TW201219512A - exhibiting a high conductivity even at a low temperature regardless of whether the constituting resin is a thermosetting resin or a thermoplastic resin - Google Patents

Abstract

The present invention provides a conductive paste capable of forming a conductive film exhibiting a high conductivity even at a low temperature of approximately 120 DEG C regardless of whether the constituting resin is a thermosetting resin or a thermoplastic resin. The technical means of the present invention involves a method for forming a conductive film, wherein a conductive paste, which is used as the wiring formation paste, and in which a C2-8 dicarboxylic acid is added to a paste, comprises a resin, a dispersion medium, and silver nanoparticles covered with an organic substance consisting of C2-8 carboxylic acid or its derivative thereof, and the conductive paste.

Description

201219512 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a conductive paste which can be used for a low-temperature treatment, a conductive paste, and a method for forming a conductive material which is excellent in electrical conductivity. Conductor-and conductive film [Prior Art] Conductive devices composed of metal particles, resins, and solvents, especially metal micro-wiring cores in electronic devices = miniaturization of electrons tends to be remarkable, so that it is required to obtain more fine wiring. The electronic equipment industry not only studies the ceramic substrates previously used, but also studies the application of the substrate formed by the ancient eight. (d), this: the second material is usually _ poor, and the first (four) narrative age will be relegated to the right in order to suppress the conductivity = heat treatment (for example, in the atmosphere and forging for i hours, etc.) (4). Therefore, in order to make such a substrate, the industry is expected to form a conductive paste of a conductive film even by a low temperature test. ~ Ancient as a conductive paste that can form a conductive film even by cutting at a low temperature. / 疋: ^ Years (5) began to study the use of nano-sized metal particles with different physical properties and micron-sized particles (average primary particle size) A paste of ~200 nm, hereinafter referred to as a metal non-particle particle"), solves the above problem. A paste which is particularly suitable for fine wiring can be provided by using such a particle. However, since the activity of the metal nano-teacher is extremely high, most of the particles are on the surface of which is a protective layer formed of organic matter and the independence of the stone-particles is 099137434 3 201219512. However, such a protective layer can effectively function when preserving particles, but has a hindrance effect when exhibiting metallic properties. In this case, even if the wiring has been formed, it is sometimes not practical because of the large resistance. According to the technique described in Patent Document 1, when a substance having ion exchange ability is added to the nano-sized silver particle paste, the organic protective film on the surface of the silver particles can be peeled off. Also recorded, even at 丨50. 〇 Heat treatment for about 10 minutes can also obtain wiring with a volume resistivity of 4 to 10 // Ω · cm. However, if the technique disclosed in this document is used, it is necessary to adopt a special coating method of dry 〇n wet or wet on wet, and it is difficult to form complicated fine wiring. Patent Document 2 discloses a conductive paste containing an epoxy resin and a phenol resin, which comprises a monobasic acid having a side chain composed of an alkyl group and a dibasic acid having an alicyclic structure. . Further, it is described that the monobasic acid functions as an oxide film for removing the surface of the silver particles in the paste, and a wire having a volume resistivity of 17 to 25 cm is obtained by heat treatment at 180 ° C for 10 minutes. However, the technique described in Patent Document 2 has not yet achieved sufficient conductivity in a region of less than 150 C. [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-132736 [Patent Document 2] Japanese Patent Laid-Open No. 2009-298963 (Summary of the Invention) 099137434 4 201219512 (Problems to be Solved by the Invention) It is desirable to use heat treatment in the vicinity of a substrate or the like which is particularly low in heat resistance. In other words, the conductive particles are contacted and sintered by the second degree of deformation, and the conductive = hot paste has an extremely high utility value and can be applied to various applications. However, the prior art of θ v electrical pasting has not yet provided a conductive paste at a low temperature. In addition, it is expected that if it is possible to provide a kind of paste that is not limited to the type of resin, it can be designed to meet the needs of the package. The purpose of the month, and the field of application will also be completed by a invention that is fulfilled by such requirements. That is, what is not disclosed in this book is a metal conductive film which can be formed by heat treatment at a low temperature of about 12 rc, which exhibits low volume resistivity. More specifically, it is not conductive as follows. Slim paste: Whether the resin of the constituent component is a thermosetting resin or a heat recordable resin, (4) the difference in the material is considered, and (4) the conductive film exhibiting a low resistance under the condition of 2 temperature treatment. (Means for solving the problem) The conductive paste which can form a conductive film of the present invention is specifically a metal particle, a dispersion medium, a resin, and a carbon number which are coated with an organic substance composed of a carboxylic acid having 2 to 8 turns or a derivative thereof. In the present specification, the term "derivative" means a structure in which a main structure has a carboxylic acid structure having 2 to 8 carbon atoms, and one part of the molecule is substituted by another functional group. The metal type is "silver", especially the "resin type silver paste 099137434 5 201219512. The total weight of the paste added to the paste is 0. 〇5~9 Λ - 竣 acid relative to conductivity 2.0 quality. /. In terms of temperature, the boiling point of the silver particles, the boiling point of the citric acid or the carboxylic acid of 2 to 8 is formed. The main component of the surface is more preferably the carbon number. Resin-type silver-dispersed dispersing agent. Preferably, the paste-forming step comprises the step of allowing the metal particles to have the conductive paste of the above-mentioned composition by having the silver-based grade (9) and having the conductive paste of the above composition at 60. The conductive film obtained in minutes has a calcination value of 2.G or less. b When the color of the conductive yarn is not the same, a* The method for forming the conductive wiring of the present invention has the following steps: The step of applying the paste to the substrate; and subjecting the coated conductive paste to a metal film by heat treatment in the atmosphere or in an inert gas atmosphere at a condition τ of HK) to C. (Effect of the Invention) By the configuration of the above-mentioned conductive paste, in particular, by adding a dicarboxylic acid to its constitution, a wiring having a low resistance can be formed even at a temperature lower than the temperature of the previous heat treatment. Hardenable or thermoplastic resin _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In terms of price and reliability, the most common use is silver. Therefore, in the present specification, an example in which silver particles are used as the conductive particles will be specifically described, but the present invention is also applicable to substances other than silver. In the case where silver nanoparticles are used in the present invention, the average primary particle diameter calculated using a TEM 'Transmission Electron Microscope' photograph is 200 nm or less, preferably i~15〇nm, more preferably 10~100 nm. By using particles having such a particle diameter, a conductive film having a south conductivity can be formed even if heat treatment is performed at a low temperature of about 120 °C using a resin paste. The evaluation of the average primary particle diameter by a transmission electron microscope was carried out as follows. First, 2 parts by mass of the washed silver nanoparticles are added to a mixed solution of 96 parts by mass of cyclohexane and 2 parts by mass of oleic acid, and dispersed by ultrasonic waves. The dispersion solution was dropped into a Cu microgrid with a support film, and allowed to dry, thereby making a TEM sample. Using a transmission electron microscope (JEM-100CXMark-Π type manufactured by JEOL Ltd.) to observe the fine particles of the TEM sample produced, the particles observed in the bright field were observed at an acceleration voltage of 1 〇〇 kv. Image. Further, the image magnification is set to 300,000 times by enlarging the image. In order to calculate the particle size from the obtained photograph, the particle size can be directly measured by a vernier caliper or the like, and the particle size can be calculated by using an image analysis software. The average primary particle size at this time was obtained by measuring at least 200 results for each of the independent particles in the TEM photograph, and the average value thereof was calculated. The silver content in the silver nanoparticles coated with the organic coating can be obtained by the following method: a weighing sample (silver nanoparticle coated with an organic coating) is placed in an ash dish for ash determination by 0.5 g or more. And in the muffle furnace (10) god

