Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/14—Conductive material dispersed in non-conductive inorganic material
  • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L21/00—Compositions of unspecified rubbers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
  • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/08—Metals
  • C08K2003/0806—Silver
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general

Definitions

• the present invention relates to a conductive composition, a conductor in which the conductive composition is solidified, a laminate structure having a layer of the conductor, and an electronic component provided with the conductor or the laminate structure.
• a paste-like conductive composition in which a metal powder is mixed with an organic binder is used as a material for forming a patterned conductor such as an electrode of a printed wiring board or the like.
• a desired conductor can be formed by applying it in a pattern and then solidifying it, but the resulting conductor generally has high hardness. Therefore, in a flexible printed wiring board, there is a demand for a conductive composition in which a solidified conductor has bending resistance.
• a conductive composition in which an elastomer is used as an organic binder containing metal powder and the conductor has elasticity as well as flexibility (see Patent Document 1). etc).
• the resistance value may be rapidly increased or broken in some cases when the conductor is repeatedly stretched and contracted to some extent.
• a conductive composition capable of obtaining a conductor excellent in the stability of the electrical resistance, even in the case of repeated expansion and contraction or stretching.
• an object of the present invention is to provide a conductive composition capable of obtaining a conductor excellent in stability of electric resistance even when the repetition of expansion and contraction and the expansion are increased.
• another object of the present invention is to provide a conductor obtained by solidifying such a conductive composition, a laminate structure having a layer of the conductor, and an electronic component comprising the conductor or laminate structure. It is to be.
• the present inventors repeated expansion and contraction by setting a silver powder having a specific average primary particle diameter to which a surface treatment is applied as a conductive metal powder to be blended in an elastomer in a specific aggregation state in the composition. It has been found that a conductive composition capable of obtaining a conductor excellent in the stability of the electrical resistance can be realized even in the case or when it is greatly stretched to, for example, 400% or more.
• the present invention is based on such findings.
• the conductive composition of the present invention is a conductive composition containing an elastomer and silver powder,
• the silver powder is surface-treated,
• the silver powder has an average primary particle size of 1.0 ⁇ m or less and an apparent porosity of 50 to 95%,
• the cumulative 95% particle size (D95 particle size) in the particle size distribution of the secondary particles of the silver powder is 3.0 to 25.0 ⁇ m.
• the silver powder is preferably contained in an amount of 60 to 95% by mass in solid content with respect to the entire conductive composition.
• the conductor according to another embodiment of the present invention is obtained by solidifying the above-mentioned conductive composition.
• a laminated structure according to another embodiment of the present invention has a layer of the above-mentioned conductor on a substrate.
• An electronic component according to another embodiment of the present invention comprises the layer of the conductor or the laminated structure.
• silver powder having a specific average primary particle diameter subjected to a surface treatment is brought into a specific aggregation state in the composition as the conductive metal powder to be blended into an elastomer. Even when the expansion and contraction are repeated and the expansion is increased, a conductor excellent in the stability of the electric resistance can be obtained.
• the conductive composition of the present invention contains an elastomer and silver powder, and by blending a specific silver powder in the elastomer, the electric resistance is not limited to the case of bending but also to the case of expansion or contraction or to the case of large expansion.
• the conductor etc. which are excellent in stability of can be obtained.
• the conductive composition of the present invention can be suitably used to form a conductor for a wearable device such as an extracorporeal device, a body surface device, an electronic skin device, or an intracorporeal device, utilizing such characteristics. it can.
• a wearable device such as an extracorporeal device, a body surface device, an electronic skin device, or an intracorporeal device, utilizing such characteristics. it can.
• each component which the electroconductive composition of this invention contains is explained in full detail.
• the silver powder constituting the conductive composition of the present invention is surface-treated, and the average primary particle diameter is 1.0 ⁇ m or less, preferably 0.1 to 1.0 ⁇ m, and the apparent porosity is 50 to 50 95%, preferably 60 to 95% is used.
• the average primary particle size of silver powder is obtained by observing silver powder in a powder state at a magnification of 10,000 with a scanning electron microscope, and randomly extracting 10 primary particles.
• the apparent porosity P is an index representing the aggregation state of primary particles of silver powder before being mixed with an elastomer.
• compression of the filled silver powder proceeds.
• the apparent porosity becomes small after compression.
• the apparent porosity is large because of the voids inside the aggregation. Thereby, the aggregation state of primary particles of silver powder can be evaluated as apparent porosity.
