TW200408475A - Copper flake powder, method for producing copper flake powder, and conductive paste using copper flake powder - Google Patents

Abstract

The purpose of the present invention is to provide a copper flake powder for a conductive paste, which has a thin particle thickness and powder characteristics applicable to formation of a fine electrode or circuit, and a method for producing such a copper flake powder are provided. Particles of a copper powder are plastically deformed to form the copper flake powder, which is characterized in that the weight cumulative particle diameter D50 measured by a laser diffraction/scattering particle size distribution measuring method is 10 μ m or less, the value of SD/D50 is 0.55 or less and the value of D90/D10 is 4.5 or less, which values are expressed by using the weight cumulative particle diameters D10, D50, D90 measured by a laser diffraction/scattering particle size distribution measuring method and the standard deviation SD of the particle size distribution measured by a laser diffraction/scattering particle size distribution measuring method. The copper flake powder can be stably produced by plastically deforming, i.e. compressing, medium beads of small particle size into flakes using a high-energy ball mill.

Description

200408475 V. Description of the invention (1) ___ The technical field to which the invention belongs ... The present invention relates to a manufacturing method and a conductive paste for making moon-shaped steel powder using the scale-shaped copper powder and the scale-shaped copper powder Thing. Previous technology: Copper powder has been itchy. Conductive pastes are generally applied to: j = raw materials for electrical pastes. Various electrical connections of the capacitor's external electrodes. Board :::: Cheng and Tao actually pass. Etc., to ensure that the electrically conductive copper powder is generally in the shape of a spherical shape, and the wafer-shaped component is improved when the material is lean; processing to form the conductive hole 丨 _ | Thin film and viscosity characteristics of printed circuit objects; when using conductive to control conductive paste, etc., and solidified or fired to shape the body;: ;;: the wiring of the conductor does not increase the electrical of the conductor circuit, etc. In the case of the impedance circuit f, it is required to have a high film density (in terms of phenol I) such that the formed conductor circuit can be maintained. In order to respond to market requirements, 'copper powders with a slightly spherical shape are used. At present, the copper powder of the King 1 is not only a copper powder (referred to in this specification as "~ The shape of the copper powder is flake-shaped or flat, and the shape is shaped like a piece of copper powder.)). When the scale increases, the contact area between the powder particles also follows the specific surface area and electrical impedance of the two largest powder particles, and effectively improves the conductor circuit. For the above method, please refer to Japanese Patent Publication No. 6-287762, No. 8-3256 1 No. 2, etc. ^ Second report (Heisei) No.

200408475 V. Description of the invention (2) The particle size and thickness of the powder product are not uniform, there is no slight cracking, and there is a non-1 = a certain proportion exists in it, and it can be seen that there are non-widening particle sizes distributed. At the same time, it is difficult to control the tablet to form a conductive paste. The viscosity of the paste is quite complicated, and the shortcomings of the conductivity are unstable. The condition of the thixotropic element of the “heart” paste made the possession club 1A Beyu Yaba on the outside of the wafer-shaped element formed by the immersion method, such as a crystal moon and the moon. In the ay ^ series, the wafer is immersed in the conductive paste external electrode. The surface of the aa sheet is coated with a conductive paste to miniaturize the crystal as the spring needs, and the external electrode has a thin film with the following qualities. Also = demand "Conductive paste must be moist," the conductive paste is wet to the wafer-shaped electrical paste, and can be attached thinly, = the surface has a good moisturization. When pulled up, the wafer-shaped element " Construction: conductive paste; good thixotropic properties that do not flow, ^ conductive lean coating must be in a state, and must have a sintering process that can maintain 誃 4 and maintain the shape when pulled up The state of the finished shape-maintaining ability, the shape of the film-like shape, y, is obtained by using the well-known scaly copper powder to achieve the above-mentioned good thixotropic properties. However, the isoelectric lean material can still be processed to form a conductive paste. ': ,, and η: It is known that scaly copper powder is used in the junction circuit to improve the electrical resistance to a certain extent = the electric lean material is burned ', The goal of resistance, but still unable to: m3-5876-PF (Nl) .ptd $ 8,200,408,475 V. Description of the invention (3) Improving the density of the film layer to become conductive to form a chip-shaped conductor circuit Therefore, the use of a conductor f that is conventionally thick and precise can limit the improvement of electrical impedance. In addition, when adding the second object 2 and wiring the circuit shape, or immersing the electrodes, etc., not only can not respond to the final sintering = precision and thinning of the electrodes, etc., but also cause the ^ ί etc. The shape stability and the surface state cause problems. It is known that the conductive paste of scaly copper powder is limited to conductor circuits and the like having a large pattern. It is important to propose a scaly copper powder which can be widely used for thin and electric circuits. Summary of the invention: -4 ·: t 'The present inventors will pay attention to the problem of the familiar scale-like copper powder in the growth of j: the existence of coarse powder with an average particle size of 5 times, and the uneven thickness of the powder. : I has a uniform particle size distribution, etc., and considers the relationship between powder characteristics and film formation, and has developed a four-piece copper powder as described below. The invention will be described below. <Flake-like copper powder of the present invention> Various scaly copper powders are known to be investigated by Ben Moming and others, D10 ^ D50 .d '/ d ί Μ;? ^ ^ # ^ ^ ^ ^ ^ 1 / 、 U / 〇 、 5 盘 /, 90% particle size disk is the most heavy.. 〇1σ ^ ςN .. t々 卞 仫 ”dare to large plate diameter, which is made of scale-like copper powder 〇 g / SN Dlspersant 5 of 〇 1% aqueous solution (_ _⑶ ^ mesh mixing 'using an ultrasonic homogenizer (FUS-300T) for about 5 minutes to disperse it' and then using laser diffraction scattering 200408475 Sample _ Di〇D50 D90 Djuax SD SD / D50 D90 / D10 (jti m) _1 10.13 26.15 46.77 104.70 18.31 0.70 4.62 2 2.88 6.28 14.09 44.00 4.15 0.66 4.89 3 2.71 5.87 13.14 52.33 3.86 0.66 4.85 4 2.81 8.20 21.38 52.33 ΊΛΊ 0.87 7.61, the results listed in Table 1 It is known that the scale-like copper powder has a variety of powder characteristics, and it will indeed change according to the powder characteristics of the raw materials used. In Table 1, the standard ρ measurement and # i value should be observed first. ° This standard deviation value sd is an index of the deviation value of the total particle size value of the laser diffraction scattering particle π This value siiiZ is large. Therefore, it can be known that the 5 standard deviation values measured here are in the range of 3. 86 31 to m, and your value is covered by 1 _ T and the particle size difference between the valley groups Although it is large. Then, 'observation of the variation number shows that it is scattered in the range of 0.66 to 0.87, the value of the two different = number f, can be scattered in the range of 4.62 to 7.61. D D9〇 / Values indicated by DiQ% 5. Explanation of the invention (4) The values measured by the Micro Trac HRA 9320-X100 model (manufactured by Leeds + Northrup) of particle size measuring device. η _ represents the coarse particles with the maximum particle diameter measured by laser diffraction and scattering. The figure 2 shows the image of U? 10.47 flake copper powder (3 types). = Observe this The copper scales of the familiar scale

