CN110366460A - Silver chlorate is coated particle - Google Patents
Silver chlorate is coated particle Download PDFInfo
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- CN110366460A CN110366460A CN201880015339.5A CN201880015339A CN110366460A CN 110366460 A CN110366460 A CN 110366460A CN 201880015339 A CN201880015339 A CN 201880015339A CN 110366460 A CN110366460 A CN 110366460A
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- Prior art keywords
- silver
- silver chlorate
- particle
- chlorate
- coated
- Prior art date
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- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 title claims abstract description 99
- 239000002245 particle Substances 0.000 title claims abstract description 73
- 229910052709 silver Inorganic materials 0.000 claims abstract description 53
- 239000004332 silver Substances 0.000 claims abstract description 53
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 70
- 229910021607 Silver chloride Inorganic materials 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000004020 conductor Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000005016 dendritic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 238000004616 Pyrometry Methods 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
Landscapes
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Powder Metallurgy (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
- Conductive Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
When the present invention provides one kind for example in the conductive paste for being mixed in composition organism electrode, it is able to maintain that stable electric conductivity, and the coating particle of the silver chlorate for cutting down the usage amount of silver.It includes: at least part on surface contains the core of the dendron shape of silver；It is coated at least part of, the silver chlorate coating made of silver chlorate on the surface of the core.
Description
Technical field
The present invention relates to a kind of silver chlorates to be coated particle, and surface at least part is coated with silver chlorate, and is related to one kind
Particle, suitable for instead of the silver chloride particle such as the organism electrode for medical instrument.
Background technique
It measures in the medical instruments of Biont informations such as electrocardiogram, has used the silver-silver chloride electrode quilt of silver and silver chlorate
As the organism electrode that the electric signal from organism is contacted and received with organism.Such organism electrode has can be anti-
The organism electrode and disposable biological body electrode used again, from the point of view of cost effective and saving resource demand, especially
It is the usage amount that silver is cut down in disposable biological body electrode requirement.
Therefore, disposable biological body electricity consumption ultimate ratio is as used following substance: as shown in Figure 1, by spherical or thin slice (scale)
Conductive paste made of the particle of shape, i.e. Argent grain 4 and silver chloride particle 6 and resin 3 are compounded is coated on the table of the conductive materials such as carbon 2
Substance made of face.The intracorporal electric signal of biology is as required, to make the conductive materials such as electrolyte gel by ionic conduction
It is present in organism surface and organism between electrode 1, by the way that organism electrode 1 is connected directly or indirectly to biology
The electric signal of organism can be conveyed to organism electrode 1 by body surface face, and the organism for having received the electric signal of organism is used
The silver chloride particle 6 of electrode surface is ionized into silver ion 5 and chloride ion 8.Then, in the silver ion 5 ionized out and as molecule
Giving and accepting for electronics 7 is carried out between existing Argent grain 4, thus electric signal becomes electrical conduction from ionic conduction, can pass through conduction
Material 2 conveys Biont information to mensuration machine.
However, Argent grain 4 and silver chloride particle 6 high cohesion as possessed by its difference in specific gravity and silver chloride particle 6
And difficult fragmentation, it is difficult to be dispersed in conductive paste.Therefore, in previous organism electrode, to obtain stable conduction
Property, it needs to be 80~90 mass % or more by silver (also comprising the silver from silver chlorate) compounding in conductive paste, therefore have into one
Step cuts down the leeway of the usage amount of silver.
Changed in addition, disclosing a kind of surface by spherical Argent grain in patent document 1 by chemical reaction as chlorination
Particle made of silver, and record it is suitable for glucose detection sensors, reference electrode.
However, when the present inventor attempts in organism electrode using particle substitution silver chloride particle, it was found that with
Lower problem: i.e. electric conductivity is insufficient sometimes, and the connection reliability between organism electrode and organism is insufficient.
[existing technical literature]
[patent document]
Patent document 1:WO1998003431A1.
Summary of the invention
[technical problems to be solved by the inivention]
It is the product used for reference that the present invention, which is with the above problem, and the object of the present invention is to provide a kind of for example biological with composition is mixed in
When in the conductive paste of body electrode, it is able to maintain that stable electric conductivity, and the silver chlorate for cutting down the usage amount of silver is coated particle.
