CN113717577A - Water-based conductive ink and preparation method thereof, and flexible heating cloth and preparation method thereof - Google Patents

Water-based conductive ink and preparation method thereof, and flexible heating cloth and preparation method thereof Download PDF

Info

Publication number
CN113717577A
CN113717577A CN202010456503.5A CN202010456503A CN113717577A CN 113717577 A CN113717577 A CN 113717577A CN 202010456503 A CN202010456503 A CN 202010456503A CN 113717577 A CN113717577 A CN 113717577A
Authority
CN
China
Prior art keywords
water
aqueous
conductive ink
conductive
content
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
CN202010456503.5A
Other languages
Chinese (zh)
Inventor
张�林
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.)
Material And Industrial Technology Research Institute Beijing
Original Assignee
Material And Industrial Technology Research Institute Beijing
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 Material And Industrial Technology Research Institute Beijing filed Critical Material And Industrial Technology Research Institute Beijing
Priority to CN202010456503.5A priority Critical patent/CN113717577A/en
Publication of CN113717577A publication Critical patent/CN113717577A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D31/00—Materials specially adapted for outerwear
    • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
    • A41D31/06—Thermally protective, e.g. insulating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Textile Engineering (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The invention relates to the field of intelligent clothes and discloses water-based conductive ink and a preparation method thereof, and flexible heating cloth and a preparation method thereof. The aqueous conductive ink comprises 25-60 wt% of aqueous resin, 5-20 wt% of conductive filler, 30-45 wt% of water and 1-10 wt% of aqueous auxiliary agent, wherein the aqueous resin is a mixture of 900 ten thousand aqueous anionic polyurethane with the weight average molecular weight of 100 and 900 ten thousand and 10-90 ten thousand water-soluble acrylic resin with the weight average molecular weight of 10-90 ten thousand. The conductive ink disclosed by the invention is low in resistance, excellent in kneading resistance and water resistance, capable of being applied to a hard electrothermal film, and capable of being widely applied to a flexible substrate, namely the field of intelligent wearing, so that the technical requirements of the conductive ink in the field of intelligent wearing are met, and the important bottleneck of electrothermal ink application is broken through.

Description

Water-based conductive ink and preparation method thereof, and flexible heating cloth and preparation method thereof
Technical Field
The invention relates to the field of intelligent clothing, in particular to water-based conductive ink and a preparation method thereof, and flexible heating cloth and a preparation method thereof.
Background
At present, cold-proof thermal clothes appearing at home and abroad are basically divided into two types according to the control of a heat source: one type is passive heat-generating warm-keeping clothes, namely passive heat-generating clothes, and the aim of heat resistance and warm keeping is achieved by increasing the content of static air, which is a more traditional warm-keeping mode; the other type is warm clothes which actively generate heat, namely actively generate heat, and convert the heat into heat energy through external energy sources, thereby achieving the purpose of assisting the heating of human bodies. The development of the heat-generating warm-keeping clothes is very significant, because the heat generation quantity of the human body is always limited, when the external temperature is reduced to a certain degree, the regulation cannot be achieved by the muscular vasoconstriction of the human body particularly under the extremely severe external environment. In addition, people have a demand for warmth retention of clothes, and the clothes are comfortable, beautiful, light and thin. Therefore, it is very necessary to develop intelligent heating clothes.
The carbon-based conductive ink is functional ink consisting of conductive filler, a binder, a solvent and an auxiliary agent. Conductive ink belongs to filling type composite materials, the conduction mechanism of the conductive ink is complex, and the conductive ink generally relates to two aspects of the formation of a conductive path and how to conduct electricity after the path is formed. The research suggests that the conductivity of the conductive ink is mainly the result of the combined action and mutual competition of 3 conduction mechanisms of seepage theory, tunnel theory and field emission theory. At present, traditional electrically conductive hot ink all coats and uses as the electric heat membrane on rigid base materials such as PET membrane, though the resistance is low, but has neither resistant the defect of rubbing nor water proofness to and generate heat the temperature not high, easy fracture, cohesiveness are not good, easily peel off and pollute the environment scheduling problem, be difficult to satisfy electrically conductive ink in the technical demand of intelligent wearing field, lead to unable the bottleneck of breaking through electrically conductive hot ink and using.