• the shape of the primary particles of silver powder is preferably substantially spherical, and the substantially spherical primary particles are present in the conductive composition in the form of secondary particles in which three-dimensional and randomly connected. Then, as described above, silver powder can follow the elongation deformation of the elastomer in the solidified product of the conductive composition without reducing the contact points between the primary particles even when the solidified product of the conductive composition is greatly expanded.
• the shape of the primary particles of silver powder is not limited to one having a substantially spherical shape, and it is needless to say that silver powder having a shape other than a substantially spherical shape may be contained within the range not impairing the effects of the present invention. .
• silver powder having an average primary particle size and apparent porosity in the above range commercially available silver powder can be used, and a commercially available silver powder can be used as a specific average primary particle using a classifier or the like. You may obtain by classifying to silver powder which has a diameter and an apparent porosity.
• the silver powder used in the present invention (that is, silver powder before being prepared as the conductive composition) preferably has an average secondary particle diameter of 5.0 to 40.0 ⁇ m, more preferably more than 10.0 It is -40.0 ⁇ m, more preferably more than 15.0 to 40.0 ⁇ m.
• the average secondary particle diameter of silver powder before preparing as a conductive composition means the average value (D50) of the particle diameter which measured the silver powder in powder state by the laser diffraction scattering type particle size distribution measuring method. Do.
• the silver powder (silver powder before being prepared as the conductive composition) used in the present invention has a DBP oil absorption of 30 to 200 ml / 100 g measured in accordance with JIS K 6217-4 (2017). Is preferred.
• the DBP oil absorption of silver powder means a value obtained by measuring the amount of dibutyl phthalate absorbed in 100 g of silver powder according to JIS K 6217-4, and in the present invention, the degree of connection of primary particles of silver powder And the degree of aggregation.
• the conductive composition of the present invention is dispersed in an elastomer using the above-described silver powder, and the cumulative 95% particle diameter (D95 particle diameter) in the particle size distribution of secondary particles of silver powder in the conductive composition In the range of 3.0 to 25.0 ⁇ m.
• the present invention is preferably a silver powder having a surface treated specific average primary particle diameter as described later and in a specific aggregation state (ie a specific apparent porosity), preferably a specific DBP oil absorption.
• Controlling the aggregation state of the silver powder in the composition ie, making the cumulative 95% particle size in the particle size distribution of the secondary particles into a specific range
• the silver powder having the composition is blended into an elastomer to make a composition
• the silver powder constituting the conductive composition of the present invention maintains a certain aggregation state in which a plurality of primary particles are connected three-dimensionally and randomly even when mixed or kneaded with an elastomer, in the conductive composition. It is considered to be dispersed. That is, when silver powder having a specific apparent porosity is mixed or kneaded with an elastomer, secondary particles having a large particle diameter among secondary particles in which primary particles of silver powder are aggregated are disintegrated and become smaller to some extent.
• this invention-specific effect is achieved. That is, it is a silver powder having a surface-treated average primary particle diameter of 1.0 ⁇ m or less as described later, and having an apparent porosity of 50 to 95%, preferably a silver powder having a DBP oil absorption of the above range.
• the composition is prepared by compounding and dispersing it in an elastomer, the aggregation of silver powder is appropriately broken down, and the composition is stirred or kneaded so that the D95 particle diameter becomes 3.0 to 25.0 ⁇ m.
• the secondary particles of silver powder have a suitable appearance of voids and the elastomer sufficiently enters into the voids, the contact between primary particles is reduced even when the solidified product of the conductive composition is greatly extended. It is believed that the silver powder can follow the elongation deformation of the elastomer without
• the cumulative 95% particle size (D95 particle size) in the particle size distribution of the secondary particles of silver powder in the conductive composition is determined by mixing or kneading the silver powder and the elastomer with the conductive composition obtained by laser diffraction scattering particle size It can be measured by distribution measurement.
• the conductive composition is diluted with a measurement solvent (propylene glycol monomethyl ether acetate) so as to be 3000% by mass, and secondary particles of silver powder are After stirring appropriately so as not to collapse, the particle size distribution is measured in a measurement range of 0.020 ⁇ m to 1000.00 ⁇ m, with the refractive index of the particles being 1.33 and the refractive index of the solvent being 1.40, and the particle size distribution
• the value calculated as the 95% cumulative particle diameter of the above is defined as the D95 particle diameter.
• the conductive composition of the present invention since the silver powder surface-treated so that the D95 particle diameter is in the above range is dispersed in the conductive composition, the conductive composition is composed of such a conductive composition. It is considered that even when the solidified material is repeatedly expanded and contracted or greatly expanded, a conductor excellent in stability of the electrical resistance can be obtained.