200408475 V. Description of the invention (5) The thickness of the body itself is small, but its thickness is not as large as / 1, &gt; edge 士士 &gt; X solubility, especially the shape of the powder is large J deviation A, Not a girl. Moreover, it changes with the production, and the non-scaled spherical copper powder is visible again. Therefore, it can be seen from FIG. 2 that the status of film sales is clear and quite wide. "If the particle size distribution of the flake copper powder uses the conventional scale-y paste with these powder characteristics, and it is used to manufacture ceramic capacitors, and powder is used to make sintered circuits of conductive ceramic substrates: == ;: Extremely, low-temperature sintering V, ^ θ & Wind shape is accurate, and the peak and deviation of Tang produce, and "," method, the external electrode and sintering circuit, etc. According to the research results of the inventors, the yarn is reduced. The properties are as described in the scope of the patent application, and the "7 copper powder powder made by the method" Ximudan g Qukou &quot; η Tian She, Fan She scattering type particle size measurement, measured Cumulative particle size, below 丨 〇 # m, weight of diffraction scattering particle size measurement method ¥ _ + ^ Wangli system product particle size DJ) D, 溆 =, measured by particle size measurement method 4 The obtained particle size distribution ^ partial sy indicates that the SD / D5Q value is less than 0.55, and SD / is poor; then, when a conductive paste is processed and the wiring of the core is performed, the following is not only = The circuit with a small film thickness and a good film density is obtained, and the thixotropic property of the conductor 5 ::: is formed by using this conductive paste, and f can be significantly improved; The accuracy of the shape and the like. 1B &gt; t-scan: large: submicroscopic observation of the invention, the m-picture and the second picture, the scaly copper powder of the first picture = 2: the conventional scaly copper powder shown in the second picture The same, and, of Thai grains. Moreover, within a range recognizable by the scanning electron microscope,

