[go: up one dir, main page]

CN115260836A - Reference electrode silver-silver chloride conductive ink for CGM and preparation method thereof - Google Patents

Reference electrode silver-silver chloride conductive ink for CGM and preparation method thereof Download PDF

Info

Publication number
CN115260836A
CN115260836A CN202211207991.1A CN202211207991A CN115260836A CN 115260836 A CN115260836 A CN 115260836A CN 202211207991 A CN202211207991 A CN 202211207991A CN 115260836 A CN115260836 A CN 115260836A
Authority
CN
China
Prior art keywords
silver
resin
conductive ink
silver chloride
cgm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211207991.1A
Other languages
Chinese (zh)
Inventor
亢佳萌
祁金宇
赵平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Shennapus Artificial Intelligence Technology Co ltd
Original Assignee
Beijing Shennapus Artificial Intelligence Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Shennapus Artificial Intelligence Technology Co ltd filed Critical Beijing Shennapus Artificial Intelligence Technology Co ltd
Priority to CN202211207991.1A priority Critical patent/CN115260836A/en
Publication of CN115260836A publication Critical patent/CN115260836A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/52Electrically conductive inks
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301Reference electrodes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Wood Science & Technology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Conductive Materials (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention discloses reference electrode silver-silver chloride conductive ink for CGM (CGM) and a preparation method thereof, wherein the conductive ink comprises the following components in percentage by mass: 4-10% of resin, 13-20% of solvent, 2-4% of curing agent, 70-80% of conductive filler and 1-3% of auxiliary agent. The conductive filler comprises silver and silver chloride, and the mass ratio of the silver to the silver chloride is 2:1-1:1. The reference electrode silver-silver chloride conductive ink for CGM has the advantages of low sheet resistance, good adhesive force, good biocompatibility, stable electrode potential, small polarization and the like, can be used for screen printing, and is simple in preparation method and low in cost. The reference electrode silver-silver chloride conductive ink prepared by the invention is specially applied to preparation of CGM reference electrodes.