• the aggregation state of the silver powder in the conductive composition is too disintegrated, so when the solidified product of such a conductive composition is greatly stretched, primary deformation of the silver powder is caused by this elongation deformation. The point of contact between particles decreases.
• the apparent secondary void of the silver powder in the conductive composition has a suitable apparent void, and the elastomer sufficiently enters the void. It is considered that the silver powder can follow the elongation deformation of the elastomer without reducing the contact points between the primary particles even when the solidified product of such a conductive composition is greatly expanded.
• the silver powder in order for the silver powder to be present in the form as described above, the silver powder has high affinity with the elastomer by surface treatment, and the primary particles of the silver powder are connected to each other and a void is appropriately present. It is necessary to have a cohesive structure (secondary particles).
• surface-treated silver powder in order to adjust the above-mentioned DBP oil absorption amount and the affinity of silver powder and an elastomer, surface-treated silver powder is used.
• the surface treatment of the silver powder include a wet method in which silver powder is charged into a solution containing a dispersion and stirring, and a dry method in which a solution spray containing a dispersion is stirred while stirring silver powder.
• surface treatment may be performed in combination with a surfactant.
• a dispersant used for such surface treatment for example, protective colloids such as fatty acids, organic metals, and gelatin can be used, but fatty acids are considered in view of the possibility of mixing of impurities and improvement of adsorption with hydrophobic groups. Or a salt thereof.
• this dispersant one obtained by emulsifying fatty acid or a salt thereof with a surfactant may be used.
• Preferred dispersants are fatty acids having 6 to 24 carbon atoms, and stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, linolenic acid and the like can be more preferably used. These fatty acids are considered to be less harmful to wiring layers and electrodes using the conductive composition.
• the above-mentioned fatty acids may be used alone or in combination of two or more.
• the silver powder as described above is adjusted so that the D95 particle diameter of secondary particles of silver powder is in the range of 3.0 to 25.0 ⁇ m by blending the elastomer described later and a solvent as necessary, and stirring or kneading. Do.
• stirring or kneading can be performed using a stirrer such as a dissolver or butterfly mixer, or a kneader such as a roll mill or bead mill, but the rotational speed of the stirrer and / or the kneader at that time, a stirring blade or a kneader
• the conditions can be adjusted according to various conditions such as the shape of, the stirring or kneading time, the temperature at the time of stirring or kneading, the packing ratio of beads, and the interval between rolls.
• the content of silver powder in the conductive composition is preferably 60 to 95% by mass based on the total solid content contained in the conductive composition.
• the conductor of low resistance value can be easily obtained as it is 60 mass% or more. When the content is 95% by mass or less, disconnection is less likely to occur during expansion and contraction.
• the elastomer contained in the conductive composition according to the present invention can be used without particular limitation as long as it is a material having rubber elasticity at room temperature, for example, rubber, thermoplastic elastomer, functional group-containing elastomer, block copolymer, etc. It can be used suitably.
• the rubber may be any of diene-based rubber and non-diene-based rubber, and known ones may be used alone or in combination of two or more.
• thermoplastic elastomer styrene based elastomers, olefin based elastomers, urethane based elastomers, polyester based elastomers, polyamide based elastomers, acrylic based elastomers, silicone based elastomers, etc. may be mentioned, and they may be used alone or in combination of two or more. be able to.
• the functional group-containing elastomer is preferably a urethane type or an olefin type from the viewpoint of stretchability, and has a functional group such as a (meth) acryloyl group, an acid anhydride group, a carboxyl group or an epoxy group from the viewpoint of solvent resistance. Is preferred.
• a block copolymer As a block copolymer, a block copolymer of a hard segment and a soft segment can be used, and can be used alone or in combination of two or more.
• the block copolymer is low in crystallinity and weak in intermolecular force, so when it is mixed with silver powder, it has a low glass transition point (hereinafter abbreviated as Tg) compared to other rubbers. Is flexible and stretchable, which is preferable.
• block copolymers are suitable for the formation of electrical conductors for wearable devices.
• block copolymers of a hard segment having a Tg of less than 150 ° C. and a soft segment having a Tg of less than 0 ° C. are more preferable.
• the glass transition point Tg is measured by differential scanning calorimetry (DSC).
