WO2017154978A1 - 伸縮性導体シート及び伸縮性導体シート形成用ペースト - Google Patents
伸縮性導体シート及び伸縮性導体シート形成用ペースト Download PDFInfo
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- WO2017154978A1 WO2017154978A1 PCT/JP2017/009219 JP2017009219W WO2017154978A1 WO 2017154978 A1 WO2017154978 A1 WO 2017154978A1 JP 2017009219 W JP2017009219 W JP 2017009219W WO 2017154978 A1 WO2017154978 A1 WO 2017154978A1
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- 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
- C08K2201/001—Conductive additives
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- 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
- C08K2201/003—Additives being defined by their diameter
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- 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
- C08K2201/016—Additives defined by their aspect ratio
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Definitions
- the present invention relates to a stretchable conductor sheet used for electrical wiring and the like. More specifically, it is a stretchable conductor sheet that has improved durability against repeated stretching, and can be used for wiring parts, electrode parts, etc. when incorporating electronics into clothes and the like, and a stretchable conductor used therefor
- the present invention relates to a sheet forming paste.
- wearable electronic devices intended to use electronic devices having input / output, arithmetic and communication functions in close proximity to or close to the body have been developed.
- wearable electronic devices for example, devices having an accessory-type outer shape such as a wristwatch, glasses, and earphones, textile integrated devices in which electronic functions are incorporated in clothes, and the like are known.
- Electronic equipment requires electrical wiring for power supply and signal transmission.
- the electrical wiring is required to be stretchable in accordance with the stretchable clothes. Since electrical wiring made of metal wires and metal foils is not inherently practically stretchable, they are placed in a corrugated or repeated horseshoe shape to give them a pseudo stretch function. The method is used.
- wiring can be formed by regarding the metal wire as an embroidery thread and sewing it onto clothes.
- this method is not suitable for mass production because the elasticity of the metal is not insufficient.
- a method of forming a wiring by etching a metal foil is a general method for manufacturing a printed wiring board.
- a technique is known in which a metal foil is bonded to a stretchable resin sheet and a corrugated wiring is formed by a technique similar to that of a printed wiring board to make a pseudo stretchable wiring (see Non-Patent Document 1).
- This method is to give a pseudo expansion / contraction characteristic by twisting deformation of the corrugated wiring part, but the metal foil also changes in the thickness direction due to twisting deformation, so it is very uncomfortable when used as part of clothing. A certain feeling of wearing was not preferable.
- permanent plastic deformation occurs in the metal foil, and there is a problem in the durability of the wiring.
- Conductive particles such as silver particles, carbon particles, carbon nanotubes and elastomers such as stretchable urethane resin, natural rubber, synthetic rubber, solvent, etc. are kneaded to form a paste, directly on clothes or stretchable film base
- the wiring is printed and drawn in combination with a material or the like (see Non-Patent Document 2).
- a conductive composition comprising conductive particles and a stretchable binder resin can realize a stretchable conductor.
- the conductive composition obtained from such a paste is deformed at the binder resin portion when subjected to external force, and the conductivity is maintained within a range where the electrical chain of the conductive particles is not interrupted. Not too much.
- the specific resistance observed macroscopically is higher than that of metal wires and metal foils, but the cured product of the composition itself has elasticity, so there is no need to take the shape of corrugated wiring, etc. Since the thickness has a high degree of freedom, it is practically possible to realize a low resistance wiring compared to a metal wire.
- Patent Document 1 discloses a technique for suppressing a decrease in conductivity during elongation by combining silver particles and silicone rubber, and further covering the conductive film on the silicone rubber substrate with silicone rubber.
- Patent Document 2 discloses a combination of silver particles and a polyurethane emulsion, and it is said that a conductive film having high conductivity and high elongation can be obtained.
- the conductive particles can be secured by adding inorganic particles to the composition and the fabric using the stretchable conductor sheet as a wiring, for example, if the stretchable conductor sheet is repeatedly twisted, the specific resistance of the sheet There was a risk that the electrical signal corresponding to the movement of the subject would not be appropriately reflected (second problem).
- this invention makes it a 1st subject to provide the stretchable conductor sheet which shows isotropic electroconductivity when it expand
- the predetermined direction means the direction of application of the stretchable conductor sheet forming paste
- the vertical direction means the direction perpendicular to the direction of application of the stretchable conductor sheet forming paste.
- the second object of the present invention is to provide a stretchable conductor sheet having a small change in specific resistance even when repeatedly twisted and a paste for forming a stretchable conductor sheet used therefor.
- a third object of the present invention is to provide a stretchable conductor sheet having a small change in specific resistance even after repeated washing and a paste for forming a stretchable conductor sheet used therefor.
- the first invention capable of solving the first problem is that at least conductive particles, inorganic particles surface-treated with one or both of Al and Si hydroxides and / or oxides, and tensile elasticity
- the blending amount of the inorganic particles is preferably 2.0 to 30% by mass in a total of 100% by mass of the conductive particles and the inorganic particles.
- the average particle size of the inorganic particles is preferably smaller than the average particle size of the conductive particles.
- the conductive particles have an average particle size of 0.5 to 20 ⁇ m, and the conductive particles are preferably silver particles.
- Another aspect of the present invention is a paste for forming a stretchable conductor sheet used for producing the stretchable conductor sheet, wherein at least one of the conductive particles, Al, Si, or both hydroxides and / or Inorganic particles surface-treated with an oxide, a flexible resin having a tensile modulus of 1 MPa to 1000 MPa, and a solvent, and the blending amount of the inorganic particles is 100 in total of the conductive particles and the inorganic particles.
- the blending amount of the flexible resin is 7 to 35% by mass in a total of 100% by mass of the conductive particles, the inorganic particles, and the flexible resin.
- This is a paste for forming a stretchable conductor sheet.
- the second invention that has solved the second problem is a thickness containing at least conductive particles, inorganic particles having an aspect ratio of less than 1.5, and a flexible resin having a tensile elastic modulus of 1 MPa to 1000 MPa.
- Twisting cycle Twist in the positive direction (3600 °), return to the initial state, negative direction, 10 rotations ( ⁇ 3600 °), return to the initial state
- the inorganic particles are preferably surface-treated with one or both of Al and Si hydroxides and / or oxides.
- the blending amount of the inorganic particles is preferably 2.0 to 30% by mass in a total of 100% by mass of the conductive particles and the inorganic particles.
- the average particle size of the inorganic particles is preferably smaller than the average particle size of the conductive particles.
- the conductive particles have an average particle size of 0.5 to 20 ⁇ m, and the conductive particles are preferably silver particles.
- a paste for forming a stretchable conductor sheet used for producing the stretchable conductor sheet comprising at least conductive particles, inorganic particles having an aspect ratio of less than 1.5, and a tensile elastic modulus. 1 to 1000 MPa of a flexible resin and a solvent, and the amount of the inorganic particles is 2.0 to 30% by mass in a total of 100% by mass of the conductive particles and the inorganic particles, A paste for forming a stretchable conductor sheet is included, wherein the blending amount of the flexible resin is 7 to 35% by mass in a total of 100% by mass of the conductive particles, the inorganic particles, and the flexible resin.
- a third invention that has solved the third problem is a stretchable conductor sheet containing at least conductive particles and a flexible resin having a tensile elastic modulus of 1 MPa to 1000 MPa, and has a porosity of 10 volumes. It is an elastic conductor sheet characterized by being not less than 50% and not more than 50% by volume.
- the conductive particles are aggregated silver particles having an average particle size of 0.8 to 10 ⁇ m, and further have an aspect ratio of less than 1.5 and an average particle size of 0.5 times or less of the aggregated silver particles.
- the elastic conductor sheet contains inorganic particles, and the thickness of the stretchable conductor sheet is 3 to 800 ⁇ m, and the specific resistance after repeating 10% compression 100 times is preferably within 2.4 times the initial specific resistance.
- the inorganic particles are preferably surface-treated with one or both of Al and Si hydroxides and / or oxides.
- the blending amount of the inorganic particles is preferably 2.0 to 30% by mass in a total of 100% by mass of the aggregated silver particles and the inorganic particles.
- the average particle diameter of the inorganic particles is preferably smaller than the average particle diameter of the aggregated silver particles.
- a paste for forming a stretchable conductor sheet used for producing the stretchable conductor sheet wherein the aggregated silver particles have an average particle size of 0.8 to 10 ⁇ m and an aspect ratio of 1. Containing inorganic particles having an average particle diameter of less than 5 and 0.5 times or less of the aggregated silver particles, a flexible resin having a tensile elastic modulus of 1 MPa or more and 1000 MPa or less, and a solvent.
- the total amount of the aggregated silver particles and the inorganic particles is 2.0 to 30% by mass, and the amount of the flexible resin is the total of the aggregated silver particles, the inorganic particles, and the flexible resin.
- a paste for forming a stretchable conductor sheet which is 7 to 35% by mass in 100% by mass, is included.
- a stretchable conductor composition containing a conductive filler and a binder resin generally has a conductive anisotropy depending on the direction depending on the extrusion direction or the coating direction when forming a sheet.
- Efforts have been made to minimize the anisotropy of conductivity by engineering measures such that the anisotropy of conductivity is usually negligible.
- the electrical conductivity of the sheet obtained from the stretchable conductor composition is lowered by the accumulation of the interruption of the conductive path due to the microcracks generated during stretching. Such microcracks tend to occur in the direction perpendicular to the extension direction when first extended.
- the first invention specific inorganic particles are contained in the composition or sheet.
- non-conductive inorganic particles inhibit the conductivity, so that a very small amount of nano-sized silica particles are added for the purpose of improving printing characteristics. Apart from that, it is usually not preferred to use.
- the inorganic particles surface-treated with one or both of the hydroxides and / or oxides of Al and Si increase the dispersibility of the inorganic particles in the flexible resin.
- the resin part When the resin part is deformed by an external force, it functions as a key point of resin deformation (crank), and when the external force is removed and shrinks, the resin tries to shrink with the local center as the key point. Compared to, it becomes easier to restore to a shape close to the state before expansion and contraction. For this reason, the occurrence of microcracks during the first stretching deformation can be suppressed, and further, the inorganic particles disperse the microcrack directionality. As a result, the XY direction anisotropy is greatly improved. To express the effect.
- the change in the specific resistance can be reduced even when repeated torsion is received (hereinafter sometimes referred to as torsion resistance).
- the effect is considered to be manifested by the following mechanism of action.
- the inorganic particles function as the key to the resin deformation (the key), and when the deformation stretched in the plane direction is restored to the original state, the key is the local center As the resin returns to the initial state, the anisotropy of restoration is reduced.
- this is expanded to three-dimensional deformation, the same effect is exhibited in the thickness direction by using inorganic particles having a smaller aspect ratio, and the three-dimensional deformation such as torsion is also observed.
- Inorganic particles function as the key to the deformation of the resin (the key), and when the twist is removed, the resin returns to the initial state with the key as the local center. Therefore, the shape is closer to the state before twisting than when there is no key.
- the restoring force after twisting in a predetermined direction for example, positive direction
- the restoring force after twisting in the direction opposite to the predetermined direction for example, negative direction
- the stretchable conductor sheet of the present invention is horseshoe-shaped wiring (corrugated wiring) (see FIG. 7), the deformation is absorbed not by stretch resistance but by twist resistance, so that the stretch rate is substantially low. It will be suppressed and the stretch durability will be further improved.