Description

Reference electrode silver-silver chloride conductive ink for CGM and preparation method thereof
Technical Field
The invention relates to the technical field of conductive ink, in particular to reference electrode silver-silver chloride conductive ink for CGM and a preparation method thereof.
Background
The dynamic blood glucose monitoring (CGM) is a new blood glucose monitoring technology, the glucose concentration of subcutaneous interstitial fluid is monitored by a glucose sensor to reflect the blood glucose level of an organism, continuous and comprehensive blood glucose information in a certain time period can be provided, and the CGM has a unique advantage for the evaluation of blood glucose fluctuation.
At present, silver-silver chloride electrode materials for measuring electroencephalogram (EEG), electrocardiogram (ECG), electromyogram (EMG) or Electrooculogram (EOG) signals have been widely reported, but the silver-silver chloride electrode materials are rarely applied to CGM.
Most of the existing silver-silver chloride electrodes are disposable or have short service life, and the problems of adhesive force reduction, poor conductivity, larger electrode potential deviation, larger noise, unstable baseline and the like can be caused after long-term use, while the reference electrode for CGM requires the characteristics of long service life, good biocompatibility, strong adhesive force and the like.
Disclosure of Invention
The invention aims to provide silver-silver chloride conductive ink of a reference electrode for CGM (CGM) and a preparation method thereof, and aims to solve the problems that the existing silver-silver chloride electrode is short in service life, and the adhesion is reduced, the conductivity is poor, the electrode potential deviation is large and the like due to long-term use.
In one aspect, an embodiment of the present application provides a silver-silver chloride conductive ink, which includes, by mass: 4-10% of resin, 13-20% of solvent, 2-4% of curing agent, 70-80% of conductive filler and 1-3% of auxiliary agent, wherein the conductive filler comprises silver and silver chloride, and the mass ratio of the silver to the silver chloride is 2:1-1:1. The silver content is too low to cause poor conductivity, and the silver content is too high to cause the silver chloride content to be too low, so that the service life is greatly weakened, and therefore, the mass ratio of the silver to the silver chloride is defined as 2:1-1:1.
The resin content in the conductive ink of the present invention may be 4%,5%,6%,7%,8%,9%,10%, or any range therebetween, such as 4% -6% or 4% -8%.
The solvent content in the conductive ink of the present invention can be 13%,14%,15%,16%,17%,18%,19%,20%, or any range therebetween, such as 13-18%.
The conductive filler content in the conductive ink of the present invention can be 70%,71%,72%,73%,74%,75%,76%,77%,78%,79%,80%, or any range therebetween, such as 72% -80% or 74% -80%.
The reference electrode silver-silver chloride conductive ink for CGM has good conductivity and long service life. The reference electrode silver-silver chloride conductive ink for CGM has stable electrode potential and good adhesive force. The preparation method of the reference electrode silver-silver chloride conductive ink for CGM is simple, low in cost and good in consistency. The silver-silver chloride conductive ink for the CGM reference electrode has good biocompatibility and is specially applied to preparation of the CGM reference electrode.
In some embodiments, the resin is one of polyester resin, polyurethane resin, epoxy resin, acrylic resin, phenolic resin, alkyd resin, silicone resin, vinyl chloride-vinyl acetate resin, petroleum resin, phenoxy resin, polyimide resin, or a mixture of at least two thereof.
In some embodiments, the resin is a polyester resin and/or a polyurethane resin. Wherein the polyester resin may be a low Tg polyester resin, for example, the glass transition temperature Tg of the polyester resin may be-20 ℃ to 20 ℃, because the low Tg polyester resin is more flexible. Preferably, the number average molecular weight of the polyester resin may be 6000 to 30000.
Preferably, the polyester resin is an amorphous polyester resin.
Preferably, the polyurethane resin is thermoplastic polyurethane. Further, the polyurethane resin may be a polyester type or polyether type polyurethane resin.
Preferably, the Shore hardness of the polyurethane resin is 60-95A, the tensile strength is greater than 40MPa, and the elongation at break is greater than 300%.
In some embodiments, the solvent is one or a mixture of at least two of isopropyl alcohol, n-propyl alcohol, ethylene glycol, propylene glycol, glycerol, n-butanol, ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate, dibasic ester (commonly known as methyl nylon acid, DBE for short), isophorone, and terpineol.
In some embodiments, the curing agent is a blocked polyisocyanate, wherein the polyisocyanate is one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene isocyanate, polyphenylmethane polyisocyanate, or a mixture of at least two thereof. Preferably, the unblocking temperature of the curing agent is 80-120 ℃.
