueous dispersing agent such as partial alkyl ester, polyalkylene polyamine, etc.; Cationic amine polymer-based dispersing agent, Yue-based acrylic acid alkyl ester amine of copolymer, etc., but if part of the present invention suitable for • preferred compound particles, it does not exclude exemplified here was the outer shape of the structure. As the dispersing agent, the following names are known as the following. Examples are: Flouren DOPA-15B, Flouren DOPA-17 (Co-Profit Chemical Co., Ltd.); SOLPLUS® AX5, SOLPLUS® TX5, Solsperse 9000, Solsperse 12000, Solsperse 17000, Solsperse 20000,

Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 35100, 098122526 19 201024004

Solsperse 54000, SOLTHIX 250 (made by Lubrizol Co., Ltd.); EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA7462, EFKA4400, EFKA4300, EFKA6225, EFKA4047 EFKA4020 EFKA4401 EFKA4330 EFKA6700, EFKA4060, EFKA4050, EFKA4402, EFKA4340, EFKA6780, EFKA4080, EFKA4055, EFKA4403, EFKA6220, EFKA6782,

EFKA8503 (manufactured by Efka Additives); AJISPER PA111, AJISPER PB71, AJISPER PB821, AJISPER PB822, AJISPER PN411, FAMEX® L_12 (made by Ajinomoto Fine-Techno Co., Ltd.); TEXAPHOR-UV2 TEXAPHOR-UV61 (Cognis Japan Co., Ltd.) 3 DisperBYK106, DisperBYK116, DisperBYK142, DisperBYK162, DisperBYK166, DisperBYK170, DisperBYK180 'DisperBYK193, DisperBYK2020, DisperBYK2070,); DisperBYKIOl DisperBYK108, DisperBYK130, DisperBYK145, DisperBYK163, DisperBYK167, DisperBYK171, DisperBYK182, DisperBYK2000, DiSperBYK2025, DisperBYK2155,, DisperBYK102, DisperBYKlll, DisperBYK140 , DisperBYK161, DisperBYK164, DisperBYK168, DiSperBYK174, DisperBYK192, DisperBYK2001, DisperBYK2050, DisperBYK2164, 098122526 20 201024004 BYK220S, BYK300, BYK306, BYK320, BYK322, BYK325, B YK3 3 0, B YK3 40, B YK3 5 0, B YK3 7 7 , B YK3 7 8, B YK3 8 ON, BYK410, BYK425, BYK430 (BYK-Chemie · Japan shares Limited company system); DISPARON 1751N, DISPARON 1831, DISPARON 1850, DISPARON 1860, DISPARON 1934, DISPARON DA-400N, DISPARON DA-703-50, DISPARON DA-725, DISPARON DA_705, DISPARON DA-7301, DISPARON φ DN-900 DISPARON NS-5210, DISPARON NVI-8514L, HIPLAD ED-152, HIPLAD ED-216, HIPLAD ED-251, HIPLAD ED-360 (Hashimoto Kasei Co., Ltd.); FTX-207S, FTX-212P, FTX-220P, FTX-220S, FTX-228P, FTX-710LL, FTX-750LL, FTERGENT® 212P, FTERGENT® 220P, FTERGENT8 222F, FTERGENT® 228P, FTERGENT® 245F, FTERGENT® 245P, FTERGENT® 250, FTERGENT® • 251, FTERGENT® 710FM, FTERGENT® 730FM,

FTERGENT9 730LL, FTERGENT® 730LS, FTERGENT® 750DM, FTERGENT® 750FM (manufactured by Neos Co., Ltd.); AS-1100, AS-1800, AS-2000 (manufactured by Toagosei Co., Ltd.); KAOCER® 2000, KAOCER® 2100, KDH_ 154, MX-2045L, HOMOGENOL L-18, HOMOGENOL L-95, RHEODOL SP-010V, RHEODOL SP-030V, RHEODOL SP-L10, RHEODOL SP-P10 (made by Kao Co., Ltd.); EVAN U103, SEANOL 098122526 21 201024004