@ P-5876-PF (Nl) .ptd Page 11 200408475 V. Description of the invention (6) It is also easy to know that its particle size distribution is very concentrated and accumulated :: heart = diffraction diffraction scattering particle size measurement method The measured weight is 1 work center below i ϋ # m, and the article dua is recognized to the above weight f ^ nbu. ”According to the research results, the cumulative particle size of D5G is not within 1 〇 # m. In the conductors such as the conductive springs, mouths, etc. formed by the scaly steel powder described above, the thick-shaped 厚 macro # + used in the above-mentioned wirings, etc., "ίΐ :; Filling properties of layered windows 状: like: get proper thixotropic properties, and good electrical properties, especially good electrical conductivity: :: good solvent migration Stability of quality. Objects form thin conductors, and they also benefit from smoothing. Even if the density of the slag layer inside the conductive paste is poor, the shape and soil form a thin film layer. The conductor is added and the end of the sintered circuit is destroyed. ^ Increasing the electrical impedance of the circuit ", etc. The surface becomes coarse, such as bad sugar, etc. 2 The linearity leads to the weight of the sintered circuit particle size measurement method. Accumulation In addition, the long-distance production of scaly copper powder particles with laser diffraction scattering in the direction of the long axis. The thickness of the flat copper is 1 scale and 2 pieces. The powder particles of the copper powder are preferably long. Diameter: (average length, / average, and degree) powder particles of 3 to 20 0. It is determined by the length of 7 仏 / 1000 average processing degree. Generally, the length-diameter ratio of the buckle is based on the value of the powder. The smaller the flaky copper powder, the thinner the flake copper powder; the longer the diameter / average thickness is less than 3, the thicker it is. Therefore, the 'aspect ratio (average is not as good as the conductive paste) The object is added with mm .: -5876-PF (Nl) .ptd Page 12 V. Description of the invention (7) Workers' nets in the lack of viscosity characteristics. M. ffrt diameter / average thickness) exceeds 2 〇〇 时 体 贝。 In addition, the aspect ratio (average long cracks and other poor shape, and the shape of _ caused by bending, or the thickness of the turtle becomes too thin, so that η | |, scaly copper powder The binder resin of the powder particle machine resin produces uniform sentence 2 :: It is difficult to have a particle size with a shot type when it is electrically lean. Ί :: The characteristic is that when the laser diffraction is used to diffuse a large weight, the accumulated particle size is d. When the value is used as a benchmark Most: 'According to the laser diffraction diffraction maximum weight cumulative particle diameter D ^ method reset the cumulative particle diameter ι and because the scale of the present invention [_] / [D5〇] is less than 5. Therefore, the roughness of Lu Jian Granules, so there is no such as in the conventional scale-like copper powder. In addition, because of the above: the product is quite concentrated. The plasticity is mechanically plastic. The 4 pieces of copper powder are slightly spherical copper powder particles. In a specific system, t [is formed into a scaly shape, so the inventors of the manufacturing process studied: = Deviation is very common. Therefore, scaly copper according to physical characteristics ^ j ^ If it contains 7〇 Wt% or more has the powder characteristics of the above mentioned powder, A :, clean, even if the rest of the scaly copper is processed, the wiring electrical parts can be used to perform the stability of the conductive paste. : The property is thin; while ensuring the shape of the circuit (the method for making scaly copper powder is clear in the present method), the method cannot be used to stably produce flaky copper powder. ^ That is, the conventional scale-like copper powder is produced by the wet method, or The method of the dry method, the atomizing method is 200408475 V. invention is described in (8): m: t :: Shang ϊ plastically deformed into a ball mill pulverization, a bead mill, etc., and it is formed flat flakes?. So that "producing immediately = and 'in this manufacturing method' itself will form a specific cohesive state at first, if there is no known compression and deformation, it will still be the same. # &Amp; $ Selling to maintain the cohesive state between copper powders and produce pressure ::::: ;; In the scale-like copper powder with cohesive state, the powder particles are not 因此 Therefore, the inventors proposed to leave first, and then enter the pole to make the wheel sound. = Spherical copper powder's condensed shape # &amp; / 2 'After eight years, the powder particles are compressed and deformed to form%. Two = The manufacturing method is disclosed in the scope of the patent application "-kind 3 ♦ ^' 々 、 衣 仏 /, including · The copper powder in the condensed state is processed for private use, and the penetration point is used; the copper beads with good grains of ϊ 田 丁 k = = = 6 or less, and the dispersibility of 5 or less are referred to as' copper's "Powder particles" use a particle size of 0. 0 plastic deformation to make them scaly ". ，，， 雷雷 解 3 = Copper powder means that even if the so-called hydrazine reduction method ^ solution f4 wet method or the atomization method dry method, etc., will still ^, condensed state. That is, in the formula method, 'easy to form powder ~ solution is the original raw material; in the case of copper powder'-generally, the so-called hydrazine reduction method, cleaning, filtration, and copper powder of 2% are used to break through 2%. Form a specific condensate in the manufacturing process: get

Page 14

rhW 92i3-5876-PF (Nl) .ptd 200408475 V. Description of the Invention (9) In addition, the copper powder slurry described below refers to a substance in the form of a slurry containing hydrazine reduction powder and the like. "Granulation" in this manual = 々: The powder in the agglomerated state is separated as much as possible to form primary particles ^ / 日 仏 &amp; For the purpose of granulation, the granulation method can be used for example Machines, South-speed Conductor Jet Airflow Type, Impact Grinder, Centrifugal Grinder, Media Stirring Grinder, High Water Pressure Grinder, etc. However, according to the results of studies by the present inventors, from the viewpoint of the guilty degree of the granulation treatment, it is preferable to adopt the two granulation methods described below. These two methods have in common the fact that the contact between the copper powder particles and the inner part of the device, stirring blades, pulverizing media and other parts is minimized, and the collision between particles is used to granulate. That is, it is possible to make contact as much as possible, and to suppress the occurrence of damage to the surface, increase the surface roughness, and so on. = 造 =: 间 ： ;; Quite enough to smooth the powder in agglomerated state. The surface of the granules can be granulated by the collision between the granules, and the granules can be granulated. The centrifugal force method is used to apply the centrifugal force to the dry steel in the condensed state; The "benefit drawing of a circular orbit jealousy" mentioned here refers to a process of blowing the condensed copper powder such as entangled centrifugal force to cause circulation of the two particles, and using this process to produce the d grains. Collisions with each other are used to make a classifier. This t 'can also use the commercially available centrifugal force of wind to blow. The purpose of the 5' wind classifier is not to classify, but the attacked copper powder is blown up as if depicting a circular orbit, and produced; 2ai3-5876 -PF (Nl) .ptd Page 15 200408475 V. Description of the invention (10) --- Health cycle. ^ Bu Another granulation method is to use a centrifugal fluid pulverizer 'to granulate copper powder slurry containing copper powder in agglomerated state. The "fluid pulverizer using centrifugal force" described here is to cause the copper powder slurry to flow in a circular manner at high speed, and the condensed copper powder collides with each other in the solvent by the centrifugal force generated at this time. For the device used for granulation. The above-mentioned granulation treatment may be repeated a plurality of times if necessary, and the degree of granulation treatment may be arbitrarily selected according to the required quality. Complete granulation treatment. Copper has a new powder property that has been condensed. In addition, the cohesion described in ΐ :: 丨 ΐ is explained here. Using laser diffraction and scattering J microsecond = ^ the cumulative particle diameter measured by your weight ^, and the average particle diameter obtained with the scanning electronic display dpi value m ~ the cohesion degree 1 is set to I 6 or less. Here, when the degree of cohesion is less than 1.6, "is almost completely monodispersed.%. Value ΐ ϊ: ΐ =: Formula i! Weight cumulative particle diameter measured by the measurement method