In F〇31〇) manufactured by Scientific Co., Ltd., it is heated to 700 ° C at a rate of about 忉 / min, and the organic coating present on the surface of the silver nanoparticles is removed. The ash dish was taken out in a stage where the temperature in the furnace reached 500 ° C or lower, and it was cooled to normal temperature in a desiccator, and the weight of the sample after cooling was compared with the weight before heat treatment. Further, the organic substance covering the surface can be known from the gas component measured under an inert gas atmosphere using a heating analysis device such as TG_MS or gc_ms. The silver nanoparticles used in the present invention have the above average primary particle diameter and are coated with the surface of the organic material. Specifically, as the organic substance, an organic substance composed of a carbonic acid of 2 to 8 or a derivative thereof can be preferably used. Specifically, the present invention is not limited to the following, but examples thereof include caprylic acid, enanthk acid, capr〇ic acid, valeric acid, and diced as saturated fatty acids. Butyric acid, propionic acid (Pr〇pi〇nic acid), and the like. Further, examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, caproic acid, pimelic acid, and suberic acid. Examples of the unsaturated fatty acid include 099137434 8 201219512 hexadienoic acid, maleic acid, and the like. Among the above, in particular, when the surface of the silver nanoparticles is coated with caproic acid, heptanoic acid, adipic acid or hexadienoic acid, the form of the powder can be easily produced. Provided • Such a powder form makes it easy to formulate when forming a paste as in the present invention. Further, the particles formed by coating the surface with such a substance can be easily collected while being agglomerated while maintaining the form of primary particles. At this time, the agglomerate block is at least a size that can be recovered by five kinds of c of JISp_38〇1, and thus can be regarded as 2.5 // in or more. Further, when the filtration is carried out, a clear liquid solution can be obtained, so that the above-mentioned 2.5 #m reduction (secondary) particle size is different from the average particle diameter of the so-called silver particles by 1%). The reason for this is that the above-mentioned particle diameter of the silk is D5. For the value, the filter is not used for the month b; the agglomerates passed through will increase. Therefore, it can also be explained that the agglomerated (secondary) particle diameter is not an average value but forms agglomerates having a size of at least about 2.5 Å. Further, if a low temperature is applied (the dry operation is not performed, it may be recovered in the form of dry particles. Further, silver nanoparticles coated with a plurality of organic substances may be used, or different average-secondary particle diameters may be used. Silver nano particles are used together. &lt;Silver submicron particles&gt; The inventors have found that even if a certain size of silver particles is used, it is possible to exhibit silver nanoparticles with satisfactory conditions. 'The wrong fruit. Compared with the silver nanoparticles, the average particle size (〇5 core is 〇5~ 扣4, etc. The particle% is silver submicron particles. As a specific aspect, it is used for the fee m 4 is 099137434 S. 201219512 The organic acid is used to coat the surface of the particle with an organic substance composed of a tickic acid having 2 to 8 carbon atoms or a derivative thereof. The resin is not limited to the following, but may be a caprylic acid of a saturated fatty acid. Wide: acid (enanthic acid), caproic acid, valeric acid, butyric acid, propionic acid, etc. Further, as the dicarboxylic acid, oxalic acid can be cited. , propionic acid, succinic acid, glutaric acid, adipic acid, g Examples of the unsaturated fatty acid include hexadienoic acid, maleic acid, etc. The particles may be formed by coating the silver particles in advance at the production stage, or may be used in advance for commercially available particles. In the present specification, "silver particles" include "silver nanoparticles" and "silver submicron particles". <Dispersion medium> The paste system of the present invention is formed by replacing the coating material. Silver particles (including silver nanoparticles and silver)

Disperse into the dispersion medium. The dispersing medium used at this time is preferably a polar I agent. If the polar solvent is used, the vapor is lowered, so it is suitable for operation. Cold, especially in the case where the money is compatible with various resins, it is preferred to use an organic solvent such as a ketone system, a ketone system, a ketone system, an alcohol system or a solvent. Specific examples of the diterpene and the amines include glycols such as water and octanediol, ethanol, oxime, and methyl groups. (10) Alcohol, butyl carbitol, carbitol alcohol acetic acid, Texan笨 笨 氧基 oxypropanol, two. Dibutyl glycol alone ether B (four) early shouting, B a private early 曱 乙 峻 _, 099137434 2U1219512 ethylene glycol monoethyl ether acetate, methoxybutyl phthalate diethylene glycol single yin vinegar Ethyl lactic acid and methic acid; especially the 'conductive paste' is usually used for printing. Preferably, the use of a low volatility forming circuit during printing is carried out by using a solvent of rosin or butyl carbitol acetate vinegar or octane = more preferably as a combination of the agents.兮w ^, &quot; also 'can also use a variety of dissolution and use. The amount of the solvent is preferably 60 ft% ^ T ® ^; the secret fat and metal components minus / ° below, more preferably 5 〇% by mass &lt;dispersant component&gt; ° In the paste of the present invention, it is also possible to add a dispersion of appropriately dispersed silver particle powder Γ = such a dispersant' to ensure particle independence in the paste: It has affinity with the surface of the particles, and it can also be used for halving. It can also be used as a general-purpose one. It can also be used in a single type. It can also be combined with the amount of silver nanoparticles. The silver total mass of the silver micro-recorder is 3.0% by mass or less, preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. As a dispersing agent having the above properties, a representative one is a fatty acid salt ( Soap), α-renering fat _ salt (Cong), alkyl benzoate (ABS), direct-bonding benzoate (LAS), alkyl sulfate (AS), alkyl ether sulfur (tetra) salt Low molecular anionic (anisnic) compounds such as (AES), alkyl triacetate, fatty acid ethanol decylamine, polyoxyethylene hydride Low molecular nonionic compounds such as alkyl ether (AE), polyoxyethylene alkyl benzoquinone (ΑΡΕ), sorbitol, sorbitol, alkyl tridecyl ammonium salt, dialkyl dimethyl ammonium chloride Alkyl pyridine chloride