DC902B, NOIGEN EA-167, PLYSURF A219B, PLYSURF AL (manufactured by Daiichi Kogyo Co., Ltd.); MEGAFAC® F-477, MEGAFAC® 480SF, MEGAFAC® F-482 (manufactured by DIC Corporation); SEALFAITH SAG503A, Dynol 604 (manufactured by Nissin Chemical Industry Co., Ltd.); SN Spurs 2180, SN Spurs 2190, SN Leveller S-906 (manufactured by San Nopco Co., Ltd.); S-386, S420 (manufactured by AGC SEIMI CHEMICAL Co., Ltd.), and the like. ❹ Furthermore, appropriate mechanical dispersion treatment can also be used for dispersion adjustment. When the mechanical dispersion treatment is carried out, any method known in the art can be employed without significantly modifying the derivatized particles. Specifically, for example, ultrasonic dispersion, disperser, three-roll mill, ball mill, bead mill, twin-shaft kneader, self-propelled blender, etc. can be used alone or in combination. Hereinafter, the measurement method used in the present invention will be described. (Measured from the average value of the primary particle size of the TEM image)

2 parts by mass of the dry state silver particle powder was added to a mixed solution of 5% by mass of cyclohexane and 2 parts by mass of oleic acid, and dispersed by ultrasonic waves. The dispersion solution was dropped on a Cu microgrid having a support film and dried to form a TEM sample. The microgrid made using a transmission electron microscope (JEM-iOOCXMarkA type manufactured by JEOL Ltd.), according to the viscous V accelerating voltage, the particle image used in the bright field is magnified by 30,000 times and 174,000 times. Take a picture. - The average of the sub-particles (4) is calculated by the (4) image analysis software (Asahi Kasei Engineering Co., Ltd. 098122526 22 201024004 Co., Ltd. A-Jun (registered trademark)). The image analysis soft system recognizes each particle according to the color shading. For the TEM image of Π4, _ times, according to "particle brightness", "dark", "noise removal filter": "Yes", "Circular threshold" : "20", "overlap": "50" condition, circular particle analysis is performed and the average particle diameter is measured. When the bank has a number of condensed particles or shaped particles, it is considered unmeasurable. (Changing the coefficient of variation from the primary particle diameter) • Calculate the average value and the standard deviation from the measured values measured by the above measurement method, and calculate the standard deviation divided by the average value as the coefficient of variation and calculate Out. '(Measurement of copper content in silver particle powder) If there is a silver component remaining, there is a possibility that an analysis error may occur. Therefore, in order to remove the silver component, the following pretreatment is performed. Silver particle powder l〇g was placed in a 3 〇〇ml conical beaker, and then 15 ml of a nitric acid solution was added to dissolve the silver particle powder. The dissolved solution was heated on a hot plate set to 250 T: and concentrated to such an extent that it did not evaporate and dry. After the concentrated solution was allowed to cool, pure water was added. No white turbidity or floats were found in the solution. If white turbidity or floating matter appears in the solution, repeat the steps of adding nitric acid, heating and concentrating, and allowing to cool until it disappears. Calcium chloride is formed by adding hydrochloric acid to a solution free of white turbidity and floating matter. Then, it was separated into silver chloride and a filtrate by solid-liquid separation by filtration, and the filtrate was subjected to copper amount analysis using ICP-MS (AGILENT 7500i manufactured by Agilent Technologies Co., Ltd.). 6 098122526 23 201024004 (Specific surface area by BET method) Measurement) 0.2 g of silver particle powder was subjected to a treatment for 20 minutes in an N 2 atmosphere of 25 t: and 45 cc/min, and then it was carried out using 4S-U2 manufactured by Yuasa_i〇nics or an equivalent of the product. (Measurement of TAP density) The measurement method described in JP-A-2007-263860 was used. (Volume Resistance Value of Silver Film) The silver particle powder was paste-formed and coated on a glass substrate. The coated glass substrate was fired by a dryer (manufactured by YAMATO SCIENTIFIC Co., Ltd.) at the temperature and time shown in each of the examples and the comparative examples. The volume resistivity per Ιμηη of the thickness of the fired film was measured using a resistivity meter (LORESTAGP manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the film thickness was measured by a surface roughness meter (Surfcom 1500D manufactured by Tokyo Seimitsu Co., Ltd.). The measurement is carried out, whereby the volume resistance value of the film can be calculated. [Examples] The following examples are described in detail. (Example 1) In the examples 1 to 7, the reaction tank was a 5 L reaction tank. In addition, in order to perform the drop, a bladed spoiler is placed in the center of the reaction tank. A thermometer for monitoring the temperature is provided in the reaction tank, and in addition, the nozzle is set in such a manner that the solution can supply nitrogen from the lower portion. 098122526 24 201024004 First, 3400 g of water was placed in the reaction vessel, and in order to remove residual oxygen, the lower portion of the reaction vessel was flowed into the nitrogen at a flow rate of 3000 mL/min for 600 seconds. Then, it was supplied from the upper portion of the reaction vessel at a flow rate of 3000 mL/min, and the reaction sample was allowed to form a nitrogen atmosphere. Then, the temperature was adjusted while stirring was carried out in such a manner that the temperature of the solution in the reaction tank became 6 Torr. Then, 7 g of a 28% by mass ammonia water as ammonia was put into the reaction vessel, and then the mixture was stirred for 1 minute in order to make the solution uniform. • Next, 45.5 g of hexanoic acid (manufactured by Wako Pure Chemical Industries Co., Ltd.) as a protective agent (manufactured by Wako Pure Chemical Industries Co., Ltd.) was added, and stirring was carried out for 4 minutes in order to protect: