JP2016219202A - Conducive liquid composition, conductive member, manufacturing method of conductive member, electric and electronic member, and electric and electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive liquid composition containing silver-containing particles, capable of alleviating a burning condition for obtaining a conductive member from the conductive liquid composition.SOLUTION: There is provided a conductive liquid composition containing silver-containing particles, a thermoplastic polyurethane resin, and an ester solvent, and the ester solvent preferably contains acetic acid ester. The silver-containing particles may contain coated silver particles with a nitrogen-containing material as a coating agent and may further contain a solvent having lower vapor pressure than that of the ester solvent.SELECTED DRAWING: None

Description

  The present invention includes a conductive liquid composition, a conductive member formed from the conductive liquid composition, a method for manufacturing the conductive member, the conductive member, or a conductive member manufactured by the manufacturing method. The present invention relates to an electronic component and an electric / electronic device including the electric / electronic component.

  Patent Document 1 describes a method of synthesizing coated silver particles having a size of several nm to 100 nm by an organic acid crosslinked silver alkylamine complex thermal decomposition method. The coated silver particles described in Patent Document 1 exhibit good dispersibility, sinterability, and conductivity, and the method for producing coated silver particles described in Patent Document 1 is a method that facilitates mass synthesis. .

JP 2014-40630 A

  A liquid composition containing silver-containing particles such as silver-coated particles produced by the production method described in Patent Document 1 (this composition is also referred to as “conductive liquid composition” in this specification). The conductive member is appropriately disposed on a substrate such as a resin film using a technique such as coating, printing, and the conductive liquid composition disposed on the substrate is heated and baked to form a conductive member on the substrate. Can be formed.

  Here, the conductive liquid composition is not formed only from silver-containing particles, but usually a component that serves as a binder (also referred to as “binder component” in this specification) and a component that serves as a solvent (silver-containing particles). And a component that disperses or dissolves the component that becomes the binder). These binder components and solvents not only affect the physical properties (viscosity, etc.) of the conductive liquid composition, but also conditions for firing the conductive member from the conductive liquid composition (specifically, the firing temperature and It also affects the firing time.)

  The present invention relates to a conductive liquid composition containing silver-containing particles, wherein the firing conditions for obtaining a conductive member from the conductive liquid composition are relaxed (specifically, the firing temperature is lowered and Conductive liquid composition capable of realizing at least one of shortening firing time), conductive member formed from this conductive liquid composition, and method for producing conductive member using the above conductive liquid composition It is an object of the present invention to provide an electric / electronic component including an electric wiring made of the conductive member or the conductive member manufactured by the manufacturing method, and an electric / electronic device including the electric / electronic component.

  One embodiment of the present invention provided to solve the above problems is a conductive liquid composition containing silver-containing particles, a thermoplastic polyurethane resin, and an ester solvent. By containing the thermoplastic polyurethane resin and the ester solvent, it is possible to relax the firing conditions when obtaining a conductive member from the conductive liquid composition. With regard to the firing temperature, it is possible to form a conductive member from a conductive liquid composition even if the firing temperature is relatively low, specifically 100 ° C. or less, more specifically about 80 ° C. is there.

  In the conductive liquid composition according to the present invention, the silver-containing particles may contain coated silver particles having a nitrogen-containing substance as a coating agent. Specific examples of the coated silver particles having a nitrogen-containing substance as a coating agent include the coated silver particles disclosed in Patent Document 1. When the silver-containing particles have a nitrogen-containing material as a coating agent, the thermoplastic polyurethane resin contained in the conductive liquid composition functions as a binder component and a dispersant for the silver-containing particles at the same time. There is. In addition, since the above-mentioned coated silver particles are easily dispersed in the ester solvent, problems due to aggregation of the silver-containing particles are unlikely to occur.

  The vapor pressure at 20 ° C. of the ester solvent contained in the conductive liquid composition according to the present invention is preferably 10 Pa or more and 300 Pa or less. Since the ester solvent has the above-mentioned characteristics with respect to the vapor pressure, it is possible to relax the firing conditions when obtaining a conductive member from the conductive liquid composition and to ensure appropriate handling of the conductive liquid composition. It may be realized more stably.