- the stretchable conductor sheet of the third invention includes a predetermined range of voids inside. Usually, in a conductive composition containing a conductive filler and a matrix resin, such voids are not preferred because they impede conductivity.
- moderately controlled voids exhibit a mechanical buffering effect that absorbs compression deformation and prevents buckling failure during compression.
- the change in specific resistance when repeatedly subjected to compression deformation can be reduced (that is, compression resistance can be imparted), and washing resistance can also be improved.
- FIG. 1 is a diagram showing an example of a method for forming a stretchable conductor sheet of the present invention on a fabric by a direct printing method.
- FIG. 2 is a diagram showing an example of a method for forming the stretchable conductor sheet of the present invention on a fabric by a transfer method.
- FIG. 3 is a photograph of a cross section of the stretchable conductor sheet of the present invention taken with a scanning electron microscope.
- FIG. 4 is a diagram in which a wiring made of the stretchable conductor sheet of the present invention is formed on a glove-type device.
- FIG. 5 is a diagram showing an example of wiring formed by the stretchable conductor sheet of the present invention.
- FIG. 6 is a diagram showing an example in which the wiring of FIG. 5 is used for a shirt.
- FIG. 7 is a diagram showing an example of a horseshoe-shaped wiring formed from the stretchable conductor sheet of the present invention.
- a first invention is a stretchable conductor sheet containing at least conductive particles, a flexible resin, and inorganic particles, and the inorganic particles are surfaced by one or both of Al and Si hydroxides and / or oxides.
- the feature is that the rate of change of the specific resistance at the time of extension in the extension direction when the sheet is extended by 40% of the original length in both directions orthogonal to each other is less than ⁇ 10%. is there.
- the second invention is a stretchable conductor sheet containing at least conductive particles, a flexible resin, and inorganic particles, and the aspect ratio of the inorganic particles is less than 1.5, and the twist cycle of the twist test is performed.
- a feature is that the specific resistance of the sheet after repeating 100 times is within 3.0 times the initial specific resistance.
- the third invention is a stretchable conductor sheet containing at least conductive particles and a flexible resin, and is characterized in that the porosity is 10 volume% or more and 50 volume% or less.
- the conductive particles used in the first to third inventions are common.
- the conductive particles are preferably made of a substance having a specific resistance of 1 ⁇ 10 ⁇ 1 ⁇ cm or less and a particle diameter of 100 ⁇ m or less.
- Examples of the substance having a specific resistance of 1 ⁇ 10 ⁇ 1 ⁇ cm or less include metals, alloys, carbon, doped semiconductors, conductive polymers, and the like.
- the conductive particles preferably used in the present invention are metal particles such as silver, gold, platinum, palladium, copper, nickel, aluminum, zinc, lead and tin, alloy particles such as brass, bronze, white copper and solder, silver-coated copper Hybrid particles, metal-plated polymer particles, metal-plated glass particles, metal-coated ceramic particles, and the like.
- the conductive particles may be only one type or two or more types.
- the conductive particles are particularly preferably silver particles from the viewpoint of high conductivity and cost.
- silver particles examples include scaly silver powder or aggregated silver powder, and these silver powders are preferably used as the main component in conductive particles.
- the term “aggregation” means that the primary particles are aggregated three-dimensionally, and the shape of the primary particles is not particularly limited, and may be spherical or indefinite. The shape of the aggregated silver powder is not particularly limited, and may be indefinite.
- “used as a main component” means that silver powder is used at a ratio of 90% by mass or more in 100% by mass of conductive particles.
- the silver particles are preferably 93% by mass or more, more preferably 96% by mass or more, still more preferably 99% by mass or more, and particularly preferably 100% by mass in 100% by mass of the conductive particles.
- Scaly silver powder and agglomerated silver powder are preferable in that they can form a conductive network even with a low filling amount because they have a larger specific surface area than spherical silver powder and the like.
- Aggregated silver powder is more preferable in that it is not in a monodispersed form, and since the particles are in physical contact, it is easy to form a conductive network.
- the particle size of the scaly silver powder is not particularly limited, but the average particle size (50% D) measured by the dynamic light scattering method is preferably 0.5 to 20 ⁇ m, more preferably 0.7 to 18 ⁇ m, and still more preferably. It is 0.9 to 15 ⁇ m, and more preferably 1.1 to 12 ⁇ m.
- the average particle diameter exceeds 20 ⁇ m, it becomes difficult to form fine wiring, and clogging occurs in the case of screen printing.
- the average particle size is less than 0.5 ⁇ m, the particles cannot be contacted with each other at low filling, and the conductivity may be deteriorated.
- the particle diameter of the agglomerated silver powder is not particularly limited, but the average particle diameter (50% D) measured by a light scattering method is preferably 0.8 to 20 ⁇ m, more preferably 1 to 20 ⁇ m, still more preferably 2 to 15 ⁇ m, particularly The thickness is preferably 3 to 12 ⁇ m.
- the average particle size exceeds 20 ⁇ m, dispersibility is lowered and pasting becomes difficult.
- the average particle diameter is less than 0.8 ⁇ m (particularly less than 1 ⁇ m), the effect as an agglomerated powder is lost, and good conductivity may not be maintained when the filling is low.
- the aspect ratio of the conductive particles is preferably less than 1.5, more preferably 1.45 or less, and further preferably 1.40 or less. If the aspect ratio of the conductive particles is larger than the above range, stretchability and torsion resistance may be reduced.
- the blending amount of the conductive particles is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and still more preferably 60 to 85% by mass in a total of 100% by mass of the flexible resin, inorganic particles, and conductive particles. %. If the blending amount is smaller than the above range, the conductivity may not be sufficiently secured. On the other hand, when the said compounding quantity is larger than the said range, there exists a possibility that a stretching property and isotropic conductivity may fall.
- aggregated silver particles having an average particle diameter of 0.8 to 10 ⁇ m As the conductive particles, particularly high compression resistance can be realized.
- the above-mentioned aggregated silver particles only need to improve not only the conductivity of the sheet but also the porosity, and amorphous aggregated silver powder or the like can be used.
- the particle diameter of the aggregated silver powder used for achieving particularly high compression resistance is not particularly limited, but the average particle diameter (50% D) measured by the light scattering method is 0.8 to 10 ⁇ m. More preferably, it is 0.9 to 9 ⁇ m, more preferably 1.0 to 8 ⁇ m, and still more preferably 1.1 to 7 ⁇ m.
- the average particle diameter exceeds 10 ⁇ m, dispersibility is lowered and pasting becomes difficult.
- the average particle diameter is less than 0.8 ⁇ m, the effect as an agglomerated powder is lost, and good conductivity may not be maintained with low filling.
- the amount of the aggregated silver particles is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and still more preferably 60 to 85% by mass in the total of 100% by mass of the flexible resin, the inorganic particles, and the aggregated silver particles. %. If the blending amount is smaller than the above range, the conductivity may not be sufficiently secured. On the other hand, when the said compounding quantity is larger than the said range, there exists a possibility that a stretching property and compression resistance may fall.
- the inorganic particles used in the first invention are surface-treated with one or both of Al and Si hydroxides and / or oxides.
- the surface treatment means that one or both of hydroxides and / or oxides of Al and Si are formed on the surface of the inorganic particles.
- the product and / or oxide may be formed on at least a part of the surface of the inorganic particles, preferably all.
- Such inorganic particles contribute to an improvement in dispersibility in a flexible resin, and can exhibit isotropic properties when stretched in different directions. This isotropic conductivity is considered to be manifested by the following mechanism action.
- the inorganic particles function as a key for resin deformation, and when the external force is removed and the resin part shrinks, the resin tends to contract with the key as a local center.
- the restoring force after expansion / contraction in the X direction becomes equal to the restoring force after expansion / contraction in the Y direction. Therefore, even when expansion or contraction in a specific direction at the time of washing or wearing is applied, the conductivity in the Y direction after expansion or contraction in the X direction does not decrease, and isotropic conductivity can be exhibited.
- the inorganic particles include particles of barium sulfate, titanium oxide, zinc oxide, and the like.
- particles of barium sulfate and titanium oxide are preferable from the viewpoints of particle size control and surface treatment.
- barium sulfate particles ferrous barium sulfate, which is a pulverized product of barite mineral called natural barite, and so-called precipitated barium sulfate produced by a chemical reaction can be used. It is preferable to use precipitated barium sulfate which can easily control the particle size.
- Titanium oxide may be any of anatase type, rutile type or brookite type.
- a conventionally known method can be employed. For example, if a substance capable of becoming one or both of hydroxides and / or oxides of Al and Si is added to an inorganic particle-containing solution slurry and heated. Good.
- the hydroxide and / or oxide of one or both of Al and Si include oxides such as SiO 2 and Al 2 O 3 , hydroxides such as Al (OH) 3 and Si (OH) 4, and the like. It is done.
- Examples of substances that can become one or both of hydroxides and / or oxides of Al and Si include sodium silicate and sodium aluminate. What is necessary is just to dripped at the inorganic particle containing solution slurry as aqueous solution when using these. For example, a solution of a substance that can become one or both of Al and Si hydroxides and / or oxides is dropped into the inorganic particle-containing solution slurry, and the mixture is heated (for example, 40 to 100 ° C., preferably 50 to 90 ° C.). C.), neutralization with acid (for example, dilute sulfuric acid), and drying, one or both of Al and Si hydroxides and / or oxides adhere to the surface of the inorganic particles.
- acid for example, dilute sulfuric acid
- the inorganic particles is preferably subjected to a surface treatment with one or more selected from SiO 2 and Al 2 O 3, and more preferably surface-treated with SiO 2 and Al 2 O 3.
- the deposition amount of the SiO 2 and Al 2 O 3 is preferably 0.2% by mass or more and 5% by mass or less, and preferably 0.5% by mass or more and 4% by mass in the total mass of 100% by mass of the inorganic particles and the surface treatment substance amount. % Or less is more preferable.
- the deposition amount of Si and Al is preferably 0.5 to 50, more preferably 2 to 30 with respect to the barium element 100 in terms of element ratio by fluorescent X-ray analysis.
- the average particle size of the inorganic particles determined by the dynamic light scattering method is preferably 0.01 to 18 ⁇ m, more preferably 0.03 to 12 ⁇ m, still more preferably 0.05 to 8 ⁇ m, and further
- the thickness is more preferably 0.1 to 5 ⁇ m, particularly preferably 0.2 to 3 ⁇ m.
- the average particle size of the inorganic particles is preferably smaller than the average particle size of the conductive particles.
- the average particle diameter of the conductive particles is preferably 1.5 times or more, more preferably 2.0 times or more, further preferably 2.4 times or more, more preferably 4.0 times the average particle diameter of the inorganic particles. A ratio of twice or more is particularly preferable.
- the average particle diameter of the conductive particles may be 30 times or less than the average particle diameter of the inorganic particles. When the average particle diameter of the inorganic particles exceeds this range, the unevenness of the surface of the coating film obtained increases, and the coating film tends to break when stretched. On the other hand, when the average particle size of the inorganic particles is smaller than this range, the effect of improving the stretch durability is small, the viscosity of the paste is high, and it becomes difficult to manufacture the paste.
