TW201005758A - Copper powder for conductive paste, and conductive paste - Google Patents

Abstract

A copper powder for a conductive paste contains 0.1 atm%-10 atm% of Si (silicon) and 0.1 atm%-10 atm% of In in the particle. It is preferable that the copper powder for a conductive paste contains 0.1 atm%-10 atm% of Ag (silver) in the particle. It is also preferable that the copper powder for a conductive paste contains 0.01 atm%-0.5 atm% of P (phosphorus). The ratio of Si/In (atm ratio) is preferably 0.5-5. The copper powder for a conductive paste is preferably manufactured by an atomization method.

Description

201005758 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a copper powder for a conductive paste and a conductive paste using the same. In particular, the present invention relates to a copper powder suitable for a conductive paste for forming various electrical contact members for forming a conductor circuit for a screen circuit or a multilayer electrode of a ceramic capacitor, and the like. Conductive paste for copper powder. [Prior Art] Cheng: t 口二# ♦ 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易 易It is widely used as a conductive material of a conductive paste or the like. The conductive f can be obtained, for example, by mixing various additives such as a resin such as an epoxy resin and a curing agent in copper powder. The copper powder can be produced by the following method: a precipitation reduction method from a solution containing a copper salt by using a reducing agent, heating and gasification of a copper salt, and further using a refrigerant such as an inert gas or water in the gas phase. An atomization method in which the molten copper is cooled and powdered, and the like. Wet-making method*, the atomization method is relatively widely used, and the residual concentration of the impurities in the copper powder obtained can be one of the internal ones”, and the self-surface use of the obtained copper powder particles can also be used. There is an advantage of atomizing enamel. Therefore, when the amount of the copper powder produced by the conductive material of the conductive paste is generated, it has the advantage that the gas can be cured when the paste is cured, and the oxidation can be greatly suppressed. 141244.doc 201005758 a copper powder is suitable for a conductive material of a conductive paste because of its high conductivity, and has a drawback that the oxidation resistance is deteriorated as the particle size becomes fine. In order to improve the disadvantage, the following countermeasures are adopted: The surface of the particle is coated by the oxidizing property Z (Patent Document 1), or the surface of the particle is coated with an inorganic oxide (Patent Document 2), etc. Patent Document 1: Japanese Patent Laid-Open No. HM52630 Patent Document 2: Open 2〇〇5_]29424号 [Summary of the Invention] Recently, when a circuit using a conductive guide page is formed, it is necessary to make the circuit enter a certain degree, and the grain size of the conductive powder for the conductive paste is also required. And "this (four)" in order to ensure the properties of the paste and the reliability of the electric powder must be fine and the unevenness of the particle size is small, and will not damage the lead. In addition, if attention is paid to improvement of oxidation resistance, it can be dealt with by techniques such as Patent Documents 1 and 2. Specially required: The technologies of the literatures 1 and 2 depend on the coating technique, and therefore require components other than copper, that is, components that are damaged and conductive. Not only: There is a problem that the coating material is peeled off from the copper particles as the core material. It is homogeneous and contains: =, and it is also expected that the constituent particles are not found to be satisfactory. The purpose of the above-mentioned steel powder is to provide a copper powder for a conductive paste which does not impair the conductivity Γ particle size but is excellent in oxygen resistance. Further, the present invention provides a steel powder for a conductive paste having a small unevenness in shape and particle size and a low degree of inclusion/minus. 141244.doc 201005758 + The results of the research conducted by the Maoyue and others in order to solve the above problems have found that if the inside of the copper powder particles - θ I5 3 has special stems of Si and In, the above problems can be solved and completed. this invention. The copper powder for conductive paste of the present invention is characterized in that it contains atm% to 10 atm% of Si' in the inside of the particle and contains 0.1% of atm%~i gamma%, and another aspect of the present invention is one type The above conductive paste is a conductive paste of copper powder. Effect of invention