[technological means for solving technical problem]
Silver chlorate of the present invention is coated particle: at least part on surface contains the core of the dendron shape of silver；It is coating
At least part of, the silver chlorate coating made of silver chlorate on the surface of the core.
The core can be made from silver, also may include containing from selected in the group being made of gold, copper, nickel it is at least one kind of in
Core, and it is coated at least part of, the outer core that is made from silver of the core surface.
Can be following technical scheme: the average grain diameter that the silver chlorate is coated particle be 1 μm~100 μm.
Can be following technical scheme: the specific surface area that the silver chlorate is coated particle be 0.5~5.0m2/g。
Can be following technical scheme: the silver chlorate be coated in particle, and silver contains with the silver chlorate in the total amount of silver chlorate
Proportional (silver chlorate/(silver+silver chlorate)) is 5 mass of mass %~95 %.
Can be following technical scheme: the silver chlorate be coated particle and be suitable for silver-silver chloride electrode.
[invention effect]
Silver chlorate according to the present invention is coated particle, such as with situation about being mixed in the conductive paste for constituting organism electrode
Under, even if reducing the compounding amount of the silver for cream, also it is able to maintain that stable electric conductivity.Therefore, by using energy of the present invention
It is enough to provide than previous cheap and high reliablity organism electrode.
Detailed description of the invention
Fig. 1] it is previous silver-silver chloride electrode schematic diagram made of conductive material applying conductive cream；
Fig. 2] it is that the silver chlorate that one embodiment of the present invention is related to is coated silver use in particle as core, dendron shape
The electron microscope picture (multiplying power: 10000 times) of grain；
Fig. 3] and it is that the silver chlorate that one embodiment of the present invention is related to is coated particle, i.e., the surface of core shown in Fig. 1 contains 10
The silver chlorate of the silver chlorate of quality % is coated the electron microscope picture (multiplying power: 10000 times) of particle；
Fig. 4] and it is that the silver chlorate that one embodiment of the present invention is related to is coated particle, i.e., the surface of core shown in Fig. 1 contains 20
The silver chlorate of the silver chlorate of quality % is coated the electron microscope picture (multiplying power: 10000 times) of particle；
Fig. 5] and it is that the silver chlorate that one embodiment of the present invention is related to is coated particle, i.e., the surface of core shown in Fig. 1 contains 30
The silver chlorate of the silver chlorate of quality % is coated the electron microscope picture (multiplying power: 10000 times) of particle；
Fig. 6] and it is that the silver chlorate that one embodiment of the present invention is related to is coated particle, i.e., the surface of core shown in Fig. 1 contains 70
The silver chlorate of the silver chlorate of quality % is coated the electron microscope picture (multiplying power: 10000 times) of particle；
Fig. 7] it is the schematic diagram for being used for the circuit of measured impedance characteristic in embodiment.
Specific embodiment
Next, more specifically describing embodiments of the present invention.
The silver chlorate that one embodiment of the present invention is related to is coated particle: at least part on surface contains silver
The core of dendron shape；At least part of, the silver chlorate coating made of silver chlorate on the surface of tegmental nuclei.
Here, dendron shape refers to the shape comprising the dendritic processes from particle surface 1 outstanding or more, for example, such as
Shown in the electron microscope picture of Fig. 2~6, can enumerate a portion from major branch bifurcated, in planar or dimensionally grow
Shape substance, but be not limited to these, also can be only the major branch of no bifurcated.
The core is dendron shape, and at least part on its surface contains silver and is then not particularly limited, and can be made from silver,
Contain metal, metallic compound, inorganic compound or the organic compound other than silver.Specifically, the metal energy other than silver
Enough enumerate gold, copper, nickel etc..So that silver chlorate is coated the shape of particle as nuclear energy by using the substance of dendron shape is also tree
Prominent shape.
It is excellent from the viewpoint of the simplicity of manufacture, conductive stability in foregoing illustrative material about the core
It is selected as the core being made from silver.The Argent grain of the dendron shape is for example able to use through side described in No. 4149364 patent of special permission
The Argent grain of method manufacture.