- the blending amount of the inorganic particles is preferably from 2.0 to 30% by mass, more preferably from 2.5 to 20% by mass, and from 3.0 to 15% by mass in the total 100% by mass of the conductive particles and the inorganic particles. More preferably, 3.4 to 10% by mass is even more preferable. If the blending amount exceeds this range, the conductivity of the obtained coating film surface is lowered, and the stretchability may be lowered. On the other hand, when the said compounding quantity is smaller than this range, it will become difficult to express isotropic conductivity.
- the aspect ratio of the inorganic particles is preferably less than 1.5, more preferably 1.4 or less, and further preferably 1.3 or less.
- the lower limit of the aspect ratio may be about 1.0, for example.
- the inorganic particles used in the second invention have an aspect ratio of less than 1.5, preferably 1.45 or less, and more preferably 1.40 or less.
- the aspect ratio is 1.5 or more, the restoring force at the time of twisting tends to decrease, and the change in specific resistance may increase.
- the lower limit of the aspect ratio may be about 1.0, for example.
- the inorganic particles are preferably surface-treated with one or both of Al and Si hydroxides and / or oxides. Such inorganic particles contribute to an improvement in dispersibility in a flexible resin and contribute to torsion resistance.
- the inorganic particles it is sufficient that the aspect ratio satisfies the above range, and specifically, those exemplified in the first invention can be used.
- the inorganic particles are preferably surface-treated with one or both hydroxides and / or oxides of Al and Si, as in the first invention.
- the average particle size of the inorganic particles determined by the dynamic light scattering method is preferably 0.01 to 12 ⁇ m, more preferably 0.03 to 10 ⁇ m, still more preferably 0.05 to 8 ⁇ m, and further
- the thickness is more preferably 0.1 to 5 ⁇ m, particularly preferably 0.2 to 3 ⁇ m.
- the average particle size of the inorganic particles is preferably smaller than the average particle size of the conductive particles as in the first invention.
- the amount of the inorganic particles is preferably in the same range as the first invention.
- the said compounding quantity is smaller than the range mentioned above, it will become difficult to express twisting resistance.
- aggregated silver particles having an average particle size of 0.8 to 10 ⁇ m are used as the conductive particles, the aspect ratio is less than 1.5, and the average particle size is 0.5 of the aggregated silver particles. It is preferable to use inorganic particles that are twice or less.
- the inorganic particles used in the third invention preferably have an aspect ratio of less than 1.5, as in the second invention.
- the average particle size of the inorganic particles is preferably smaller than the average particle size of the aggregated silver particles.
- the average particle diameter of the inorganic particles is preferably 0.5 times or less, more preferably 0.45 times or less, still more preferably 0.40 times or less, more preferably 0.35 times the average particle diameter of the aggregated silver particles. A ratio of 2 times or less is particularly preferable.
- the average particle size of the inorganic particles is preferably 0.10 times or more the average particle size of the aggregated silver particles. When the average particle diameter of the inorganic particles exceeds this range, the unevenness of the surface of the coating film obtained becomes large, and the coating film tends to break when stretched. On the other hand, if the average particle size of the inorganic particles is smaller than this range, the effect of improving stretch durability is small, the viscosity of the paste is high, and paste production may be difficult.
- the amount of the inorganic particles is preferably in the same range as the first invention.
- the blending amount is smaller than the above range, compression resistance is hardly exhibited.
- the flexible resin used in the first to third inventions is common, and a flexible resin having a tensile elastic modulus of 1 MPa to 1000 MPa is used.
- Examples of the flexible resin in the present invention include thermoplastic resins, thermosetting resins, and rubbers having a (tensile) elastic modulus of 1 to 1000 MPa.
- rubber is preferable.
- examples of rubber include urethane rubber, acrylic rubber, silicone rubber, butadiene rubber, nitrile group-containing rubber such as nitrile rubber and hydrogenated nitrile rubber, isoprene rubber, sulfurized rubber, styrene butadiene rubber, butyl rubber, chlorosulfonated polyethylene rubber, Examples include ethylene propylene rubber and vinylidene fluoride copolymer.
- nitrile group-containing rubber chloroprene rubber, chlorosulfonated polyethylene rubber and styrene butadiene rubber are preferable, and nitrile group-containing rubber and styrene butadiene rubber are particularly preferable.
- the (tensile) elastic modulus of the flexible resin is preferably 3 to 600 MPa, more preferably 10 to 500 MPa, still more preferably 15 to 300 MPa, still more preferably 20 to 150 MPa, and particularly preferably 25 to 100 MPa.
- the rubber containing a nitrile group is not particularly limited as long as it is a rubber or elastomer containing a nitrile group, but nitrile rubber and hydrogenated nitrile rubber are preferable.
- Nitrile rubber is a copolymer of butadiene and acrylonitrile. If the amount of bound acrylonitrile is large, the affinity with metal increases, but the rubber elasticity contributing to stretchability decreases conversely. Accordingly, the amount of bound acrylonitrile is preferably 18 to 50% by mass, more preferably 30 to 50% by mass, and particularly preferably 40 to 50% by mass in 100% by mass of a nitrile-containing rubber (for example, acrylonitrile butadiene copolymer rubber).
- the content ratio of styrene and butadiene is preferably 70/30 to 30/70, more preferably 60/40 to 40/60, based on mass.
- the alkali metal content of the flexible resin is preferably 4000 ppm or less, more preferably 2000 ppm or less, further preferably 1000 ppm or less, still more preferably 500 ppm or less, and particularly preferably 100 ppm or less.
- Conductive particles (especially aggregated silver particles) and nitrile groups, which have excellent affinity with conductive particles (especially aggregated silver particles), are preferentially adsorbed on the surface of the conductive particles (particularly aggregated silver particles), so that the conductive particles (particularly aggregated silver particles) and nitrile in the coating film
- the rubber containing the group is not completely dispersed uniformly, resulting in uneven distribution and non-uniformity such as a sea-island structure. For this reason, even though the conductive particles (particularly aggregated silver particles) have a low filling amount, a conductive network is easily formed. Good stretchability and repeated stretchability can be achieved by increasing the rubber component by reducing the amount of conductive particles (particularly aggregated silver particles).
- the blending amount of the flexible resin is preferably 7 to 35% by mass, more preferably 8 to 30% by mass, out of a total of 100% by mass of conductive particles (particularly aggregated silver particles), inorganic particles and flexible resin. More preferably, it is 9 to 25% by mass, and still more preferably 10 to 22% by mass.
- the blending amount of the flexible resin is small, the stretchability of the conductor sheet is lowered and the stretch durability may be lowered.
- the amount of the flexible resin is large, the conductivity is lowered, and the isotropic conductivity and the compression resistance may be lowered.
- the composition (excluding the solvent) constituting the stretchable conductor sheet is melt-kneaded and compounded at a temperature at which the flexible resin component is sufficiently softened, and melt extrusion is performed.
- a method of forming a film by a machine can be exemplified. This method is preferably used when high productivity is required.
- the material constituting the stretchable conductor sheet is further blended with a solvent capable of dissolving and dispersing the flexible resin component, and after processing into a slurry or paste,
- the manufacturing method which makes it a sheet
- One of the aspects of the first invention is a paste for forming a stretchable conductor sheet used for producing a stretchable conductor sheet, and is a hydroxide of at least one of conductive particles, Al, Si, or both And / or inorganic particles surface-treated with an oxide, a flexible resin having a tensile modulus of 1 MPa or more and 1000 MPa or less, and a solvent, and the blending amount of the inorganic particles includes the conductive particles and the inorganic particles.
- the blending amount of the flexible resin is 7 to 35 mass in the total 100 mass% of the conductive particles, the inorganic particles, and the flexible resin. %, A paste for forming a stretchable conductor sheet is included.
- One aspect of the second invention is a paste for forming a stretchable conductor sheet used for producing a stretchable conductor sheet, at least conductive particles, inorganic particles having an aspect ratio of less than 1.5 And a flexible resin having a tensile modulus of 1 MPa to 1000 MPa, and a solvent, and the blending amount of the inorganic particles is 2.0 to 30 mass in a total of 100 mass% of the conductive particles and the inorganic particles. %, And the amount of the flexible resin is 7 to 35% by mass in a total of 100% by mass of the conductive particles, the inorganic particles, and the flexible resin. Includes paste.
- One of the aspects of the third invention is a paste for forming a stretchable conductor sheet used for producing a stretchable conductor sheet, wherein at least conductive particles and a flexible material having a tensile elastic modulus of 1 MPa or more and 1000 MPa or less.
- a stretchable conductor comprising a flexible resin and a solvent, wherein the amount of the flexible resin is 7 to 35% by mass in a total of 100% by mass of the aggregated silver particles and the flexible resin Includes sheet forming paste.
- Inorganic particles having an average particle size of 0.5 times or less of the aggregated silver particles, a flexible resin having a tensile modulus of 1 MPa to 1000 MPa, and a solvent, and the amount of the inorganic particles is The total amount of the particles and the inorganic particles is 2.0 to 30% by mass, and the amount of the flexible resin is 100% by mass of the aggregated silver particles, the inorganic particles, and the flexible resin.
- the stretchable conductor sheet forming paste is preferably 7 to 35% by mass.
- the blending amount of the conductive particles (particularly aggregated silver particles) is preferably 30 to 80% by mass, more preferably 35 to 75% by mass, and still more preferably 40 to 70% by mass in 100% by mass of the paste for forming a stretchable conductor sheet. %.
- the blending amount of the inorganic particles and the blending amount of the flexible resin are preferably the same as described above.
- the paste for forming a stretchable conductor sheet of the present invention contains a solvent.
- the solvent in the present invention is preferably water or an organic solvent.
- the content of the solvent should be appropriately adjusted depending on the viscosity required for the paste, and is not particularly limited.
- the total mass of conductive particles (particularly aggregated silver particles), inorganic particles, flexible resin and solvent is 100.
- the boiling point of the organic solvent is preferably 100 ° C. or higher and lower than 300 ° C., more preferably 130 ° C. or higher and lower than 280 ° C. If the boiling point of the organic solvent is too low, the solvent volatilizes during the paste manufacturing process or when the paste is used, and there is a concern that the component ratio constituting the paste is likely to change. On the other hand, if the boiling point of the organic solvent is too high, the amount of residual solvent in the dry-cured coating film increases, which may cause a decrease in the reliability of the coating film.
- organic solvent examples include ester solvents, ether solvents, ether ester solvents, ketone solvents, alcohol solvents, aromatic hydrocarbon solvents, and the like.
- ester solvent examples include ⁇ -butyrolactone, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and the like.
- ether solvents include diethylene glycol, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol, tetraethylene glycol monobutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether. Etc.
- ether ester solvent examples include propylene glycol monomethyl ether acetate, butyl glycol acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoacetate, triethylene glycol diacetate and the like.
- ketone solvents examples include cyclohexanone and isophorone.
- alcohol solvents examples include benzyl alcohol, terpionol, n-dodecanol and the like.
- aromatic hydrocarbon solvent examples include toluene, xylene, Exube Chemical's Solvesso 100, 150, 200, diamylbenzene, triamylbenzene, and the like.
- AF Solvent No. 4 (boiling point: 240 to 265 ° C.), No. 5 (boiling point: 275 to 306 ° C.), No. 6 (boiling point: 296 to 317 ° C.) manufactured by Nippon Oil Corporation No. 7, (boiling point: 259-282 ° C.), and No. 0 solvent H (boiling point: 245-265 ° C.), etc., and two or more of them may be included if necessary.