S 099137434 11 201219512 镔Special low-molecular cationic (cati〇nic) compound, pyrolysis-based sugar beet test, Shihuang-based beet test, lecithin and other low molecular amphoteric compounds, or naphthoate furfural condensate, Polystyrene sulfonate, polyacrylate, copolymer salt of vinyl compound and carboxylic acid monomer, polymer aqueous dispersant represented by carboxymethyl cellulose, polyvinyl alcohol, etc.; polyalkyl acrylate a polymer non-aqueous dispersing agent for polyalkylene polyamine; and a polymeric cationic dispersing agent such as polyethyleneimine or mercapto methacrylate copolymer, but as long as it is suitable for the particles of the present invention, Constructors other than those exemplified herein are not excluded. As the dispersing agent, the following names are known, but the dispersing agents other than those described in the present item having the above properties are not excluded. For example, 'ViewLight LCA-H, LCA-25H, etc. manufactured by Sanyo Chemical Co., Ltd., Flowlen DOPA-15B manufactured by Kyoei Chemical Co., Ltd., etc., Solplus AX5, Solsperse 9000, Solthix manufactured by Lubrizol Co., Ltd., Japan 250, etc., EFKA 4008 manufactured by EFKA Additives, Ajisper PA111 manufactured by Ajinomoto Fine-Techno Co., Ltd., TEXAPHOR-UV21 manufactured by Cognis Japan Co., Ltd., Disper BYK2020 or BYK220S manufactured by BYK-Chemie Japan Co., Ltd. Etc., Disparlon 1751N, Hiplaad ED-152, etc. manufactured by Nanben Chemical Co., Ltd., FTX-207S, Ftergent 212P manufactured by NEOS Co., Ltd., AS-1100 manufactured by East Asia Synthetic Co., Ltd., etc., Kao shares limited 099137434 12 201219512 Kaocer 2000, KDH-154, MX-2045L, Homogenol L-l8, Rheodol SP-010V, etc. manufactured by the company, Epan U103, Sharol DC902B, Noigen EA-167, Plysurf A2·, etc. manufactured by First Industrial Pharmaceutical Co., Ltd. McAfee Co., Ltd. manufactured by Megafac F-477, etc. SN Sperse 2180 manufactured by San N〇pC〇 Co., Ltd., manufactured by the company, West Africa, SAG5〇3A, Dynol 604, etc.

SN Leveler S-906, etc., S-386, etc. Further, in addition to the dispersant, various additives are printed. The rheology control agent, the antifoaming agent, (3 &lt;resin&gt;' may also be added to improve the stability of the paste or may, for example, be a leveling agent, a viscosity modifier, an anti-settling agent, etc. In the paste, the resin can be a well-known thermosetting resin, which can be used as a resin. The amount of the resin to be added is preferably set as follows: phase · Yinnai green And the total mass of the silver and the total mass of the resin of the silver submicron particles are preferably 2 to 2 G mass%, preferably 15 cc / 〇 right added resin amount is too much, then the resin S exceeds after calcination* In the case of the wiring, the wiring is extremely inferior in conductivity. Therefore, if the addition is reduced to the right, the adhesion between the wiring and the substrate cannot be ensured. Therefore, it is necessary to add at least about 2% by mass. (Thermoplastic resin) In the present invention, any of known thermoplastic resins can be used,