• the ratio of hard segment to soft segment in such block copolymer is preferably in the range of 20:80 to 50:50. If it is in this range, it is preferable because disconnection is unlikely to occur at the time of extension of the conductor obtained by solidifying the conductive composition. More preferably, it is 25:75 to 40:60.
• a hard segment in a block copolymer a methyl (meth) acrylate unit, a styrene unit, etc. are mentioned.
• the soft segment unit include n-butyl acrylate and butadiene unit.
• the block copolymer is preferably a triblock copolymer of polymethyl (meth) acrylate / poly n-butyl (meth) acrylate / polymethyl (meth) acrylate.
• the block copolymer may be used alone or in combination of two or more.
• (meth) acrylate is a term that generally refers to acrylate and methacrylate, and the same applies to other similar expressions.
• the block copolymer may be a commercially available product.
• An example of a commercially available product is an acrylic triblock copolymer manufactured using Arkema living polymerization.
• SBM type represented by polystyrene-polybutadiene-polymethyl methacrylate
• MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate
• carboxylic acid modification treatment or hydrophilic group modification treatment MAM N type or MAM A type can be used.
• SBM types are E41, E40, E21 and E20.
• MAM types are M51, M52, M53 and M22.
• MAM N types are 52N and 22N.
• An example of the MAM A type is SM4032XM10.
• Another example of a commercially available product is Kuraray's Clarity.
• the clarity is a block copolymer derived from methyl methacrylate and butyl acrylate.
• a block copolymer containing the above (meth) acrylate polymer block can be obtained, for example, by the method described in JP-A-2007-516326 or JP-A-2005-515281.
• the weight average molecular weight of the block copolymer is preferably 20,000 to 400,000, more preferably 50,000 to 300,000.
• the weight average molecular weight is 20,000 or more, the desired effects of toughness and flexibility can be obtained, and it is excellent when the conductive composition is formed into a film and dried or applied to a substrate and dried. Tackiness is obtained.
• the weight average molecular weight is 400,000 or less, the conductive composition has a good viscosity, and higher printability and processability can be achieved.
• the weight average molecular weight is 50,000 or more, an excellent effect is obtained in the alleviation to external impact.
• the tensile elongation at break of the block copolymer according to the measuring method of the international standard ISO 37 of the International Organization for Standardization is preferably 100 to 600%.
• the tensile elongation at break is 100 to 600%, the elasticity of the conductor and the stability of the electrical resistance are excellent. More preferably, it is 300 to 600%.
• Tensile elongation at break (%) (Elongation at break (mm)-Initial dimension mm) / (Initial dimension mm) ⁇ 100
• a sulfur-based vulcanizing agent, a non-sulfur-based vulcanizing agent and the like are usually used for the rubber and the functional group-containing elastomer.
• the silver powder in the wiring may be corroded by oxidation or sulfurization due to sulfur contained in the vulcanizing agent in the elastomer, and from such a viewpoint In the above, it is preferable not to contain a sulfur-based vulcanizing agent.
• the conductive composition of the present invention may contain a slight amount of a sulfur compound (within the range not to adversely affect the effects unique to the present invention) as long as the conductivity is not adversely affected.
• the elastomer may contain known additives such as a softener and a plasticizer.
• the softener include mineral oil-based softeners and vegetable oil-based softeners, and examples of the mineral oil-based softeners include various oils such as paraffinic process oil, naphthenic process oil and aromatic process oil.
• Vegetable oil-based softeners include castor oil, beard oil, linseed oil, rapeseed oil, soybean oil, palm oil, coconut oil, peanut oil, pine oil, tall oil, etc. These softeners may be used alone or in combination. Two or more may be used in combination. Desired rubber elasticity and extensibility can be adjusted by the addition amount of the softener.
• the elastomer as described above is preferably blended in a proportion of 5 to 40% by mass, and more preferably 14 to 28% by mass, based on the total solid content contained in the conductive composition.
• the blending amount of these block copolymers is preferably 85 to 100% by mass with respect to all the elastomers including the other elastomers.
• the stretchability of the formed coating film becomes better.
• other organic binders such as thermoplastic resins other than the elastomer may be used in combination as long as the effects of the present invention are not impaired.
• the conductive composition of the present invention can use an organic solvent for adjusting the composition or adjusting the viscosity for applying to a substrate.
• ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether a
• the conductive composition of the present invention may further comprise a thermosetting component.
• thermosetting component examples include polyester resin (urethane modified product, epoxy modified product, acrylic modified product etc.), epoxy resin, urethane resin, phenol resin, melamine resin, vinyl which can form a film by increasing molecular weight by curing reaction and crosslinking. Base resins and silicone resins.