dissolve. Then, 23 g of an aqueous solution of 5 〇 mass % hydrazine (manufactured by Otsuka Chemical Co., Ltd.) as a reducing agent was added (to be 4.82 equivalents with respect to silver), and this was used as a reducing agent solution. In a separate container, 33.8 g of a silver nitrate crystal (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in an aqueous solution of silver nitrate in water i8 〇g, and this was used as a cerium silver salt aqueous solution. In the silver salt aqueous solution, copper nitrate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 1 ppm in terms of copper in terms of copper. Further, the copper nitrate trihydrate addition here is an aqueous solution of copper nitrate trihydrate which is known in advance, and is adjusted by adding a thinner. Further, the aqueous silver salt solution was adjusted to a temperature of 60 ° C as the reducing agent solution in the reaction vessel. Then, the silver salt aqueous solution was added to the reducing agent solution at a time, and the reaction was started by mixing. At this time, the color of the slurry was changed immediately after the end of the addition, 098122526 25 201024004. The stirring system was continuously carried out, and the mixture was aged for 10 minutes in this state. Then, the stirring was stopped, and solid-liquid separation was performed by suction filtration, and washing was performed with pure water until the conductivity of the washing waste liquid became less than 2 〇μ8/(; ηη, and dried at 4 ° C for 12 hours. 'Therefore, the fine silver particle powder is obtained. In addition, since the obtained powder has high sensitivity to heat, drying at this temperature or higher may become bulk silver. (Example 2) In addition to silver salt The aqueous solution of copper nitrate trihydrate added to the aqueous solution was changed to the amount of 5 ppm in terms of copper in terms of copper, and Example 1 was repeated (Example 3) except for the nitric acid added in the aqueous silver salt solution. The copper trihydrate aqueous solution was changed to an amount of 10 ppm in terms of copper, and the same Example 1 was repeated. (Preparation of silver-containing particle dispersion) 6 6 g of silver particle powder and terpineol were obtained. 4 g of the mixture was mixed, and the silver-containing particle dispersion liquid was prepared by performing a 90-second treatment at 1400 rpm for 10 times in three rolls. (Production and firing of a silver coating film) Particle dispersion in glass carrier The coating was carried out by using an applicator, and then it was baked at 150 ° C for 30 minutes using a dryer (manufactured by YAMATO SCIENTIHC Co., Ltd.), and was also fired for 30 minutes according to 2〇〇098122526 26 201024004 C. The sample was measured for each volume resistance value. (Example 4) The silver particle production step of Example 3 was repeated except that the copper source added to the silver salt aqueous solution was changed to cuprous oxide. Example 5) Example 1 was repeated except that the aqueous solution of copper tribromide trihydrate added to the aqueous silver salt solution was changed to an amount of 100 ppm relative to silver in terms of steel. Example 5 was repeated except that the copper source added to the silver salt aqueous solution was changed to copper powder. (Example 7) The aqueous solution of copper nitrate trihydrate added to the aqueous silver salt solution was changed to The copper conversion was repeated with respect to the amount of silver of 100 ppm. The rest of Example 1 was repeated. (Example 8) In Examples 8 to 13, the reaction tank was a 200 L reaction tank, and the same was set in the 5 L reaction tank. Mixing rod, thermometer And a nitrogen nozzle. First, 137 kg of water was placed in the reaction vessel, and in order to remove residual oxygen, nitrogen was introduced from the lower portion to 2 〇L/min for 600 seconds, and then, from the upper portion of the reaction vessel, 2 〇L/min. Nitrogen: The inside of the reaction tank should be made into a nitrogen atmosphere. Then, according to the way the temperature of the solution in the reaction tank becomes 6 Gt: - the temperature is adjusted while mixing. 098122526 27 201024004 Then, it will be 28 mass as ammonia. After 282 g of ammonia water was put into the reaction tank, the mixture was stirred for 1 minute in order to make the solution uniform. Then, 1818.8 g of hexanoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) as a protective agent was added (relative to the silver-based molar ratio) 08), and stirring was carried out for 4 minutes in order to dissolve the protective agent. Then, an aqueous solution of 596 g of hydrazine hydrate (manufactured by Otsuka Chemical Co., Ltd.) as a reducing agent was added to 596 g (4.82 equivalents with respect to silver), and this was used as a reducing agent solution. In a separate container, silver nitrate crystals (manufactured by Wako Pure Chemical Industries Co., Ltd.) 1350_3 g of silver nitrate aqueous solution dissolved in 7200 g of water were prepared and used as a silver salt aqueous solution. To the silver salt aqueous solution, a copper nitrate trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 〇 325 g (10 ppm in terms of copper with respect to silver) was further added. Further, the aqueous silver salt solution was applied as 60 as the reducing agent solution in the reaction tank. (The temperature is adjusted. Then, the silver salt aqueous solution is added to the reducing agent solution at a time, and the reaction is started to carry out the (4) reaction. The continuation is carried out, and the akiji mic is cooked in this form. Then 'stop (four), use pressure The filter was separated by a filter and washed with pure water until the conductivity of the cleaning solution was less than 2 μs/cm. After drying at 4 G ° C for 12 hours or more, fine silver particles were obtained. (Preparation of dispersion) The fine silver particle powder obtained was added to a solvent or the like to prepare a dispersion liquid, and a small amount of fine silver particle powder i_〇g and butyl carbitol acetate vinegar (manufactured by Wako Pure Chemical Industries, Ltd.) 10 0g, and 098122526 28 201024004