S 099137434 13 201219512 It is preferable to add an acrylic resin, a polyester resin or a polyamino phthalate resin as a well-known person, but it is not excluded to use other than those described in the present item having the above properties. Resin. The polyamino phthalate resin is not particularly limited as long as it is a commercially available thermoplastic amino phthalic acid vinegar resin. For example, a thermoplastic urethane resin obtained by polymerizing a polyol component and an organic polyisocyanate as essential components and using a chain extender or a terminator as an optional component can be mentioned. Here, examples of the polyisocyanate to be used include HDI 'hexamethylene diisocyanate, LDI ' lysine isocyanate, and isophorone diisocyanate (HDI ' hexamethylene diisocyanate). IPDI, isophorone diisocyanate), XDI, xylylene diisocyanate, hydrogenated benzodiazepine diisocyanate (H6-XDI), hydrogenated diphenyl diisocyanate (H12-MDI, Hn-methylene) Diphenyl diisocyanate), trans 1,4-cyclohexane diisocyanate, tetramethyl xylylene diisocyanate, 1,6,11-undecane triisocyanate, 1, 8-Diisocyanate-4-isocyanatomethyl octane, 1,3,6-hexa-indenyl triisocyanate, bicycloheptane triisocyanate, tridecyl hexamethylene diiso citrate (TMDI, trimethyl hexamethylene diisocyanate) or the like, and among them, HDI, IPDI, H6-XDI, H12-MDI are more preferable in terms of small yellow denaturation. Further, as the polyol to be used together with the above polyisocyanate, it is considered to be preferable as a low crystallinity of the polyol. Specifically, it can be exemplified: polyethylene adipate 099137434 14 201219512 (PEA, polyethylene adipate), polybutylene adipate (PBA), polycarbonate (PCD, polycarbonate), polytetradecene 0 (acrylic resin) such as PTMG 'polytetramethyleneglycol, polycaprolactone polyester, polypropylene glycol (PPG), etc. means having a (meth) acrylate unit and/or (A) Base) Acrylic unit as a constituent resin. It may also be a constituent unit such as a derivative derived from (fluorenyl) acrylate or (mercapto)acrylic acid. Here, the (meth) acrylate unit means, for example, a constituent unit derived from (meth) decyl acrylate, (mercapto) ethyl acrylate, (mercapto) n-propyl acrylate, ( N-butyl acrylate, n-butyl phthalate, (meth) acrylic acid, cyclohexyl acrylate, 2-ethylhexyl acrylate, Benzyl) benzyl acrylate, dicyclopentyloxyethyl (mercapto) acrylate, dicyclopentanyl (decyl) acrylate, chloromethyl (meth) acrylate, 2-oxoethyl (meth) acrylate, (mercapto) 2-hydroxyethyl acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth) acrylate, (meth) acrylate 2 3,4,5-tetrahydroxypentyl ester, 2-(hydroxymethyl) acrylate decyl ester, 2-(hydroxyindenyl) acrylate ethyl ester, 2-(hydroxyethyl) decyl acrylate, and the like. On the other hand 'as a (meth)acrylic unit, for example, means a constituent unit derived from the following monomers: acrylic acid, mercaptoacrylic acid, crotonic acid, 2-(hydroxymethyl)acrylic acid, 2-(hydroxyethyl) Acrylic, etc. As the polyester resin, any of generally known resins can be used. The method for producing 4 099137434 15 201219512 can be exemplified by the formation of a low molecular diol and a polycarboxylic acid or an ester thereof [anhydride, a lower leuco (carbon number 1 to 4) ester, a brewing compound, etc.] Or the like, or a low molecular diol as a starting agent, the lactone monomer can be combined to form a long length. Further, it is also possible to use a mixture of two or more of these. (Thermosetting Resin) In the present invention, any of the known thermosetting resins can be used. As a specific example, the thermosetting resin may be selected from the group consisting of an anthracene resin, an epoxy resin, an unsaturated eucalyptus, an isocyanate compound, a melamine resin, a gland resin, a polyoxo resin, and the like. Here, the epoxy resin and the phenol resin will be described. &lt; A "Nuclear Oxygen Resin" has the effect of improving the weatherability of the coating. Specifically, as the % oxygen resin, a mixture of any of a monoepoxy compound and a polyepoxy compound may be used. Here, as a monoepoxy compound, glycerin _, hexyl glycidol (10), phenyl glycidol enigma, dilute four ^ / Guanggan to the second butyl styl glycidol, epoxy, Oxygen, n-p-tolyl glycidyl hydrazine, acetic acid glycidol vinegar, butyric acid, "@@日, hexanoic acid glycidol, benzoic acid glycidol vinegar, etc. As an oxime oxygen compound, for example, it is exemplified: Phenolphthalein, bisphenol F, bisphenol S, tetramethyl bisphenol quinone, tetradecyl bisphenol F, tetradecyl bis (5) decyl bisphenol S, tetrabromobisphenol A, tetra bisphenol A, Four (four) epoxy resins obtained by glycidylation of four types such as tetrafluorobis 0; the other two diterpenoids of the bismuth-septyl naphthalene, 9,9·bis (four provinces-based phenyl) Resin; diglycerolized 1,1,1-tris(4-hydroxyphenyl)fluorene 099137434 201219512 聋-cabin phase &amp;, benzyl) fluorenylethyl)phenyl)ethylidene bisphenol Epoxy resin; (10), *, basic base ethane quinone tetraphenols to benzene age secrets, (four) conversion W oxygen resin; benzene (four) vine varnish, desertification double 3 eight AW, double sputum secret varnish, Desertified water An epoxidized varnish such as varnish, which is obtained by shrinking condensed glycerin, such as lyophilized lyophilized glycerin, etc.; A silky epoxy resin such as zebraic acid; a polybasic acid such as formic acid which is obtained by glycidylating a phthalic acid-based epoxy resin; Benzene and other amine compounds '(4) an amine such as A or m-oil ester, ±,,, 7 glycerides or isocyanuric acid trihydrate, its glycidyl epoxy resin, etc. Oxygen = base; Μ 'oxocyclohexanoic acid brewed (iv) polycyclic di-high _ stability from the viewpoint of the preferred yield 罝 &amp; (four) eight listener towel, glycidyl epoxy resin due to the house It has an overwhelming advantage, so the excellent side _言,更#2\, the hardened joint or the heat-resistant epoxy resin. It is better to shrink the glycidylate into a class, by h /, The oxy-resin is especially suitable for the epoxy resin of the epoxy tree formed by the double-anti-A and the glycidation of the double-F (the L-good is Further, the epoxy equivalent is preferably 099137434 17 201219512 300 or less. Very good #衣乳 ▲ quantity is greater than 300, body, resistance value, and so that _ no ^ / nuclear will become solid as heat Hard _=== 故 仏 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲 甲In addition to the organic matter, there are two renegade bismuths. By selecting Tim::5' can be selected to two: containing the organic-coated _'" bismuth paste at low temperature for heat treatment, silver nanoparticles Or = the child will also be sintered, and the formation of high (10) granules is shown in the following: r electrical lifting component, which can be exemplified as having two. B - Cichong - acid, succinic acid, glutaric acid and so on. If the total amount of rock red is in the structure, the activity is lowered and when the conductive paste containing silver nano- or silver is heat-treated at a low temperature, it becomes difficult to cause the silver nanoparticle=microparticle to be sintered, resulting in difficulty in formation. Shows a highly conductive n-electrode film. In addition, if the amount of carbon used is too high, the substance added may be: sintered or left in the film, resulting in difficulty in performance and poor suppression. Electric change ', and more specifically' as the total number of carbon in the structure of the two Wei's is more suitable for carbon number 2~8' is preferably 2~7, more preferably 2~5, sub, 闺二Jun. 099137434 18 201219512 The total weight of the above-mentioned forming force with respect to the conductive paste is G 〇 5 〜 2 〇 by mass%, preferably in the range of 0, 1 to 1.5% by mass. Regarding the amount of the two kinds of oxic acid contained in the conductive|'s raw paste, for example, a high-performance liquid chromatography (HpLc, mgh卩 (4) 継 ^ 祝