  From the viewpoint of more stably realizing the firing conditions when obtaining the conductive member from the conductive liquid composition and increasing the dispersibility of the silver-containing particles, the above-mentioned conductive liquid composition contains The ester solvent preferably contains an acetate ester.

  The content of the ester solvent contained in the conductive liquid composition according to the invention is a mass ratio (also referred to as “first ratio” in the present specification) with respect to the silver-based content of the silver-containing particles. ) Is preferably 10% or more and 30% or less. When the first ratio is within the above range, it is possible to more stably realize the relaxation of the firing conditions when obtaining the conductive member from the conductive liquid composition and the improvement of the handling property of the conductive liquid composition. Can be made.

  The conductive liquid composition according to the present invention may further include a solvent having a vapor pressure lower than that of the ester solvent (also referred to as “low-volatile solvent” in the present specification). By containing such a low-volatile solvent, the handleability of the conductive liquid composition may be improved.

  The content of the thermoplastic polyurethane resin is an amount such that a mass ratio (also referred to as “second ratio” in this specification) to the silver-converted content of the coated silver particles is more than 1% and less than 10%. Is preferred. When the first ratio is within the above range, it is possible to more stably realize improving the shape stability of the conductive member obtained by firing and improving the handleability of the conductive liquid composition.

The coated silver particles are: (1) a silver compound that can be decomposed by heating to form metallic silver;
(2) It is preferably formed from a silver-containing liquid composition containing alkylamine.

  As another aspect of the present invention, there is provided a conductive member formed from the conductive liquid composition according to the present invention. Since the conductive liquid composition according to the present invention contains an ester solvent as a solvent as described above, it is possible to relax firing conditions when obtaining a conductive member from the conductive liquid composition. .

  The conductive member preferably has a volume resistivity of 100 μΩ · cm or less.

  As another aspect of the present invention, there is provided an electric / electronic component comprising an electrical wiring comprising the conductive member according to the present invention.

  As another aspect of the present invention, there is provided an electric / electronic apparatus comprising the electric / electronic component according to the present invention.

  According to another aspect of the present invention, a disposing step of disposing the conductive liquid composition according to the present invention on a substrate; and heating the conductive liquid composition disposed on the substrate. There is provided a method for producing a conductive member, comprising a firing step of firing the silver-containing particles contained in the conductive liquid composition to form a conductive member on the substrate. According to this manufacturing method, a conductive member can be formed from the conductive liquid composition according to the present invention.

  In the method for producing a conductive member according to the present invention, the heating temperature of the conductive liquid composition in the baking step may be 80 ° C. or less. Even when the heating temperature (baking temperature) is 80 ° C. or lower and a relatively low temperature, a conductive member having excellent conductivity can be produced.

  In the method for producing a conductive member according to the present invention, the heating time of the conductive liquid composition in the baking step is 5 minutes or less as the time (baking time) when the conductive liquid composition is heated to 80 ° C. It may be. As described above, it is possible to manufacture a conductive member having excellent conductivity even at a low temperature for a short time.

  In the method for producing a conductive member according to the present invention, the volume resistivity of the conductive member obtained by the firing step is preferably 100 μΩ · cm or less.

  In the method for producing a conductive member according to the present invention, in the arranging step, the printed material of the conductive liquid composition is formed on the substrate by printing an ink (conductive ink composition) made of the conductive liquid composition. May be arranged. When the arranging step is performed by printing, the conductive member can be manufactured with excellent productivity.

  As yet another aspect of the present invention, there is provided an electric / electronic component comprising an electric wiring made of a conductive member manufactured by the manufacturing method according to the present invention.

  As still another aspect, the present invention provides an electric / electronic apparatus comprising the electric / electronic component according to the present invention.

  The conductive liquid composition according to the present invention can relax the conditions when firing the conductive member from the conductive liquid composition. Further, according to the present invention, a conductive member formed from the conductive liquid composition, an electric / electronic component including an electric wiring formed of the conductive member, an electric / electronic device including the electric / electronic component, and the above-described A method for producing a conductive member using the conductive liquid composition is provided.

  Hereinafter, the conductive liquid composition, the conductive member formed from the conductive liquid composition, the manufacturing method of the conductive member, the conductive member, or the manufacturing method according to the embodiment of the present invention is manufactured. An electrical / electronic component including a conductive member and an electrical / electronic device including the electrical / electronic component will be described.