In addition, from the viewpoint of the silver-colored usage amount of further reduction, in the case that the above-mentioned material other than silver is used for core,
Nuclear energy enough include silver other than above-mentioned metal material made of kernel, be coated the core surface it is at least part of, by
Outer core made of silver.The nuclear energy is enough using for example according to common method, by replacing, plating is coated method, reduction plating is coated method
Nuclear particle made of surface with the metallic particles of the coating dendron shape that become kernel of silver is more specifically able to use
Silver made of the surface of copper particle making according to special open 2013-1917 bulletin the method, with the coating dendron shape of silver wraps
Copper powder etc..
It is coating that the surface of the core can all be chlorinated silver-colored coating, can also surface a part be chlorinated silver-colored coating quilt
It covers, exposes silver existing for the surface of a part of core.
The average grain diameter that the silver chlorate is coated particle is not particularly limited, such as in the case where being used for conductive paste, preferably
It is 1 μm~100 μm, more preferably 3 μm~10 μm.Here, average grain diameter, which refers to, passes through laser diffraction scattering method in this specification
Partial size (primary particle size) at aggregate-value 50% in resulting size distribution.
The specific surface area that the silver chlorate is coated particle is not particularly limited, for example, in the case where being used for conductive paste, preferably
For 0.5~5.0m2/ g, more preferably 1.0~2.0m2/g.Here, specific surface area, which refers to, puts measurement sample in this specification
Enter in vacuum drier, carry out handling for 2 hours at normal temperature, later, after filling sample makes sample room become intensive, is placed
In BET specific surface area measurement device, the value measured after the preceding processing of degassing in 60 minutes is carried out at 40 DEG C of temperature.
The silver chlorate is coated content ratio (silver chlorate/(silver of the silver in particle with the silver chlorate in the total amount of silver chlorate
+ silver chlorate)) it is not particularly limited, the preferably 5 mass % of mass %~95, more preferably 10 mass of mass %~70 %.Here,
In this specification, the content (quality %) that silver chlorate is coated silver chlorate and silver in particle is following values: using being able to carry out difference
Show that heat analysis (DTA) or Differential Scanning Calorimetry measure the device of (DSC) with regard to chlorination argentum reagent or argentum reagent and silver chlorate coating
Grain measures under the conditions of as shown below, DTA curve or DSC curve is found out, from peak area formula (1) or the formula of melting peak
(2) resulting value is calculated.In addition, as it appears from the above, silver chlorate is coated the core of particle by the kernel and coating kernel of gold, copper, nickel etc.
In situation made of the outer core of the silver layer on surface, it can also measure by the same method.In addition, the feelings of the content in measurement silver
, it is preferable to use the DSC of pyrometry under condition.
The determination condition > of < silver chlorate
Sample size about 10mg；
10 DEG C/min of heating rate；
Measuring temperature range room temperature~500 DEG C；
Temperature condition is cooled to 350 DEG C, is warming up to 480 DEG C again from room temperature to after 480 DEG C；
Atmosphere nitrogen, flow: 150ml/min；
Sample container aoxidizes aluminum (style of opening)；
Standard substance Al203；
Reference substance quality about 10mg.
1 > of < formula
Silver chlorate is coated the silver chloride content (quality %) in particle=(peak area of the silver chlorate of the coating particle of every 1g silver chlorate
Value)/(peak area value of the silver chlorate of every 1g chlorination argentum reagent) × 100 (1).
< silver determination condition >
Sample size about 10mg；
10 DEG C/min of heating rate；
Measuring temperature range room temperature~1000 DEG C；
Temperature condition is cooled to 800 DEG C, is warming up to 1000 DEG C again from room temperature to after 1000 DEG C；
Atmosphere nitrogen, flow: 150ml/min；
Sample container aoxidizes aluminum (style of opening)；
Standard substance Al203；
Reference substance quality about 10mg.
2 > of < formula
Silver chlorate is coated the silver content (quality %) in particle=(peak area value that every 1g silver chlorate is coated the silver of particle)/(every
The peak area value of the silver of 1g argentum reagent) × 100 (2).