Ch_atGgi; aphy), polymer-based reverse phase chromatography for green recognition. &lt;Production of Conductive Paste&gt; The conductive paste according to the present invention is produced by coating the surface of silver nanoparticles with an organic substance having a carbon number of 2 to 8 as described above. The method for producing the silver * rice particles of such a composition is not limited in any way. For example, a method of replacing the surface of the silver nanoparticles with a carbon having a carbon number in the above range can be exemplified. Further, silver nano particles and a conductivity-enhancing component having the above properties and a dispersing agent added as the case may be added to the above polar solvent. Furthermore, silver submicron particles may also be incorporated herein. Thereafter, it is introduced into a kneading defoaming machine to form a kneaded material of the component. Thereafter, mechanical dispersion treatment is performed as the case may be to form a paste. In the above mechanical dispersion treatment, any of the known methods can be employed without the significant modification of the silver particles. Specifically, an ultrasonic dispersion, a disper, a three roll mill, a ball mill, a beads-mill, and a two-axis kneader can be exemplified (tW0-axis kneader) ), self-propelled mixers, etc., which may be used alone or in combination. &lt;Evaluation of Conductive Film&gt; 099137434 19 201219512 (Printing method) The conductive paste prepared by printing with a screen printing machine or a metal mask was subjected to evaluation of the conductive film after calcination. In addition, the pastes used in the examples and the comparative examples were produced so as to have a viscosity of 30 Pa · s in order to prevent the occurrence of stains such as stains, and the blending amounts are as shown in Tables 1 to 3. (Screen printing) A screen having a film thickness of 34 /z m was printed on a polyethylene terephthalate film (Liimirror 75 S10 manufactured by Toray) in a line width of 3 〇〇 #m. The obtained printed substrate was placed in a melon burner (DKM400 manufactured by Yamato Scientific Co., Ltd.) and heat-treated at 120 ° C for 60 minutes in the atmosphere to calculate the volume resistivity of the obtained product. (Metal mask printing) A metal mask of a film thickness of 30 //m was used to physically print onto the alumina in a pattern of 1 mm. The obtained printed substrate was placed in a calciner (DKM400 manufactured by Yamato Scientific Co., Ltd.), and heat-treated at 120 ° C for 60 minutes in the air to calculate the volume resistivity of the resultant. &lt;Calculation of Volume Resistivity&gt; (Wiring) The wire resistance of the wiring formed on the substrate by screen printing was measured using a two-terminal type resistivity meter (3540 Milliohm HiTESTER manufactured by Konica Electric Co., Ltd.), and The thickness of the conductive film was measured by a surface roughness meter (Surfcom 1500D model manufactured by Tokyo Seimitsu Co., Ltd.). 099137434 20 201219512 Finally, the volume resistivity of the wiring is calculated according to the following formula (1). Volume resistivity (// Ω · cm) = measured resistance (Ω) Χ film thickness (/zm) x line width 〇 m) + line length (/zm) xl02 _··(1) (solid film) The mold was printed on the substrate, and the surface resistance of the formed 10 mm □ pattern of the conductive film was measured by a four-terminal type resistivity meter (Loresta GP MCP-T610 type manufactured by Mitsubishi Chemical Corporation), and the surface roughness meter was used ( The thickness of the conductive film was calculated by measuring the thickness of the conductive film by the Surfcom 1500D model manufactured by Tokyo Precision Co., Ltd. Finally, the volume resistivity of the solid film of the 10 mm □ pattern was calculated according to the formula (2). Volume resistivity (//Ω · cm) = surface resistance (0/□) &gt;&lt; Film thickness (/zm) xl00 (2) &lt;Color difference&gt; The paste was 2.0 to 2.5 cm in length and 1.5 in width. The ~2.0 cm body was printed on a glass substrate (EAGLE XG), and the paste was baked in the air at 120 ° C for 60 minutes to form a film, and the color of the obtained film was measured. Further, the color difference measurement was carried out using a color difference measuring device (SQ-2000 manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement results are described by the L*a*b* color system. In particular, the paste of the present invention is characterized by the a* value when represented by the L*a*b* color system, and when the additive containing the dibasic acid is not added, the value becomes higher than 2.0. In the case of adding, a value of 2.0 or less is displayed. That is, when the a* value is higher than 2.0, the electric resistance of the electroconductive film is extremely high. 099137434 21 201219512 The value 'below the case where the electric resistance of the electroconductive film is lower than 2.0. In other words, in the present invention, when the completed conductive film contains a dilute acid to form a conductive film having excellent conductivity, it can be judged based on the color tone of the conductive film. (Evaluation of crystal growth due to calcination) A paste of 1 〇mm □ was printed on a copper hull plate, and the paste was calcined at 120 ° C for 60 minutes to form a film, and the film was kneaded. The ray diffraction measurement 'determines the crystal seed diameter and confirms the degree of crystal growth. In this case, the X-ray diffraction apparatus (RINT-2100 manufactured by RIGAKU Co., Ltd.) was used. The lamp tube was measured using a cobalt lamp tube at a lamp tube voltage of kV and a lamp current of 30 mA. The degree of growth of the crystallizer is calculated as the diameter of the crystallizer. In particular, since it is carried out on the diffraction surface of Ag (lll), it is determined in the range of 2 Θ = 40 to 50 ° (scanning speed: 167. 167 / min). Further, the crystal seed diameter was calculated by the Scherrer method. [Examples] First, an example of using silver nanoparticles described in Table 1 will be described. &lt;Example 1&gt; (Synthesis Example of Silver Nanoparticles) An example of producing silver nanoparticles coated with adipic acid was disclosed as a production example of the particles shown in the examples. In a 500 mL beaker, 13.4 g of silver nitrate (manufactured by Toyo Chemical Co., Ltd.) was dissolved in 72.1 g of pure water to prepare a silver solution. 099137434 22 201219512 ,, and 1.34 L of pure water was poured into a 5 B beaker, and a nitrogen gas was introduced to remove dissolved oxygen, and the temperature was raised to 6 (TC. Adding hexahydrate 夂(made by Heguang Pure M Co., Ltd.) n 9 g.