1. Conductive Liquid Composition The conductive liquid composition according to one embodiment of the present invention contains silver-containing particles, a thermoplastic polyurethane resin, and an ester solvent.

  The silver containing particle which the electroconductive liquid composition which concerns on one Embodiment of this invention contains is a granular substance which can produce | generate the metal silver which has electroconductivity by baking. Silver contained in the silver-containing particles may be metallic silver or an ionic state. After firing, each particle is combined with other particles in a conductive state to form a conductive member as a whole. The size of the silver-containing particles is not limited. You may have a submicron magnitude | size like the covering silver particle demonstrated below.

  Specific examples of the silver-containing particles include coated silver particles that use a nitrogen-containing substance as a coating agent. Such coated silver particles can be produced by the production method disclosed in Patent Document 1, that is, the organic acid crosslinked silver alkylamine complex thermal decomposition method.

  Among organic acid-crosslinked silver alkylamine complex thermal decomposition methods, (1) formed from a silver-containing liquid composition containing a silver compound that can be decomposed by heating to produce metallic silver and (2) an alkylamine. Preferably there is.

  Silver compounds that can be decomposed by heating to produce metallic silver include silver carboxylates in which silver atoms are combined with carboxylic acids such as formic acid, acetic acid, oxalic acid, malonic acid, benzoic acid, and phthalic acid, as well as silver chloride and silver nitrate. And silver carbonate. Among these, the silver compound preferably contains silver oxalate, and preferably consists of silver oxalate, from the viewpoints of easily producing metallic silver by decomposition and hardly generating impurities other than silver.

  Examples of the alkylamine include alkyl monoamines and alkyldiamines in which an amino group is bonded to a part of the alkyl group. As alkyl monoamines, amylamine (boiling point 104 ° C), 2-ethoxyethylamine (105 ° C), 4-methoxybutylamine, butylamine (78 ° C), diethylamine (55 ° C), propylamine (48 ° C), isopropylamine (34 ° C) Ethylamine (17 ° C), dimethylamine (7 ° C), dipropylamine (107 ° C), dibutylamine (159 ° C), hexylamine (131 ° C), cyclohexylamine (134 ° C), heptylamine (155 ° C), 3-butoxypropylamine (170 ° C), octylamine (176 ° C), nonylamine (201 ° C), decylamine (217 ° C), 3-aminopropyltriethoxysilane (217 ° C), dodecylamine (248 ° C), hexadecyl Amine (330 ° C), oleylamine 349 ° C.), octadecylamine (232 ℃ (32mmHg)) and the like are exemplified. As the alkyl diamine, ethylenediamine (118 ° C), N, N-dimethylethylenediamine (105 ° C), N, N'-dimethylethylenediamine (119 ° C), N, N-diethylethylenediamine (146 ° C), N, N'-diethyl Ethylenediamine (153 ° C), 1,3-propanediamine (140 ° C), 2,2-dimethyl-1,3-propanediamine (153 ° C), N, N-dimethyl-1,3-diaminopropane (136 ° C) N, N′-dimethyl-1,3-diaminopropane (145 ° C.), N, N-diethyl-1,3-diaminopropane (171 ° C.), 1,4-diaminobutane (159 ° C.), 1,5 -Diamino-2-methylpentane (193 ° C.), 1,6-diaminohexane (204 ° C.), N, N′-dimethyl-1,6-diaminohe Sun (228 ℃), 1,7- diamino heptane (224 ℃), 1,8- diamino-octane (225 ° C.) and the like are exemplified. Among these, alkylamines having a boiling point in the range of 130 to 150 ° C., such as hexylamine, cyclohexylamine, and N, N-diethylethylenediamine, are preferable, and hexylamine is more preferable.

The alkylamine may be composed of one type of compound or may be composed of a mixture of a plurality of types of compounds. The amount of alkylamine used is not limited as long as a complex compound can be appropriately formed from a silver compound and an alkylamine.
A silver containing liquid composition may contain components other than said (1) silver compound and (2) alkylamine as needed. Examples of such components include urea.

  The conductive liquid composition according to one embodiment of the present invention contains a thermoplastic polyurethane resin as a binder component.