Disclosure of Invention
The invention aims to overcome the problems of poor machine washing performance, low heating temperature, easiness in cracking, poor caking property, easiness in peeling, environmental pollution and the like of the traditional conductive ink due to poor water resistance and poor rubbing property in the prior art, provides a water-based conductive ink and a preparation method thereof, and provides a flexible heating cloth and a preparation method thereof on the basis.
In order to achieve the above object, a first aspect of the present invention provides an aqueous conductive ink, comprising an aqueous resin, a conductive filler, water and an aqueous assistant, wherein the aqueous resin comprises 25 to 60 wt%, the conductive filler comprises 5 to 20 wt%, the water comprises 30 to 45 wt%, and the aqueous assistant comprises 1 to 10 wt%, based on the weight of the aqueous conductive ink, the aqueous resin is a mixture of an aqueous anionic polyurethane having a weight average molecular weight of 100-.
The second aspect of the invention provides a preparation method of water-based conductive ink,
the method comprises the following steps:
(1) mixing the conductive filler, the water-soluble acrylic resin and the water-based auxiliary agent with part of water, and then grinding and/or ultrasonically treating the mixture to obtain a dispersion suspension;
(2) mixing the dispersion suspension, the water-based anionic polyurethane and the rest water, adding a grinding medium, stirring, and filtering;
the conductive filler, the water-soluble acrylic resin, the water-based auxiliary agent, the water-based anionic polyurethane and the water are used in such amounts that the content of the water-based resin in the prepared water-based conductive ink is 25-60 wt%, the content of the conductive filler is 5-20 wt%, the content of the water is 30-45 wt% and the content of the water-based auxiliary agent is 1-10 wt%; the water-based resin is a mixture of water-based anionic polyurethane and water-soluble acrylic resin;
the weight-average molecular weight of the waterborne anionic polyurethane is 100-900 ten thousand; the weight average molecular weight of the water-soluble acrylic resin is 10-90 ten thousand.
The third aspect of the invention provides a flexible heating cloth which comprises the water-based conductive ink
The fourth aspect of the invention provides a preparation method of flexible heating cloth, which comprises the steps of coating the waterborne conductive ink provided by the first aspect of the invention or the waterborne conductive ink prepared by the preparation method provided by the second aspect of the invention on a base material cloth, drying to obtain conductive cloth, silk-screening nano silver paste on the conductive cloth through silk-screen printing, drying to obtain a conductive silver paste electrode, and fixing a copper foil on the conductive silver paste electrode to obtain the flexible heating cloth.
Through the technical scheme, the conductive ink disclosed by the invention is low in resistance, excellent in performances in the aspects of rubbing resistance and water resistance, capable of being applied to a hard electrothermal film, and also capable of being widely applied to a flexible substrate, namely the field of intelligent wearing, so that the technical requirements of the conductive ink in the field of intelligent wearing are met, and the important bottleneck of the application of the electrothermal ink is broken through.
Drawings
FIG. 1 is a thermographic profile of a flexible heat generating cloth produced in example 1;
fig. 2 is a machine-washing data graph of the flexible heating cloth manufactured in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a water-based conductive ink which comprises water-based resin, conductive filler, water and a water-based auxiliary agent, wherein the water-based conductive ink comprises 25-60 wt% of the water-based resin, 5-20 wt% of the conductive filler, 30-45 wt% of the water and 1-10 wt% of the water-based auxiliary agent, and the water-based resin is a mixture of water-based anionic polyurethane with the weight average molecular weight of 100-900 ten thousand and water-soluble acrylic resin with the weight average molecular weight of 10-90 ten thousand.