In some embodiments, the conductive filler is in the shape of one or a mixture of at least two of a plate, a sphere, a wire, a rod, a needle, a dendrite, and the like.
In some embodiments, the conductive filler has a size of 0.1 μm to 10 μm, which is the largest size of a single conductive filler, and specifically may be a length, a particle diameter, and the like. Preferably, the conductive filler has a specific surface area of 0.8 to 3m 2 (ii) g, tap density of 1.5-6g/cm 3
In some embodiments, the auxiliary agent comprises one or a mixture of at least two of a defoamer, an adhesion promoter, a wetting dispersant, an antioxidant, and an anti-settling auxiliary agent.
Preferably, the auxiliary agent comprises an adhesion promoter and a wetting dispersant.
Preferably, the defoaming agent can be one of polysiloxane defoaming agent, silicone defoaming agent and polyether defoaming agent or a mixture of at least two of the polysiloxane defoaming agent, the silicone defoaming agent and the polyether defoaming agent.
Preferably, the adhesion promoter is a silane coupling agent adhesion promoter.
Preferably, the wetting and dispersing agent is one of modified polyurethane polymer, copolymer with acid group, modified polysiloxane or mixture of at least two of the modified polyurethane polymer, the copolymer with acid group and the modified polysiloxane.
On the other hand, the embodiment of the present application provides a method for preparing the silver-silver chloride conductive ink, which includes the following steps:
s1, placing the resin and the solvent in a beaker, stirring and dissolving, uniformly stirring at the heating temperature of 60-90 ℃ and the stirring speed of 300-600rpm to a clear and transparent state, cooling to room temperature for later use, then adding the curing agent and the auxiliary agent into the dissolved resin, and uniformly stirring to obtain a carrier;
s2, placing the carrier, the silver and the silver chloride in a sample tank, stirring for pre-dispersion, stirring for a period of time, standing, then grinding and dispersing, wherein the fineness of the ground ink is less than 10 mu m, then filtering, wherein a filter screen is a 325-mesh polyester screen, and filtering to obtain the silver-silver chloride conductive ink.
The preparation method of the reference electrode silver-silver chloride conductive ink for CGM is simple, can be used for silk-screen printing, and has low cost and good consistency.
In a third aspect, the present application provides a use of the silver-silver chloride conductive ink in an in vivo dynamic blood glucose monitoring sensor.
The invention has the beneficial effects that:
1. the reference electrode silver-silver chloride conductive ink for CGM has good conductivity and strong adhesive force.
2. The reference electrode silver-silver chloride conductive ink for CGM has the advantages of stable electrode potential, small polarization and long service life.
3. The silver-silver chloride conductive ink for the CGM reference electrode has good biocompatibility and is specially applied to preparation of the CGM reference electrode.
4. The preparation method of the reference electrode silver-silver chloride conductive ink for CGM is simple, can be used for silk-screen printing, and has low cost and good consistency.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent from and readily appreciated by reference to the following description of the embodiments taken in conjunction with the accompanying drawings,
wherein:
FIG. 1 is an electrode stability curve of a reference electrode silver-silver chloride conductive ink for CGM in example 1 of the present application;
FIG. 2 is an electrode stability curve of a reference electrode silver-silver chloride conductive ink for CGM in example 2 of the present application;
FIG. 3 is an electrode stability curve of a reference electrode silver-silver chloride conductive ink for CGM in example 3 of the present application;
fig. 4 is an electrode stability curve of the reference electrode silver-silver chloride conductive ink for CGM in comparative example 1;
fig. 5 is an electrode stability curve of the reference electrode silver-silver chloride conductive ink for CGM in comparative example 2.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
Interpretation of terms:
conductive ink: the conductive ink is a paste ink prepared by dispersing a conductive material in a vehicle, and is commonly called paste ink. Has a certain degree of conductive property, and can be used for printing conductive points or conductive circuits. Gold-based conductive inks, silver-based conductive inks, copper-based conductive inks, carbon-based conductive inks, and the like have been put into practical use and used for materials such as printed circuits, electrodes, plating primers, keyboard contacts, printed resistors, and the like. Among them, silver-based conductive inks are widely used for conductive printing of membrane switches. When the printing material is polyester, the silver powder can be dispersed into the polyester resin binder, and the pasty conductive ink can be prepared.