  The type of the thermoplastic polyurethane resin is not limited as long as it is a polymer having a urethane bond. Polymers of polyols such as polyether polyols, polyester polyols, and polycarbonate polyols and isocyanate compounds such as aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanates can be used. The thermoplastic polyurethane resin may be composed of one kind of resin, or may be composed of a mixture of plural kinds of resins.

  The molecular weight (weight average molecular weight Mw, number average molecular weight Mn) of the thermoplastic polyurethane resin is not limited. These are appropriately set according to the characteristics that the conductive liquid composition should have, for example, the viscosity.

  The content of the thermoplastic polyurethane resin in the conductive liquid composition is preferably such that the mass ratio (second ratio) to the silver equivalent content of the coated silver particles is more than 1% and less than 10%. By setting the second ratio to more than 1%, it is possible to stably realize the adhesion of the conductive member formed from the conductive liquid composition to the substrate. From the viewpoint of more stably realizing the adhesion of the conductive member to the substrate, the second ratio may be preferably 2% or more, and more preferably 3% or more. is there. Since the thermoplastic polyurethane resin remaining on the conductive member is insulative, it is stably realized that the decrease in the conductivity of the conductive member is less likely to occur by setting the second ratio to less than 10%. From the viewpoint of more stably realizing that the conductive member has good conductivity, the second ratio may be preferably 7% or less, and more preferably 5% or less.

  The conductive liquid composition according to one embodiment of the present invention contains an ester solvent as a solvent component. As ester solvents, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, acetic acid (iso ) Amyl, cyclohexyl acetate, octyl acetate, nonyl acetate, ethyl lactate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, heptyl propionate And octyl propionate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl propionate, isoamyl propionate, and γ-butyrolactone. The ester solvent may be composed of one kind of substance or may be constituted as a mixture of plural kinds of substances.

  The ester solvent preferably has a vapor pressure at 20 ° C. of 10 Pa to 300 Pa. When the vapor pressure of the ester solvent at 20 ° C. is within the above range, the firing conditions for obtaining a conductive member from the conductive liquid composition are alleviated and the handling property of the conductive liquid composition is appropriately ensured. May be more stably realized. The vapor pressure at 20 ° C. of the ester solvent is more preferably 20 Pa or more and 200 Pa or less, and particularly preferably 30 Pa or more and 100 Pa or less.

  From the viewpoint of more stably realizing the firing conditions when obtaining the conductive member from the conductive liquid composition and enhancing the dispersibility of the silver-containing particles, the ester contained in the conductive liquid composition The system solvent preferably contains an acetate ester, more preferably an acetate ester. When the silver-containing particles contain the above-mentioned silver-coated particles, acetates should be used as the ester solvent from the viewpoint of easy dispersion and availability of the silver-coated particles in the conductive liquid composition. Is particularly preferred. Among the acetate esters, octyl acetate having a vapor pressure of 53 Pa at 20 ° C. is an example of a preferable acetate ester.

  The content of the ester solvent contained in the conductive liquid composition is preferably such that the mass ratio (first ratio) to the silver-converted content of the silver-containing particles is 10% or more and 30% or less. When the first ratio is within the above range, the firing conditions for obtaining the conductive member from the conductive liquid composition can be relaxed and the handling property of the conductive liquid composition can be improved more stably. Is done. The first ratio may be more preferably 10% or more and 30% or less, and may be particularly preferably 15% or more and 20% or less.

  The conductive liquid composition according to the present invention may further include a solvent (low volatile solvent) having a vapor pressure lower than that of the ester solvent. Examples of such low volatile solvents include alcohol solvents and glycol solvents. Specific examples of alcohol solvents include hexyl alcohol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, heptyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, and undecyl. Alcohol, lauryl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, α-terpineol, terpineol C, L-α-terpineol, dihydroterpineol, terpinyloxyethanol, dihydroterpinyloxyethanol, manufactured by Nippon Terpene Chemical Co., Ltd. Tersolve MTPH, Tersolve DTO-210, Tersolve THA-90, Tersolve THA-70, cyclohexanol, 3-methoxybutanol, diacetone alcohol, 1,4-but Examples include tandiol, octanediol, and the like, fine oxocol 140N, fine oxocol 1600, fine oxocol 180, fine oxocol 180N, and fine oxocol 2000 manufactured by Nissan Chemical Industries. Specific examples of the glycol solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, hexylene glycol, polyethylene glycol, and polypropylene glycol. The low volatility solvent may be composed of one kind of substance or may be constituted as a mixture of plural kinds of substances.