The manufacturing method that silver chlorate of the invention is coated particle is not particularly limited, and according to common method, can pass through chemistry
Reaction makes silver existing for the surface of the core of dendron shape be changing into silver chlorate, such as can manufacture by the following method: preparing dendron
The Argent grain of shape makes its reaction at normal temperature in aqueous sodium hypochlorite solution.At this point, passing through the anti-of appropriate adjustment chemical concentration etc.
Answer condition that can manipulate the production quantity of silver chlorate, also adjustable silver chlorate is coated the mass ratio of silver and silver chlorate in particle.
In addition, according to reaction condition difference, it sometimes appear that silver chlorate is coated in particle the case where containing silver oxide, but to the present invention
Effect have no influence.
The obtained silver chlorate is coated particle and can for example use with compoundings such as resins as conductive paste.Gained is conductive
Cream can be used in silver-silver chloride electrode, such as can be suitably employed in organism electrode.
By by silver chlorate of the invention be coated particle be used as with the metallic particles for being mixed in conductive paste enable to even if
Stable electric conductivity is also able to maintain that in the case where the usage amount for reducing silver.The mechanism of the effect is simultaneously indefinite, but can carry out
Speculate below.
Firstly, cohesion, the hardly possible fragmentation of silver chlorate can be reduced by the way that particle is set as dendron shape, further such that
Become to be not likely to produce precipitating in conductive paste, therefore the dispersibility of silver chlorate can be improved.In addition, due to the contact between particle
Point increases, even if reducing the usage amount of silver, is also able to maintain that stable electric conductivity.
In addition, by being set as dendron shape, the specific surface area of the silver chlorate of coating particle surface becomes larger, thus for example for
In the case where organism electrode, when measuring Biont information and the electrolysis that is present between organism electrode and organism
The contact area of matter will increase, and thus the responsiveness of organism electrode becomes fabulous.
Furthermore by being set as dendron shape, relative to be coated with containing silver chlorate of the invention be coated particle conductive paste
Conductive material (conductive material 2 for being equivalent to Fig. 1), or relative to measurement Biont information when be present in organism electrode with
The electrolyte layer of electrolyte gel, electrically conductive adhesive between organism etc., the dendritic processes that silver chlorate is coated particle are pricked
Enter, is thus also improved the effect of the connection reliability of organism electrode and organism.
[embodiment]
The following is an embodiment of the present invention, but the present invention is not limited by embodiment below.In addition, content etc. hereinafter is based on
Quality standard, unless otherwise indicated.
The detailed content of each ingredient used in embodiment, comparative example is as described below.
Argent grain A: dendron shape, Mitsui Metal Co., Ltd.'s mining industry (strain) system, average grain diameter=8.0 μm；
Argent grain B: dendron shape, Mitsui Metal Co., Ltd.'s mining industry (strain) system, average grain diameter=5.3 μm；
Silica dioxide granule: Fuji's chemistry of silicones (strain) makes " SYLYSIA710 "；
Polyester resin: Japanese synthetic chemical industry (strain) makes " LP035 ".
< silver chlorate is coated 1 > of production example of particle
Solution obtained by after the liquor natrii hypochloritis of 10 mass % of effective chlorine density is diluted 20 times is prepared for as reaction solution.Separately
On the one hand, the above-mentioned Argent grain A of 10g is put into 20g ethyl alcohol, is stirred at normal temperature 3 minutes using ultrasonic wave agitating device, is prepared
Ethyl alcohol dispersed paste.
Gained ethyl alcohol dispersed paste is mixed into above-mentioned reaction solution, is stirred 3 minutes at normal temperature using ultrasonic wave stirring.
After stirring, reaction solution and particle are separated in pressure-reducing filter, and the cleaning of particle is carried out using pure water and ethyl alcohol.Later,
By making particle air drying in vacuum desiccator, obtain being chlorinated the coating Argent grain (a) of the coating silver chlorate of silver.