The inventor creatively selects the mixture of the high molecular weight water-based anionic polyurethane (preferably polyether water-based polyurethane resin) and the medium molecular weight water-soluble acrylic resin (preferably organic silicon modified water-based acrylic resin) as the water-based resin, mainly shows that the water-soluble acrylic resin provides better adhesive force, the water-based anionic polyurethane provides excellent flexibility of the conductive ink, so that the conductive ink has excellent rubbing resistance and machine washing resistance, and the conductive filler enables the conductive ink to obtain excellent low resistance performance, and the water-based resin used as the adhesive and combined with the conductive filler successfully solves the problems of poor flexibility, low heating temperature, easy cracking, poor adhesion, easy peeling, environmental pollution and the like of the traditional conductive ink, therefore, the technical bottleneck of the electrothermal ink is broken through, and the technical requirements of the conductive ink in the intelligent wearing field are met.
The influence of different component contents on the performances of the conductive ink such as flexibility, resistivity, coating adhesion, micro-morphology and the like is considered. In a preferred embodiment of the present invention, the content of the aqueous resin is 40 to 60 wt%, the content of the conductive filler is 5 to 15 wt%, the content of water is 30 to 40 wt%, and the content of the aqueous additive is 1 to 8 wt%, based on the weight of the aqueous conductive ink. More preferably, the content of the aqueous resin is 50-60 wt%, the content of the conductive filler is 9-15 wt%, the content of the water is 30-35 wt%, and the content of the aqueous auxiliary agent is 1-5 wt% based on the weight of the aqueous conductive ink
Preferably, the content of the conductive filler is 9-15 wt% based on the weight of the aqueous conductive ink. This preferred embodiment allows the resistivity of the aqueous conductive ink to be on the order of 10 Ω.
The mass ratio of the water-based anionic polyurethane to the water-soluble acrylic resin is selected in a wide range, and preferably, the mass ratio of the water-based anionic polyurethane to the water-soluble acrylic resin is 1-5:1, more preferably 1.4-2.3: 1.
Preferably, the aqueous anionic polyurethane is polyether aqueous polyurethane resin, and the water-soluble acrylic resin is organosilicon modified aqueous acrylic resin. By adopting the preferred embodiment, the water-based conductive ink has good adhesion, flexibility, cohesiveness and environmental protection.
The polyether type waterborne polyurethane resin and the organic silicon modified waterborne acrylic resin can be obtained commercially.
According to a preferred embodiment of the present invention, the weight average molecular weight of the aqueous anionic polyurethane is 300-600 ten thousand, and the weight average molecular weight of the water-soluble acrylic resin is 30-60 ten thousand.
In the present invention, the conductive filler may be various conventional conductive fillers in the art, as long as the conductive property is good, and the processability of the aqueous ink can be improved and the original properties of the aqueous resin can be maintained. For example, the conductive filler may be at least one of a graphene dispersion liquid, a carbon nanotube dispersion liquid, and carbon black.
Preferably, the conductive filler is graphene and/or carbon nanotubes.
More preferably, the conductive filler is graphene and carbon nanotubes, and the mass ratio of the graphene to the carbon nanotubes is 1-2: 5-10.
In the present invention, the aqueous adjuvant may be any of various conventional aqueous adjuvants in the art as long as it has a good dispersing effect. For example, the aqueous adjuvant is preferably at least one of DEGO760W, BYK-190, polyacrylic acid, hydroxymethyl cellulose, sodium dodecylbenzenesulfonate, polyoxyethylene lauryl ether, fatty acid amide, coconut fatty acid diethanolamide, and anionic polyacrylamide. The DEGO760W is commercially available from Digao. The BYK-190 is a product sold in Bike chemical markets.
In the present invention, it is preferable that the water is deionized water.
The second aspect of the invention provides a preparation method of water-based conductive ink, which comprises the following steps:
(1) mixing the conductive filler, the water-soluble acrylic resin and the water-based auxiliary agent with part of water, and then grinding and/or ultrasonically treating the mixture to obtain a dispersion suspension;
(2) mixing the dispersion suspension, the water-based anionic polyurethane and the rest water, adding a grinding medium, stirring, and filtering;
the conductive filler, the water-soluble acrylic resin, the water-based auxiliary agent, the water-based anionic polyurethane and the water are used in such amounts that the content of the water-based resin in the prepared water-based conductive ink is 25-60 wt%, the content of the conductive filler is 5-20 wt%, the content of the water is 30-45 wt% and the content of the water-based auxiliary agent is 1-10 wt%; the water-based resin is a mixture of water-based anionic polyurethane and water-soluble acrylic resin;
the weight-average molecular weight of the waterborne anionic polyurethane is 100-900 ten thousand; the weight average molecular weight of the water-soluble acrylic resin is 10-90 ten thousand.