The copper powder for a conductive paste of the present invention contains a specific component other than copper in the inside of the particles, so that the conductivity is not impaired, and the fine particle size is excellent. Further, since the shape and particle size of the particles are small and the concentration of oxygen contained therein is low, the copper powder for electric conduction of the present invention can be used extremely well as a conductor circuit in a screen printing additive method. Or a conductive material such as a conductive paste for forming various electrical contact members for forming an external electrode of a ceramic capacitor. [Embodiment] An embodiment of the conductive poor copper powder of the present invention will be described. However, the scope of the present invention is not limited to the following embodiments. The copper powder for a conductive paste of the present invention is characterized in that it contains 0.1 atm% to 10 atm% 2Si in the inside of the particles and contains G"atm% to 1 〇%. Here, it is important that not only 8 Å and In are contained, but a specific amount of Si and In are contained inside the particles. The term "inside the particle" means a portion located further inside than the surface of the particle. Copper 141244.doc 201005758, which is a representative of the prior art, which is represented by the above-mentioned patent documents, also has various substances or compounds which are less conductive than copper and are coated or adhered to the copper powder which is the surface of the steel powder particles. It is effective in the modification of the oxidizing property, but such a copper powder is not the one having the f-type required by the present invention, that is, the 'Asian-African system' has characteristics that do not impair conductivity, fine particle size, and excellent oxidation resistance. . The copper powder for the conductive paste of the present invention distributes the Si and In components contained in the metal phase inside the particles. It is particularly preferable that the components are present in the interior of the particles and are not exposed on the surface of the particles. The concentration of the right Sj In component present on the surface of the particle is in the above-described distribution state, and in addition to improving oxidation resistance, To the advantage of maintaining excellent electrical conductivity. The above-mentioned knives are described in detail. The above-mentioned "intimacy exists in the vicinity of the surface of the particles" means that (1) and the chemical components do not exist on the surface of the particles, and are: in a region of a specific depth from the surface of the particles. In this case, the right Si and In components are densely present in the vicinity of the particle surface, and it is desirable to make the distribution state of the Si component coincide with the distribution state of the (four) points. In particular, when the fraction does not exist on the surface of the particle and substantially does not have a central region of the particle, it is preferable from the viewpoint of further improving oxidation resistance and further improving. The particle causes the distribution of the Mb component to be measured by the following method: the surface of the particle is scraped with an ammonia ion ore, and the element formed by the process is broken, and elemental analysis of the cut surface is performed. . Goer's knife Eight=: The conductive paste is made of steel powder. ‘In the interior of the particle, it also contains ^ /, II. In particular, it can make the oxidation resistance of wartime wartime greatly increase. For example, Δ (employment), which is described later, is an oxidation resistance index, and I41244.doc 201005758 can achieve a temperature level of 600 ° C of Δ of 20%/m 2 /cm 3 or less. Such an advantageous effect cannot be obtained for a copper powder containing a Si component or an In component individually. In the copper powder for conductive paste of the present invention, the content of Si is 0.1 atm ° / 〇 10 10 atm%, preferably 0.5 atm% to 5 atm%, more preferably 1 atm% to 3 atm%. When the content of Si is less than 0.1 atm%, the effects required by the present invention cannot be expected. When the content of Si exceeds 10 atm%, not only the conductivity is impaired, but also the effect of the addition cannot be obtained.

The content of In is 0.1 atm% to 10 atm%, preferably 0.5 atm ° / 〇 〜 5 atm%, more preferably 1 atm% 〜 3 atm%. When the content of In is less than 0·1 atm%, the effects required by the present invention cannot be expected. When the content of In exceeds 10 atm%, not only the conductivity is impaired, but also the effect of the addition is not obtained, and the manufacturing cost is also uneconomical. The copper powder for conductive paste of the present invention contains, in addition to Si and In, an Ag of preferably 0.1 atm % to 10 0 atm%, more preferably 0.5 atm% to 5 atm% of Ag, preferably. It is 1 atm%~3 atm% of Ag. When the specific amount of Ag is contained, the conductivity can be further improved while maintaining the oxidation resistance of the copper powder for the conductive paste. Moreover, manufacturing expenses have also been suppressed. It is particularly preferable that Ag exists inside the particles and is densely present near the surface of the particles and is not exposed on the surface of the particles. In particular, when Ag is not present on the surface of the particles and does not substantially exist in the central region of the particles, it is preferable from the viewpoint of further improving oxidation resistance and further maintaining conductivity. The distribution state of Ag in the particles can be measured by the same method as the measurement of the distribution state of the Si and In components described previously. Furthermore, the division of Ag 141244.doc 201005758 does not need to be consistent with the distribution of S i and ιη. In addition to Si and In, the copper powder for the month of Maoyue also contains 0.01 atm% to 〇5 atm% inside the particles. (Phosphorus), better for screening atm%~0.3 atm% p (phosphorus). When p is contained in the specific amount range, it is a steel for electrical conduction which is excellent in oxidation resistance and excellent in electrical conductivity even though the particle size is fine. Further, the characteristics of the particle shape and the particle size are small, and the concentration of the oxygen contained therein is low. In particular, it is preferable to make Si and ', 攸, even if the concentration of p is high, and the effect of improving oxidation resistance is not hindered. It is particularly preferable that p exists inside the particle and hardly exists in the vicinity of the particle surface without being exposed on the surface of the particle. In particular, when it is not present on the surface of the particles and does not substantially exist in the central region of the particles, it is preferable from the viewpoint of further improving oxidation resistance and further maintaining conductivity. The distribution state of p in the particles can be measured by the same method as the measurement of the distribution state of the components described above. Furthermore, the distribution state of P does not need to be related to the distribution of Si and In. 〜8: The copper powder for conductive paste of the present invention contains all the knives of Si, ίη, 八..., all of which are fine in particle size, but the shape and particle size of the particles are small, and the oxidation resistance is excellent. The conductivity is further improved. For the copper powder for conductive paste of the present invention, what is contained therein? The ratio can be measured by the method described in the examples below. In the copper powder for a conductive paste of the present invention, Si/In (atm ratio) is preferably 〇.5:, more preferably! ~4. When the ratio of Si/In is in the above range, the conductivity is not lowered or the manufacturing cost is increased, and the following characteristics can be maintained in a balanced manner. 141244.doc 201005758 The particle size can be made fine and can be connected to the ancient β > ^ "Emulsification resistance can make the shape and particle size of the particles less uneven, and can reduce the concentration of oxygen contained.