Silver-silver chloride electrode: the silver-silver chloride electrode (Ag/AgCl electrode) is a common reference electrode, and the characteristics are incomparable with other electrodes because the Ag/AgCl electrode has small solubility, high stability and reversibility in a high-temperature and high-pressure aqueous solution system, and the surface of the electrode can be well protected even in the presence of hydrogen. The standard electrode potential of silver chloride electrode in 1M KCL is + 0.2224V (25 ℃), and the standard electrode potential in saturated KCl is + 0.199V (25 ℃).
Dynamic blood glucose monitoring (CGM): dynamic blood glucose monitoring is one of diagnosis and treatment technologies of endocrinology department, and a dynamic blood glucose monitoring system generally consists of 5 parts including a glucose sensor, a cable, a blood glucose recorder, an information extractor and analysis software. The most recent systems on the market consist of only two parts, a glucose sensor with emission and analysis software. Glucose oxidase contained in a subcutaneous glucose sensor reacts with glucose in interstitial fluid of subcutaneous tissues, and the generated electric signal is transmitted to analysis software by the glucose sensor and then converted into blood glucose value. The technology has the double characteristics of real-time blood sugar monitoring and historical review (3, 6, 12 and 24-hour blood sugar graphs), can preset high and low blood sugar alarms, and can display the trend of rapid change of blood sugar.
Reference electrode: electrodes that are compared as a reference when measuring various electrode potentials. The reversibility of the reference electrode is good, the electrode potential is stable, and the reference electrode is close to zero potential and is not easy to polarize or passivate.
Ink adhesion: the degree of adhesion of the ink, which is the degree of adhesion of the ink to the substrate when the ink is applied to the substrate and adhered to the tape, is indicated.
Reference electrode silver-silver chloride conductive ink for CGM and a method for preparing the same according to embodiments of the present invention will be described below with reference to the accompanying drawings.
On one hand, the embodiment of the application provides a silver-silver chloride conductive ink, which comprises the following components in percentage by mass: 4% -10% of resin, 13% -20% of solvent, 2% -4% of curing agent, 70% -80% of conductive filler and 1% -3% of auxiliary agent, wherein the conductive filler comprises silver and silver chloride, and the mass ratio of the silver to the silver chloride is 2:1-1:1. The silver content is too low to cause poor conductivity, and the silver content is too high to cause the silver chloride content to be too low, so that the service life is greatly weakened, and therefore, the mass ratio of the silver to the silver chloride is defined as 2:1-1:1.
In some specific embodiments, the resin is one of polyester resin, polyurethane resin, epoxy resin, acrylic resin, phenolic resin, alkyd resin, silicone resin, vinyl chloride resin, petroleum resin, phenoxy resin, polyimide resin, or a mixture of at least two of them.
Preferably, the resin is a polyester resin and/or a polyurethane resin.
More preferably, the polyester resin is an amorphous polyester resin.
More preferably, the polyester resin is a low Tg polyester resin having a Tg of-20 deg.C to 20 deg.C because of its better flexibility.
In some specific embodiments, the polyester resin has a number average molecular weight of 6000 to 30000.
In some specific embodiments, the polyurethane resin is a thermoplastic polyurethane, which may be a polyester or polyether polyurethane resin.
Preferably, the Shore hardness of the polyurethane resin is 60-95A, the tensile strength is more than 40MPa, and the elongation at break is more than 300%.
In some embodiments, the solvent is one or a mixture of at least two of isopropyl alcohol, n-propyl alcohol, ethylene glycol, propylene glycol, glycerol, n-butanol, ethylene glycol propyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol butyl ether, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate, dibasic ester (commonly known as methyl nylon acid, DBE for short), isophorone, and terpineol.
In some specific embodiments, the curing agent is a blocked polyisocyanate, wherein the polyisocyanate is one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene isocyanate, and polyphenylmethane polyisocyanate, or a mixture of at least two thereof.
In some specific embodiments, the curing agent has an unblocking temperature of 80-120 ℃.
In some specific embodiments, the shape of the conductive filler is one or a mixture of at least two of a plate, a sphere, a line, a rod, a needle, a dendrite, and the like.
In some specific embodiments, the conductive filler has a size of 0.1 μm to 10 μm, which is the largest dimension of a single conductive filler, and specifically may be a length, a particle size, and the like.
In some specific embodiments, the conductive filler has a specific surface area of 0.8 to 3m 2 (ii) g, tap density of 1.5-6g/cm 3
In some specific embodiments, the auxiliary agent comprises one or a mixture of at least two of a defoaming agent, an adhesion promoter, a wetting dispersant, an antioxidant, and an anti-settling auxiliary agent.