Ammonia water (manufactured by Wako Pure Chemical Industries, Ltd.) 2 82 g to adjust the pH by adding the ammonia water to start the reaction. This was stirred while adding hydrazine hydrate (purity of 8% by weight / manufactured by Otsuka Chemical Co., Ltd.) to 5.96 g after 5 minutes from the start of the reaction. After 9 minutes from the start of the reaction, silver was added to reduce the reaction. Thereafter, 30 knives were thermally formed to form silver nanoparticle coated with hexadienoic acid. Thereafter, it was filtered with No5C filter paper and washed with pure water to obtain silver nanoparticle aggregates. The ruthenium agglomerates were dried in a vacuum dryer under the conditions of 8 Torr and 12 hours to obtain agglomerates of dry powder of silver nanoparticles. The agglomerates thus known are suitably obtained by, for example, replacing the organic matter on the surface of the particles or directly using the same method as described above. (Production of conductive paste) 70 g of dried hexadienoic acid-coated silver nanoparticles particle aggregates (average particle diameter: 100 nm) and butyl carbitol acetate (manufactured by Wako Pure Chemical Co., Ltd.) 8.9 g, thermoplastic polyurethane phthalate resin Urearno 8001 (manufactured by Arakawa Chemical Industry Co., Ltd.) 22 3 g, polymer 糸 pigment dispersant Ajisper PA-111 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) 0.35 g, Malonic acid (manufactured by Wako Pure Chemical Co., Ltd.) was 0.14 g and mixed. £ 099137434 23 201219512 By using a two-grinding machine (EXAKT Apparatebaus, M-80S type), the mixture thus obtained is passed 5 times to make a poor paste. The obtained conductive paste was printed on a substrate, and heat-treated at a temperature of C and 60 (hereinafter referred to as "120 C for 60 minutes") to form a conductive film. The volume resistivity of the obtained conductive film was 24 // Ω · cm under the treatment of 12 〇 for 6 〇. The above crystal diameter measured by X-ray diffraction is 37.65 nm. 7 The calcined film obtained was slightly mixed with a yellow color. After the color of the film was determined by a color difference meter, L* was 60.9, a* was 1.04, and b* was 9.3. Further, after observing the morphology of the calcined film by SEM (Scanning Electron Microscope), the morphology as shown in Fig. 3 was confirmed. Figure 3 is a 300,000-fold SEM photograph in which the i scale is equivalent to 1 melon. As can be seen from the photograph, the block which is initially in the form of particles is spliced every two to three to form one. From this, it was confirmed that even if a low temperature of 120 ° C was used, the morphology of the primary particles was not maintained, but grain growth occurred. &lt;Comparative Example 1&gt; Example 1 was repeated except that malonic acid as an additive was not added in Example 1. The physical properties of the obtained calcined film are shown in Table 1. The crystallite diameter measured by X-ray was 29.90 nm. Further, the obtained film was slightly mixed with a red color, and after obtaining the color of the film by a color difference meter, 'L* was 63.5, a* was 4.04, and b* was 4.1. Further, after observing the morphology of the calcined film by Sem, the morphology as shown in Fig. 4 was confirmed. Fig. 4 is a photograph of the same magnification as 099137434 24 201219512, and the scale of the photo t is equivalent to! p. Comparing Fig. 2' with Fig. 3, it can be confirmed that the fine particles (4) have their shoulders. It can be seen that the fine particles are used because of the low temperature of 12 叱.