  By containing such a low-volatile solvent, the handleability of the conductive liquid composition may be improved. In particular, when the conductive liquid composition is used as the conductive ink composition, the conductive ink composition is required to quickly volatilize the solvent when positioned on the substrate (substrate). When positioned on a screen mesh or roll at a stage prior to positioning on the substrate (substrate), the volatilization of the solvent is limited, maintaining the properties as a liquid composition and having an appropriate viscosity. It is required to do. By appropriately containing a low-volatile solvent in the conductive liquid composition and adjusting the volatility of the conductive liquid composition, it becomes easy to meet the above requirements. In the case where the conductive liquid composition contains a low volatile solvent, the type and content of the low volatile solvent are not limited. What is necessary is just to set suitably according to the objective which contained the low-volatile solvent suitably.

  The conductive liquid composition according to one embodiment of the present invention may contain a dispersant as a component other than the silver-containing particles, the thermoplastic polyurethane resin, and the solvent. When the silver-containing particles contain coated silver particles, for example, a fatty acid such as oleic acid may be mixed with the amine mixture as a dispersant. In particular, it is effective to add an appropriate fatty acid when an amine mixture having a small average molecular weight of alkylamine is used, for example, by containing a large proportion of short-chain alkylamine. However, if an excessive amount of fatty acid is used, the desorption temperature of the protective film from the coated silver particles tends to increase, so the amount of dispersant added is relative to the metallic silver atoms contained in the reaction system. It is desirable to make it 5 mol% or less. The content of the dispersant in the conductive liquid composition is not limited. It is appropriately set in consideration of the type of dispersant, the viscosity of the conductive liquid composition, the conductivity of the conductive member obtained from the conductive liquid composition, and the like. The conductive liquid composition according to one embodiment of the present invention preferably contains substantially no components other than the solvent as components other than the silver-containing particles and the thermoplastic polyurethane resin.

The conductive liquid composition according to one embodiment of the present invention is typically used in applications in which a conductive liquid composition is disposed on a substrate and then fired to form a conductive member. When the step of disposing the conductive liquid composition on the substrate is performed by printing, it is preferable that the pattern of the coated silver particle-containing composition can be formed on the substrate by performing the step. The specific method of printing used for this purpose is arbitrary. The conductive liquid composition according to one embodiment of the present invention does not contain a binder component other than the thermoplastic polyurethane resin, and the viscosity measured under the condition of a shear rate of 38.4 s ⁻¹ is 5 Pa · s or more. In such a case, it can be suitably used as an ink for plate printing such as gravure offset printing excellent in industrial mass productivity. When such an ink is used, a conductive liquid composition having a fine pattern (for example, printing a plurality of lines of about 30 μm in a space of about 30 μm) can be printed on the substrate. The viscosity is preferably 7 Pa · s or more from the viewpoint of facilitating the formation of a printed material comprising the fine pattern conductive liquid composition on the substrate.

2. Conductive Member A conductive member according to an embodiment of the present invention is formed from the conductive liquid composition according to the above-described embodiment of the present invention. As described above, since the conductive liquid composition according to one embodiment of the present invention contains silver-containing particles and a thermoplastic polyurethane resin, the conductive member formed from such a composition has high conductivity. The volume resistivity of the conductive member can be 100 μΩ · cm or less. In a preferred embodiment, the volume resistivity of the conductive member can be 50 μΩ · cm or less. Further, as described above, the conductive member according to a preferred embodiment of the present invention can be manufactured by a manufacturing method including plate printing which is excellent in industrial mass productivity.

3. Method for Producing Conductive Member The conductive member according to one embodiment of the present invention described above is obtained by using a conductive liquid composition according to one embodiment of the present invention, for example, by a method including an arrangement step and a firing step described below. Can be manufactured.

(1) Arrangement Step In the arrangement step, the conductive liquid composition according to one embodiment of the present invention is arranged on a substrate. The shape and material of the substrate are not limited. The shape of the substrate may be a plate shape or a three-dimensional shape such as a cylindrical shape. Furthermore, you may have a complicated shape with an unevenness | corrugation.