The silver chloride content that gained silver chlorate is coated Argent grain (a) is 21 mass %, specific surface area 1.10m2/g。
< silver chlorate is coated 2 > of production example of particle
Solution obtained by after the liquor natrii hypochloritis of 10 mass % of effective chlorine density is diluted 5 times has been used as reaction solution
Argent grain B is stated to substitute above-mentioned Argent grain A, in addition to this as above-mentioned production example 1, silver chlorate has been obtained and has been coated Argent grain
(b).The silver chloride content that gained silver chlorate is coated Argent grain (b) is 76 mass %, specific surface area 1.06m2/g。
< silver chlorate is coated 3 > of production example of particle
In addition to using above-mentioned Argent grain B come other than substituting above-mentioned Argent grain A, other steps obtain as above-mentioned production example 1
Silver chlorate is coated Argent grain (c).The silver chloride content that gained silver chlorate is coated Argent grain (c) is 21 mass %, and specific surface area is
1.06m2/g。
The production > of < electrode
Be compounded (quality %) according to shown in table 1, by above-mentioned gained silver chlorate be coated particle and Argent grain B, silica dioxide granule and
Polyester resin mixing, is diluted with methyl ethyl ketone (MEK) and prepares electrode conductive paste.Electrode is applied with conductive paste using coating machine
It is distributed on silver vapor deposition polyethylene terephthalate (PET) film, is made it dry in 120 DEG C of drying oven 3 minutes.So that electric
Pole layer with a thickness of 30 μm.It is bonded conductive gel on its electrode layer and prepares organism electrode sample.
< appraisal procedure >
With regard to gained organism electrode sample, to American Standard Association (ANSI:American National Standards
Institute standard (the AAMI-EC12:Association for of) prepared, disposable ECG examination electrode
The Advancement of Medical Instrumentation EC-12) required by impedance operator (ACZ: exchange resistance
Anti-, impedance is labeled as Z) it is evaluated.
Specifically, each organism of fitting conductive gel uses electrode sample as electrode to 12, as shown in fig. 7, system
Make following circuit: being connected resistor 10, function generator 11 of the above-mentioned electrode to 12 and series connection with parallel way, then
The circuit being formed by connecting with power supply 9 measures AC impedances to 12 with regard to 12 groups of electrode respectively, is averaged.As above-mentioned mark
Organism electrode under quasi- is no more than 10Hz, 100 μ Ap-p(Ap-p: by maximum current value and the minimum electricity of exchange electrometric determination
The difference of flow valuve) application under the average value of impedance need for 2k Ω or less.
[table 1]
The results are shown in Table 1, for being compounded the silver of 80~90 mass % or more in the conductive paste of previous organism electrode,
In contrast, particle is coated by using the silver chlorate of dendron shape of the present invention, even if by the content of the silver in conductive paste
It substantially cuts down to 33.6~63.7 mass %, can also obtain impedance operator required for organism electrode.
[number explanation]
1 silver-silver chloride electrode
The conductive material of 2 carbon etc.
3 resins
4 silver medals (Ag)
5 silver ions (Ag+)
6 silver chlorates (AgCl)
7 electronics (e-)
8 chloride ions (Cl-)
9 power supplys
10 resistors
11 function generators
12 have been bonded electrode pair made of each electrode sample of conductive gel
Claims (7)
1. a kind of silver chlorate is coated particle, the silver chlorate is coated particle and includes: at least part on surface contains the tree of silver
The core of prominent shape；
It is coated at least part of, the silver chlorate coating made of silver chlorate on the surface of the core.
2. silver chlorate according to claim 1 is coated particle, it is characterised in that: the core is made from silver.
3. silver chlorate according to claim 1 is coated particle, it is characterised in that: the core includes containing from by gold, copper, nickel
At least one kind of kernel selected in the group of composition, and be coated the core surface it is at least part of, be made from silver it is outer
Core.
4. silver chlorate described in any one according to claim 1~3 is coated particle, it is characterised in that: the silver chlorate quilt
The average grain diameter for covering particle is 1 μm~100 μm.
5. silver chlorate described in any one according to claim 1~4 is coated particle, it is characterised in that: the silver chlorate quilt
The specific surface area for covering particle is 0.5~5.0m2/g。
6. silver chlorate described in any one according to claim 1~5 is coated particle, it is characterised in that: silver and silver chlorate
The content ratio (silver chlorate/(silver+silver chlorate)) of silver chlorate in total amount is 5 mass of mass %~95 %.