- Such an organic solvent is appropriately contained so that the stretchable conductor sheet forming paste has a viscosity suitable for printing or the like.
- isophorone is preferable from the viewpoint that the organic solvent is less likely to volatilize when the paste is prepared and the organic solvent is sufficiently volatilized when the paste is applied.
- an epoxy resin can be blended with the paste for forming a stretchable conductor sheet of the present invention.
- a preferable epoxy resin in the present invention is a bisphenol A type epoxy resin or a phenol novolac type epoxy resin.
- an epoxy resin curing agent When compounding an epoxy resin, an epoxy resin curing agent can be blended.
- a known amine compound, polyamine compound, or the like may be used as the curing agent.
- the blending amount of the curing agent is preferably 1 to 30 parts by mass and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the epoxy resin.
- the blending amount of the epoxy resin and the curing agent is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, and further preferably 1.5 to 15 parts by mass with respect to 100 parts by mass of the flexible resin. Part.
- the stretchable conductor sheet forming paste of the present invention is a known organic material such as a leveling agent, an antioxidant, and an ultraviolet absorber, from the viewpoint of imparting printability and adjusting the color tone, as long as the content of the invention is not impaired.
- Inorganic additives can be blended.
- Conductive particles especially agglomerated silver particles
- inorganic particles and flexible resin are mixed with a solvent, and then mixed and dispersed by a disperser such as a dissolver, a three-roll mill, a self-revolving mixer, an attritor, a ball mill, or a sand mill.
- a disperser such as a dissolver, a three-roll mill, a self-revolving mixer, an attritor, a ball mill, or a sand mill.
- the paste for forming a stretchable conductor sheet obtained as described above is applied by a technique such as a die coater, a squeegee coater, an applicator, a comma coater, or screen printing (preferably by an applicator or a comma coater).
- the stretchable conductor sheet can be obtained by using a solution film-forming method in which it is applied to a substrate having releasability and dried to form a sheet. This method can be produced even in a small amount, but is a preferable method when a relatively thin sheet is required.
- heating may be performed for a predetermined time in, for example, the air, a vacuum atmosphere, an inert gas atmosphere, or a reducing gas atmosphere.
- the heating temperature is, for example, 100 to 150 ° C., preferably 110 to 130 ° C.
- the heating time is, for example, 10 to 40 minutes, preferably about 20 to 30 minutes.
- the thickness of the stretchable conductor sheet obtained through the paste state is 3 to 800 ⁇ m, preferably 8 to 500 ⁇ m, more preferably 12 to 300 ⁇ m, and still more preferably Is 20 to 180 ⁇ m.
- the thickness of the stretchable conductor sheet obtained through the paste state is preferably 3 to 800 ⁇ m, more preferably 8 to 500 ⁇ m, still more preferably 12 to 300 ⁇ m, and particularly preferably. Is 20 to 180 ⁇ m.
- the thickness of the sheet is less than 3 ⁇ m, durability against expansion and contraction is lowered, and there is a possibility that conductivity is lowered.
- the thickness of the sheet is more than 800 ⁇ m, sufficient stretchability is difficult to obtain, and there is a possibility that sufficient fit cannot be obtained when used for a fabric.
- the stretchable conductor sheet of the present invention can be formed into a sheet with a stretchable conductor sheet forming paste alone (form a conductive layer), and can be formed into a sheet having an insulating layer on at least one surface as necessary. It is preferable that the insulating layer has elasticity like the elastic conductor sheet. As a material for the insulating layer, a polymer material having a low elastic modulus is preferable as in the case of the flexible resin constituting the stretchable conductor sheet forming paste. When the stretchable conductor sheet is used as an electrical wiring, the insulating layer has a function as an adhesive layer between the stretchable conductor sheet and the base material. Further, when it is provided on the side opposite to the base material when it is used as electric wiring, that is, on the surface side, it functions as an insulating coat layer (insulating portion).
- the resin forming the insulating layer is not particularly limited as long as it is an insulating resin, and examples thereof include polyurethane resins, silicone resins, vinyl chloride resins, and epoxy resins. Among these, polyurethane resins are preferable from the viewpoint of adhesiveness with the conductive layer.
- the polyurethane-based resin is preferably, for example, a polyester-based polyurethane resin, a polyether-based polyurethane resin, or a polycarbonate-based polyurethane resin, and more preferably a polyester-based polyurethane resin from the viewpoint of the stretchability of the coating film.
- the insulating layer is obtained by dissolving or dispersing a resin in a solvent (preferably water), applying or printing on a substrate or cloth fabric to form a coating film, and then volatilizing and drying the solvent contained in the coating film. May be prepared.
- a solvent preferably water
- the viscosity of the resin solution may be 400 mPa ⁇ s or less
- a thickener such as an acrylic polymer may be used as a viscosity modifier.
- the film thickness of the insulating layer is, for example, 5 to 200 ⁇ m, preferably 8 to 150 ⁇ m, more preferably 14 to 90 ⁇ m, and further preferably 20 to 70 ⁇ m. If the insulating layer is too thin, the insulating effect will be insufficient, and if the insulating layer is too thick, the stretchability of the fabric or the like may be hindered or the comfort may be hindered.
- the insulating layer formed on the cloth fabric is usually partially impregnated into the cloth fabric, but the film thickness may be any thickness including the portion impregnated into the fabric fabric.
- the thickness of the insulating layer excluding the impregnated portion is, for example, 5 to 200 ⁇ m, preferably 8 to 150 ⁇ m, more preferably 14 to 90 ⁇ m, and further preferably 20 to 70 ⁇ m.
- the stretchable conductor sheet of the present invention can be formed into a sheet having another conductor layer containing carbon as a conductive filler on at least one surface as necessary. This form is particularly preferred when the conductive particles used in the paste for forming a stretchable conductor sheet are metal particles.
- the resin material constituting the conductor composition containing carbon as a conductive filler is preferably a polymer material having a low elastic modulus.
- the conductor composition layer containing carbon as a conductive filler functions as a contact material when the stretchable conductor sheet forming paste is used as an electrode part.
- a method for forming an insulating layer and / or a conductive composition layer containing carbon as a conductive filler on one side or both sides of a stretchable conductive sheet will be described below.
- the melt molding method When the melt molding method is used as a method for producing the sheet, the melt molding may be repeated by sequentially stacking the sheets.
- a two-layer die or a three-layer die can be used to simultaneously extrude a plurality of layers into a sheet.
- solution coating and drying and curing may be similarly performed by sequentially stacking sheets.
- a sheet produced by the melt extrusion method with a solution film forming method
- a sheet produced by the solution film formation method may be overlaid by a melt extrusion method.
- a multi-layered sheet can be obtained by sequentially performing overprinting by a screen printing method or the like.
- an insulating layer and / or a layer of a conductor composition containing carbon as a conductive filler is formed on a sheet produced by a melt extrusion method or a solution film formation method by a method such as screen printing, stencil printing, or ink jet printing. It can also be formed as a shape.
- the insulating layer may function as an adhesive layer.
- a stretchable conductor sheet, an insulating layer sheet, an adhesive sheet, a conductor composition sheet containing carbon as a conductive filler, etc. can be used alone.
- a known adhesive or hot melt resin may be used for bonding. Further, when the respective sheets maintain thermoplasticity, the sheets can be fused and bonded together.
- a stretchable conductor resin sheet is used alone, and preferably a sheet having an insulating layer and / or a stretchable conductor composition layer containing carbon as a conductive filler on at least one side is processed into a predetermined shape, and clothes or clothes
- the electrical wiring may be formed by being attached to a fabric that becomes the original fabric.
- a known adhesive or hot melt resin may be used for attaching the sheet to the fabric.
- the material used for bonding is preferably flexible.
- the insulating layer sheet can be used as a hot-melt material by leaving the insulating layer sheet in a B-stage that is in a semi-dried and semi-cured state. It is also possible to bond the stretchable conductor sheet to the fabric by heating and pressurizing using the B stage.
- a fabric having electrical wiring composed of a stretchable conductor sheet can be produced by directly printing an electrical wiring pattern on the fabric using a stretchable conductor sheet forming paste (see FIG. 1).
- the manufacturing method includes the step of preparing the temporary support 2 (A), the step of fixing the fabric 1 on the temporary support 2 (B), and printing the stretchable conductor sheet forming paste 3 on the fabric 1 to expand and contract.
- the step (E) of forming the stretchable carbon 5 (electrode part) on the conductive conductor sheet 3 and the step (F) of separating these laminates from the temporary support 2 may be included.
- a printing method As a printing method, a screen printing method, a lithographic offset printing method, a paste jet method, a flexographic printing method, a gravure printing method, a gravure offset printing method, a stamping method, a stencil method, and the like can be used. It is preferable to use a stencil method. A method of directly drawing wiring using a dispenser or the like may be interpreted as printing in a broad sense.
- Printing is a method of obtaining a textile product such as clothing by printing a predetermined pattern on a fabric such as a woven fabric, a knitted fabric, a nonwoven fabric, or synthetic leather, which is a raw fabric of clothing or textile product, and then cutting and sewing. It is also possible to print in the state of a finished textile product or a sewing intermediate.
- the paste for forming a stretchable conductor sheet on a fabric in advance or partially after a flexible resin material such as polyurethane resin or rubber is applied as a base.
- the cloth may be temporarily hardened with a water-soluble resin to facilitate handling for printing. Further, it may be temporarily fixed to a harder plate material for printing.
- Garment with wiring obtained by printing a paste for forming a stretchable conductor sheet directly on the fabric partially enters the fabric of the fabric whose base and / or stretchable conductor are the base material, realizing strong adhesion it can. Even when printing via the underlayer, a stretchable conductor sheet-forming paste and a material with good adhesion can be appropriately selected for the underlayer, so that it is possible to obtain a garment having an electric wiring layer having good adhesion. it can.
- the wiring made of the stretchable conductor sheet of the present invention can be provided with a stretchable insulating cover coat by a printing method or a laminating method as necessary.
- a surface layer made of a composition in which carbon particles are mainly used as conductive fillers can be provided as conductive particles on the electrode surface intended to come into contact with the human body surface.
- the composition using such carbon particles as the main component of the conductive filler is preferably a carbon paste using the same flexible resin as that of the stretchable conductor sheet of the present invention as a binder.
- gold or tin can be plated on a portion used as an electrical contact with the discrete component.
- a fabric having stretchable wiring can be produced by printing an electrical wiring pattern on an intermediate medium using the above-described paste for forming a stretchable conductor sheet and transferring it to the fabric (see FIG. 2).
- the manufacturing method includes a step (A) of preparing the release support 6, a step (B) of partially forming the stretchable carbon 5 (electrode part) on the release support 6, and the release support 6.
- the step (C) of forming the stretchable cover 4 (insulating portion) in a portion other than the stretchable carbon 5 (electrode portion), on the stretchable carbon 5 (electrode portion) and the stretchable cover 4 (insulating portion) A step (D) of forming the stretchable conductor sheet 3 by printing the stretchable conductor sheet forming paste 3, and applying an adhesive 7 on the stretchable conductor sheet 3 and on the end of the stretchable cover 4 (insulating portion).
- the process (E), the process (F) which transfers the obtained laminated body to the fabric 1, and the process (G) which removes the mold release support body 6 may be included.