• the conductive composition of the present invention may contain other components as long as the effects of the present invention are not impaired.
• additives such as a coupling agent and a photopolymerization initiator may be included.
• the conductive composition of the present invention can be produced, for example, by kneading an elastomer dissolved in a solvent and the silver powder described above.
• a kneading method for example, a method using a stirring and mixing apparatus such as a roll mill may be mentioned. Specifically, an elastomer is dissolved in an organic solvent to prepare a resin solution having a solid content of 50% by mass, silver powder is compounded with this resin solution, and after preliminary stirring and mixing with a stirrer, kneading with a triple roll mill is performed. Thus, the conductive composition can be obtained. Depending on the type of elastomer used and the blending ratio of the organic solvent, a liquid conductive composition or a paste-like (semi-solid) conductive composition can be obtained.
• the conductive composition as described above can be formed into a conductor, for example, by pattern application on a substrate and heat treatment.
• heat treatment include drying treatment and thermosetting treatment.
• a conductor excellent in stretchability and stability of electrical resistance can be obtained.
• application suitability is also improved by using the silver powder as described above.
• the conductive composition described above can be solidified to form a conductor.
• a coating film made of a conductive composition can be formed, dried, and solidified to form a conductive layer.
• Solidification of the conductive composition is performed by drying or heat treatment of the conductive composition. Examples of heat treatment are hot air drying or heat curing. Prior to heat treatment, molding may be performed.
• a layer of a conductor can be obtained by applying the above-mentioned conductive composition on a substrate so as to have a desired shape, and then solidifying to obtain a layer of a conductor.
• the layer of conductor may be of various shapes depending on the application used.
• the present invention can be suitably applied to conductor circuits and wiring.
• coating said conductive composition on a base material and forming a coating film pattern, and the process of solidifying the patterned coating film are included.
• a masking method or a method using a resist can be used to form a coating film pattern.
• the pattern forming process includes a printing method and a dispensing method.
• the printing method include gravure printing, offset printing, screen printing and the like, and in the case of forming a minute circuit, screen printing is preferable. Further, gravure printing and offset printing are suitable as a large area coating method.
• the dispensing method is a method of forming an extrusion pattern from a needle by controlling the application amount of the conductive composition, and is suitable for forming a partial pattern such as an earth wiring or forming a pattern on a portion having unevenness.
• any electrically insulating material can be used without particular limitation, and paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass Cloth / Non-Woven-Epoxy resin, Glass cloth / Paper-Epoxy resin, Synthetic fiber-Epoxy resin, Fluorine resin ⁇ Polyethylene ⁇ Polyphenylene ether, Polyphenylene oxide ⁇ All grades using composite materials such as polyphenylene oxide ⁇ cyanate ester (FR-4 etc.) Copper-clad laminates, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate and polyethylene naphthalate, sheets or films made of plastics such as polyimide, polyphenylene sulfide and polyamide, urethane, silicone rubber, acrylic rubber, butadiene Sheet or film comprising a crosslinked rubber, such as arm, polyester, polyurethane, polyolefin, such as a sheet or
• the conductor can be applied to applications described later.
• a stretchable material for example, a rubber or a thermoplastic elastomer
• the material having stretchability the same one as the above-mentioned elastomer component can be used.
• the extracorporeal device and the body surface device can be used besides the conductor circuit and the wiring. It can be suitably used to form a conductor for wearable devices such as electronic skin devices and internal devices. Moreover, the layer of a conductor can also be applied to the electrode of a flexible printed circuit board. Furthermore, the conductive composition of the present invention is also suitable for forming a layer of a conductor such as an actuator electrode. In addition, it is also suitable for forming a conductor of a design which has been difficult to realize due to the lack of sufficient stretchability and stability of electrical resistance. For example, the following may be mentioned.
• the conductor of the present invention can be applied as a wiring material for wearable bio-sensors worn to acquire / transmit action potentials / bio-information generated from animals and plants including humans. Although it is essential for the sensor to be attached to a place closely or closely to the surface tissue of animals and plants including human beings, the surface tissue is stretched and shrunk. In the conventional hard substrate and flexible substrate, there is no follow-up property to the installation place to be stretched and shrunk, the installation place of the sensor becomes limited, and the resulting biological information is also limited. According to the conductor of the present invention, since the sensor wiring material can be applied to the surface layer tissue of animals and plants including human beings, it is possible to make the wearable biological sensor wearable even in the place where the expansion and contraction occur.