The powder particles are not completely separated, that is, merged; 并 Fractional particle size: the aggregated state of J Π f particles. Laser diffraction diffractors), the direct observation of the copper powder observed by the electron microscope (SEM) of $ 22,22 based on the observation image :: == the average particle size obtained, because it is obtained by SEM Shirt image, so it can accurately capture the primary particles, and at the same time

V. Explanation of the invention (11) Complete: The existence of the condensed state of the powder particles can be photographed. Measured: In D / η obtained by the laser diffraction scattering particle size measurement method, the particle size of the particle is controlled by the inventors of D, etc., and the average particle size obtained by the image analysis Dia is D50 / DIA. The value is taken as the internal sore T). That is, it is assumed that the value of 5 0 /, IA in the same group of copper powders can be measured 5 Π... There is a state of condensate that will reverse the accuracy. 'Applying the above theory' exists at this time, if; Therefore, the value of ^ is larger than. Every time, the amount of M ^ ^ determined to be completely condensed without copper powder particles will be unrestricted ^, when the cohesive production; M pull 1A, the degree of cohesion D5q / DiA value is close to 1. Because ^ 又 rag ~, temple ’can be said to be a single point of the aggregate state without powder.

A bet ^ and there may be cases where the value is less than 1. In theory, if it is = 6, the value is less than i, but in fact, even if it is not circle i, the value of cohesion can be obtained if it is less than 1. In addition, in the present specification, the image analysis of the copper powder obtained by observation with a scanning electron microscope (SEM) is performed using Ip_1000pc manufactured by Asahi Engineering Co., Ltd., with a roundness threshold of 1, and an overlap of 2.0. Set this to analyze the circular particles to find the average particle diameter DIA. The slightly spherical copper powder that has been granulated in the above-mentioned method is processed by a high-moon b-cap mill to compress the copper powder particles to plastically deform them to form scaly copper powder. The scale-shaped copper powder of this final product has a weight cumulative particle size measured by laser scattering scattering particle size measurement method of 10 "m in terms of JI 丄. In order to obtain an appropriate aspect ratio of the above powder, Compressive deformation 2 Cumulative copper powder (hereinafter referred to as "original powder") that has undergone granulation treatment is measured using laser diffraction scattering particle size measurement as the basis for weight cumulative particle size ^, and taking the scale into consideration The degree of processing, to use it as a judgment index /. also

200408475 V. Description of the invention (12) That is, by using a raw powder having an appropriate weight corresponding to the degree of processing of the powder particles, powder characteristics such as appropriate weight after dust shrinkage deformation can be obtained. '' Only the thickness of the high-energy ball mill described here refers to the use of media beads to compress the steel powder, whether it is carried out in a state where the copper powder is dried in a device such as a bead mill, a machine, etc. Powder, ^ = Generic term for devices that are sexually deformed. In the present invention, the choice of the size of the media beads is very important. 1 let

Firstly, the particle diameter should be set to 0.5mm with the particle diameter of the beads as the setting. If i 5 A is more than ^^ 5, the pressure of the medium beads will be increased by two. If the particle diameter of the medium beads exceeds. The copper powder particles in the interior are prone to coagulation. This ball mill is plastically deformed to form a thick one: the scale-like fruit can not obtain a concentrated particle size distribution due to the wide production of agglomerated particles. Distribution becomes pink. 〃 And it is a scaly copper dandan dish of the south ’) 丨 The glutinous pearl is preferably a micro-bead. If the specific gravity of the medium beads is not used, the specific gravity is about 3.0 ~ 6. The medium will be too light, and the copper powder particles, because of the weight productivity of the medium beads, this is not industrially available for a long time, and considering its production If the specific gravity exceeds 6.5g / cm3, it will be used. In contrast, if the compressive deformation force of t of the medium beads increases, the weight of p — ^ negative beads will be too heavy, copper powder particles &gt; scale-like copper powder is also Rongxian * powder particles are easy to agglomerate. The = case obtained by the above method. The powder characteristics of the scale-like steel powder of the invention can effectively produce products with the present bamboo. And, using this scale

200408475 V. Description of the invention (13) The conductor made of copper powder (13) The shape of the conductive paste gives good stability to the formed conductor. Because of the "conductive paste" of the circuit and ceramic capacitor, the above-mentioned invention can not only control the time change easily, but also the quality. Therefore, good quality is achieved when the benefit is set to be the same as the content of the conductive powder. Considering the content of the conductive paste and the conductive paste, the content of the copper powder in the above-mentioned configuration and the scale of the electrically-poor substance are quite excellent. When the conductor is used, even if the thickness of the conductor is made thin, the electrical impedance can be kept low and the shape of the conductor can be maintained. This is very suitable for sintering external electrodes of printed circuit boards. Bright scaly copper powder is used to produce conductive paste with poor conductive viscosity, and it is less likely to get good thixotropy with conductive paste easily. Use the scaly copper powder of the present invention for conductive paste The type and scale-like nature of the flaky T-shaped organic resin can be set according to the purpose and method of use. What kind of grade can be set compared with the conventional scale-like copper powder? The type of organic resin of the pre-conductive paste, the particle size of the flake-like copper powder, etc. are determined as appropriate. The embodiment will be described in detail below with reference to examples. : Example 1 In this example, the copper powder obtained from the raw materials by the following method is used as a raw powder, and the manufacturing method of the present invention is used to manufacture scaly copper powder.