- a printing method similar to direct printing can be selected as appropriate.
- a cover coat layer, a composition layer using carbon particles as a main component of the conductive filler, and the like can be provided.
- the stretchable conductor sheet of the present invention has thermoplasticity, and can be transferred by thermocompression bonding to the fabric.
- a hot melt layer can be formed on a wiring pattern printed on an intermediate medium in advance as a base layer, and then transferred to a fabric.
- a hot melt layer may be provided in advance on the fabric side as an image receiving layer.
- a thermoplastic urethane resin or a flexible resin similar to the binder component of the paste for forming a stretchable conductor sheet of the present invention can be used.
- a so-called release sheet such as a polymer film or paper having a release layer on the surface may be used as the intermediate medium.
- a film, sheet, plate, or the like having a surface made of a difficult-to-adhere material such as a fluorine resin, a silicone resin, or polyimide can be used.
- a metal plate such as stainless steel, hard chrome-plated steel plate, or aluminum plate.
- the component constituting the stretchable cover preferably contains, for example, a flexible resin, an epoxy resin, a curing agent, and a solvent from the viewpoint of exhibiting stretchability similar to that of the stretchable conductor sheet.
- a stretchable cover constitutes an insulating portion for the stretchable conductor sheet.
- the component constituting the stretchable carbon preferably contains a flexible resin, conductive carbon, and a solvent from the viewpoint of exhibiting stretchability similar to that of the stretchable conductor sheet or stretchable cover.
- the conductive carbon include ketjen carbon and nanocarbon tubes.
- Such stretchable carbon constitutes the electrode portion of the stretchable conductor sheet.
- the elongation percentage of the stretchable conductor sheet can be calculated by the following formula.
- L0 represents the distance between the marked lines of the test pieces, and ⁇ L0 represents the increase in the distance between the marked lines of the test pieces.
- the sheet resistance at the time of extension was read as a value 30 seconds after reaching a predetermined degree of extension.
- Elongation rate (%) ( ⁇ L0 / L0) ⁇ 100
- the specific resistance of the stretchable conductor sheet may be measured as follows. Thickness gauge SMD-565L (manufactured by TECLOCK) was used for the film thickness, and sheet resistance was measured for four test pieces using Loresta-GP MCP-T610 (manufactured by Mitsubishi Chemical Analytech), and the average value was used.
- the isotropy is evaluated based on the specific resistance when the coating direction is extended by 40% and the specific resistance when the direction is extended by 40% perpendicular to the coating direction. That is, in both directions perpendicular to each other, the rate of change of the specific resistance when stretched in the stretched direction when stretched by 40% of the original length is less than ⁇ 10%, preferably ⁇ 9.0% or less. ⁇ 8.0% or less is more preferable, and ⁇ 7.5% or less is more preferable.
- the twist resistance of the stretchable conductor sheet of the second invention can be evaluated based on the change in specific resistance after repeating the twist cycle of the twist test 100 times.
- the torsion test uses a sample with a width of 10 mm and a length of 100 mm (fixed at one end in the longitudinal direction of the sample and twisted by rotation of the other end), and the torsion cycle is twisted by 10 rotations (3600 °) in the positive direction. Return, twisted in the negative direction 10 turns ( ⁇ 3600 °), and returned to the initial state.
- the specific resistance of the stretchable conductor sheet can be calculated under the same conditions as in the first invention.
- the specific resistance (henceforth a specific resistance change after a torsion test) of the elastic conductor sheet after repeating the twist cycle of the said torsion test 100 times is 3.0 times the initial specific resistance. Is preferably within 2.8 times, more preferably within 2.6 times, still more preferably within 2.4 times, even more preferably within 2.2 times, and particularly preferably. Is within 2.0 times.
- the stretchable conductor sheet has a porosity of 10% by volume to 50% by volume, preferably 15% by volume to 50% by volume, more preferably 15% by volume to 48% by volume, Preferably they are 16 volume% or more and 46 volume% or less. If the porosity is small, the washing durability may be reduced. On the other hand, if the porosity is large, stretchability and conductivity may be lowered.
- the porosity of the stretchable conductor sheet can be calculated from the apparent specific gravity and the actual specific gravity obtained from the charging ratio.
- the compression resistance of the stretchable conductor sheet of the third invention can be evaluated based on a change in specific resistance after repeating 10% compression 100 times (hereinafter, referred to as a specific resistance change after compression test).
- Specific resistance change (times) specific resistance of stretchable conductor sheet after 100% compression 100 times / specific resistance of stretchable conductor sheet in initial state
- the specific resistance of the stretchable conductor sheet can be calculated under the same conditions as in the first invention.
- the specific resistance of the stretchable conductor sheet after repeating 10% compression 100 times is preferably within 2.4 times the initial specific resistance, more preferably within 2.2 times, and even more preferably. Is within 2.0 times, particularly preferably within 1.8 times. If the stretchable conductor sheet of the present invention falls within such a change in specific resistance after compression, it can be said that the sheet has sufficient compression resistance.
- the stretchable conductor sheet of the third invention When the stretchable conductor sheet of the third invention is used for washing, the change in specific resistance after washing in the stretchable conductor sheet is small, and the washing durability is excellent.
- JIS L0844 is used as the washing condition, and the washing durability is calculated by calculating the specific resistance of the elastic conductor sheet after washing and the initial specific resistance of the elastic conductor sheet.
- Specific resistance / initial specific resistance of stretchable conductor sheet That is, using a machine washing machine and a washing net, after 5 consecutive washings, one shade is one cycle and this is repeated 10 cycles, and the specific resistance of the stretchable conductor sheet and the initial stretchability before washing Washing durability may be evaluated by using a ratio with the specific resistance of the conductor sheet (hereinafter, sometimes referred to as washing durability specific resistance change) as an index.
- the specific resistance of the stretchable conductor sheet after 10 cycles of 5 consecutive washings and 1 shade drying is preferably within 4.0 times, more preferably 3.5 times the initial specific resistance. Is more preferably within 3.0 times, and even more preferably within 2.5 times. If the stretchable conductor sheet of the present invention is within such a change in specific resistance after washing, it can be said that it has sufficient washing durability.
- Mooney viscosity was measured using an SMV-300RT “Mooney Viscometer” manufactured by Shimadzu Corporation.
- ⁇ Elastic modulus> The flexible resin was heat compression molded into a sheet shape having a thickness of 200 ⁇ 20 ⁇ m, and then punched into a dumbbell mold defined by ISO 527-2-1A to obtain a test piece. A tensile test was performed by a method specified in ISO 527-1 to obtain an elastic modulus.
- ⁇ Average particle size> The average particle size was measured using a light scattering type particle size distribution measuring device LB-500 manufactured by Horiba.
- composition analysis of inorganic particles was performed using a fluorescent X-ray analyzer (fluorescent X-ray analyzer system 3270, manufactured by Rigaku Corporation), and the amounts of Al component and Si component were measured.
- the deposition amount of the Al component and Si component is calculated by converting the detected Al component and the metal compound of the Si component into oxides (that is, the Al component is converted into Al 2 O 3 and the Si component is converted into SiO 2 ). To express.
- the elongation rate was calculated by the following formula.
- L0 represents the distance between the marked lines of the test pieces, and ⁇ L0 represents the increase in the distance between the marked lines of the test pieces.
- the sheet resistance at the time of extension was read as a value 30 seconds after reaching a predetermined degree of extension.
- Elongation rate (%) ( ⁇ L0 / L0) ⁇ 100
- the elongation evaluation of the conductive film is the direction in which the direction in which the conductive paste is applied is defined as the elongation direction of the test piece (in the table, indicated as specific resistance at the time of application direction elongation) and the direction orthogonal to the application direction.
- the direction of extension of the test piece in the table, indicated as specific resistance during vertical extension in the coating direction.
- FIG. 3 shows a photograph of a cross section obtained by cutting Example 31 shown in Table 4-3 below in the thickness direction at a magnification of 1000 with a scanning electron microscope.
- the release PET film was squeegee-coated with a paste for forming a stretchable conductor sheet and dried and cured under predetermined conditions to obtain a stretchable conductor sheet having a thickness of 100 ⁇ m.
- the obtained stretchable conductor sheet was punched into a circle having a diameter of 50 mm, and 10 sheets were stacked, and this was used as a sample.
- the specific resistance of 10 samples was measured at the center of each test piece, and the average value was obtained. This was defined as a specific resistance (initial specific resistance) ⁇ i before the test.
- a universal testing machine manufactured by Shimadzu Corporation was used, and the lower side was a fixed thick plate, a sample was placed on the thick plate, and a metal cylinder with a diameter of 20 mm and a height of 10 mm with a flat bottom surface was placed thereon. Then, a cycle of 10% compression and release in the thickness direction was applied 100 times (1 cycle / second) by applying a ball seat type plank from the top. The specific resistance at the center of each sheet (10 sheets) of the sample after the compression operation was measured, and the average value was obtained. This was defined as a specific resistance ⁇ e after 100 compression tests.
- Washing conditions were performed in accordance with JIS L0844. Specifically, using a machine washing machine, a washing net, and a detergent (attack made by Kao Co., Ltd.), after 5 consecutive washings, 10 shades were repeated with 1 shade drying as 1 cycle. The specific resistance of the stretchable conductor sheet after washing 50 times was measured, the change from the initial specific resistance (specific resistance after washing / initial specific resistance) was determined, and the washing durability was evaluated.
- R1 to R3 shown in Table 1 below were used as the flexible resin.
- [Production example] ⁇ Polymerization of flexible resin (synthetic rubber material)> In a stainless steel reaction vessel equipped with a stirrer and a water cooling jacket, 54 parts by mass of butadiene, 46 parts by mass of acrylonitrile, 270 parts by mass of deionized water, 0.5 parts by mass of sodium dodecylbenzenesulfonate, naphthalenesulfonic acid 2.5 parts by mass of sodium condensate, 0.3 part by mass of t-dodecyl mercaptan, 0.2 part by mass of triethanolamine, and 0.1 part by mass of sodium carbonate were charged.
- Table 1 shows the evaluation results of the obtained flexible resin (synthetic rubber resin) (R1). Thereafter, the same operations were carried out by changing the charged raw materials, the polymerization conditions, the washing conditions, etc., and the flexible resins (R2) and (R3) shown in Table 1 were obtained.
- the abbreviations in the table are as follows.
- NBR acrylonitrile butadiene rubber
- Inorganic particles P1 barium sulfate particles
- barium sulfate particles surface-treated with SiO 2 and Al 2 O 3 were prepared by the following procedure.
- a Werman pump having a suction port diameter of 40 mm, a discharge port diameter of 25 mm, an internal volume of 850 mL, and an impeller rotation speed of 2380 rpm was used as a reaction tank.
- Inorganic particles P2 titanium oxide particles R-62N manufactured by Sakai Chemical Industry were used. The average particle size was 0.3 ⁇ m. The titanium oxide particles were surface-treated with SiO 2 and Al 2 O 3 . The content of SiO 2 and Al 2 O 3 was more than 0.1% by mass. The aspect ratio was 1.4.