7. silver chlorate described in any one according to claim 1~6 is coated particle, it is characterised in that: the silver chlorate quilt
Particle is covered for silver-silver chloride electrode.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017068518A JP6654164B2 (en) | 2017-03-30 | 2017-03-30 | Silver chloride coated particles |
| JP2017-068518 | 2017-03-30 | ||
| PCT/JP2018/007980 WO2018180190A1 (en) | 2017-03-30 | 2018-03-02 | Silver chloride coated particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110366460A true CN110366460A (en) | 2019-10-22 |
Family
ID=63675570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880015339.5A Pending CN110366460A (en) | 2017-03-30 | 2018-03-02 | Silver chlorate is coated particle |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6654164B2 (en) |
| KR (1) | KR20190130638A (en) |
| CN (1) | CN110366460A (en) |
| WO (1) | WO2018180190A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10873081B2 (en) | 2016-06-30 | 2020-12-22 | Tatsuta Electric Wire & Cable Co., Ltd. | Electrode material |
| JP6612984B2 (en) * | 2016-06-30 | 2019-11-27 | タツタ電線株式会社 | Silver chloride paste |
| JP6785856B2 (en) | 2016-06-30 | 2020-11-18 | タツタ電線株式会社 | Biological electrodes and methods for forming bioelectrodes |
| WO2021181752A1 (en) * | 2020-03-13 | 2021-09-16 | タツタ電線株式会社 | Bioelectrode |
| KR102650140B1 (en) | 2021-05-06 | 2024-03-21 | 주식회사 아이센스 | Paste for reference electrode, reference electrode, and biosensor including the same |
| EP4442777A1 (en) * | 2023-04-04 | 2024-10-09 | Henkel AG & Co. KGaA | Electrically conductive ink composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998003431A1 (en) * | 1996-07-23 | 1998-01-29 | Medisense, Inc. | Silver chloride particles |
| JP2011144441A (en) * | 2010-01-18 | 2011-07-28 | Namics Corp | Silver-coated nickel powder and method for producing the same |
| JP5907301B1 (en) * | 2015-05-15 | 2016-04-26 | 住友金属鉱山株式会社 | Silver-coated copper powder, copper paste using the same, conductive paint, conductive sheet, and method for producing silver-coated copper powder |
| CN105980055A (en) * | 2014-02-04 | 2016-09-28 | 拓自达电线株式会社 | Process for manufacturing supported nanocolloidal particles, and supported nanocolloidal particles |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4697643B2 (en) * | 2009-09-07 | 2011-06-08 | 福田金属箔粉工業株式会社 | Aggregate of electrolytic copper powder and method for producing the electrolytic copper powder |
| US10486231B2 (en) * | 2015-08-31 | 2019-11-26 | Mitsui Mining & Smelting Co., Ltd. | Silver-coated copper powder |
| JP6542077B2 (en) * | 2015-09-01 | 2019-07-10 | 京セラ株式会社 | Method of producing conductive paste and conductive paste |
-
2017
- 2017-03-30 JP JP2017068518A patent/JP6654164B2/en active Active
-
2018
- 2018-03-02 WO PCT/JP2018/007980 patent/WO2018180190A1/en active Application Filing
- 2018-03-02 CN CN201880015339.5A patent/CN110366460A/en active Pending
- 2018-03-02 KR KR1020197032181A patent/KR20190130638A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998003431A1 (en) * | 1996-07-23 | 1998-01-29 | Medisense, Inc. | Silver chloride particles |
| JP2011144441A (en) * | 2010-01-18 | 2011-07-28 | Namics Corp | Silver-coated nickel powder and method for producing the same |
| CN105980055A (en) * | 2014-02-04 | 2016-09-28 | 拓自达电线株式会社 | Process for manufacturing supported nanocolloidal particles, and supported nanocolloidal particles |
| JP5907301B1 (en) * | 2015-05-15 | 2016-04-26 | 住友金属鉱山株式会社 | Silver-coated copper powder, copper paste using the same, conductive paint, conductive sheet, and method for producing silver-coated copper powder |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018180190A1 (en) | 2018-10-04 |
| JP6654164B2 (en) | 2020-02-26 |
| KR20190130638A (en) | 2019-11-22 |
| JP2018168445A (en) | 2018-11-01 |
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