In the preparation method provided by the invention, the specific types and the amounts of the aqueous resin, the conductive filler, the water and the aqueous auxiliary agent are selected and used as described above, and are not described in detail herein.
According to the method provided by the invention, the conductive filler, the water-soluble acrylic resin, the water-based auxiliary agent and part of water are mixed and dispersed, and then the water-based anionic polyurethane is added to the mixture and the rest of the water is ground, so that the interaction of the components is facilitated, and the conductivity and the washing resistance of the prepared water-based conductive ink are improved.
The specific operations of grinding and ultrasound in step (1) are not particularly limited in the present invention, and can be performed according to the conventional techniques in the art. Preferably, the average particle size of the solid particles in the dispersion suspension is 1-2 μm, preferably 500-1500 nm. The specific operations of grinding and ultrasound preferably meet the requirement of the average particle size of solid particles in the dispersion suspension, and are more favorable for improving the conductivity and the washing resistance of the prepared water-based conductive ink.
The method has a wide selection range of the water usage in the step (1) and the step (2), and can be properly selected according to the usage of other components in the step (1) and the step (2) so as to meet the requirement of material dispersion as a reference. Preferably, the amount of water used in step (1) is from 10 to 90% by weight, more preferably from 20 to 80% by weight, based on the total amount of water used in step (1) and step (2).
In the present invention, the grinding media may be conventional in the art. For example, the grinding media may be zirconium beads.
The rotation speed of the stirring in step (2) is not particularly limited in the present invention, and may be, for example, 800-.
The stirring time in step (2) of the present invention is selected from a wide range, and may be, for example, 1 to 10 hours, preferably 2 to 6 hours.
The third aspect of the invention also provides a flexible heating cloth which comprises the water-based conductive ink.
The fourth aspect of the invention provides a preparation method of flexible heating cloth, which comprises the steps of coating the waterborne conductive ink provided by the first aspect of the invention or the waterborne conductive ink prepared by the preparation method provided by the second aspect of the invention on a base material cloth, drying to obtain conductive cloth, silk-screening nano silver paste on the conductive cloth through silk-screen printing, drying to obtain a conductive silver paste electrode, and fixing a copper foil on the conductive silver paste electrode to obtain the flexible heating cloth.
The coating and screen printing may be performed by any conventional method in the art, and the present invention is not particularly limited thereto.
In the present invention, preferably, the drying conditions include: the drying temperature is 100-120 ℃, and the drying time is 5-15 min.
The flexible heating cloth prepared by the water-based conductive ink with strong adhesive force, strong flexibility and low resistance has the characteristics of uniform heating, high heating efficiency and high stability.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the square resistance parameter is measured by a four-probe method;
the waterborne anionic modified polyurethane is a commercial product of Bayer company products with the trade name of Dispercoll series;
the organic silicon modified water-based acrylic resin is a commercial product with the trademark of AC-832 of Zhuhaijili company.
Example 1
1. Composition of water-based conductive ink
Based on the weight of the aqueous conductive ink, 55 wt% of aqueous resin (Dispercoll U42, 35 wt%, weight average molecular weight of 400 ten thousand; AC-832, 20 wt%, weight average molecular weight of 40 ten thousand), 1 wt% of carbon nanotubes, 9 wt% of graphene, 30 wt% of deionized water and 5 wt% of aqueous auxiliary agent (TEGO760W, sodium dodecyl benzene sulfonate).
2. Preparation of aqueous conductive ink
(1) Mixing conductive filler, water-soluble acrylic resin and water-based auxiliary agent with part of deionized water (accounting for 50 percent of the total amount of the deionized water), and then grinding and carrying out ultrasonic treatment to obtain a dispersion suspension (the average particle size of solid particles is 1.5 mu m);
(2) and mixing the dispersed suspension, the water-based anionic polyurethane and the rest water, adding a grinding medium zirconium bead, carrying out high-speed stirring grinding (the rotating speed is 800rpm), filtering after grinding for 4 hours, and discharging to obtain the water-based conductive ink.