- Inorganic particles P3 (barium sulfate particles)> As the inorganic particles P3, precipitated barium sulfate TS-1 manufactured by Takehara Chemical Co., Ltd. was used. As a result of analysis in the same manner as the inorganic particles P1, it was determined that the content of SiO 2 was 0.1% by mass or less, the content of Al 2 O 3 was 0.1% by mass or less, and it was not substantially contained. The average particle size determined by the same method was 0.6 ⁇ m. The aspect ratio was 1.5.
- Inorganic particles P4 barium sulfate particles
- plate-like barium sulfate HF manufactured by Sakai Chemical Industry Co., Ltd. was used.
- the average particle size determined by the same method was 4.0 ⁇ m.
- the aspect ratio was 13.3.
- D1 to D4 shown in Table 3 below were used as the conductive particles (silver particles).
- conductive particles D1 scaly silver powder (FA-D-3 manufactured by DOWA Electronics Co., Ltd., average particle size 1.3 ⁇ m) was used.
- ⁇ Conductive particle D2> As the conductive particles D2, amorphous aggregated silver powder (G-35 manufactured by DOWA Electronics Co., Ltd., average particle size 6.0 ⁇ m) was used.
- conductive particles D3 amorphous aggregated silver powder obtained by wet-classifying the conductive particles D2 (G-35 manufactured by DOWA Electronics) was used.
- the average particle size was 2.1 ⁇ m.
- conductive particles D4 spherical silver particles D4
- spherical silver powder AG2-1 manufactured by DOWA Electronics, average particle size 1.3 ⁇ m
- Example 1 [Paste for forming elastic conductor sheet] As shown in Table 4-1, each component was blended and then kneaded in a three-roll mill to prepare stretchable conductor sheet forming pastes of Examples 11 to 17 and Comparative Examples 11 to 13.
- Example 2 [Paste for forming elastic conductor sheet] As shown in Table 4-2, each component was blended and then kneaded in a three-roll mill to prepare stretchable conductor sheet forming pastes of Examples 21 to 27 and Comparative Examples 21 to 23.
- Example 3 [Paste for forming elastic conductor sheet] As shown in Table 4-3, each component was blended and then kneaded in a three-roll mill to prepare stretchable conductor sheet forming pastes of Examples 31 to 39 and Comparative Examples 31 and 32.
- Polyurethane resin (“Ulliano (registered trademark) W600” manufactured by Arakawa Chemical Industries, Ltd. (polyester anionic aqueous polyurethane, urethane resin content 35% by mass, isopropyl alcohol 5% by mass, viscosity 300-30 mPa ⁇ s (25 ° C.)) 9
- a resin for forming an insulating layer was prepared by mixing 4 parts by mass of a mixed solution of 1 part by mass with a thickener (“Act Gel AP200” manufactured by Senka Co., Ltd., acrylic acid polymer) and 10 parts by mass of water.
- the insulating layer forming resin is applied to the release sheet so that the film thickness (dry film thickness) of the first insulating layer is 35 ⁇ m, and is dried in a hot air drying oven at 100 ° C. for 20 minutes or more to obtain the first insulation. A layer was formed.
- Example 12 the paste for forming a stretchable conductor sheet prepared in Example 12, Example 22, or Example 31 was applied onto the release sheet so as to have a dry film thickness of 60 ⁇ m, and then heated in a 120 ° C. hot air drying oven. By drying for 30 minutes or more, a sheet-like conductive layer with a release sheet was produced. The conductive layer attached to this release sheet was cut into a length of 15 cm and a width of 1 cm, the release sheet was peeled off, and a conductive layer was laminated on the first insulating layer.
- the same insulating layer forming resin as that in which the first insulating layer is formed is applied to a region having a length of 10 cm and a width of 3 cm so as to cover the laminated conductive layer so as to have a dry film thickness of 35 ⁇ m.
- a second insulating layer was formed to obtain a conductive laminate.
- This laminate was cut into a horseshoe shape to produce a horseshoe wiring (see FIG. 7). All of the obtained horseshoe-shaped wirings exhibited expansion / contraction characteristics.
- a water-dispersible urethane resin is coated to a rectangular pattern of 50 mm from the front hem to the collar of a knit sportswear (shirt) and a length of 450 mm so that the dry basis weight is 50 mg / cm 2 , dried and cured, and then urethane. An underlayer was formed.
- Example 11 Two wires having a width of 10 mm and a length of 430 mm were placed on the urethane tree layer so that the distance from the end of the urethane base layer was approximately 10 mm, so that the dry film thickness was 28 ⁇ m, Example 11, Using the stretchable conductor sheet forming paste obtained in Example 21 or Example 32, it was formed by screen printing and dried and cured in a dry oven at 120 ° C. for 30 minutes to obtain a sports shirt with wiring. Each hem 15 mm and collar 15 mm of the obtained wiring was covered with a masking tape, coated with water-dispersible urethane, and further dried to insulate the wiring.
- the masking tape is peeled off, and a stretchable carbon paste C17 (flexible resin (R1) 24 parts by mass, ketjen black 4 parts by mass, isophorone 30 parts by mass) is screen-printed so as to cover the part covered with the masking tape.
- a stretchable carbon paste C17 flexible resin (R1) 24 parts by mass, ketjen black 4 parts by mass, isophorone 30 parts by mass
- a stainless steel hook is sewn to the electrode hem and collar of the resulting sports shirt with wiring, using a combination of sewing thread and conductive thread, and detachable mini pins using both hooks on the hem and collar.
- a jack was attached. When a headphone stereo was connected through the sports shirt with a mini pin jack, music reproduced with good sound quality could be enjoyed both at rest and during jogging.
- a synthetic leather glove is put on a flat handprint made of a 5 mm-thick plastic plate so as not to be wrinkled, and Example 11, Example 21, or Example 32 is used by using a screen printer.
- the paste for forming a stretchable conductor sheet obtained in the above was printed in the shape of a conductive pattern shown in FIG. Subsequently, it dried at 100 degreeC for 120 minutes, and the glove with a wiring was obtained.
- a lead wire was attached to the electrode corresponding to the wrist of the obtained glove with wiring using a conductive adhesive, and the resistance change of the wiring according to the bending of each joint was read by a multi-channel resistance measuring instrument.
- a stretchable insulating resin ink (7.5 parts by weight of epoxy resin, 30 parts by weight of a flexible resin (R2), 0.5 parts by weight of a curing agent, which becomes a cover coat layer on a release PET film having a thickness of 125 ⁇ m.
- a predetermined pattern was dried and cured.
- the pattern corresponds to a land portion that covers the periphery of the electrode portion in a ring shape and an insulating coat portion that covers an electric wiring portion made of a stretchable conductor.
- the land portion covers the outer periphery 3 mm of the electrode pattern, which will be described later, and the width of the ring is 5 mm.
- the insulating coat part has a width of 16 mm and covers a stretchable conductor having a width of 10 mm.
- the dry thickness of the cover coat layer was adjusted to 20 ⁇ m.
- stretchable carbon paste (C17) (flexible resin (R1), 4 parts by mass of ketjen black, and 30 parts by mass of isophorone were preliminarily stirred in the part to be the electrode part, and then kneaded and dispersed in a three-roll mill. Printed) and dried and cured.
- the electrode part is a circle having a diameter of 50 mm arranged concentrically with the ring of the cover coat layer printed earlier.
- the dry film thickness of the stretchable carbon paste layer was 15 ⁇ m.
- the electrode part and the electric wiring part were printed using the paste for forming a stretchable conductor sheet obtained in Example 12, Example 22, or Example 31 to be a stretchable conductor.
- the electrode portion has a donut shape with a diameter of 50 mm, and is arranged concentrically with the ring-shaped land portion.
- the electric wiring part has a width of 10 mm.
- the thickness of the stretchable conductor portion was repeatedly printed and dried, and the dry thickness was 50 ⁇ m (see FIG. 5).
- the stretchable insulating resin ink used for the cover coat layer is printed so as to overlap all the printed patterns including the cover coat layer, and the solvent is intentionally left, so that tackiness remains, 60 ° C. for 10 minutes.
- the transfer operation was performed to obtain a transferable printed electrode wiring sheet.
- the transferable printed electrode wiring obtained by the above steps is superimposed on a predetermined portion of the sports shirt turned upside down, and hot pressed to transfer the printed material from the release PET film to the sports shirt, and further at 115 ° C. for 30 minutes. It dried and obtained the sports shirt with an electrical wiring (refer FIG. 6).
- the obtained sports shirt with electrical wiring has a circular electrode with a diameter of 50 mm at the intersection of the left and right posterior axilla lines and the seventh rib, and further an electrical wiring with a stretchable conductor composition with a width of 10 mm from the circular electrode to the center of the chest Is formed inside.
- the wiring extending from the left and right electrodes to the center of the chest has a gap of 5 mm at the center of the back of the neck, and both are not short-circuited (see FIG. 6).
- a stainless steel hook is attached to the front side of the sports shirt at the center of the back of the neck without the cover coat layer on the left and right wiring parts, and a thin metal wire is twisted to ensure electrical continuity with the wiring parts on the back side.
- the elastic conductor composition layer and the stainless steel hook were electrically connected using a conductive thread.
- a sports shirt incorporating a heart rate measurement function was produced as described above. The shirt was worn by the subject, and electrocardiographic data was obtained for resting, walking, running, cycling, driving, and sleeping.
- the obtained electrocardiogram data has low noise, high resolution, and quality that can be analyzed from the heartbeat interval change, electrocardiogram waveform, etc., as the electrocardiogram mental state, physical condition, fatigue level, sleepiness, tension level, etc. It was.
- the stretchable conductor sheet forming paste according to the present invention it is possible to form an electrical wiring directly or indirectly on a textile or fabric product such as a stretchable textile or fabric using a printing method.
- the electrical wiring on the fiber product obtained by the paste for forming the stretchable conductor sheet of the present invention is not limited to the application examples shown in the application examples, but information on the human body, that is, biopotentials such as myoelectric potential and cardiac potential. Wearable device for detecting biological information such as body temperature, pulse, blood pressure etc.
- wearable device incorporating a sensor for measuring clothes pressure, clothing incorporating an electric heating device
- Clothing that uses body pressure to measure body size, sock-type devices to measure the pressure on the soles, clothing with flexible solar cell modules integrated in textiles, wiring parts such as tents and bags, joints It can be applied to wiring parts such as low-frequency treatment devices and thermal treatment devices, and sensing units for bending degree.
- Such wearable devices can be applied not only to the human body but also to animals such as pets and livestock, or mechanical devices having a telescopic part, a bent part, etc. It can also be used as electrical wiring for systems that are connected. It is also useful as a wiring material for patchable devices that are used by being attached to human skin and mucous membranes, implant devices that are used by being embedded in the body, and edible devices that are applied to the digestive tract.