Preferably, the defoaming agent can be one of polysiloxane defoaming agent, silicone defoaming agent and polyether defoaming agent or a mixture of at least two of the polysiloxane defoaming agent, the silicone defoaming agent and the polyether defoaming agent.
Preferably, the adhesion promoter is a silane coupling agent type adhesion promoter.
Preferably, the wetting and dispersing agent is one or a mixture of at least two of modified polyurethane polymer, acid-group-containing copolymer and modified polysiloxane.
On the other hand, the embodiment of the present application provides a method for preparing the silver-silver chloride conductive ink, which includes the following steps:
s1, preparation of a carrier: putting the resin and the solvent into a beaker, stirring and dissolving, heating to 60-90 ℃, stirring at the speed of 300-600rpm, mixing and stirring uniformly to a clear and transparent state, cooling to room temperature for later use, then adding the curing agent and the auxiliary agent into the dissolved resin, and stirring uniformly to obtain a carrier;
s2, preparing silver-silver chloride conductive ink: placing the obtained carrier, silver and silver chloride in a sample tank, pre-dispersing with a stirrer at 500rpm for 5min, and standing for 2h. And grinding and dispersing the pre-dispersed slurry by using a three-roll machine, wherein the fineness of the ground ink is less than 10 mu m, filtering, wherein a filter screen is a 325-mesh polyester screen, and filtering to obtain the silver-silver chloride conductive ink.
In a third aspect, the embodiment of the present application provides an application of the silver-silver chloride conductive ink in an in vivo dynamic blood glucose monitoring sensor.
The present application is further illustrated by the following specific examples and comparative examples.
Example 1
The reference electrode silver-silver chloride conductive ink for CGM comprises the following components in percentage by mass: 5% of polyurethane resin, 14% of solvent, 2% of curing agent, 51% of silver powder, 27% of silver chloride powder, 0.5% of adhesion promoter and 0.5% of wetting dispersant.
The preparation method of the reference electrode silver-silver chloride conductive ink for CGM comprises the following steps:
s1, preparation of a carrier: putting the resin and the solvent into a beaker, stirring and dissolving, heating to 80 ℃, stirring at the speed of 500rpm, uniformly mixing and stirring to a clear and transparent state, cooling to room temperature for later use, then adding the curing agent and the auxiliary agent into the dissolved resin, and uniformly stirring to obtain a carrier;
s2, preparing silver-silver chloride conductive ink: placing the obtained carrier, silver and silver chloride in a sample tank, pre-dispersing with a stirrer at 500rpm for 5min, and standing for 2h. And grinding and dispersing the pre-dispersed slurry by using a three-roll machine, wherein the fineness of the ground ink is less than 8 mu m, filtering, and obtaining the silver-silver chloride conductive ink after filtering, wherein a filter screen is a 325-mesh polyester screen.
The reference electrode silver/silver chloride conductive ink for CGM has the advantages of good conductivity, long service life, stable electrode potential, good adhesive force, simple preparation method, low cost, good consistency and good biocompatibility.
Example 2
The reference electrode silver-silver chloride conductive ink for CGM comprises the following components in percentage by mass: 5% of polyester resin, 17% of solvent, 2% of curing agent, 50% of silver powder, 25% of silver chloride powder, 0.5% of adhesion promoter and 0.5% of wetting dispersant.
The preparation method of the reference electrode silver-silver chloride conductive ink for CGM refers to example 1.
The reference electrode silver/silver chloride conductive ink for CGM has the advantages of good conductivity, long service life, stable electrode potential, good adhesive force, simple preparation method, low cost, good consistency and good biocompatibility.
Example 3
The reference electrode silver-silver chloride conductive ink for CGM comprises the following components in percentage by mass: 3% of polyester resin, 2% of polyurethane resin, 16% of solvent, 2% of curing agent, 50% of silver powder, 26% of silver chloride powder, 0.5% of adhesion promoter and 0.5% of wetting dispersant.
The preparation method of the reference electrode silver-silver chloride conductive ink for CGM refers to example 1.
The reference electrode silver/silver chloride conductive ink for CGM has the advantages of good conductivity, long service life, stable electrode potential, good adhesive force, simple preparation method, low cost, good consistency and good biocompatibility.
Comparative example 1
The reference electrode silver-silver chloride conductive ink for CGM comprises the following components in percentage by mass: 3% of polyester resin, 19% of solvent, 2% of curing agent, 50% of silver powder, 25% of silver chloride powder, 0.5% of adhesion promoter and 0.5% of wetting dispersant.
The preparation method of the reference electrode silver-silver chloride conductive ink for CGM refers to example 1.
Comparative example 2