• the wiring used for the wearable biological sensor can be formed by screen printing or a dispensing method
• the signal wiring can be miniaturized, which is considered to contribute to the miniaturization of the sensor device.
• a plastic film such as polycarbonate is used as the base substrate, and one that is heat-pressed after design printing is adopted ing.
• a conductor wiring comprising a laminated structure in which the conductor of the present invention is provided on a stretchable base has no disconnection at the time of extension and has a characteristic that a change in resistance value is suppressed.
• an expandable / deformable electronics device having a soft wiring in a soft housing. It can be suitably used as a pressure sensor, a touch sensor, or for antenna wiring.
• the conductor wiring which consists of a laminated structure which provided the layer of the conductor of this invention on the elastic base material can be utilized as a wiring board sheet which can be expanded-contracted.
• such conductor wiring can be attached to the surface of an object having a three-dimensional shape such as a molded product while being stretched or deformed without causing disconnection of the wiring. Therefore, the laminated structure which provided the layer of the conductor of this invention on the elastic base material can be suitably utilized for a pressure sensitive sensor, a touch sensor, or antenna wiring.
• Silver powder A Silver powder having an average primary particle diameter of 0.3 ⁇ m and an apparent porosity of 92%, which has been surface-treated with linolenic acid.
• Silver powder B Silver powder having an average primary particle diameter of 0.5 ⁇ m and an apparent porosity of 63%, which has been surface-treated with linolenic acid.
• Silver powder C Silver powder having an average primary particle diameter of 1.3 ⁇ m and an apparent porosity of 44%, which has been surface-treated with linolenic acid.
• the average primary particle diameter of silver powder observes silver powder by 10,000 times using a scanning electron microscope (manufactured by Nippon Denshi Co., Ltd., JSM-6360L), and the particles of 10 silver powder particles randomly extracted The diameter was measured and taken as the average value.
• the apparent porosity P of each silver powder was calculated as follows. That is, the silver powder is filled in a cylindrical container, the container is vibrated several times, the silver powder is replenished until the top surface of the silver powder reaches a certain height, and the amount of silver powder filled in the container is M (g) A load of 1 kg is applied to the top of the silver powder using a cylinder with an outer diameter matched to the inside diameter of the container, and left for 1 hour.
• ⁇ Preparation of Conductive Composition> The following two types were prepared as an elastomer for preparing a conductive composition. ⁇ Elastomer A (manufactured by Kuraray Co., Ltd., LA2330) Elastomer B (manufactured by Kuraray Co., Ltd., LA 2250) Polyester C (Toyobo Co., Ltd., Byron 290) For the elastomers A and B described above, the elastomer was dissolved in diethylene glycol monoethyl ether acetate to prepare a resin solution so as to have a solid content of 50% by mass. Moreover, about polyester C, it was made to melt
• the above silver powder and a resin solution of an elastomer or polyester are compounded according to the composition shown in Table 1 below, and after preliminary stirring and mixing with a stirrer, using a 3-roll mill (EXAKT, EXAKT 50), 3-roll mill
• the electroconductive composition which concerns on embodiment was obtained by changing and kneading
• the numerical value of the compounding quantity of an elastomer or polyester and silver powder represents a mass part.
• the secondary particle D95 particle diameter of silver powder contained in the obtained conductive composition was measured.
• the particle size of D95 was as follows. First, the conductive composition was diluted with 3000% by mass of propylene glycol monomethyl ether acetate to prepare a solution. The solution is used with a laser diffraction / scattering particle size distribution analyzer (manufactured by Microtrac Bell, TM 3000), and the refractive index of the particles is 1.33, the refractive index of the solvent is 1.40, 0.020 ⁇ m to 1000 The particle size distribution was measured in the measurement range of .00 ⁇ m, and the cumulative particle size of 95% was determined from the particle size distribution, and was used as the D95 particle size.
• Each conductive composition is applied to a substrate by screen printing, heat treated at 80 ° C. for 30 minutes, conductor having a line width of 1 mm, a thickness of 20 ⁇ m and a length of 40 mm Were formed on the substrate.
• a urethane film manufactured by Takeda Sangyo Co., Ltd., TG 88-I, 70 ⁇ m thick
• the evaluation results are shown in Table 1.
• the D95 particle size is 3.0 to 25 ⁇ m.
• the conductive composition (Examples 1 to 4) stirred or kneaded as described above is excellent in the stability of the electrical resistance and can obtain a conductor without disconnection even when the expansion and contraction are repeated or stretched. I understand.

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