3. Preparation method of flexible heating cloth
(1) And (3) coating the prepared water-based conductive ink on base material cloth by using a wire bar coater with the thickness of 100 mu m, drying at 110 ℃ for 10min, and taking out to obtain the conductive cloth, wherein the square resistance of the conductive cloth is 40 omega.
(2) And (3) silk-screening the nano silver paste on the conductive cloth by silk-screen printing, drying at 110 ℃ for 10min, and taking out the conductive silver paste electrode.
(3) And (3) adopting a copper adhesive tape as an electrode, sticking copper foils on two sides of the conductive silver paste electrode, and pressing back and forth by using a composite roller to prepare the flexible heating cloth. The distribution of the thermal image of the flexible heating cloth is shown in figure 1. As can be seen from figure 1, the prepared flexible heating cloth has the characteristics of uniform heating, high heating efficiency and high stability.
(4) The prepared flexible heating cloth is placed in water with detergent, the simulated machine washing operation is carried out according to GBT-3921-. As can be seen from fig. 2, the power retention rate of the heat generating cloth was still good after washing 13 times with water.
Example 2
The procedure is as in example 1, except that the composition of the aqueous conductive ink is as follows:
based on the weight of the aqueous conductive ink, 50 wt% of aqueous resin (Dispercoll U54, 35 wt%, weight average molecular weight of 450 ten thousand; AC-832, 15 wt%, weight average molecular weight of 50 ten thousand), 3 wt% of carbon nanotubes, 12 wt% of graphene, 30 wt% of deionized water, and 5 wt% of aqueous additive (BYK190, anionic polyacrylamide, weight average molecular weight of 50 ten thousand).
The square resistance of the obtained conductive cloth was 30 Ω. And the distribution of the thermal image of the prepared flexible heating cloth is similar to that of the thermal image of the flexible heating cloth in figure 1. The prepared flexible heating cloth has the characteristics of uniform heating, high heating efficiency and high stability.
The simulation machine washing operation shows that compared with the electric heating data of the flexible heating cloth before and after washing, the power conservation rate of the heating cloth after washing for 13 times is still good.
Example 3
Based on the weight of the aqueous conductive ink, 60 wt% of aqueous resin (Dispercoll U53, 35 wt%, weight average molecular weight of 500 ten thousand; AC-832, 25 wt%, weight average molecular weight of 45 ten thousand), 1 wt% of carbon nanotubes, 8 wt% of graphene, 30 wt% of deionized water and 1 wt% of aqueous auxiliary agent (coconut oil fatty acid diethanolamide).
The square resistance of the obtained conductive cloth was 80 Ω. And the distribution of the thermal image of the prepared flexible heating cloth is similar to that of the thermal image of the flexible heating cloth in figure 1. The prepared flexible heating cloth has the characteristics of uniform heating, high heating efficiency and high stability.
The simulation machine washing operation shows that compared with the electric heating data of the flexible heating cloth before and after washing, the power conservation rate of the heating cloth after 11 times of water washing is still good.
Example 4
The procedure is as in example 1, except that the composition of the aqueous conductive ink is as follows:
based on the weight of the aqueous conductive ink, 60 wt% of aqueous resin (Dispercoll U53, 40 wt%, weight average molecular weight of 500 ten thousand; AC-832, 20 wt%, weight average molecular weight of 80 ten thousand), 1 wt% of carbon nano tube, 8 wt% of graphene, 30 wt% of deionized water and 1 wt% of aqueous additive (polyoxyethylene lauryl ether) are adopted.
The square resistance of the obtained conductive cloth was 90 Ω. And the distribution of the thermal image of the prepared flexible heating cloth is similar to that of the thermal image of the flexible heating cloth in figure 1. The prepared flexible heating cloth has the characteristics of uniform heating, high heating efficiency and high stability.