The reference electrode silver-silver chloride conductive ink for CGM comprises the following components in percentage by mass: 5% of polyester resin, 8% of solvent, 1% of curing agent, 50% of silver powder, 35% of silver chloride powder, 0.5% of adhesion promoter and 0.5% of wetting dispersant.
The preparation method of the reference electrode silver-silver chloride conductive ink for CGM refers to example 1.
Comparative example 3
The reference electrode silver-silver chloride conductive ink for CGM comprises the following components in percentage by mass: 5% of polyester resin, 17% of solvent, 2% of curing agent, 25% of silver powder, 50% of silver chloride powder, 0.5% of adhesion promoter and 0.5% of wetting dispersant.
The preparation method of the reference electrode silver-silver chloride conductive ink for CGM refers to example 1.
Performance testing of reference electrode silver-silver chloride conductive inks of examples 1-3 and comparative examples 1-3
And (3) screen-printing the silver-silver chloride conductive ink on a PET film, baking for 20 minutes at 130 ℃ by using an oven, and testing after curing.
And (3) testing electrical properties: the conductivity of the sample is tested by a four-probe sheet resistance tester.
And (3) testing the adhesive force: and (3) transversely and longitudinally cutting the sample by using a 1mm hundred-grid knife, brushing the scratch by using a soft hairbrush, attaching a special adhesive tape for testing the 3M 600-1PK to the cut sample, pressing by using a hand, and strongly tearing off the adhesive tape along the vertical direction after 1 minute. If the cutting edge is completely smooth and no lattice falls off, the cutting edge is evaluated as 0 grade; if a little coating falls off at the intersection of the cuts, but the influence on the cross cutting area cannot be obviously more than 5 percent, the grade is 1; if the coating falls off at the intersection of the cuts and/or along the edges of the cuts, the affected cross cutting area is obviously more than 5 percent but not obviously more than 15 percent, the evaluation is 2 grade; if the coating falls off partially or completely as large fragments along the cutting edge and/or partially or completely on different parts of the grid, the affected cross cutting area is obviously more than 15 percent but not obviously more than 35 percent, then the coating is rated as grade 3; if the coating is peeled off along the large fragments of the cutting edge and/or some squares are partially or completely peeled off, the affected cross cutting area is obviously more than 35 percent but not obviously more than 65 percent, the coating is rated as 4 grade; if the degree of exfoliation exceeds 4, the grade is 5.
Electrode stability and life test: connecting a silk-screen CGM three-electrode sensor to an electrochemical workstation, immersing the tail end of an electrode into 5mM glucose solution, maintaining the testing temperature within the range of 37 +/-0.5 ℃, and starting stirring at the stirring speed of 180 rpm. Selecting a chronograph current curve mode (I-T), setting parameters: the test was started with the applied voltage of 0.04V and the sampling interval of 10 s. The test data is saved and analyzed.
The test results are shown in FIG. 1~5 and Table 1.
TABLE 1
Square resistance (m omega/□) Adhesion force Stability (Tian) Life span (sky)
Example 1 35 Level 0 >14 >14
Example 2 35 Level 0 >14 >14
Example 3 35 Level 0 >14 >14
Comparative example 1 30 Grade 3 5 5
Comparative example 2 50 Grade 3 7 7
Comparative example 3 Is not conductive Stage 2 - -
And (3) analyzing a test result: the sheet resistance of example 1~3 is 35 m Ω/□, and example 1~3 has better conductivity than comparative example 3. The adhesion of example 1~3 is grade 0, the adhesion of comparative example 1 is grade 3, the adhesion of comparative example 2 is grade 3, and the adhesion of comparative example 3 is grade 2, indicating that the adhesion of example 1~3 is significantly better than that of comparative example 1~3. As shown in 1~3, the curves in the figure are generally aligned, which shows that the conductive ink of 1~3 has good electrode stability, and can maintain good electrode stability for 14 days or more. As shown in fig. 4 and 5, the curve fluctuation in comparative example 1 and comparative example 2 is large, indicating that the electrode stability of the conductive ink of comparative example 1 and comparative example 2 is poor, the electrode stability of the conductive ink of comparative example 1 starts to be significantly deteriorated and does not return to normal at the later stage after 5 days of use, and the electrode stability of the conductive ink of comparative example 2 starts to be significantly deteriorated and does not return to normal at the later stage after 7 days of use. Electrode life represents the operating time before the electrode loses normal operating capability. From the test results, the working life of examples 1-3 was significantly longer than that of comparative examples 1-2.
Reason analysis:
the content of the polyester resin in comparative example 1 was 3%, that is, the resin content was lower than that in examples 1 to 3, resulting in that the sheet resistance of comparative example 1 was lower than that of examples 1 to 3, and although the conductivity of comparative example 1 was slightly better than that of examples 1 to 3, the adhesion, electrode stability and electrode life were much lower than those of examples 1 to 3. It can be concluded that the adhesion, electrode stability and electrode life are greatly affected since the resin content of comparative example 1 is not in the range of 4% to 10%.
The total of the silver powder and the silver chloride powder in comparative example 2 was 85%, and too high powder content resulted in poor dispersibility and large sheet resistance, which were higher than those of examples 1-3 and also exceeded the range of 70-80% by mass of the conductive filler of the present application. Resulting in a sheet resistance of comparative example 2 that was greater than examples 1-3, indicating that comparative example 2 was less conductive than examples 1-3. And the adhesion, electrode stability and electrode life of comparative example 2 were also greatly affected.
The silver powder content in comparative example 3 was less than the silver chloride powder content and only half of the silver chloride powder, resulting in the conductive ink of comparative example 3 being non-conductive. This results in poor conductivity due to the low silver content in the conductive ink. Since the conductive ink of comparative example 3 is not conductive, the electrode stability and electrode life test is not involved.
In the present application, the terms "some embodiments" or the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments. Furthermore, the various embodiments and features of the various embodiments described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. The silver-silver chloride conductive ink is characterized by comprising the following components in percentage by mass: 4% -10% of resin, 13% -20% of solvent, 2% -4% of curing agent, 70% -80% of conductive filler and 1% -3% of auxiliary agent, wherein the conductive filler comprises silver and silver chloride, and the mass ratio of the silver to the silver chloride is 2:1-1:1.
2. The silver-silver chloride conductive ink according to claim 1, wherein the resin is one of polyester resin, polyurethane resin, epoxy resin, acrylic resin, phenolic resin, alkyd resin, silicone resin, vinyl chloride-vinyl acetate resin, petroleum resin, phenoxy resin, polyimide resin, or a mixture of at least two thereof.
3. The silver-silver chloride conductive ink according to claim 2, wherein the resin is a polyester resin and/or a polyurethane resin.
4. The silver-silver chloride conductive ink according to claim 3, wherein the polyester resin has a glass transition temperature Tg of-20 ℃ to 20 ℃.
5. The silver-silver chloride conductive ink according to claim 1, wherein the curing agent is a blocked polyisocyanate, wherein the polyisocyanate is one of toluene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene isocyanate, and polyphenylmethane polyisocyanate, or a mixture of at least two thereof.
6. The silver-silver chloride conductive ink according to claim 1, wherein the conductive filler is in the shape of one or a mixture of at least two of a plate, a sphere, a line, a rod, a needle, and a dendrite, and the size of the conductive filler is 0.1 μm to 10 μm.
7. The silver-silver chloride conductive ink according to claim 1, wherein the auxiliary agent comprises one or a mixture of at least two of a defoaming agent, an adhesion promoter, a wetting dispersant, an antioxidant and an anti-settling auxiliary agent.
8. The silver-silver chloride conductive ink of claim 7, wherein the adjuvants include adhesion promoters and wetting dispersants.
9. The method for preparing silver-silver chloride conductive ink according to any one of claims 1 to 8, comprising the steps of:
s1, placing the resin and the solvent into a beaker, stirring and dissolving, heating to 60-90 ℃, stirring at the speed of 300-600rpm, uniformly stirring to a clear and transparent state, cooling to room temperature for later use, then adding the curing agent and the auxiliary agent into the dissolved resin, and uniformly stirring to obtain a carrier;
s2, placing the carrier, the silver and the silver chloride in a sample tank, stirring for pre-dispersion, stirring for a period of time, standing, then grinding and dispersing, wherein the fineness of the ground ink is less than 10 mu m, then filtering, wherein a filter screen is a 325-mesh polyester screen, and filtering to obtain the silver-silver chloride conductive ink.
10. Use of the silver-silver chloride conductive ink according to any one of claims 1 to 8 in an in vivo dynamic blood glucose monitoring sensor.
CN202211207991.1A 2022-09-30 2022-09-30 Reference electrode silver-silver chloride conductive ink for CGM and preparation method thereof Pending CN115260836A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211207991.1A CN115260836A (en) 2022-09-30 2022-09-30 Reference electrode silver-silver chloride conductive ink for CGM and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211207991.1A CN115260836A (en) 2022-09-30 2022-09-30 Reference electrode silver-silver chloride conductive ink for CGM and preparation method thereof