DisperBYK2020 (manufactured by BYK-Chemie Japan Co., Ltd.) 0.1 g. These were mixed in a test tube and dispersed for 10 minutes using an ultrasonic disperser. The results were evenly dispersed, and no precipitate was found even at the bottom of the test tube. In addition, even after standing for 24 hours, no sediments were found at the bottom of the test tube, and the dispersion was good. (Example 9) Example 8 was repeated except that the amount of the copper sulphate trihydrate added in the silver salt aqueous solution was changed to 20 ppm in terms of copper in terms of copper. (Example 10) Example 8 was repeated except that the amount of copper tribromide trihydrate added to the silver salt aqueous solution was changed to an amount of 50 ppm in terms of copper in terms of copper. (Example 11) Example 8 was repeated except that the amount of copper tribromide trihydrate added to the silver salt aqueous solution was changed to an amount of 100 ppm in terms of copper in terms of copper. (Example 12) Example 8 was repeated except that the amount of the copper acid terminal trihydrate added to the silver salt aqueous solution was changed to 300 ppm in terms of copper. (Example 13) 098122526 29 201024004 Example 8 was repeated except that the amount of the copper nitrate trihydrate added to the silver salt aqueous solution was changed to an amount of 500 ppm in terms of copper in terms of copper. (Comparative Example 1) Example 1 was repeated except that no copper lithosperate trihydrate was added to the silver salt solution. The reaction color was changed from about 3 seconds after the end of the addition.

(Comparative Example 2) Example 8 was repeated except that copper sulphate trihydrate was not added to the aqueous silver salt solution. (Comparative Example 3) In addition to the force added in the aqueous silver salt solution. Example 1 was repeated except that the amount of the aqueous solution of copper nitrate trihydrate was changed to 6 〇〇〇 ppm in terms of copper in terms of copper.