Keeping its original shape, B ~, and grain growth did not proceed as before. &lt;Examples 2 to 5 &gt; In addition to Example 1, the amount of malonic acid added as an additive such as L·, &amp; is changed, and the adjustment of the viscosity of the lamp is set to be performed by using a silk thread. In addition to the amount of the 丨 1 1 , , , , , 。 。 。 。 。 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻 锻In the examples i to 5, the ratio of the amount of the additive to the additive on the day of the additive, and the amount of the vol% of the amount of the coating were compared with those of the coated nano silver particle 1, and the vertical axis represents the volume resistivity (in terms of Ω•the ratio). 1. In the figure dose (mass ratio). This value is also shown in Table i /) '杈 axis is the amount of additive / the amount of coating relative to the coated dose is more than 纟 Figure 1 can be seen, if the additive (36 / Ω · cm below ) and stability. S, the volume resistivity is extremely low. Furthermore, the ratio of the added enthalpy and the amount of the additive of Fig. 1 can be expressed as the amount of tb = the coating amount of the nanoparticle of the nanoparticle silver particles (g) x nm The amount of addition of silver particles (g) / (the proportion of the coating agent of the silvery silver nanoparticles), and the ratio of the composition of the breaker. The ratio of the organic matter can be expressed as the residual weight (g) calculated by the above ash measurement and the ratio of the residual ash to the ash content is 1 to 1 (the ash treatment is specific value, the example is 4 weight (g)) ° 099137434 The composition ratio of the coating is 0.00137434. \Low 201219512 Calculated based on the metal ratio calculated by ash measurement = 99.2%). Further, in Examples 2 to 5, since the metal ratio of the nano silver particles used was 99.2%, the proportion of the coating agent was 0.008. &lt;Examples 6 to 8&gt; The method of Example 1 was repeated except that the type of the silver nanoparticles constituting the conductive paste was changed to those shown in Table 1 in Example 1. Further, the reason why the composition ratio of the resin or the like is different is that the viscosity adjustment is performed as described above. The physical properties of the obtained calcined film are shown in Table 1. &lt;Examples 9 to 10&gt; The method of Example 1 was repeated except that in Example 1, the amount of silver nanoparticles was changed to those shown in Table 1. The physical properties of the obtained calcined film are shown in Table 1. &lt;Examples 11 to 12, Comparative Examples 2 to 3 &gt; Example 1 was repeated except that the kind of the additive added in Example 1 was changed. The physical properties of the obtained calcined film are shown in Table 1. 099137434 26 201219512 [I &lt;] Comparative Example 3 〇〇I \ 1 1 I 1 2 ο 1 «ο CN 〇CO (N fS Π ο oo o Comparative Example 2 〇〇I 1 1 1 I inch ο 1 1 CN 〇cn &lt;N &lt;N &lt;〇od m ο oo o Example 12 〇〇I 1 1 inch ο &gt;〇ο cn &lt;N &lt;N CO m ο 00 Example 11 〇〇I 1 1 1 Οο ti〇CN ο CN (N n oo to Ο oo embodiment 10 〇jn I 1 \ V*) o 1 IT) rj ο inch CO r- vd Ρ; ο a\ Example 9 〇I 1 \ cn o 1 \ 1 1 wi o inch as ΓΛ ο Γ Η wear 1 embodiment 8 1 I 1 ooo ι 1 1 1 (N om &lt;N ιη η ο as CN U-) CO Example 7 1 I oolo I 1 1 1 Or*i &lt;N 卜 «ο m Ο 〇CN oo tr&gt; Example 6 t ο ο 卜 1 1 oo o 1 1 1 o CN CS od ιτ&gt; ΓΛ Ο r-&gt; (N Comparative Example 1 1 ο ο 1 t 1 1 ι ! 1 1 o Λ (N (S m ΙΤ) cn Ο CC; 〇 Example 5 ο ο 1 1 1 s ι 1 ι 1 oo oo “ m oi (N ON od m ο 卜 CN v 〇m Embodiment 4 ο ο I 1 1 'SO in o I 1 1 1 o rn CN ON OO ο 〇〇 (N Example 3 ο ο 1 1 1 go 1 1 1 1 cn o r4 (N n OO ο CN CN 〇 Embodiment 2 ο ο 1 1 1 o 1 1 1 1 沄CN m CN ίΜ r- &lt;Τ) tn ο &lt;N so m Embodiment 1 ο ο 1 1 1 2] oi 1 1 1 IT) cs o (N (N On CO ΓΛ ο cn S 1 globular ι spherical ι I Sphere | [Spherical malonate azelaic acid diacid lactic acid diglycol ♦ jw 4 nfii Urearno 8001 (poly Amino phthalate resin) BCA (butyl carbitol acetate) I ϋ B so G 100 nm 60 nm | 20 nm 100 nm rO Dun Vd rO silver butyrate particle amount (g) Adding dose (g) φί畐1 Resin amount (g) Solvent amount (g) Dispersed dose (g) Film thickness Volume resistivity step on ra drink Φ St $ ^&quot;Change disc Dini explain Mil a, 桕啭-Ji〇※ LZ K inch A- 660 s 201219512 Since it was confirmed that the addition did not depend on the particle size, it was also confirmed for the case of particles having a larger particle size. &lt;Example 13&gt; The same procedure as in Example 1 was carried out except that the hexadienoic acid-coated silver flake powder (average particle diameter: 3 Am) was used in Example 1, and the blending amount described in Table 1 was used. The conductive paste was shown in Table 2 for the physical properties of the obtained calcined film. &lt;Example 14&gt; Except that in Example 13, the amount of malonic acid added was reduced to the amount shown in Table 2, and Example 13 was repeated. The physical properties of the obtained calcined film are shown in Table 2. It is understood that although the electrical resistance is slightly higher, a conductive film can also be formed. &lt;Comparative Example 4 &gt; Example 13 was repeated except that malonic acid was not added in Example 13. The physical properties of the obtained calcined film are shown in Table 2. It is understood that if malonic acid is not added, conductivity is not obtained at all. &lt;Comparative Example 5 &gt; Example 11 was repeated except that the silver flake powder used was changed to the oleic acid (carbon number 18) coating in Example 13. The physical properties of the obtained calcined film are shown in Table 2. It is understood that even if malonic acid as a sintering accelerator is added, if oleic acid forming a long chain is used, conductivity cannot be obtained at all. &lt;Example 15&gt; In order to confirm whether or not the same effect can be obtained in the mixed state of the nanoparticle and the microparticle, 099137434 28 201219512, one half of the flake powder in Example 13 is replaced with the first embodiment. Example 13 was repeated except for the hexadienoic acid-coated silver nanoparticles used. The physical properties of the obtained calcined film are shown in Table 2. It was confirmed that a conductive film having a lower electric resistance than that of Example 13 was formed. S. 099137434 29 201219512 [&lt;Ν&lt;] Example 15 in mm ro 1 0.14 0.44 22.3 0.35 oo CN oo Comparative Example 5 1 1 ο 1_0.14 1 oi 22.3 CN 0.35 1 r- &lt;N pi 〇|Comparative Example 4 1 ο ο 22.3 VO 0.35 1 oo CN Pi 〇 Example 14 1 ο 1 0.02 0.25 22.3 oi 0.35 1 OO CN 204 Example 13 1 ο 1 丨 0.14” r4 22.3 rn 0.35 1 m G\ m Spherical piece Amount of bismuth malonate / silver particle coating dose Ureamo 8001 (polyamine phthalate resin) BCA (butyl carbitol acetate) Ajisper PA111 βτη μ Ω · cm 100 nm 3 βΤΆ 3 βϊη 1 hexadienoic acid 1_ oil Amount of silver acid particles (g) Adding dose (g) Amount of resin (g) 1 1 Solvent amount (g) Dispersing amount (g) Thickness and volume resistivity of the compounding composition evaluation wishing a dish vi砸^M铖'κ唞' Ao* 0£17£?ει660 201219512 In order to show that the effect is not only expressed in the properties of a specific resin, an example in which the type of the resin is changed to various types is disclosed. Further, these volume resistance values are shown in comparison with Fig. 2 . &lt;Example 16 and Comparative Example 6&gt; Example 1 was repeated except that the amount of the resin (thermoplastic urethane resin Urearno 8001) in Example 1 was changed to the amount shown in Table 3. Further, Comparative Example 6 is the result of the case where malonic acid was not added in Example 16. As shown in Table 3, it was found that the conductivity was greatly optimized by the addition of malonic acid. &lt;Example 17 and Comparative Example 7&gt; Except that the resin (thermoplastic polyester resin Vylon 500/Toyobo Co., Ltd.) in Example 1 was used and the amount shown in Table 3 was changed, the examples were repeated. 1. Further, Comparative Example 7 is the result of the case where malonic acid was not added in Example 17. As shown in Table 3, it was found that the conductivity was greatly optimized by the addition of malonic acid. &lt;Example 18, Comparative Example 8 &gt; In addition to using the resin (thermoplastic acrylic resin BR-102 / manufactured by Mitsubishi Rayon Co., Ltd.) in Example 1, and changing to the amount shown in Table 3, Example 1 was repeated. Further, Comparative Example 8 is the result of the case where malonic acid was not added in Example 18. As shown in Table 3, it is understood that the conductivity is greatly optimized by the addition of malonic acid. &lt;Example 19, Comparative Example 9 &gt; S. 099137434 31 201219512 Except for the use of the PL4348/Junrong chemically-based phenolic resin Re-component in Example 1, the repeated text is not added in Table 3. Malonic acid, Comparative Example 9 is the result of the addition of the case of Example 19 to the case of propylene. As shown in Table 3, it can be seen that the addition of propionic acid to the dream greatly optimizes the conductivity.戟 矣 〈 〈 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 〈 〈 实施 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 〈 实施 实施 实施 实施 实施 〈 〈 〈 实施 实施 〈 〈 〈 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施The amount shown in Table 3 is added with the addition of malonic acid, and the comparative example 10 is the result of the "monthly opening" which is not described in Example 20. For example, the diacid, the conductivity will be carried out by the product of the large towel 5, and it can be seen that by adding the propane &lt;Example 21 &gt; In addition to the silver in the example 1 and the addition amount is changed to the silver of the conductive paste as shown in Table 1. The species of the nanoparticles are shown in Table 3, and the physical properties of the resin are shown in Table 3. The procedure of the heavy gauge was carried out, and the obtained calcined film was further referred to as "the resin of Examples 16 to 2 and the volume resistivity". 2. In Comparative Examples 6 to 10, the tree used was cm), and the horizontal axis represents Shu Yue t. People are shown in Figure 2. The vertical axis is the volume resistivity (//Ω. If the resistance value is too high, it cannot be used. In the embodiment indicated by the black bar, it will be 1 (8) 〇, 'the case is expressed as "〇R" in Table 3. The difference is significant in Fig. 2. The invention of the diacid is tens of / / Ω · cm, 099137434 32 201219512 - i ^ ^ ss π