When the guided lightning I of the present invention is 4 2ηη φ and contains ρ privately, the Si/P (atm ratio) is preferably 疋4 to 200, more preferably 1 〇1 to 〇〇. If it is easy to balance the following features ', ', or "circumference, the grain size of the ruthenium can be reduced, and the oxidation resistance can be improved, and the shape and the particle size of the particles can be lowered by the concentration of oxygen contained in the particle. Similarly, when the steel powder of the present invention contains P, the In/P (atm ratio) is preferably 疋4 to 200, more preferably θ 1 _ is more preferably 〜10 to 100. When the ratio of Ρ is the above-mentioned dry circumference, the valley is easy to oxidize, and the conductivity can be improved, and the J-pull can be thinned, and the shape and particle size unevenness of the puller can be improved. Further, the concentration of oxygen contained in the mixture can be lowered. When the copper powder for conductive paste of the present invention is produced by the method of the reduction method (IV), the above advantageous effects are also expected privately. However, if the particle: Moreover, the copper for the conductive paste of the present invention is purely produced by the atomization method, and the gas atomization method and the water mist are used in the atomization method. If you want to make a particle shape, you can choose the gasification method. If you want to refine the particle, you can choose the water atomization method. Further, it is preferable that the steel powder for a conductive paste of the present invention is produced by a high-pressure atomization method in an atomization method. The particles of the copper powder obtained by the high-pressure atomization method are more pronounced or more fine. Therefore, the so-called high-pressure atomization method refers to a method of atomizing in a water atomization method at a water pressure of about 5 MPa to about 5 MPa, and a gas pressure of about MPa MPa to about 3 MPa in a gas atomization method. Method of atomization 141244.doc 201005758 c. Ben: Ming: Copper powder for conductive paste may further contain Ni, Ai, Ti, Fe, z B::g, Mn, M°, W, Ta, Zr, B , Ge, Sn,

Bi Xing Yin, at least one of the elements of the red eight element, can be improved to the conductive paste to contain = equal elements: sexual squeak, for example, - drop::: : = and other elements relative to the amount of copper added, ,. Legal profession. The data is appropriately set according to the type of the element to be added, the conductivity characteristics, or other various characteristics. The amount of addition is usually about 0.001% by mass to about 2% by mass. There is no special shape for the particle shape of copper powder for conductive paste: choice. For example, a shape such as a granular shape, a plate shape, a flake shape, or a branch:::: may be employed. Usually... seeking to be part of the cream composition == The copper powder for electric taste is preferably granular. Especially in the case of a spherical shape) vi granular system. The aspect ratio (average longitude divided by the average short diameter) · the shape of the right side of the work. Especially the shape with the aspect ratio of two right is called Spherical shape. The shape of the shape is not (4). In the case of the granular copper powder, the particles are less entangled with each other. ☆ The granular steel powder is used for the conductive material of the conductive paste, etc. The dispersibility in the paste is very good. For the copper powder for the conductive paste of the invention, the coefficient of variation (SD/D5〇) obtained from the volume cumulative particle size 〇2' quasi-deviation value SD is The true 6·(four) degree distribution is less unevenly', so that the dispersibility in the paste when the conductive paste is used for a conductive material or the like is improved, so that SO and D50 are very scattered by laser diffraction, for example. The particle size distribution measuring apparatus and the like are measured. 141244.doc -10- 201005758 In addition to the variation coefficient sn/r» The value of the silent 5^/Dso is outside the above range, regarding the value of si^d itself, Herdu The SD is 10~20 μηι, especially 13~18 μΐη, and D5〇 is 20~3〇μηι. The conductive powder f is made of copper powder, so that the average particle diameter of the secondary particles is 0.01 urn~5Π丨丨 from; μηι, which is a copper powder suitable for the formation of a fine conductor circuit, ▲ a conductive material, etc. The average particle size of the sub-particles == Image analysis by observing the photo by scanning electron microscopy, etc. Ten; This "Electrical Lean Copper Powder of Ming Dynasty makes the initial (after manufacturing) oxygen" 30 ppm~25ηη η. ^ ρρ 500 ppm, whereby it is possible to ensure conductivity: copper powder suitable for a conductive material such as a conductive paste. The oxygen concentration can be carried out by the method described in the examples below. Measurement of the difference between the [weight change rate (tg (%)) / specific surface area (SSA)] of the shoe and the shovel when the copper powder for conductive paste of the present invention is measured by the thermogravimetric differential heat (4) It is preferably 1%/mW to 60%/mVcW, and preferably 1%/m2/cm3 to 25%/m2w. The weight change rate is the weight of the copper powder in the case of a thief. The value of the reference is △ (TG / SSA) is defined as (TG / SSA) 8 〇〇 _ (Tg / ssa) 25 〇. Weight change rate TG and specific surface area SSA system It is measured by the method described in the examples described later. The oxidation resistance of the copper powder can be evaluated based on the characteristic value of Δ (lan SA). Further, the temperature region of C is referred to as When using the main conductive paste including the conductive paste for external electrode calcination of ceramic capacitors