The simulation machine washing operation shows that compared with the electric heating data of the flexible heating cloth before and after washing, the power conservation rate of the heating cloth after 10 times of washing is still good.
Example 5
The aqueous conductive ink and the flexible heating cloth were prepared according to the method of example 3, except that the conductive filler in the composition of the aqueous conductive ink was only graphene, i.e., the carbon nanotubes were replaced with graphene of equal mass. The square resistance of the obtained conductive cloth is 200 omega.
Example 6
The aqueous conductive ink and the flexible heating cloth were prepared according to the method of example 3, except that the conductive filler in the composition of the aqueous conductive ink was only carbon nanotubes, i.e., graphene was replaced with carbon nanotubes of equal mass.
The simulation machine washing operation shows that the machine washing resistance of the prepared flexible heating cloth is only measured for 7 times by comparing the electric heating data of the flexible heating cloth before and after washing.
Comparative example 1
An aqueous conductive ink and a flexible heat generating cloth were prepared according to the method of example 3, except that the aqueous resin in the composition of the aqueous conductive ink was only aqueous anionic polyurethane. The square resistance of the obtained conductive cloth is 120 omega, and the resistivity is high. The simulation machine washing operation shows that the machine washing resistance of the prepared flexible heating cloth is only measured for 6 times by comparing the electric heating data of the flexible heating cloth before and after washing.
Comparative example 2
An aqueous conductive ink and a flexible heat generating cloth were prepared in the same manner as in example 3, except that the aqueous resin was only a water-soluble acrylic resin in the composition of the aqueous conductive ink. The square resistance of the obtained conductive cloth is 115 omega, and the resistivity is high. The simulation machine washing operation shows that the machine washing resistance of the prepared flexible heating cloth is only measured for 6 times by comparing the electric heating data of the flexible heating cloth before and after washing.
In conclusion, the water-based conductive ink prepared by the invention has the advantages of good adhesive force, good flexibility, low resistance and the like, can be directly coated, and is simple and convenient to operate. The invention simplifies the traditional coating mode of the strip-shaped silk screen, not only solves the hidden danger of overheating, but also greatly simplifies the operation process. In addition, the machine washing resistance of the flexible electric heating cloth prepared by the invention is very excellent, and the requirements of the flexible electric heating cloth in the field of intelligent clothes are met.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (12)

1. The water-based conductive ink is characterized by comprising 25-60 wt% of water-based resin, 5-20 wt% of conductive filler, 30-45 wt% of water and 1-10 wt% of water-based auxiliary agent, wherein the water-based conductive ink is a mixture of water-based anionic polyurethane with the weight average molecular weight of 100-900 ten thousand and water-soluble acrylic resin with the weight average molecular weight of 10-90 ten thousand.
2. The aqueous conductive ink according to claim 1, wherein the content of the aqueous resin is 40 to 60 wt%, the content of the conductive filler is 5 to 15 wt%, the content of water is 30 to 40 wt%, and the content of the aqueous additive is 1 to 8 wt%, based on the weight of the aqueous conductive ink;
preferably, the content of the conductive filler is 9-15 wt% based on the weight of the aqueous conductive ink;
preferably, the mass ratio of the aqueous anionic polyurethane to the water-soluble acrylic resin is 1-5:1, more preferably 1.4-2.3: 1.
3. The aqueous conductive ink according to claim 1 or 2, wherein the aqueous anionic polyurethane is a polyether-type aqueous polyurethane resin, and the water-soluble acrylic resin is an organosilicon-modified aqueous acrylic resin;
preferably, the weight average molecular weight of the aqueous anionic polyurethane is 300-600 ten thousand, and the weight average molecular weight of the water-soluble acrylic resin is 30-60 ten thousand.
4. The aqueous conductive ink according to claim 1 or 2, wherein the conductive filler is graphene and/or carbon nanotubes;
preferably, the conductive filler is graphene and carbon nanotubes, and the mass ratio of the graphene to the carbon nanotubes is 1-2: 5-10.
5. The aqueous conductive ink according to claim 1 or 2, wherein the aqueous auxiliary agent is at least one of DEGO760W, BYK-190, polyacrylic acid, hydroxymethyl cellulose, sodium dodecylbenzenesulfonate, polyoxyethylene lauryl ether, fatty acid amide, coconut oil fatty acid diethanolamide, and anionic polyacrylamide.