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Abstract
Description
[捻り試験:
試料:幅10mm、長さ100mm(試料の長手方向の片端固定、他の片端の回転による捻り)
捻りサイクル:正方向10回転(3600°)捻り、初期状態への戻り、負方向10回転(-3600°)捻り、初期状態への戻り]
第一~第三の発明で用いる導電性粒子は共通しており、特に第三の発明では、導電性粒子として、平均粒子径が0.8~10μmの凝集銀粒子を用いることが好ましい。導電性粒子は、比抵抗が1×10-1Ωcm以下の物質からなり、粒子径が100μm以下の粒子が好ましい。
第一の発明では、Al、Siの一方または両方の水酸化物及び/又は酸化物によって表面処理されている無機粒子を用い、第二の発明では、アスペクト比が1.5未満である無機粒子を用いる。第三の発明では、無機粒子を用いなくてもよく、無機粒子を用いる場合は、アスペクト比が1.5未満であり、平均粒子径が凝集銀粒子の0.5倍以下である無機粒子を用いることが好ましい。
第一~第三の発明で用いる柔軟性樹脂は共通しており、引張弾性率が1MPa以上1000MPa以下の柔軟性樹脂を用いる。
等方性(%)={(塗布方向の比抵抗/塗布方向に対して直角方向の比抵抗)-1}×100
伸長率(%)=(ΔL0/L0)×100
比抵抗(Ωcm)=Rs(Ω□)×t(cm)
比抵抗変化(倍)=10%圧縮を100回繰り返した後の伸縮性導体シートの比抵抗/初期状態の伸縮性導体シートの比抵抗
得られた柔軟性樹脂をNMR分析して得られた組成比から、モノマーの質量比による質量%に換算した。
島津製作所製のSMV-300RT「ムーニービスコメータ」を用いてムーニー粘度を測定した。
樹脂を灰化処理し、得られた灰分を塩酸抽出し、原子吸光法にてナトリウム、カリウムの含有量を求め、両者を合計した。
柔軟性樹脂を厚さ200±20μmのシート状に加熱圧縮成形し、次いでISO 527-2-1Aにて規定されるダンベル型に打ち抜き、試験片とした。ISO 527-1に規定された方法で引っ張り試験を行って弾性率を求めた。
堀場製作所製の光散乱式粒径分布測定装置LB-500を用いて平均粒子径を測定した。
無機粒子の組成分析を蛍光X線分析装置(蛍光X線分析装置システム3270、理学電機株式会社製)を使用し、Al成分、Si成分量を測定した。なお、Al成分、Si成分の被着量は、検出されたAl成分、およびSi成分の金属化合物を酸化物換算(即ち、Al成分はAl2O3、Si成分はSiO2として換算)して表す。
伸縮性導体シートを幅10mm、長さ140mmにカットして試験片を作製した。自然状態(伸長率0%)の伸縮性導体シート試験片のシート抵抗と膜厚を測定し、比抵抗を算出した。膜厚はシックネスゲージ SMD-565L(TECLOCK社製)を用い、シート抵抗はLoresta-GP MCP-T610(三菱化学アナリテック社製)を用いて試験片4枚について測定し、その平均値を用いた。比抵抗は以下の式により算出した。ここで、Rsは各条件で測定されたシート抵抗、tは各条件で測定された膜厚を示す。比抵抗(Ωcm)=Rs(Ω□)×t(cm)
伸長率(%)=(ΔL0/L0)×100
伸縮性導体シート形成用ペーストの塗布方向と、塗布方向に対して直角の方向にそれぞれ幅20mm、長さ50mmにカットして試料片を作製した。それぞれの試験片を用いて、伸長率40%時の比抵抗を測定した。塗布方向と、塗布方向に対して直角方向の試験片での比抵抗の変化率(表では、40%伸長時比抵抗変化率と表記)を比較して等方性の評価とした。
等方性(%)={(塗布方向の比抵抗/塗布方向に対して直角方向の比抵抗)-1}×100
初期状態の伸縮性導体シートの比抵抗と、捻り試験の捻りサイクルを100回繰り返した後の伸縮性導体シートの比抵抗とを算出し、以下の式により比抵抗の変化(表では、捻り試験後比抵抗変化と表記)を算出した。捻り試験は、試料として幅10mm、試験長さ100mm(試料の長手方向の片端を固定し、片端を回転させることにより捻りを加える。)の試験片を用い、捻りサイクルは正方向に10回転(3600°)捻り、初期状態に戻し、負方向に10回転(-3600°)捻り、初期状態に戻すサイクルとした。
比抵抗の変化(倍)=100回捻りサイクルを繰り返した後の伸縮性導体シートの比抵抗/初期状態の伸縮性導体シートの比抵抗
伸縮性導体シートの空隙率は、見かけ比重と仕込み比から求められる実比重とから算出した。下記表4-3に示した実施例31を厚さ方向に切断した断面を走査型電子顕微鏡で1000倍で撮影した写真を図3に示す。
離型PETフィルムに伸縮性導体シート形成用ペーストをスキージコーティングし、所定の条件で乾燥硬化させて厚さ100μmの伸縮性導体シートを得た。得られた伸縮性導体シートを、直径50mmの円形に打ち抜き、10枚重ね、これを試料とした。各試験片の中央部にて10枚の試料の比抵抗を測定し、平均値を求めた。これを試験前の比抵抗(初期比抵抗)ρiとした。
比抵抗変化(倍)=ρe/ρi
洗濯の条件は、JIS L0844に準拠して行った。具体的には、機械洗濯器、洗濯ネット、洗剤(花王株式会社製アタック)を用い、5回連続洗濯後、1回陰干を1サイクルとして10サイクル繰り返した。50回洗濯後の伸縮性導体シートの比抵抗を測定し、初期比抵抗との変化(洗濯後の比抵抗/初期比抵抗)を求め、洗濯耐久性を評価した。
[製造例]
<柔軟性樹脂(合成ゴム材料)の重合>
攪拌機、水冷ジャケットを備えたステンレス鋼製の反応容器に、ブタジエンを54質量部、アクリロニトリルを46質量部、脱イオン水を270質量部、ドデシルベンゼンスルホン酸ナトリウムを0.5質量部、ナフタレンスルホン酸ナトリウム縮合物を2.5質量部、t-ドデシルメルカプタンを0.3質量部、トリエタノールアミンを0.2質量部、炭酸ナトリウムを0.1質量部仕込んだ。窒素を流しながら浴温度を15℃に保ち、静かに攪拌した。次いで過硫酸カリウム0.3質量部を脱イオン水19.7質量部に溶解した水溶液を30分間かけて滴下し、さらに20時間反応を継続した後、ハイドロキノン0.5質量部を脱イオン水19.5質量部に溶解した水溶液を加えて重合停止操作を行った。なお、重合温度は15℃であった。
NBR:アクロニトリルブタジエンゴム
SBR:スチレンブタジエンゴム(スチレン/ブタジエン=50/50質量%)
<無機粒子P1(硫酸バリウム粒子)>
無機粒子P1として、SiO2およびAl2O3によって表面処理されている硫酸バリウム粒子を次の手順で調製した。吸込口径40mm、吐出口径25mm、内容積850mL、インペラー回転数2380rpmのワーマンポンプを反応槽として用い、このポンプに濃度110g/L(1.1mol/L)、温度30℃の硫酸水溶液を700L/hの一定流量にて吸い込ませると共に、120g/L(0.71mol/L)、温度50℃の硫化バリウム水溶液を600L/hの一定流量にて吸い込ませることで調製した水スラリー(固形分95g/L)1000mLを60℃に昇温した。SiO2として4.0g相当量の珪酸ナトリウムを純水100mLで希釈して20分で滴下し、次いで、Al2O3として2.0g相当量のアルミン酸ソーダを純水100mLで希釈し、20分で滴下した。さらに反応系を70℃に昇温し、30分撹拌後、希硫酸を用いて30分かけてpH8に中和した。10分撹拌してから、ろ過し、充分に水洗してから乾燥して、乾燥チップを得て、粗砕した後、気流式粉砕機で粉砕した。得られた粉体では、基材となる硫酸バリウム粒子と被着物の合計100質量%中、SiO2として3.5質量%、Al2O3として1.7質量%が被着していた。動的光散乱法によって測定される平均粒子径は0.3μmであった。アスペクト比は1.3であった。
無機粒子P2として、堺化学工業製酸化チタン粒子R-62Nを用いた。平均粒子径は0.3μmであった。当該酸化チタン粒子は、SiO2及びAl2O3で表面処理されていた。SiO2及びAl2O3含有量は0.1質量%超であった。アスペクト比は1.4であった。
無機粒子P3として、竹原化学工業株式会社製の沈降性硫酸バリウムTS-1を用いた。無機粒子P1と同様に分析した結果、SiO2の含有量は0.1質量%以下、Al2O3の含有量は0.1質量%以下で、実質的に含有しないものと判断した。同様の方法で求めた平均粒子径は0.6μmであった。アスペクト比は1.5であった。
無機粒子P4として、堺化学工業株式会社製の板状硫酸バリウムHFを用いた。無機粒子P1と同様に分析した結果SiO2の含有量は0.1質量%以下、Al2O3の含有量は0.1質量%以下で、実質的に含有しないものと判断した。同様の方法で求めた平均粒子径は4.0μmであった。アスペクト比は13.3であった。
<導電性粒子D1>
導電性粒子D1として鱗片状銀粉(DOWAエレクトロニクス社製のFA-D-3、平均粒子径1.3μm)を用いた。
導電性粒子D2として不定形凝集銀粉(DOWAエレクトロニクス社製のG-35、平均粒子径6.0μm)を用いた。
導電性粒子D3(凝集銀粒子D3)として導電性粒子D2(DOWAエレクトロニクス社製のG-35)を湿式分級した不定形凝集銀粉を用いた。平均粒子径は2.1μmであった。
導電性粒子D4(球状銀粒子D4)として球状銀粉(DOWAエレクトロニクス社製のAG2-1、平均粒子径1.3μm)を用いた。
[伸縮性導体シート形成用ペースト]
表4-1の通りに、各成分を配合した後、3本ロールミルにて混練し実施例11~17及び比較例11~13の伸縮性導体シート形成用ペーストを調製した。
表4-1に示した実施例11~17及び比較例11~13の伸縮性導体シート形成用ペーストをテフロン(登録商標)シート上にアプリケーターによりコーティングして製膜し(塗布方向(A))、120℃で20分間乾燥し、厚さ50μmの伸縮性導体シートを形成した。得られた伸縮性導体シートについて、上述した方法にて、自然状態(伸長率0%)の比抵抗を測定した。また、塗布方向(A)における40%伸張時及び塗布方向(A)に対して垂直方向(B)における40%伸張時の比抵抗をそれぞれ測定し、比抵抗の変化率(40%伸長時比抵抗変化率)を算出した。結果を下記表4-1に示す。下記表4-1には、参考データとして、20%に伸長したときの比抵抗を測定した結果も併せて示した。
[伸縮性導体シート形成用ペースト]
表4-2の通りに、各成分を配合した後、3本ロールミルにて混練し実施例21~27及び比較例21~23の伸縮性導体シート形成用ペーストを調製した。
実施例21~27及び比較例21~23の伸縮性導体シート形成用ペーストをテフロン(登録商標)シート上にアプリケーターによりコーティングして製膜し、120℃で20分間乾燥し、厚さ50μmの伸縮性導体シートを形成した。得られた伸縮性導体シートについて、上述した方法にて、初期状態の伸縮性導体シートの比抵抗と、捻り試験の捻りサイクルを100回繰り返した伸縮性導体シートの比抵抗をそれぞれ測定し、比抵抗の変化(捻り試験の捻りサイクルを100回繰り返した伸縮性導体シートの比抵抗/初期状態の伸縮性導体シートの比抵抗)を算出した。以下、各成分とその量、比抵抗、比抵抗変化を表4-2に示す。
[伸縮性導体シート形成用ペースト]
表4-3の通りに、各成分を配合した後、3本ロールミルにて混練し実施例31~39及び比較例31、32の伸縮性導体シート形成用ペーストを調製した。