(Comparative Example 4) Example 1 was repeated except that the amount of the aqueous solution of copper nitrate trihydrate added to the aqueous silver salt solution was changed to an amount of 60,000 ppm with respect to silver in terms of copper. (Comparative Example 5) In addition to the substitution of the copper nitrate hydrate, the addition of nickel nitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was carried out in terms of nickel, and the remainder was repeated. 098122526 30 201024004 (Comparative Example 6) In addition to the substitution of copper nitrate trihydrate, an aqueous solution of iron nitrate (m) nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 100 ppm in terms of iron. Example 1 was repeated. (Comparative Example 7) After the completion of the reduction reaction of Comparative Example 1, the aqueous solution of the copper nitrate trihydrate was added in an amount of 3000 ppm in terms of copper with respect to the reaction slurry, and stirring was continued for 5 minutes in this state. Then, the stirring is stopped, and filtration and washing are performed. (Comparative Example 8) Except that the amount of the hydrazine hydrate of the reducing agent was changed to 9.6 equivalents with respect to silver, the remainder of the comparative example 1 was repeated. ^ After the start of the reduction reaction, the change in the color of the reaction mixture was immediately completed, and it was confirmed that the reaction had been completed. End. The reaction specifications of the examples and the comparative examples, the additives added during the production, the amount of addition, the Cu content contained in the silver particle powder after the reaction, the BET specific surface area of the silver particle powder in the dry state, the TAp density, and the Tem The diameter and coefficient of variation, and the volume resistance of the silver film are shown in Table 。. Further, the TEM images of Examples 3 and 5 are shown in Figs. 3 and 3, and the TEM image of Comparative Example 1 is shown in Fig. 4. The magnification of the TEM photographs was all 174, 〇〇〇 times. In addition, the bottom right arrow of the photo of Figure 2 all indicate the lion. 098122526 31 044002 1Χ20 【一<】

Si! ifesap · m O〇饀5宕1 1 1 1 1 1 1 1 1 i 1 1 1 6.06 I 33.9 1 1 I 1 1 ιρτ 乐|ΐ·1 Aflj) · m ^ G ^ ^ »n J^psi 'w^ 1-H 1 1 3.33 1 1 1 1 1 1 1 1 1 1 1 6.06 σ\ m 1 1 1 1 I-order particle size TEM diameter variation coefficient (%) r·^ (N VO 1-H On 宕卜σ\ <Ρ"Η 宕 宕 〇 〇 N N 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 CO inch mm CN tn CO Os CN (Μ CO r4 T—^ 1 1 cn m rn 1 cannot be measured, cannot be measured, cannot measure TAP density (g/can3) 1 1 CS r4 ο CN Ο CN ο <Ν ο (Ν 00 σ\ 00 r4 o CN CN CN · ο r4 r4 卜 CN o CN Ο <N Ο CN 〇CN 〇oi (N (N BET (m2/g) 21.8 28.3 30.4 29.8 29.6 28.8 29.2 21.7 cn (N 26.5 27.7 30.0 30.7 (N o CO 29.7 25.6 Η CN 〇τ*Η ^ ψ a A t ^ ®wu θϊ 3 1 1 CN 1 1 1 1 cs gas tH CM ir! 00 24.5 114.3 CM o (N d 1800 48000 1 1 1 1 Η I spot 5 13⁄43⁄4 ®Η Γ ί 1 # •塞' ι〇Ο Ο Ο 〇1000 o rH Ο Ο Ο in oo 6000 60000 〇H ο 3000 〇Reaction Grid (L) ^Ti iTi in ir> ooo Ο ο Ο CN »no (N »n iT) »〇in Additives Copper nitrate trihydrate Cuprous oxide Copper nitrate trihydrate Copper powder Copper nitrate trihydrate 1 1 Copper nitrate trihydrate nickel nitrate hexahydrate iron (III) nitrate nonahydrate copper nitrate trihydrate 1 No. 1 Example 11 1 Example 2 1 1 Example 3 1 1 Example 4 1 1 Example 5 | Example 6 1 1 Example 71 丨 Example 8 1 | Example 9 1 1 Example ιο| 1 Example ιι| 1 Example 12| 1 Example 13 丨 Comparative Example 1 丨 Comparative Example 2 | 1 Comparative Example 3 |Comparative Example 4 Comparative Example 5 1 Comparative Example ό |Comparative Example 7 丨Comparative Example 8 | e ο 9ZSZZI860 201024004 Further, FIGS. 5 and 6 show TEM images of Examples 8 and u, and FIGS. 7 and 8 show The images of Comparative Examples 6 and 7 are shown in Fig. 9, which are the images of Comparative Example 8. Further, the examples and comparative examples shown in Fig. 10 show a relationship between Cu addition and BET, and are shown in the case of a 5 L reaction and a 2G0L reaction. First, referring to Examples 1 to 7, Comparative Example 1, and FIG. 1 shown in Table 1. In Fig. 10, the vertical line is BET, and the horizontal axis is the amount of cu added to the Ag. The blank ❿ dot and the industrial white triangle refer to the results of the examples made with the 5L and 2GGL reaction tanks, respectively. In addition, the black dot mark and the black triangle mark are respectively compared with the 5L and 2〇〇L reaction tanks. Specifically, the black dot symbol is Comparative Example 1 'Black Triangle Marker Comparative Example 2. With respect to the comparative example in which Cu was not added, the BET of Example 1' at which Cu was added in an amount of 1 ppm was as high as 7 m 2 /g or more. That is, it was found that the BET of the silver particle powder was increased when the comparative example Cu was added to the examples. Further, the same effect can be obtained by adding and adding copper powder (Example 6) and cuprous oxide (Example 4), and thus it is known that the effect of the present invention can be obtained irrespective of the form of the copper component added. Further, the effect was apparent from the addition of Cu ippm and reached saturation near 10 ppm. From this, it is known that a very small amount of copper addition has a very significant effect on the increase in BET. Further, when the TEM image of Comparative Example 1 shown in Fig. 4 was observed, in addition to the small particles mixed with the coarse particles, there were many coagulated particles. On the other hand, the photograph of Example 1 shown in Fig. 1 can clearly identify primary particles, and no coarse particles are found by 098122526 33 201024004. From this view of the county, when the domain is known, the condensed particles will reduce the effect of achieving particle size integration. This phenomenon is also exhibited in accordance with the coefficient of variation obtained from the TEM image. That is, the coefficient of variation of the example W is a small value of 17 to 21%, and the particle size distribution is very narrow. However, if FIG. 4 is viewed, the particle size distribution is significantly broadened. Further, when viewing Figs. 1 to 3, when silver is added, all of the silver particles are isolated in isolation, and the dispersibility is extremely excellent, and the particle diameter variation is small.