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Illvd-^dv so · 67/ (S)BW--(60)峒i# money &amp; inch £?εΙ660s 201219512 Further, in the above embodiments and comparative examples, Examples 1, 2, 7, and 18, The relationship between the measurement results of 19 and the color of Comparative Examples 1, 2, 8, and 9 and the volume resistivity are shown in Table 4. In all of the examples in which the volume resistivity is several tens (//? · cm), a* is 2.0 or less, and the comparative example in which a* is more than 2.0 or more has a very high volume resistivity. In the case of the L*a*b* measurement method, the value of a* is 2.0 or less. It is shown that if the color is not red and b* is 10 or more, yellow is mixed. Further, Fig. 5 shows the relationship between a* and volume resistivity (//Ω · cm). The vertical axis represents the volume resistivity (//Ω · cm), and the horizontal axis represents a*. It is understood that if a* is 2.0 or less, the volume resistivity is lowered. Further, the one drawn in Fig. 5 also includes an example in which the resin is different, and Fig. 5 shows that if the dicarboxylic acid of the present invention is contained, the volume resistivity can be lowered regardless of the kind of the resin. 099137434 34 201219512 L_t匕Comparative Example 91 60.7 4.68 11.8 360 Comparative Example 8 62.5 6.91 Bu vd 6300 Comparative Example 2 | 55.4 1 2.20 ^}· Pi 〇Comparative Example 1 63.5 4.04 inch · 实施 Example 19 60.2 | 0.34 10.2 On Example 18 66.0 -0.46 1 15.5 1 00 Example 7 . „62.7 J 0.04 r—Η Example 2 60.1 | -1.45 15.5 \〇ΓΟ Example 1 60.9 | 1.04 cn * h-1 % Volume resistivity (#Ω · cm) - κκ-660 201219512 (Industrial Applicability) The conductive paste according to the present invention can be suitably used for "printed electronics, which can be used in the current industry" and prints CPU (Central Processing) Unit, central processing unit), printing 脬曰 / , printed label, full printed display, sensor, printed wiring board 'organic solar cell, e-book, nano-printed LED (Light Emitting Diode), liquid crystal PDP (Plasma Display Panel) Panel, printed memory, etc. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the mass ratio of the sintering accelerating component of Examples 1 to 5 and the organic material on the surface of the coated particle, and the volume resistivity. Fig. 2 is a graph showing the case of adding malonic acid as a sintering promoting component to each resin and the volume resistivity in the case where it is not added. Further, in the case where the sintering-promoting component of the polyurethane phthalate resin and the polyester resin is not added, the range is exceeded (〇verrange), and it is expressed as "exceeding the display range" for the sake of convenience. Fig. 3 is a scanning electron micrograph (direct magnification of 500,000 times) of a calcined film obtained by treating in the atmosphere and at UOt: for 6 minutes in the case where the sintering accelerating component is added in the embodiment. . 4 is a broom-type electron micrograph of a calcined film obtained by treating in the atmosphere at 120 ° C for 60 minutes in the case where the sintering-promoting component is not added in Comparative Example 1, with a direct magnification of 500,000 times. ). Figure 5 shows that the paste will be applied to the atmosphere at 12 Torr. 〇6〇分099137434 36 201219512 The color difference of the calcined film formed by heat treatment of the clock is expressed by the L*a*b* color system. The graph of the relationship between the a* value and the volume resistivity. £ 099137434 37

Claims (1)

201219512 VII. Shen 5 Qing Patent Fanyuan: 1. A conductive paste comprising silver particles coated with an organic substance composed of a carbon number of 2 to 8 or a derivative thereof = 2 to 8 carboxylic acid.默默 2. If the patent application scope α “古丄心心屯性猢t”, the above-mentioned 》 性 糊 糊 甩 甩 甩 甩 甩 甩 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于3. For example, the conductive paste of the i or the second item of the application may contain the polydispersant of the above-mentioned 匕3 to disperse the silver particles. 4. In the scope of the patent application, the above-mentioned conductive The paste is subjected to a heat treatment, and the conductive paste of the member is such that the silver is in contact with or welded to each other, and the wiring is formed to have a conductive property by using a conductive film. The winner of the item, the winner of the item, and the range of items 1 to 4 of the μ profit range - \付有, and L*a5i!b* 6. - the formation method of the conductive 貘, and the a* in the 糸The value is less than 2.0. The range of any one of items 1 to 4 includes the following steps: applying the patent procedure; and performing heat treatment under the step of applying the conductive paste of the inert gas or the inert gas to the substrate. The steps of the body in the soil and in the 100~200ΐ 099137434 38