Hot temperature zone. Therefore, it is very important that the copper powder in this region has resistance to J41244.doc 201005758 oxidation. When Δ(TG/SSA) is in the above preferred range, the oxidation resistance of the copper powder can be sufficiently promoted and high conductivity can be ensured. In the present invention, the amount of Si and Bu contained in the particles is set within the above range, whereby the value of V) of the copper powder can be set to the above preferred range. In particular, the inside of the particle contains the above range of amounts? Thereby, it is easier to make the value of Δ (TG/SSA) of the copper powder to the above preferred range. Next, a preferred specific manufacturing method of the copper powder for a conductive paste of the present invention will be described. The copper powder for a conductive paste of the present invention can be produced by the following method: by adding a specific amount of the component to the molten copper in the form of a mother alloy or a compound, or by casting or projecting a pellet After adding a specific amount of the In component in the form of an alloy or the like, it is powdered by a specific atomization method. According to the above-mentioned manufacturing method, it is possible to produce a copper powder which has a fine particle size but is resistant to oxidation and which does not impair the balance of conductivity. It can also produce a shape and a particle size of the particles, and the unevenness is small. Copper powder containing a low degree of oxygen. The reason is uncertain, / Japanese Pui Ren speculated that the reason is that ... in the range that does not damage the conductivity of copper particles, Wo ~ σ; has been condensed The Si and the copper in the copper alloy can capture the oxygen in the copper particles, thereby suppressing the oxidation. In the conductive luxury of the present invention, the addition of Si and In components is added. The Ag component, on the one hand, can ensure the oxidation resistance of the copper powder on the one hand, and further improve the conductivity on the one hand. In addition to the addition of Si and In components, 1^, ^