Publications (1)

Publication Number Publication Date
CN115260836A true CN115260836A (en) 2022-11-01

Family

ID=83757844

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211207991.1A Pending CN115260836A (en) 2022-09-30 2022-09-30 Reference electrode silver-silver chloride conductive ink for CGM and preparation method thereof

Country Status (1)

Country Link
CN (1) CN115260836A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115954137A (en) * 2022-12-29 2023-04-11 苏州泓湃科技有限公司 Platinum-carbon slurry for CGM sensor detection electrode and preparation method and application thereof
CN115966331A (en) * 2022-12-29 2023-04-14 苏州泓湃科技有限公司 Silver/silver chloride slurry for reference electrode of CGM (CGM) biosensor and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105559797A (en) * 2015-12-23 2016-05-11 上海第二工业大学 Portable dynamic continuous blood glucose monitoring instrument oriented at medical IoT (Internet of Things)
US20170108460A1 (en) * 2015-10-15 2017-04-20 Arkray, Inc. Biosensor and Manufacturing Method of Biosensor
CN108982604A (en) * 2018-08-04 2018-12-11 北京怡成生物电子技术股份有限公司 The portable monitoring system of analyte in a kind of dynamic METHOD FOR CONTINUOUS DETERMINATION body fluid
CN109645986A (en) * 2018-11-30 2019-04-19 昆明贵金属研究所 A kind of low temperature curing silver/silver chloride paste for flexible biological electrode and preparation method thereof
CN110453260A (en) * 2019-08-23 2019-11-15 厦门大学 A wearable sensor for sweat detection and its preparation method
CN111707723A (en) * 2020-06-09 2020-09-25 上海三屹电子科技有限公司 Silver/silver chloride slurry with high signal-to-noise ratio for biological detection electrode and preparation method thereof
CN114496345A (en) * 2021-12-30 2022-05-13 上海宝银电子材料有限公司 Silver chloride conductive silver paste and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170108460A1 (en) * 2015-10-15 2017-04-20 Arkray, Inc. Biosensor and Manufacturing Method of Biosensor
CN105559797A (en) * 2015-12-23 2016-05-11 上海第二工业大学 Portable dynamic continuous blood glucose monitoring instrument oriented at medical IoT (Internet of Things)
CN108982604A (en) * 2018-08-04 2018-12-11 北京怡成生物电子技术股份有限公司 The portable monitoring system of analyte in a kind of dynamic METHOD FOR CONTINUOUS DETERMINATION body fluid
CN109645986A (en) * 2018-11-30 2019-04-19 昆明贵金属研究所 A kind of low temperature curing silver/silver chloride paste for flexible biological electrode and preparation method thereof
CN110453260A (en) * 2019-08-23 2019-11-15 厦门大学 A wearable sensor for sweat detection and its preparation method
CN111707723A (en) * 2020-06-09 2020-09-25 上海三屹电子科技有限公司 Silver/silver chloride slurry with high signal-to-noise ratio for biological detection electrode and preparation method thereof
CN114496345A (en) * 2021-12-30 2022-05-13 上海宝银电子材料有限公司 Silver chloride conductive silver paste and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
郑德海: "《现代网印油墨选择与使用手册》", 31 December 2000, 中国轻工业出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115954137A (en) * 2022-12-29 2023-04-11 苏州泓湃科技有限公司 Platinum-carbon slurry for CGM sensor detection electrode and preparation method and application thereof
CN115966331A (en) * 2022-12-29 2023-04-14 苏州泓湃科技有限公司 Silver/silver chloride slurry for reference electrode of CGM (CGM) biosensor and preparation method and application thereof
CN115954137B (en) * 2022-12-29 2024-08-02 苏州泓湃科技有限公司 Platinum-carbon slurry for detection electrode of CGM sensor and preparation method and application thereof

Similar Documents

Publication Publication Date Title
JP3088704B2 (en) Thick film composition for manufacturing medical electrodes
JP3958688B2 (en) Thick film conductor composition for use in biosensors
DE69624000T2 (en) ELECTRICAL LADDER FOR BIOMEDICAL ELECTRODES AND BIOMEDICAL ELECTRODES MADE THEREOF
CN115260836A (en) Reference electrode silver-silver chloride conductive ink for CGM and preparation method thereof
CA1139931A (en) Cohesive nonsticky electrically conductive gel composition
JP3394218B2 (en) Conductor composition used for electrochemical sensor and working electrode used for electrochemical biosensor
CN109645986B (en) A kind of low temperature curing silver/silver chloride paste for flexible biological electrode and preparation method thereof
JP2018533160A (en) Silver-silver chloride composition and electrical device containing the same
US5505200A (en) Biomedical conductor containing inorganic oxides and biomedical electrodes prepared therefrom
DE19545364A1 (en) Disposable electrode for providing electrical contact with skin or scalp for electro-encephalograph and electrocardiograph tests
CN114334218B (en) Silver-silver chloride slurry for flexible electrocardio detection electrode and application thereof
US4658826A (en) Skin preparatory composition for use with electrocardiograph and electroencephalograph monitoring electrodes
CN112164489B (en) Conductive carbon paste for blood glucose test paper, preparation method thereof and blood glucose test paper
EP4442777A1 (en) Electrically conductive ink composition
CN115966331B (en) Silver/silver chloride slurry for CGM biosensor reference electrode, and preparation method and application thereof
JPH0669442B2 (en) Medical conductive adhesive and medical adhesive electrode using the same
CN116895397B (en) Low-temperature curing silver chloride slurry and preparation method and application thereof
CN114280369A (en) Method for detecting reliability of electrocardio-electrode
CN119350662A (en) A biogel electrode based on double network cross-linking and its preparation method and application
CN115954137A (en) Platinum-carbon slurry for CGM sensor detection electrode and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20221101

RJ01 Rejection of invention patent application after publication