-^ 13-5876-PF (Nl) .ptd Page 19 ZUU4US4 / ^ V. Description of the invention (14) In the powder characteristics of the household sample in the present example / scattering particle size measurement by Tiandian, The average particle diameter of the laser winding D / D ΐίί Γ is. .2〇 ”, so the cohesion degree calculated as I / is 175. For the raw materials described above, a commercially available 1 = wind classifier manufactured by Nissin Engineering Co., Ltd. was used, and the rotation speed was 650,000 rpm. Collision occurs between powders in the I 3 polymerization state to perform the granulation process. Object M2: The copper powder (original powder) that has not been granulated by the mesh U i is analyzed by laser diffraction scattering; 7 Zhiping: The weight cumulative particle diameter measured by Γ is 0.33 ^, and the image solution ΓΓΐίΙ ^ tDlA ^ ° ^ 5 -D50 / DIA „tt ^^ 3 is 1.50, so it can be confirmed that it has been fully performed Granulation treatment. 1 n ROW, use the DISPERMAT wide 5226 quality disperser manufactured by VMG — GETZMANN company, with a specific gravity of 5 8g / cm3 and a diameter of ϋ: Which? Zirconium beads 8 ° 〇g as a medium bead, this granulated ^ Γ 日 士 Λ5§ decanoic acid was mixed in a solvent 'into the speed of 200 rpm, guarded, treated, by compressing the original The powder particles make it plastically deformed &gt; 'to form a slightly spherical scale-like copper powder. The properties of the scaly copper powder obtained above are one, and it has an average particle size of 0.05 as described below. The ratio of [Dmax] / [M · J, and no coarse particles larger than 5 were found; the weight cumulative particle diameter of the Leeray diffraction scattering particle size measurement method Diq (〇26 and m): ^ (0 · 40 center), D9G (0.67 // m), and laser diffraction: standard deviation of particle size distribution measured by diameter measurement method, SD / D5 of particle size. The value was 0.38 and the D9q / d value was 2.58. π Table 200408475 V Description of the Invention g5) ,, ^ *** — m. The average particle size of the powder particles that make up this scaly copper powder; the degree refers to the use of epoxy resin to control people. Also 0 · 0 5 # The material is called J with a scanning electron microscope with 1 0 0 0 0 times the magnification 2 = Chengzhi scales: Γ 'to directly observe the thickness of the scale-like copper powder, and V. This test: the value. "Bu, the following is implemented: in the tablet: the number of powders is multiplied by the thickness f, and the scales are also obtained: =: = the thickness of the scale-like indium t, the thickness of the 芈 -shaped copper powder can be observed with appropriate observation In addition, let's just observe the powder particles with a scanning electron microscope (the magnification is 2). Observe the powder particles and evaluate them. About μ: shirt &quot; 涊 之 scale The average pain of the long diameter of the copper powder: the long diameter of the flake copper powder, the following examples and pairs: the [average particle size] / [average thickness] of the == diameter ratio refers to the above-mentioned bright scales The conditions that a copper powder should have: Therefore, it is to meet the requirements of this invention f: J 2 etc. Use the scaly copper powder passed to make pine oil 1 Measure the change of the viscosity of conductive paste Hh 丨, t 咚 糸 conductive lean matter is composed of organic resin with 65% by weight of scale adhesive resin, and is made of 糸 糸 conductive paste. At this time, the composition of organic resin is shaved pine oil. Alcohol and 7wt ° / G ethyl cellulose. Next, 'measure the viscosity of the terpineol-based conductive paste just formed as mentioned above *. This description The viscosity of the production line using a # Toki Corporation, Model RE-105U of the viscometer, and to 〇.11__ leaf 1. The measured knock

200408475 V. Description of Invention (16). Hereinafter, the viscosity measured at a rotation speed of 0.1 lrpm is referred to as "A viscosity", and the viscosity measured at a rotation speed of 1.0 rpm is referred to as "β viscosity". That is, the A &amp; viscosity was 380 Pa · s and the β viscosity was 160 Pa · s. Next, find the derivative = [viscosity ratio of thixotropic property index of raw s-like substance (= [A viscosity] / [β viscosity]) 2 · 4. The larger the viscosity ratio, the better the thixotropic properties of the conductive paste. Example 2: Copper powder obtained from the raw materials from &amp; in the present example using the following method

: ,,, raw meal, and using the manufacturing method of the present invention to produce scaly copper powder. In the powder properties of the raw materials used in this κ example, the laser diffraction diffraction particle size is used to measure the%, and the weight cumulative particle size D5Q measured in aa is determined to be 0.85 // = The average particle size obtained from the analysis was 〇48 // ι ^, so the degree of cohesion calculated by D50 / D1A was 177. λ car: Disperse the raw materials in pure water as copper powder slurry, and use a commercially available centrifugal umbrella, fi ne f 1 ow mi 1 1 made by t Kota, a fluid cup crusher using centrifugal force. Mnn privately 丄 立 丄 w ^ dU〇〇rpm circulates to make the cohesive powder particles collide, and the field technology to perform the granulation process. The σ results show $ &amp;, skin t, you say 、 ++ Force ^ W copper powder (original powder), the average new cumulative cumulative particle size obtained by laser diffraction scattering analysis ^ is G · 73 ^, and the cohesion degree of the image and the output is l 4q Invasion 1 &quot; is 0.49, so, calculated with D50 / DiA &amp; ^ 9 'This can confirm that sufficient granulation treatment has been performed. Then' recognize with phase ^ 考 w @ ^ u 于 实施 例The method of 1, using the above-mentioned raw powder 500g to complete the granulation process, M 丄 wide g by compression of the powder of the original powder to make it plastic &quot;