In addition to the addition of the p component, it is presumed that the surface tension of the surface of the pavilion/liquid at the time of atomization can be reduced, and A can be effectively averaging the particle shape or emulsification in the melt. Similarly to the Si component, the addition of the P component 141244.doc 201005758 adds a specific amount of the p component to the molten copper in the form of a master alloy or a compound. For the reasons explained above, it is preferred to employ a high pressure atomization method in the above production method. However, compared with the gas atomization method, when the water atomization method is used, the yield of Si, In, and p is low, so Si&In needs to be added with respect to the net amount of the target copper powder.丨 ~ (7) times the amount, p needs to add 1 to 100 times the amount. In the atomization method, the target copper powder can be successfully produced, for example, by appropriately controlling the temperature of the melt, the diameter of the nozzle for atomizing the solution, the pressure of the atomization spray, the temperature of the gas or water, and the like. . In the above production method, the copper powder obtained by the atomization method can also be subjected to reduction treatment. By this reduction treatment, the oxygen concentration on the surface of the copper powder which is easily oxidized can be further reduced. From the viewpoint of workability, the reduction treatment is preferably a reduction of gas. The gas for the reduction treatment is not particularly limited. For example, a reducing gas such as hydrogen, ammonia or butane gas can be used. The above reduction treatment is preferably carried out at 15 (rc to 30 (at a temperature of rc, 1 which is preferably carried out at a temperature of 17 (TC to 210%). The reason is that if the temperature of the reduction treatment is as described above Within the range, it is possible to prevent the reduction treatment from being reduced by the reduction rate and to reduce the aggregation or sintering of the copper powder. If the temperature of the reduction treatment is HC~2UTC, the oxygen concentration can be effectively reduced on the one hand. It is preferable to suppress the aggregation or sintering of the copper powder. In the above manufacturing method, it is preferable to classify the copper powder obtained by the atomization method. The classification can be easily carried out by the following means. :U target grain 141244.doc 201005758 degrees is medium ~ way, so that .^ Μ ^ device, from the copper powder will be coarse grain /, let the first explained the coefficient of variation 5 〇) 〇 · 2 ~ 〇. In the case of the classification of the copper powder, for example, an epoxy resin or the like and a hardener of various additives are blended and mixed, whereby copper for the conductive paste of the present invention can be produced. Powder conductive paste. The location of this conductive paste is In the technical field, there is no need to elaborate on the details. For the conductive paste, the copper powder contained in the crucible has a fine particle size, but the oxidation resistance and the conductivity are balanced, and the shape of the filament is less uneven. Moreover, the concentration of oxygen contained therein is low. Therefore, the conductive paste is extremely suitable for formation of various electrical contact members such as formation of a conductor circuit of a screen printing addition method or formation of an external electrode of a laminated ceramic capacitor. In addition, the copper powder for conductive paste of the present invention can also be used for internal electrodes of laminated ceramic capacitors, wafer parts such as inductors or registers, single-plate capacitor electrodes, tantalum capacitor electrodes, resin multilayer substrates, and ceramics ( LTCC, L〇wc〇_ fired Ceramic 'low temperature common heat ceramics') multilayer substrate, flexible printed circuit board (FPC 'Flexible Printed Circuits), antenna switch module, PA (P〇Wer Amplifier 'power amplifier) module or high Modules such as frequency active furnace wave, PDP (Plasma Display Panel) front panel and back panel or electromagnetic shielding film for PDP color filter, crystalline solar power Surface electrode and back surface extraction electrode, conductive adhesive, EMI (Electromagnetic Interference) mask, Rp ID (Radio Frequency Identification), pc keyboard, etc., diaphragm switch, anisotropic conductive film ( ACF/ACp, 141244.doc •14- 201005758

Anisotropic Conductive Film/Anisotropic Conductive Paste). Hereinafter, the present invention will be described in further detail based on the following examples and comparative examples. (Example 1)