6. The preparation method of the water-based conductive ink is characterized by comprising the following steps of:
(1) mixing the conductive filler, the water-soluble acrylic resin and the water-based auxiliary agent with part of water, and then grinding and/or ultrasonically treating the mixture to obtain a dispersion suspension;
(2) mixing the dispersion suspension, the water-based anionic polyurethane and the rest water, adding a grinding medium, stirring, and filtering;
the conductive filler, the water-soluble acrylic resin, the water-based auxiliary agent, the water-based anionic polyurethane and the water are used in such amounts that the content of the water-based resin in the prepared water-based conductive ink is 25-60 wt%, the content of the conductive filler is 5-20 wt%, the content of the water is 30-45 wt% and the content of the water-based auxiliary agent is 1-10 wt%; the water-based resin is a mixture of water-based anionic polyurethane and water-soluble acrylic resin;
the weight-average molecular weight of the waterborne anionic polyurethane is 100-900 ten thousand; the weight average molecular weight of the water-soluble acrylic resin is 10-90 ten thousand.
7. The preparation method according to claim 6, wherein the average particle size of the solid particles in the dispersion suspension is 1-2 μm, preferably 500-1500 nm.
8. The preparation method according to claim 6, wherein the content of the aqueous resin is 40 to 60 wt%, the content of the conductive filler is 5 to 15 wt%, the content of water is 30 to 40 wt%, and the content of the aqueous additive is 1 to 8 wt% based on the weight of the aqueous conductive ink;
preferably, the content of the conductive filler is 9-15 wt% based on the weight of the aqueous conductive ink;
preferably, the mass ratio of the aqueous anionic polyurethane to the water-soluble acrylic resin is 1-5:1, more preferably 1.4-2.3: 1.
9. The production method according to claim 6, wherein the conductive filler is graphene and/or carbon nanotubes;
preferably, the conductive filler is graphene and carbon nanotubes, and the mass ratio of the graphene to the carbon nanotubes is 1-2: 5-10.
10. The production method according to claim 6, wherein,
the water-based anionic polyurethane is polyether type water-based polyurethane resin, and the water-soluble acrylic resin is organic silicon modified water-based acrylic resin;
preferably, the weight average molecular weight of the aqueous anionic polyurethane is 300-600 ten thousand, and the weight average molecular weight of the water-soluble acrylic resin is 30-60 ten thousand;
preferably, the aqueous auxiliary agent is at least one of DEGO760W, BYK-190, polyacrylic acid, hydroxymethyl cellulose, sodium dodecyl benzene sulfonate, polyoxyethylene lauryl ether, fatty acid amide, coconut oil fatty acid diethanolamide and anionic polyacrylamide.
11. A flexible heating cloth, which is characterized by comprising the water-based conductive ink of any one of claims 1 to 5 or the water-based conductive ink prepared by the preparation method of any one of claims 6 to 10.
12. A preparation method of flexible heating cloth is characterized by comprising the steps of coating the water-based conductive ink of any one of claims 1 to 5 or the water-based conductive ink prepared by the preparation method of any one of claims 6 to 10 on a base material cloth, drying to obtain conductive cloth, silk-screening nano silver paste on the conductive cloth through silk-screen printing, drying to obtain a conductive silver paste electrode, and fixing a copper foil on the conductive silver paste electrode to obtain the flexible heating cloth;
preferably, the drying conditions are: the drying temperature is 100-120 ℃, and the drying time is 5-15 min.