実施例31~39及び比較例31、32の伸縮性導体シート形成用ペーストをテフロン(登録商標)シート上にアプリケーターによりコーティングして製膜し、120℃で20分間乾燥し、厚さ50μmの伸縮性導体シートを形成した。得られた伸縮性導体シートについて、上述した方法にて、初期比抵抗及び10%圧縮時の比抵抗をそれぞれ測定し、比抵抗の比を算出した。また、洗濯後の比抵抗(洗濯耐久性)、洗濯耐久性比抵抗変化(洗濯後の比抵抗/初期比抵抗)を評価した。以下、各成分とその量、空隙率、比抵抗、比抵抗変化、洗濯後の比抵抗(洗濯耐久性)、洗濯耐久性比抵抗変化(洗濯後の比抵抗/初期比抵抗)を表4-3に示す。
上記実験1~実験3で得られた伸縮性導体シート形成用ペーストを導電層に用い、当該シートの両面に第1絶縁層及び第2絶縁層を設けた積層体を作製し、これを馬蹄形状に切断して馬蹄配線(波形配線)を作製した。
ポリウレタン樹脂(荒川化学工業社製「ユリアーノ(登録商標)W600」(ポリエステル系アニオン性水性ポリウレタン、ウレタン樹脂含有量35質量%、イソプロピルアルコール5質量%、粘度300~30mPa・s(25℃))9質量部に、増粘剤(センカ社製「アクトゲルAP200」、アクリル酸系重合物)1質量部と水10質量部との混合液4質量部を混合して、絶縁層形成用樹脂とした。
ニット製スポーツウェア(シャツ)の前側の裾から襟部まで50mm、長さ450mmの矩形パターンに、水分散性ウレタン樹脂を乾燥目付で50mg/cm2となるようにコーティングし、乾燥硬化させてウレタン下地層を形成した。次いでウレタン樹層上に幅10mm、長さ430mmの配線2本をウレタン下地層の端からの距離がおおむね10mmとなるように配置して、乾燥膜厚が28μmとなるように、実施例11、実施例21、または実施例32で得られた伸縮性導体シート形成用ペーストを用いて、スクリーン印刷により形成し、ドライオーブンにて120℃30分間、乾燥硬化し、配線付きスポーツシャツを得た。得られた配線の各々裾部15mm、襟部15mmをマスキングテープで覆い、水分散性ウレタンをコーティングし、さらに乾燥することにより、配線部の絶縁を施した。さらにマスキングテープを剥がし、マスキングテープで覆われていた部分を覆うようにスクリーン印刷法にて伸縮性カーボンペーストC17(柔軟性樹脂(R1)24質量部、ケッチェンブラック4質量部、イソホロン30質量部を予備撹拌した後に、三本ロールミルにて混練分散したもの)を乾燥膜厚15μmとなるように印刷し、120℃20分間乾燥硬化し、その部分を電極部とした。
5mm厚のプラスチック板で作られた平面状の手形に、合成皮革製の手袋を、皺が出ないように履かせ、スクリーン印刷機を用いて、実施例11、実施例21、または実施例32で得られた伸縮性導体シート形成用ペーストを、図4に示す導電パターン状に印刷した。次いで、100℃にて120分間乾燥し、配線付き手袋を得た。得られた配線付き手袋の手首相当部分の電極に導電性接着剤を用いてリード線を取り付け、各関節の屈曲に応じた配線の抵抗変化が多チャンネルの抵抗測定器により読み取れるように構成した。
厚さ125μmの離型PETフィルムに、まずカバーコート層となる伸縮性絶縁樹脂インク(C18)(エポキシ樹脂7.5質量部、柔軟性樹脂(R2)30質量部、硬化剤0.5質量部をイソホロン30質量部に混合溶解したもの)を所定のパターンに印刷し、乾燥硬化した。パターンは電極部の周囲をリング状にカバーするランド部と伸縮性導体から成る電気配線部をカバーする絶縁コート部に相当する。ランド部は後述する電極パターンの外周3mmを覆い、リングの幅は5mmである。絶縁コート部は幅16mmであり、幅10mmとなる伸縮性導体をカバーする。カバーコート層の乾燥厚さは20μmとなるように調製した。
2:支持体
3:伸縮性導体シート形成用ペースト(伸縮性導体シート)
4:伸縮性カバー
5:伸縮性カーボン
6:離型支持体
7:接着剤
Claims (17)
- 少なくとも導電性粒子、
Al、Siの一方または両方の水酸化物及び/又は酸化物によって表面処理されている無機粒子、及び
引張弾性率が1MPa以上1000MPa以下の柔軟性樹脂、を含有する厚さ3~800μmの伸縮性導体シートであって、
直交する2つの方向においていずれも元の長さの40%伸張した際の伸長方向における伸張時の比抵抗の変化率が±10%未満であることを特徴とする伸縮性導体シート。 - 前記無機粒子の配合量が、前記導電性粒子と前記無機粒子の合計100質量%中、2.0~30質量%である請求項1に記載の伸縮性導体シート。
- 前記無機粒子の平均粒子径が前記導電性粒子の平均粒子径より小さい請求項1又は2に記載の伸縮性導体シート。
- 前記導電性粒子の平均粒子径が0.5~20μmであり、前記導電性粒子が銀粒子である請求項1~3のいずれかに記載の伸縮性導体シート。
- 請求項1~4のいずれかに記載の伸縮性導体シートを製造するために使用される伸縮性導体シート形成用ペーストであって、
少なくとも導電性粒子、
Al、Siの一方または両方の水酸化物及び/又は酸化物によって表面処理されている無機粒子、
引張弾性率が1MPa以上1000MPa以下の柔軟性樹脂、及び
溶剤、を含有し、
前記無機粒子の配合量が、前記導電性粒子と前記無機粒子の合計100質量%中、2.0~30質量%であり、
前記柔軟性樹脂の配合量が、前記導電性粒子と前記無機粒子と前記柔軟性樹脂の合計100質量%中、7~35質量%であることを特徴とする伸縮性導体シート形成用ペースト。 - 少なくとも導電性粒子、
アスペクト比が1.5未満である無機粒子、及び
引張弾性率が1MPa以上1000MPa以下の柔軟性樹脂を含有する厚さ3~800μmの伸縮性導体シートであって、
以下の捻り試験の捻りサイクルを100回繰り返した後のシートの比抵抗が、初期比抵抗の3.0倍以内であることを特徴とする伸縮性導体シート。
[捻り試験:
試料:幅10mm、長さ100mm(試料の長手方向の片端固定、他の片端の回転による捻り)
捻りサイクル:正方向10回転(3600°)捻り、初期状態への戻り、負方向10回転(-3600°)捻り、初期状態への戻り] - 前記無機粒子が、Al、Siの一方または両方の水酸化物及び/又は酸化物によって表面処理されている請求項6に記載の伸縮性導体シート。
- 前記無機粒子の配合量が、前記導電性粒子と前記無機粒子の合計100質量%中、2.0~30質量%である請求項6又は7に記載の伸縮性導体シート。
- 前記無機粒子の平均粒子径が前記導電性粒子の平均粒子径より小さい請求項6~8のいずれかに記載の伸縮性導体シート。
- 前記導電性粒子の平均粒子径が0.5~20μmであり、前記導電性粒子が銀粒子である請求項6~9のいずれかに記載の伸縮性導体シート。
- 請求項6~10のいずれかに記載の伸縮性導体シートを製造するために使用される伸縮性導体シート形成用ペーストであって、
少なくとも導電性粒子、
アスペクト比が1.5未満である無機粒子、
引張弾性率が1MPa以上1000MPa以下の柔軟性樹脂、及び 溶剤、を含有し、
前記無機粒子の配合量が、前記導電性粒子と前記無機粒子の合計100質量%中、2.0~30質量%であり、
前記柔軟性樹脂の配合量が、前記導電性粒子と前記無機粒子と前記柔軟性樹脂の合計100質量%中、7~35質量%であることを特徴とする伸縮性導体シート形成用ペースト。 - 少なくとも導電性粒子、及び
引張弾性率が1MPa以上1000MPa以下の柔軟性樹脂、を含有する伸縮性導体シートであって、
空隙率が10体積%以上50体積%以下であることを特徴とする伸縮性導体シート。 - 前記導電性粒子は、平均粒子径が0.8~10μmである凝集銀粒子であり、
更に、アスペクト比が1.5未満であり、平均粒子径が前記凝集銀粒子の0.5倍以下である無機粒子、を含有し、
前記伸縮性導電体シートの厚さは3~800μmであり、
10%圧縮を100回繰り返した後の比抵抗が、初期比抵抗の2.4倍以内である請求項12に記載の伸縮性導体シート。 - 前記無機粒子が、Al、Siの一方または両方の水酸化物及び/又は酸化物によって表面処理されている請求項12又は13に記載の伸縮性導体シート。
- 前記無機粒子の配合量が、前記凝集銀粒子と前記無機粒子の合計100質量%中、2.0~30質量%である請求項12~14のいずれかに記載の伸縮性導体シート。
- 前記無機粒子の平均粒子径が前記凝集銀粒子の平均粒子径より小さい請求項12~15のいずれかに記載の伸縮性導体シート。
- 請求項13~16のいずれかに記載の伸縮性導体シートを製造するために使用される伸縮性導体シート形成用ペーストであって、
少なくとも平均粒子径が0.8~10μmである凝集銀粒子、
アスペクト比が1.5未満であり、平均粒子径が前記凝集銀粒子の0.5倍以下である無機粒子、
引張弾性率が1MPa以上1000MPa以下の柔軟性樹脂、及び
溶剤、を含有し、
前記無機粒子の配合量が、前記凝集銀粒子と前記無機粒子の合計100質量%中、2.0~30質量%であり、
前記柔軟性樹脂の配合量が、前記凝集銀粒子と前記無機粒子と前記柔軟性樹脂の合計100質量%中、7~35質量%であることを特徴とする伸縮性導体シート形成用ペースト。
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CN110233774A (zh) * | 2019-05-28 | 2019-09-13 | 华中科技大学 | 一种Socks代理服务器的分布式探测方法和*** |
CN110233774B (zh) * | 2019-05-28 | 2020-12-29 | 华中科技大学 | 一种Socks代理服务器的探测方法、分布式探测方法和*** |
WO2022059608A1 (ja) * | 2020-09-18 | 2022-03-24 | ナミックス株式会社 | ストレッチャブル導電性ペースト及びフィルム |
US11932771B2 (en) | 2020-09-18 | 2024-03-19 | Namics Corporation | Stretchable conductive paste and film |
WO2023153213A1 (ja) * | 2022-02-10 | 2023-08-17 | 東洋紡株式会社 | 義肢 |
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TWI708266B (zh) | 2020-10-21 |
TWI736363B (zh) | 2021-08-11 |
EP3428220A4 (en) | 2020-02-26 |
US11427689B2 (en) | 2022-08-30 |
US20220363849A1 (en) | 2022-11-17 |
JP6973372B2 (ja) | 2021-11-24 |
TW202040594A (zh) | 2020-11-01 |
JPWO2017154978A1 (ja) | 2019-01-10 |
TW201743340A (zh) | 2017-12-16 |
EP3428220A1 (en) | 2019-01-16 |
US20190077930A1 (en) | 2019-03-14 |
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