After filling in a chamber of a gas atomizing device (manufactured by Nisshin Kasei Co., Ltd., Neva_GP2 type) and a raw material dissolution chamber with nitrogen gas, the raw material is heated and dissolved in a carbon crucible provided in a dissolution chamber to form a melt. Specifically, in the melt in which electrolytic copper is dissolved, 1.77 g of metal ruthenium (NIKSIL manufactured by Nippon Metal Chemical Industry Co., Ltd.) and 7'20 g of metal indium are added to prepare a refining liquid of _g, and the mixture is thoroughly stirred. mixing. Thereafter, the melt was cut at 125 (TC, 3_G MPaT from the nozzle of σ diameter 0.5 coffee to obtain copper powder containing Shi Xi and indium inside the particle. Thereafter, the copper obtained was screened by using 53 _ test _ Known as the final copper powder, the copper powder obtained is not characterized by Table 2. In the copper powder, the coffee is not exposed on the surface of the particles and is located in the vicinity of the surface of the particles. (Example 2~ 14) In addition to the metal indium, the same operation as that of the implementation of m was carried out as shown in Table 1. The metal ruthenium alloy was added (the color was 15 mass%), and copper powder was obtained (Comparative Examples 1 to 8) and silver. Material and copper-phosphorus to indium, and steel phosphorus master alloy (phosphorus other than the same as in Example 1 as shown in Table 1 added metal bismuth 15% by mass), the amount of operation to obtain steel powder 141244.doc •15- 201005758 [Table 1] Si addition amount (g) In addition amount (S) Ag addition amount (g) Cu-P mother alloy addition amount (R) Example 1 1.77 7.20 - - Example 2 7.09 14.40 - - Example 3 7.09 28.79 - - Example 4 10.64 28.79 - - Example 5 31.50 121.29 - - Example 6 7.09 28.79 27.06 - Example 7 1.77 7.20 - 1.30 Example 8 3.55 14.40 - 1.30 Example 9 7.09 28.79 - 1.30 Example 10 10.64 28.79 - 1.30 Example 11 31.50 121.29 - 1.30 Example 12 7.09 28.79 - 0.26 Example 13 7.09 14.40 - 13.03 Implementation Example 14 7.09 28.79 27.06 1.30 Comparative Example 1 7.09 - - - Comparative Example 2 - 28.79 - - Comparative Example 3 0.28 1.01 - - Comparative Example 4 7.09 - - 1.30 Comparative Example 5 - 28.79 - 1.30 Comparative Example 6 0.28 1.01 - 1.30 Comparative Example 7 43.44 152.10 - 1.30 Comparative Example 8 - The copper powders obtained in the examples and the comparative examples were evaluated by the following methods. The results are shown in Tables 2 to 6. (1) Shi Xi, The indium and the content of the solution were dissolved in an acid, and the solution was analyzed by ICP (Inductively Coupled Plasma). The results are shown in Table 2. (2) Oxygen concentration using oxygen and nitrogen analyzer (Minchang Manufacturing Co., Ltd. limited The company manufactures "EMGA-520 (model)" for analysis. The results are shown in Table 2. Further, in order to evaluate the deterioration of oxidation resistance over time, SK-141244.doc -16-201005758 8000 manufactured by Sanyo Seiko Co., Ltd. was used, and the temperature was raised to 200 C at a gas flow rate of 8 L/min and a temperature increase rate of i〇°C/min. Thereafter, the oxygen concentration of the sample held at the same temperature for 1 hour was also measured. The results are shown in Table 5. (3) A (TG/SSA) Using a differential thermogravimetric simultaneous measurement device (TG/DTA, Thermo Gravimetric/Differential Thermal Analyzer) (manufactured by SII, TG/DTA 6300 high temperature type) (heating rate··i〇°C/ Minute, gas flow rate: 200 mL/min), and Tg (%) at 40 ° C to 800 ° C was measured. On the other hand, the specific surface area can be determined from the particle size distribution measured by a particle size measuring device (manufactured by Kyocera Corporation, MICRO-TRACK MT-3000 type). The TG/SSA is calculated arithmetically based on the measured values of the two. The results are shown in Table 3. In the same table, TG/SSA and 800 at 250 °C are also recorded. (: The difference between TG/SSA is the value of A(TG/SSA). Further, TG/SSA at each temperature is divided by TG/SSA of pure copper powder of Comparative Example 8 (described in Table 4 as [ The value obtained by TG/SSA]Cu) is shown in Table 4. (4) The particle shape was observed by a scanning electron microscope. The results are shown in Table 2. (5) D50, SD, SD/D50 will be 0· 2 g of the sample was put into 100 ml of pure water, and after being irradiated for 3 minutes, the ultrasonic wave was dispersed, and the particle size distribution measuring apparatus ("MICRO-TRACK (trade name) FRA (model)" manufactured by Nikkiso Co., Ltd. was used. The volume cumulative particle diameter D5 〇 and the standard deviation value SD and the coefficient of variation SD (SD/D5 〇) were respectively obtained. The results are shown in Table 2. (6) Volume resistivity 141244.doc 17 201005758 Sample 15 g was put into the tube In the container, a measurement sample obtained by compression molding at a pressing pressure of 40 χΙΟ 6 Pa (408 kgf/cm 2 ) was formed, and for the measurement sample, Loresta AP and Loresta PD-41 type (all manufactured by Mitsubishi Chemical Corporation) were used. The results are shown in Table 6. 141244.doc 18- 201005758