  As the material of the substrate, for example, thermoplastic resin, thermosetting resin, glass, paper, metal, silicon, inorganic material and metal material, and composite materials of these materials (as specific examples of the substrate using such a composite material) A glass epoxy substrate can be used). Examples of the thermoplastic resin include polyethylene, polyethylene terephthalate, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polycarbonate, polyacetal, polybutylene terephthalate, polyphenylene oxide, polyamide, Polyphenylene sulfide, polysulfone, polyethersulfone, polyether-etherketone, polyarylate, aromatic polyester, aromatic polyamide, fluororesin, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polymethyl methacrylate And cellulose acetate.

  Examples of the thermosetting resin include phenol resin, urea resin, xylene resin, urea resin, melamine resin, epoxy resin, silicon resin, diallyl phthalate resin, furan resin, aniline resin, acetone-formaldehyde resin, alkyd resin, and the like. It is done.

Inorganic materials mean inorganic compounds such as oxides, carbides, nitrides and borides. For example, alumina (Al ₂ O ₃ ), silicon nitride (SiN), silicon carbide (SiC), aluminum nitride ( AlN), zirconium boride (ZrB ₂ ) and the like.

  The method for disposing the conductive liquid composition on the substrate is not limited. Examples include offset printing, gravure printing, gravure offset printing, relief printing, flexographic printing, screen printing, inkjet printing, and the like; spin coating, dipping, bar coating, roll coating, spraying, and the like. In the arranging step, the printed material of the conductive liquid composition may be arranged on the substrate by performing ink (conductive ink composition) made of the conductive liquid composition by printing exemplified above. When the arranging step is performed by printing, the conductive member can be manufactured with excellent productivity. Among printing, plate printing such as offset printing and screen printing is preferable because of excellent industrial mass productivity.

(2) Firing step In the firing step, the conductive liquid composition disposed on the substrate is heated. By this heating, the silver-containing particles contained in the printed material are fired to form a conductive member on the substrate. The firing temperature is appropriately set, but may be 100 ° C. or lower, for example, about 80 ° C. When the silver-containing particles contain silver-coated particles, the alkylamine-based substance, which may be a kind of material constituting the protective film in the silver-coated particles, is silver-coordinated through its amino group. It is considered that it is weakly bound to the surface of the particle and can be removed relatively easily by heating. Therefore, for example, even when the firing temperature of the conductive liquid composition disposed on the substrate is about 100 ° C. or less, the alkylamine-based substance easily desorbs from the coated silver particles, so that the silver particles directly It is considered that contact (bonding) has been realized. When the material constituting the substrate is made of a resin-based material, the firing temperature is preferably as low as possible. In this case, it may be preferably 90 ° C. or lower, and may be 80 ° C. or lower. It may be more preferable.

  The firing time is not limited. When the heating temperature is the above temperature, the silver-containing particles contained in the conductive liquid composition can be fired usually by setting the firing time to about 5 minutes or more. By extending the firing time, it is possible to increase the conductivity of the conductive member obtained by firing, but there is a limit to increasing the conductivity of the conductive member by extending the firing time, usually the firing time If it is about 2 hours, even if the firing time is extended further, the degree of improvement in the conductivity of the conductive member is slight. From the viewpoint of improving the balance between conductivity improvement and productivity improvement for the conductive member, the firing time may be preferably 2 hours or less, and more preferably 1 hour or less. , 30 minutes or less may be more preferable, and 10 minutes or less may be particularly preferable. By using the conductive liquid composition according to one embodiment of the present invention, the obtained conductive member can have a volume resistivity of 100 μΩ · cm or less, even with this degree of firing time. In a preferred example, it is possible to have a volume resistivity of 50 μΩ · cm or less.

4). Electric / Electronic Component and Electric / Electronic Device An electric / electronic component according to an embodiment of the present invention includes an electric wiring made of the conductive member according to the above-described embodiment of the present invention. As described above, the conductive member according to the embodiment of the present invention can have a volume resistivity of 100 μΩ · cm or less, and can have a volume resistivity of 50 μΩ · cm or less. is there. Therefore, the electrical wiring made of the conductive member according to an embodiment of the present invention has high conductivity even when it is made of a thin film having a thickness of about 7 μm. Even when the width is narrow, it is difficult to cause a problem that the wiring resistance becomes high or the wiring is peeled off from the substrate. Therefore, it is possible to reduce the size of the electric / electronic component.