Next, Reference Examples 8 to 13, Comparative Example 2, and Figs. 5 and 6 will be referred to. As with the addition of several reactions, the enthalpy of the recording powder increased. In addition, the 200L reaction can also produce the remainder of the recording. It is known that the manufacturing method of the present invention is an irrelevant reaction specification, and the particle size variation can be improved. Further, the case where the two-parent reaction is observed from Fig. 10, the relationship between the amount of the copper component added and the BET is a more gentle slope than the case of several reactions, and it is excellent from the viewpoint of manufacturing. That is, as described above, when the silver particle powder having the desired BET is produced by the (four)' amount of the copper component added, the control range of the amount of the copper component added becomes t in the 200 L reaction, and thus it is simple. The desired silver particles are obtained. Next, reference is made to Comparative Examples 3 and 4. In Comparative Examples 3 and 4, the amount of copper contained in the silver particles 6,000 ppm (0.6% by mass) and 6 〇〇〇〇 ppm (6% by mass) was also increased. When the silver particles of Comparative Examples 3 and 4 were formed into a silver film, the deterioration of the electric resistance value was considered to be due to this. Further, reference is made to Comparative Examples 5 and 6 and Figs. 7 and 8. In Comparative Examples 5 and 6, respectively, 098122526 34 201024004, in place of the copper component, the nickel component and the iron component were added, and the effects of the present invention could not be obtained. It is known that a copper component must be added in the production method of the present invention. Further, reference is made to Comparative Example 7. In Comparative Example 7, the copper component was added after the completion of the reduction reaction, but the effect of the present invention could not be obtained. In the production method of the present invention, the copper component must be added before the end of the reduction reaction. Further, when Comparative Example 8 and FIG. 9 were observed, it was found that by increasing the amount of the reducing agent, the reduction reaction was accelerated, but it was found from the drawing that most of the coarse particles occurred. From this, it is found that the presence of the copper component is necessary for the particle size distribution and the dispersibility if the reduction reaction is simply accelerated. Further, in the present embodiment, the copper component is previously mixed with the silver component and mixed with the reducing agent in the liquid phase. Therefore, since the copper component is already present in the mixed solution from the time when the reduction reaction starts, the end point of the reduction reaction is judged by the color change of the reaction slurry. However, there is a case where the reduction reaction itself is not completed even if the color change of the reaction slurry is completed. Therefore, the reduction reaction is carried out only by using the silver compound solution, the protective agent and the reducing agent solution, and the effect of the present invention can be obtained by adding a copper component even when the color change of the reaction slurry is completed. (Industrial Applicability) The production method of the present invention is capable of easily producing silver particles as a small size even in a large-scale reaction, and thus is excellent in mass productivity. Further, since the silver particle size of the present invention has a small particle size variation and can redisperse various solvents, it is suitably used as a dispersion liquid for metal wiring applications. 098122526 35 201024004 [Simple Description of the Drawings] Fig. 1 is an image taken at 17 times magnification of the particles produced in Example 1. 2 is a τ 脳 image taken by a particle obtained in Example 3 at 174 〇〇〇. Fig. 3 is a TEM image of the particles produced in Example 5 taken at 174 〇〇〇. Fig. 4 is an image of the particles produced in Comparative Example 1 taken at 174,000 times. Fig. 5 is a view showing the image of the particles produced in Example 8 taken at 倍 (8) times. Fig. 6 is a TEM image of the particles produced in Example 11 taken at 174 〇〇〇. Fig. 7 is a TEM image of the particles prepared in Comparative Example 5 taken at 174 〇〇〇. Fig. 8 is a TEM image of a particle produced in Comparative Example 6 taken at 174 〇〇〇. Fig. 9 is a TEM image of a particle obtained in Comparative Example 8 taken at 174,000 times. Fig. 10 is a graph showing the relationship between the amount of copper component added and the specific surface area of Bet in the relevant 5 L reaction between the examples and the comparative examples. 098122526 36