Q <N \DS (Ν \〇(Ν ψ-^ cn IT) 00 Ο § (N in GC to 00 m Ον 3 Q 〇Ο ο Ο 〇〇d ο d ο d Ο Ο ο do 〇ο 〇〇 Ο d Q 〇〇CN δ ίο T—^ tr> s 00 ι—Η S <N i〇o 卜g On v〇cn S 00 cn d. iri ι〇τ· Η <d rn 1—^ ΓΠ r~H ^6 inch · rn νο rH inch r~H (N 〇(N cn 00 00 τ~Ή m ιη 00 ^T) yr) On m 沄m 汔(N ι〇(Ν ό ό (Ν (Ν (Ν iri (N 00 (N 00 (N 00 N 〇 〇 N N N N N N N N N N 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 93.0 102.5 111.3 168.6 87.6 99.4 109.1 93.0 83.7 98.0 85.3 97.9 92.5 181.3 113.4 P -( inch Ο 〇〇Ο 1 194.5 1 1-Η »-Η ίΤι Ο »—Η (N a Ο 00 m cK m Oi (Ν r—Η inch 1 I 1 I σ< m (N CN PU 10.0 inch 1 193.3 ΓΠ ΓΛ 00 v〇rn ύ 5 1 ι 1 〇< m od IT) inch r—Η 1 1 I οό m 1 r—Η CN in g rH Ο σ\ os Ό ΟΟ ΟΟ 沄〇 沄〇 s ο m α 〇 α α α α α α α α 00 00 00 00 00 00 00 00 — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — ο r~H o Ph I 1 1 I 1 ο S 0.049 _1 (Ν ^Τ) Ο s ί 〇 寸 τ Η 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 ο o ο oa 1 1 1 1 1 1.99 I 1 I 1 III 〇5 τ·_ Η 1 1 1 1 1 I 1 ν〇S ON 〇\ s (Ν On ON (Ν ΙΤ) 1.03 go OS CN Ον FH Ο S 〇\ 〇\ s Ο »' Η (Ν οό i-Η Ο (Ν T-^ 〇6 1-Η 1-^ ο <N Ο •Λ 〇〇\α\ s 00 〇\ ON 00 Os 沄SSG\ ON ν〇00 S ΟΟ ΟΝ sg 00 OS 0.08 cn Ο τ—Η (N (Ν 00 TH Ο (Ν <Ν ri 00 (Ν τ-Η r瞧蜱(Ν Ο ^H (Ν rn 寸 寸Γ- ΟΟ Ον o (Ν m inch < κ (N m inch 00 5 4.·£) 雀•ώ •ώ Λ5) 嵩 (K m bomb < -iJ Jj -Ο 〇J -Ο JU Jj £ 141244.doc -19- 201005758 [εί A(TG/SSA) 55.656 46.391 12.759 9.191 5.852 12.705 58.888 22.093 10.904 10.128 7.078 25.722 18.726 10.772 78.148 67.057 •-- 77.262 60.635 62.57 73.708 10.379 82.791 οο ΙΤϊ ο Η 800°C 56.287 46.783 12.976 9.502 6.013 12.930 1 59.280 22.476 ' 11.217 | 10.466 1 7.243 26.066 19.013 11.123 78.928 67.490 78.489 60.963 1 63.140 75.087 10.568 T84.041 700°C丄33.706 11.395 4.432 3.662 2.583 4.554 28.994 1 7.555 | 3.871 4.048 | 2.968 | 8.748 5.773 I 4.518 48.934 34.175 56.930 37.780 32.953 48.988 3.581 64.125 600°C 15.133 3.361 1.874 1.543 0.974 1.970 13.494 2.822 1.831 1.751| 1.150 2.893 2.459 1.842 22.645 21.557 36.910 12.356 16.853 31.582 1.380 40.462 500°C 5.218 1.450 0.951 0.864 0.471 0.984 3.259 1.300 1.109 1.036 0.545 1.181 ! 1.120 0.893 5.888 7.207 20.576 2.638 6.041 12.185 0.655 28.211 400°C 2.734 0.995 0.625 0.649 0.295 0.773 1.561 0.897 0.771 0.784 i 0.324 0.8 40 0.881 0.624 2.161 3.163 13.117 0.880 2.973 4.983 0.412 15.831 300°C 1 1.000 0.618 0.362 0.411 0.205 0.403 0.654 0.493 0.412 0.464 1 0.215 0.502 0.489 0.456 1.024 0.866 3.659 0.483 0.928 2.290 0.235 1 4.334 250〇C 1 0.631 0.392 0.217 0.311 0.161 0.225 0.392 0.383 0.313 0.338 0.165 I 0.344 0.287 0.351 0.780 0.433 1.227 0.328 0.570 1.379 0.189 1.25 200°C 0.405 0.308 0.160 0.247 0.113 0.165 0.211 0.267 丨0.235 0.267 1 0.121 0.248 0.184 0.265 0.654 0.275 0.390 0.253 0.398 0.613 0.153 0.238 1 150°CI 0.243 0.116 0.101 0.157 0.082 0.136 0.111 0.162 0.135 0.183 0.078 0.134 0.102 0.176 0.438 0.147 plant).273 0.144 0.237 0.203 0.108 0.101 A fifth embodiment Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Example 1 Example 2 1 Example 3 Example 4 141244.doc -20- 201005758 [Table 4 ] [TG/SSAl/[TG/SSAlcu 150°C 200°C 250. . 300 ° C 400 ° C 500 ° C 600 ° C 700 ° C 800 ° C Example 1 2.399 1.700 0.504 0.230 0.172 0.185 0.379 0.527 0.670 Example 2 1.145 1.292 0.313 0.142 0.063 0.051 0.084 0.178 0.557 Example 3 0.998 0.672 0.174 0.083 0.039 0.033 0.047 0.069 0.154 Example 4 1.554 1.035 0.249 0.095 0.041 0.031 0.039 0.057 0.113 Example 5 0.812 0.473 0.129 0.047 0.019 0.017 0.024 0.040 0.072 Example 6 1.360 0.697 0.180 0.093 0.049 0.035 0.049 0.071 0.154 Example 7 1.102 0.884 0.313 0.151 0.098 0.115 0.338 0.453 0.705 Example 8 1.602 1.121 0.306 0.113 0.057 0.046 0.071 0.118 0.267 Example 9 1.338 0.984 0.250 0.095 0.049 0.039 0.046 0.060 0.133 Example 10 1.811 1.119 0.270 0.107 0.049 0.037 0.044 0.063 0.125 Example 11 0.772 0.506 0.132 0.050 0.020 0.019 0.029 0.046 0.086 Example 12 1.323 1.040 0.275 0.116 0.053 0.042 0.072 0.137 0.310 Example 13 1.020 0.782 0.230 0.114 0.056 0.040 0.061 0.090 0.227 Example 14 1.764 1.108 