  Moreover, if a conductive member is manufactured by the manufacturing method according to the embodiment of the present invention, it is possible to form a conductive member having a fine shape (fine pattern) on a substrate made of various materials at a low temperature. Specifically, for example, an electric wiring having a width of several tens of μm can be formed along the surface of the base made of a resin material. Therefore, the electrical / electronic component provided with the electrical wiring made of the conductive member by the manufacturing method according to the embodiment of the present invention can be a component manufactured with a high degree of design freedom in terms of material and shape.

  A specific example of such an electric / electronic component is a touch panel. The touch panel may be disposed on the front surface of the display device. In this case, the entire thickness is required to be thin. There is also a need to expand the detection area. For this reason, the wiring of the touch panel is required to be thinner and narrower. One means for meeting these requirements is to reduce the volume resistivity of the wiring. Furthermore, the curved surface of the touch panel has begun to be demanded. For this purpose, it is necessary to form a wiring having a low volume resistivity on the resin material. The electrical wiring made of the conductive member according to the embodiment of the present invention can meet all of these requirements.

  An electrical / electronic device according to an embodiment of the present invention includes the electrical / electronic component according to the embodiment of the present invention. As described above, since the electrical / electronic component according to an embodiment of the present invention can be miniaturized and has a high degree of design freedom for materials and shapes, the electrical / electronic device has excellent portability, savings. It is expected to have advantages such as excellent power performance. Specific examples of electrical / electronic components according to an embodiment of the present invention include so-called wearable terminals such as glasses-type information terminals and clock-type information terminals in addition to conventional information terminals such as smartphones, tablet terminals, and notebook PCs. Is mentioned.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely below, this invention is not limited to these.

(Examples 1 to 3)
As the silver compound, silver oxalate synthesized from silver nitrate (Kanto Chemical Co., Ltd., first grade) and oxalic acid dihydrate (Kanto Chemical Co., Ltd., special grade) was used. For 5.00 mmol (1.519 g) of silver oxalate, 20 mmol (1.201 g) of urea, 20.0 mmol (2.024 g) of n-hexylamine (special grade, manufactured by Tokyo Chemical Industry Co., Ltd.) and fatty acid Some oleic acid (Tokyo Kasei Co., Ltd.,> 85.0%) 0.23 mmol (0.065 g) was mixed and stirred at room temperature for 30 minutes to obtain a silver-containing liquid composition.

  The obtained silver-containing liquid composition was heated, transferred to an aluminum block heating stirrer (manufactured by Koike Seimitsu Seisakusho Co., Ltd.), and heated and stirred at a temperature setting of 110 ° C. for 10 minutes. Suspension in which silver particles exhibiting a blue or green luster are suspended in a mixture containing alkylamine by stirring until the reaction with generation of carbon dioxide proceeds with heating and the generation of carbon dioxide is completed. A liquid was obtained.

  Next, 10 mL of methanol (manufactured by Kanto Chemical Co., Ltd., first grade) is added to this suspension and stirred, and then silver particles are precipitated and separated by centrifugation (2600 G), and 10 mL of methanol is again added to the separated silver particles. In addition, by stirring and centrifuging, silver particles were precipitated and separated to obtain 1.0 g of paste-like coated silver particles.

The resulting silver-containing particles made of coated silver particles, a binder component made of thermoplastic polyurethane resin (manufactured by Arakawa Chemical Co., Ltd., Juliano 8001) and a solvent shown in Table 1 were mixed to obtain a conductive liquid composition. The types of solvents shown in Table 1 are as follows. Moreover, the numerical value regarding the binder component and solvent which are shown in Table 1 is a mass ratio (unit:%) with respect to the silver conversion content of silver containing particle | grains.
Ester solvent: Octyl acetate Low volatile solvent: Tersolve THA-90 (manufactured by Nippon Terpene Chemical Co., Ltd.)