Page 22, 200,408,475 V. Description of the invention (17): In order to use: t Kai (the original powder forms scaly copper powder. Among them, only the side of the media distributor will be DISPERMAT D— The granules of 5226 make i 'raw plastic: J, change to 10 hours in time, and form a slightly spherical scale-like copper powder by compressing the powder of the original powder, [wen shape]. 15.5 "m, the largest particle size in the characteristics U is [djm. Bu 4.7, and the ratio is not the laser diffraction scattering type particle size, and the coarse particles are used; using the diameter measurement method mWf1 ^ # and the laser diffraction scattering type particle are listed only. The marked SD / D5 of the particle size distribution of the tester. The value is 0.50 U f SD (1. 68 _). The average thickness of the flake copper powder particles; the second value of D is 3.09. 99. In addition, the average particle size of the scaly copper powder (long diameter dagger is &quot; 〇 &quot;: 'Directly observe this scale "〇. Therefore, it can be seen that it is a condition to satisfy. Seven flaky copper powder What's more, the present inventors and others used the same organic resin and mixing ratio of copper in Example 1 from copper = paste, and measured the electrical conductivity, f, oleyl alcohol, and electrical conductivity.

600 Pa · s and B viscosity was 143 pa · s. Therefore # 又。 / Jiguo, A viscosity is degree] / [B viscosity]) is 4 · 2. Viscosity ratio (= [Αviscid Example 3: Copper powder obtained from raw materials by the following method as Kishi II. The raw materials and raw materials used in this embodiment are: = ::.

200408475 V. Explanation of the invention (18) Therefore, in order to avoid repetitive description of the powder characteristics of the original powder and the powder characteristics after the granulation process, the description is omitted here. Then, the same as the embodiment! The method uses the above to complete granulation n! 500g, and compresses the powder of the original powder to plastically deform it to form a slightly spherical raw powder into a scale-like shape. Dispermat d_5226 made by MG-GETZMANN The processing time was changed to 7 hours, and the spherical powdered copper powder was formed by plastic deformation of the powder mill 7 which compressed the original powder. 36 α πΓ 上: In the characteristics of scaly copper powder obtained by Λ, the largest particle #D_ is 5. The average particle diameter described in the second column ~. The ratio is 1ϋ = 3.6, and no coarse particles larger than 5 are found; the weight cumulative particle size Di «(0. 67 # ^ 旦 、 = 土 · 50) is calculated using the weight based on the ', τΓμ political particle size measurement method. &quot; m), D9 ° (2. 80 &quot; m), and the standard deviation of the particle size distribution measured by laser diffraction scattering particles (0. Μ shown in Table ^ ◦The value is 0.53, and the value of D9 ° / Dl ° is 4. 18. In addition, the average thickness of the powder that makes up this scale &amp; Γ is 0.08 μm, and directly observe the scale Ί, 77, The average particle diameter (long diameter) is 1.3 # m, so the average aspect ratio is 1 w. 〇 ° fj ^ l itbu, ~ p *, ι can be known that it should have the scale-like copper powder to meet the present invention. The conditions are as follows: ~ Examples: The same samples were used to produce terpineol conductivity / 9 9 'using the obtained scale-like copper powder at a ratio of ^^, organic resin and mixing ratio, and measured the conductivity. The viscosity of the paste. As a result, the viscosity of A is KI, and the ratio is 13 Pa · s. Therefore, the viscosity ratio (= [A viscosity] / [B viscosity]) is

Page 24, 200408475 V. Description of the invention (19) Example 4: In this example, the copper powder obtained from the raw materials by the following method is used as the raw powder, and the manufacturing method of the present invention is used to manufacture scaly copper powder. . The raw materials and raw powder used in this example are the same as those in Example 2. Therefore, in order to avoid repetitive description of the powder characteristics of the original powder and the powder characteristics after the granulation treatment, the description thereof is omitted here. Next, in the same manner as in Example 1, 50Og of the raw powder that had been subjected to the granulation treatment was used, and the raw powder was compressed to cause plastic deformation, so that the roughly spherical raw powder was formed into scaly copper powder. Among them, only the processing time for implementing the media disperser was changed to 1 hour, and the powder of the original powder was compressed and plastically deformed to form a slightly spherical scaly copper powder. Among the characteristics of the scale-like copper powder obtained above, the large particle diameter is 1. 44 // m, and the ratio of the average particle diameter I to the following is [b] = 1.5, and no more than 5 is found. Coarse particles; weight cumulative particle size measurement based on laser% scattering scattering particle size measurement method]) 丨 π, D5G (0.95 / zm), D9G (1.43 // m), and laser = diameter The standard particle size distribution measured by the measurement method is $ γ ^ SD / D ^^ o.45 ^ ^, / 1) ^ 42.80 The average thickness of the flake copper powder is 0j 9 7。 The average particle size (long diameter) is 0.9 / z / m so straight ^ observe this scale 4.7. Therefore, it can be seen that it satisfies the condition of the present invention. The flaky copper powder should be provided. Furthermore, the inventors used the obtained flaky steel powder to achieve