0.280 0.105 0.040 0.032 0.046 0.070 0.131 Comparative Example 1 4.352 2.741 0.624 0.236 0.136 0.208 0.564 0.764 0.939 Comparative Example 2 1.465 1.176 0.349 0.200 0.199 0.255 0.540 0.534 0.803 Comparative Example 3 2.703 1.632 0.981 0.846 0.828 0.730 0.675 0.890 0.934 Comparative Example 4 1.428 1.059 0.262 0.111 0.056 0.094 0.310 0.592 0.725 Comparative Example 5 2.367 1.683 0.461 0.217 0.188 0.215 0.422 0.516 0.753 Comparative Example 6 2.010 2.565 1.102 0.530 0.315 0.433 0.792 0.766 0.893 Comparative Example 7 1.069 0.640 0.151 0.054 0.026 0.023 0.035 0.056 0.126 Comparative Example 8 1 1 1 1 1 1 1 1 1 According to Tables 3 and 4, it is clear that The copper powder of the example is excellent in oxidation resistance in a temperature range of 250 to 800 °C. Particularly, in the temperature range of 600 to 800 ° C, the copper powder of the example (copper powder containing both Si and In in the inside of the particle) and the copper powder of the comparative example (containing only Si or In inside the particle) Compared with copper powder), the oxidation property is remarkably excellent. Further, as shown in Table 5, when the copper powder of the example was kept in an oxidizing atmosphere for a long period of time, the deterioration of the oxidation resistance over time was remarkably suppressed as compared with the copper powder of the comparative example. In particular, it can be judged that although the total content of Si and In in the copper powders of Comparative Examples 1, 2, 4 and 5 is about 2 atm% and relatively large, the copper of the example is compared with 141244.doc -21 - 201005758. The total content of Si and In in the powder is about 1 atm% and relatively small, but the deterioration of oxidation resistance over time can be suppressed. [Table 5] Content (atm%) Powder oxygen amount (ppm) Si In P After maintaining for 1 hour before heating, Example 1 0.48 0.51 - 121.6 429.3 Example 7 0.50 0.52 0.050 107.1 511.2 Comparative Example 1 2.03 - - 93.0 755.7 Comparative Example 2 - 1.97 - 83.7 909.7 Comparative Example 3 0.08 0.07 - 98.0 2781.1 Comparative Example 4 1.98 - 0.051 85.3 694.3 Comparative Example 5 - 2.03 0.052 97.9 663.6 Comparative Example 6 0.08 0.07 0.051 92.5 2611.4 Further, as shown in Table 6, it was confirmed that Ag was contained. The volume resistivity of the copper powder of the composition of the composition is not inferior to that of the copper powder to which no component is added. [Table 6] Content (atm%) Volume resistivity (Ω·οώ) Si In Ag P Example 6 1.95 1.97 1.99 - 2.1χ ΙΟ'3 Example 14 1.98 1.99 1.97 0.048 2·3χ10-3 Comparative Example 8 - - - 响 0.9χ10'3 14I244.doc -22-

Claims (1)

201005758 VII. Patent application scope: 1. A copper powder for conductive paste, characterized in that it contains 〇.1 0 1〇atm% of Si (石夕)' and contains 〇.1 atm%~1 0 atm % of In (indium). The copper powder for the conductive paste of the item 1 is contained in the particle containing 0.1 atm% to 1 〇 atm% of Ag (silver). The copper powder for conductive paste of claim 1 wherein Si/In (atm ratio) is 0.5 to 5. 4 Shikou Guqing. f s member 1 of conductive poor copper powder, which contains 0.01 in the particle: atm% ~ 〇 ς 0 / υ · 5 atm% of ρ (phosphorus). 5. If the tomb of item 4 exceeds the copper powder for conductive paste, the Si/p (atm ratio) is 4 to 200. 6 · For example, the molybdenum of the item 4 is t _ L copper powder for electric moon, wherein the In/P (atm ratio) is 4 to 200. 7 · If you request an item. A copper powder for electric g is produced by an atomization method. 8. A conductive paste, which is characterized in that it contains steel powder for a baby T as described in claim 1. 141244.doc 201005758 IV. Designation Representative diagram: (1) The representative representative of the case is: (none) (2) The symbol of the symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 141244. Doc -2-