Claims (1)

201024004 VII. Patent application scope: 1_ A method for producing silver particles, in which silver compound, protective agent and reducing agent are mixed and reacted in the presence of copper. 2. The method for producing silver particles, comprising the steps of: mixing a silver compound solution with a liquid protective agent, adding a copper compound to the mixed solution, and causing the reaction liquid towel to have copper, and then avoiding A step of reducing silver ions in the solution by a liquid reducing agent. ❹ 3 A method for producing silver particles, comprising: a step of mixing a liquid solution with a liquid reducing age to obtain a mixed solution of a protective agent and a reducing agent; mixing the silver compound solution with the copper compound solution, and a step of obtaining a mixed solution of a silver compound and a copper compound; and a step of performing a reduction reaction by adding a mixed solution of the above silver compound and a copper compound in the mixed solution of the above-mentioned protection #j and a reducing agent. The method of producing silver particles according to any one of the above-mentioned items, wherein the total amount of the copper component added is in an amount of Uoooppm with respect to silver in the above reaction liquid in terms of copper. 5. The method for producing silver particles according to any one of claims 1 to 4 wherein the above reduction reaction is carried out according to ～8〇〇c. 6. The method for producing silver particles according to any one of claims 1 to 5, wherein the protective agent contains at least one of carbon, nitrogen and oxygen. 7. The manufacture of silver particles according to any one of claims -6 to 214122526 37 201024004 The above-mentioned protective agent has a boiling point of 25 〇〇c or less. The method for producing silver particles according to any one of the items 1 to 7 of the invention, wherein the functional group of the protective agent is a carboxyl group or an amine group, or one of them. 9. Silver particles containing 1 to 10 (9) ppm of copper. The arithmetic mean of the particle size measured from the TEM image is 丨~ rigid leg, and the specific surface area measured by the bET method is 5 to 4 〇m2/ g. 10. If the towel is turned over, the coefficient of variation of the above-mentioned particle size measurement value is less than 30%. 11. The silver particles according to claim 9 or claim 1G, wherein one or more protective agents containing at least one of carbon, nitrogen and oxygen are present on the surface of the silver particles. 12. The above-mentioned protective agent is derived from an organic carboxylic acid or a derivative thereof. The above-mentioned protective agent has a boiling point of 250 as described in any of claims 8 to 12. (The following. The silver particles of any one of them, the biological composition, and the carbon number of 3 to 8. One of the silver particles, 14_ of the silver particles of any one of the claims 8 to 13 of the patent, the basin The above functional group is selected from the group consisting of a thiol or an amine group. The functional group of any of the above items 8 to 14 is a silver-containing particle of the patent application. 098122526 38