200408475 V. Description of the invention (20) ί The same organic resin and mixing ratio are used to make terpineol-based conductive * = 爿 物 'and measure the viscosity of the conductive paste. As a result, the alpha viscosity was 1 / L · /, and the beta viscosity was 125Pa · S. Therefore, the viscosity ratio (= [Αviscosity] / [Βviscosity]) is 2.8. Example 5: As = Real Example: Medium 'Steel powder obtained from raw materials by using the following method: as raw materials' and using the manufacturing method of the present invention' to produce scaly steel powder Among the characteristics,

^ ^ ^ ^ &quot; 'J # ^ ί * ^ ^ D50 ^ 6. 84 ^' = The average particle size obtained from the analysis of the shirt image is ~ 4 2 0 因此, so it is calculated by D50 / DIA The degree of aggregation is h 63. For the above raw materials, a commercially available s ClaSSHier wind classifier manufactured by Nisshin Engineering Co., Ltd. was used to circulate at a speed of 6500 rpm to cause collisions between particles in a cohesive state to perform a granulation process :. , The result shows that the copper powder (original powder) that has not been granulated has a particle size of 4 92 // m as measured by laser diffraction scattering particle size method. The average particle size obtained by image analysis is Since the diameter Du is 4 · 丨 Vjjj, the cohesion degree calculated by ~ is 1 · 20, so that it can be confirmed that sufficient granulation treatment has been performed. Next, 'the same method as in Example 1 was used to complete the granulation | treatment of the original powder 500 g, and the plastic powder was compressed by compressing the original powder to deform it' to form a slightly spherical raw powder into a scale shape. Copper powder. Among them, only the processing time of the media disperser was changed to 〇0 hours, and the powder of the original powder was compressed.

Surface J ^ 3-5876-PF (Nl) .ptd Page 26 V. Description of the invention (21) The grains are plastically deformed, and the scale-like copper flakes of the scale-like shape obtained above are 40.00 / zm, Its maximum diameter is [Dmax] / [D5Q] = 4 · 2 and f is described below, and the ratio of the laser diffraction scattering particle diameter I is not found. Coarse particles above f 丨 use basis

Di〇 (4.75 / zm) ^ 50 (9.5〇 ^ m) ^ ff ^ f * g To 2.70. In addition, the composition of this scale is 0.34 'and D90 / Dl. The value is / zm. The average thickness of the R &amp; y flake copper powder is 0.80… Wen Ping = = The average particle diameter (long diameter) of the copper powder is… the conditions that the flake copper powder should have. . Therefore, it can be seen that it satisfies the Example 1 of the present invention: the same nature has the hair: 丄 and the like use the obtained scale-like copper powder to make a solid paste, and measure ΛΛ and the mixing ratio to produce terpineol. The conductivity is 90 Pa. The viscosity of the poor conductive material. As a result, A viscosity is viscosity]) is l \ viscosity is 60 ° &amp; S. Therefore, the viscosity ratio (= [A viscosity] / [B Example of your helmet 'from the example only' uses the following method to obtain copper powder J Ί p two plain poplars, 廿 $ 1 m powder. Yahe Using the manufacturing method of the present invention to produce scaly copper shots, the powder characteristics of the raw materials used in the examples are 'wound with lasers around the two scene centers: the weight accumulation measured by the measurement method The particle diameter D5 is 4.2. The average particle diameter DIA obtained after analysis is 2 · 1 0 // m, so

e ^ 3-5876-PF (Nl) .ptd page 27 200408475 V. Description of the invention (22) The cohesion calculated by d50 / dia is 2.02. For the above raw materials, a commercially available turbo-classifier wind classifier manufactured by Nisshin Engineering Co., Ltd. was used to circulate at a rotation speed of 6500 rpm to cause collision between powder particles in a cohesive state to perform a granulation process. The results show that the granulated steel powder (original powder) has a weight cumulative particle diameter D5Q measured by laser diffraction scattering particle size measurement method of 2. 80 // m, and the average particle diameter obtained by image analysis DIA is 2.00 // m. Therefore, the cohesion degree calculated by d5G / Dia is 1.40, so it can be confirmed that sufficient granulation treatment has been performed. Then, in the same manner as in Example 1, using the above-mentioned raw powder of 500 g to complete the granulation treatment, the powder of the raw powder was compressed to deform it plastically, so that the roughly spherical raw powder was formed into scaly copper. powder. Among them, only the processing time of the media disperser using the disperMAT D-5226 manufactured by VMG-GETZMANN in Example 1 was changed to 7 hours, and the powder of the original powder was compressed to deform it plastically, thereby forming a slight Spherical scale-like copper powder. Among the properties of the scaly steel powder obtained above, the large particle diameter 0_ is 20.73 vm, which is equal to [Dmax] / [D50] = 2 · 8 laser diffraction scattering type m), D50 (7.30 // m diameter The SD / D5Q value shown by the measurement method is 0. The average particle size of the granular copper powder is 0 · 3. Therefore, the ratio of the average particle size D5G described below can be 'and no value is found. Coarse particles larger than 5; using the cumulative particle size according to the particle size measurement method. (3. 8 7 from), D9G (8.51 // in), and particle size distribution by laser diffraction scattering The standard deviation SD (2.34 // m) is shown in Table 1 A and the value of D9Q / Dl ° is 2.20. In addition, the average thickness of the scale y is 0 · 70, and the scale is directly observed. The length and diameter are 7.2. Based on 111, the average aspect ratio is known as the flaky copper powder that should be provided to satisfy the present invention.