(Test Example 1) Printing Test Screen printing was performed on a PET film under the following conditions using the conductive liquid composition prepared according to the example.
"NT150" made by Neotec Japan
Printing conditions Printing speed: 70mm / s
Plate gap: 1.8mm
Screen version “Nano silver D320 ZMSC500-19-25 M11 μm” manufactured by Sonocom
Printing workability and printed matter were observed, and printing properties were evaluated based on the following criteria.
A: Printing is possible, the shape of the printed matter is appropriate, and no disconnection is recognized.
B: Although printing was possible, a portion inappropriate for the shape of the printed matter or a broken portion was observed.
C: Printing was impossible.
The evaluation results are shown in Table 2.

(Test Example 2) Sintering Test The printed matter produced by the above printing test was sintered under the condition of heating at 80 ° C. for 5 minutes. For the conductive member obtained by sintering, the film thickness was measured and the resistance value was measured to determine the volume resistivity (unit: μΩ · cm), and the sinterability was evaluated based on the following criteria.
A: The volume resistivity was 50 μΩ · cm or less.
B: Volume resistivity was more than 50 μΩ · cm.
The evaluation results are shown in Table 2.

  As shown in Table 1, when a conductive liquid composition containing an ester solvent is used, the volume resistivity is 50 μΩ · cm even under particularly relaxed sintering conditions of 80 ° C. for 5 minutes. It was confirmed that the following conductive member can be obtained.

  As described above, since the conductive member manufactured using the conductive liquid composition according to the present invention is excellent in conductivity even under relaxed sintering conditions, such a conductive member is used for electric / electronic parts. It can be suitably used for electrical wiring and the like.

Claims (19)

  A conductive liquid composition containing silver-containing particles, a thermoplastic polyurethane resin, and an ester solvent.   The conductive liquid composition according to claim 1, wherein the silver-containing particles include coated silver particles having a nitrogen-containing material as a coating agent.   The conductive liquid composition according to claim 1 or 2, wherein a vapor pressure of the ester solvent at 20 ° C is 10 Pa or more and 300 Pa or less.   The conductive liquid composition according to any one of claims 1 to 3, wherein the ester solvent includes an acetate ester.   The electroconductive liquid composition according to any one of claims 1 to 4, further comprising a solvent having a vapor pressure lower than that of the ester solvent.   Content of the said ester solvent is the electroconductivity as described in any one of Claim 1 to 5 whose mass ratio with respect to content of the silver conversion of the said silver containing particle | grain is 10% or more and 30% or less. Liquid composition.   7. The electrical conductivity according to claim 1, wherein the content of the thermoplastic polyurethane resin is an amount such that a mass ratio with respect to the content in terms of silver of the coated silver particles is more than 1% and less than 10%. Liquid composition. The coated silver particles are
(1) a silver compound that can be decomposed by heating to produce metallic silver;
(2) alkylamine,
The conductive liquid composition according to any one of claims 2 to 7, which is formed from a silver-containing liquid composition containing   A conductive member formed from the conductive liquid composition according to any one of claims 1 to 8.   The conductive member according to claim 9, wherein the volume resistivity is 100 μΩ · cm or less.   An electrical / electronic component comprising electrical wiring comprising the conductive member according to claim 9.   An electric / electronic device comprising the electric / electronic component according to claim 11. An arrangement step of disposing a conductive liquid composition according to any one of claims 1 to 8 on a substrate; and heating the conductive liquid composition disposed on the substrate A method for producing a conductive member comprising a firing step of firing the silver-containing particles contained in a liquid composition to form a conductive member on the substrate.   The manufacturing method of the electrically-conductive member described in Claim 13 whose heating temperature of the said electroconductive liquid composition in the said baking process is 80 degrees C or less.   The method for producing a conductive member according to claim 13 or 14, wherein a heating time of the conductive liquid composition in the baking step is 5 minutes or less as a time during which the conductive liquid composition is heated to 80 ° C. .   The method for manufacturing a conductive member according to claim 13, wherein the conductive member has a volume resistivity of 100 μΩ · cm or less.   The production according to any one of claims 13 to 16, wherein, in the arranging step, a printed matter of the conductive liquid composition is arranged on a substrate by printing an ink made of the conductive liquid composition. Method.   An electric / electronic component comprising an electrical wiring made of a conductive member manufactured by the manufacturing method according to claim 13.   An electric / electronic device comprising the electric / electronic component according to claim 18.