Page 28 200408475 V. Description of Invention (23) Conditions. Furthermore, the present inventors used the obtained scaly copper powder to produce a terpineol-based conductive lean substance at the same organic resin and mixing ratio as in Example 1, and measured the viscosity of the conductive paste. As a result, the A viscosity was 112 Pa · s and the β viscosity was 70 Pa · s. Therefore, the viscosity ratio (= [A viscosity] / [β viscosity]) is 1.6. Comparative example:

In this example, except that the agglomerated dry raw material used in Example 1 is not granulated, the rest is the same as in Example 1.

DYN0-MILL OL, manufactured by Willy A. Bachofen AG Maschinenfabrik, compresses copper powder particles with beads having a diameter of 0.7 mm to cause plastic deformation to form a spherical spherical copper powder. The powder characteristics of the copper powder thus obtained are listed in Sample No. 4 in Table 丨. This copper powder contains coarse particles having a maximum particle diameter of 5 times or more the average particle diameter. D ί 11 The powder characteristics of the scale-like copper powder not included in Formula No. 4 are ^ 〇5 ° (8 · 2. &Quot; m), D9 ° (21.38 "1 &quot;), the maximum particle size Γ 田 ', then [DmaX] / [D5 °] = 6.4, which is a value greater than 5. ^ ^ ^ ^ ^ ^ ^ ^ ^ IWh. The value is 4.04. In addition, m :: S = 5 ° is .87 And, the thickness is 0 75 / zm, directly-hereby, the average diameter of the copper powder particles is 7.8 &quot;, so the average particle diameter of the copper powder (the long copper powder is used for conductive性 晚 #… ', right, this scaly "" Don't make it' even if you change the organic resin

Page 29 200408475 V. Description of the Invention (24) &quot; ----- The formula 'is also difficult to control the viscosity of conductive paste, so it cannot be applied to the wiring of high-density wiring circuits. —Feng Mingming et al. Used the scale-like copper powder of sample No. 4 to measure the viscosity of the conductive paste by using the same organic resin and mixing ratio of the electrically conductive paste as in Example 1. Results Degree = 〇Pa .s, B viscosity is mPa .s, viscosity ratio (= [A viscosity] $ viscosity f]) is 1 · 1. From this result, it can be seen that the thixotropic property is worse than the conductive paste of 2: Γ, but it is not a very disparate difference. It is known that the scale-like copper powder can be scale-like. Copper powder: thick to obtain thixotropic properties, but because the particle size of the particles is wide and the average particle size is still large, it cannot be used for thin and thin sounds. Since large particles are rented, the formation of small electrodes and circuits is the same at the same degree. Industrial Applicability: By using the scale-like copper powder of the present invention, the viscosity of the paste can be obtained, and the conductive properties of the patchy sound can be obtained. The thin film and the film are formed by the electric member Mo Yuyucan & ^ good and electrical resistance, and also the county, 衮 ― = = control, so it can be formed :: easy to order

Circuit patterns, electrode shapes, etc. Furthermore, the thin, precise, and powdery manufacturing method 'can be used for what is not known: scaly copper of the moon, scaly copper powder with good particle size distribution. This is also effective in the production of scaly copper powder with good powder properties: Effectively improving the particle size distribution of the scaly steel powder with the present invention is habit 2: From this, it can be known that '本 发 | ...,忐 Achieved Concentration Score

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Claims (1)

6. Scope of patent application 1. A scale-like copper powder flake-like scale-like steel powder, the particles of which are known to undergo plastic deformation to scales are characterized by: a diffraction-diffraction-type particle size of D50 between 1 and 10 " m or less, the particle size measured by the weight of the cumulative particle diameter measured with the weight of 0, the particle size measured by the method of ΓΤ λ particle size measurement method; ° of: bias ::: 5 radiation scattering type Particle size measurement. · 55 or less and the flake-like copper powder described in the above item 1 of the patent scope, the aspect ratio (average length diameter / average thickness) of the above powder pull is 3 ~ 200 The scale-like copper powder described in item 1 or 2 of the scope of the patent application for the upper and middle protectors, 苴 medium weight 射: weight cumulative particle diameter of the scattering particle size measurement method and the maximum accumulation The ratio [Dfflax] / [D5G] of the diameter D_ is 5 or less. # 4 · A scaly copper powder, including any one of the first to the third of the scope of the patent application with a content of 70% by weight or more. The scale-like steel powder described above. 5 · Method for manufacturing scale-like copper powder is the scale described in any one of claims 1 to 4 of the scope of patent application. A method for manufacturing a copper powder having the following characteristics: granulating a copper powder in a cohesive state, and adopting a powder pellet of a copper powder having a completed granulation | treatment, a degree of cohesion below 1 · 6, and a good dispersibility; i The above-mentioned copper powder particles are compressed with a high-energy ball mill using medium beads with a thickness of 0.5 mm or less to plastically deform them to form scales. 6 • If the scope of application for patent is item 5 Manufacturing method of said scale-like copper powder ^ 213-5876-PF (N1) .ptd 33rd buy 200408475 ΪΓΓ ^ 13-5876 · PP (Ν1) · ρΐά page 34