CN202010456503.5A 2020-05-26 2020-05-26 Water-based conductive ink and preparation method thereof, and flexible heating cloth and preparation method thereof Pending CN113717577A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010456503.5A CN113717577A (en) 2020-05-26 2020-05-26 Water-based conductive ink and preparation method thereof, and flexible heating cloth and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010456503.5A CN113717577A (en) 2020-05-26 2020-05-26 Water-based conductive ink and preparation method thereof, and flexible heating cloth and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113717577A true CN113717577A (en) 2021-11-30

Family

ID=78672050

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010456503.5A Pending CN113717577A (en) 2020-05-26 2020-05-26 Water-based conductive ink and preparation method thereof, and flexible heating cloth and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113717577A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286956A (en) * 2022-09-05 2022-11-04 莆田达凯新材料有限公司 Conductive ink, stretchable conductive fabric and application thereof
CN115403981A (en) * 2022-10-10 2022-11-29 长沙岱华科技有限公司 Water-based protective adhesive and preparation method thereof
CN116715930A (en) * 2023-06-12 2023-09-08 东莞理工学院 Flexible conductive composite sensor and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108909057A (en) * 2018-09-27 2018-11-30 潍坊富烯新材料科技有限公司 A kind of carbon nanotube conducting cloth and preparation method thereof
CN110054930A (en) * 2019-03-12 2019-07-26 北京爱上地科技有限公司 A kind of aqueous double-component electric heating ink and preparation method thereof
CN110054938A (en) * 2019-03-12 2019-07-26 北京爱上地科技有限公司 A kind of aqueous flexible electric heating ink and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108909057A (en) * 2018-09-27 2018-11-30 潍坊富烯新材料科技有限公司 A kind of carbon nanotube conducting cloth and preparation method thereof
CN110054930A (en) * 2019-03-12 2019-07-26 北京爱上地科技有限公司 A kind of aqueous double-component electric heating ink and preparation method thereof
CN110054938A (en) * 2019-03-12 2019-07-26 北京爱上地科技有限公司 A kind of aqueous flexible electric heating ink and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
强涛涛: "《合成革化学品》", 31 July 2016 *
方小牛等: "《生土类建筑保护技术与策略》", 28 February 2018 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115286956A (en) * 2022-09-05 2022-11-04 莆田达凯新材料有限公司 Conductive ink, stretchable conductive fabric and application thereof
CN115403981A (en) * 2022-10-10 2022-11-29 长沙岱华科技有限公司 Water-based protective adhesive and preparation method thereof
CN115403981B (en) * 2022-10-10 2023-08-29 长沙岱华科技有限公司 Water-based protective adhesive and preparation method thereof
CN116715930A (en) * 2023-06-12 2023-09-08 东莞理工学院 Flexible conductive composite sensor and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN113717577A (en) Water-based conductive ink and preparation method thereof, and flexible heating cloth and preparation method thereof
CN107635296A (en) A kind of graphene nano silver wire composite and flexible heating membrane module
CN107141726A (en) Graphene conductive polymer composite, its preparation method and Electric radiant Heating Film therefrom
CN106941736A (en) A kind of graphene electric heating film and preparation method thereof
CN108192577A (en) A kind of fire-retardant graphene flexible membrane of high heat conduction and preparation method thereof
CN111073059B (en) Nano-cellulose electrothermal film and preparation method thereof
CN107129752A (en) A kind of graphene nano silver wire composite mortar and preparation method thereof
KR20080030410A (en) Conductive ink-composition for flat type pyrogen and flat type pyrogen using with the ink composition
CN109777113A (en) A kind of insulating heat-conductive silicon rubber composite material and preparation method thereof
CN103108906A (en) Conductive polymer composition for ptc element with decreased ntc characteristics, using carbon nanotube
CN110467846A (en) A kind of preparation method of oiliness electric heating conversion ink and prepared ink
CN106470505A (en) Energy-conserving and environment-protective high temperature resistant type far-infrared health-care semiconductor heating slurry
CN110312330A (en) A kind of safety electric film and preparation method thereof
CN109769314A (en) A kind of flexibility carbon composite electric heating film and its application
CN109972409A (en) A kind of containing graphene water-based electric heating functional paint electrically conductive composition and its application
CN107592685A (en) A kind of method for preparing double heating layer graphene Electric radiant Heating Films
Huang et al. Metal mesh embedded in colorless shape memory polyimide for flexible transparent electric-heater and actuators
TW200832453A (en) Composition for electric-heating film and electric-heating film and electric-heating device manufactured by the same
CN109246870A (en) A kind of preparation method of full printing low pressure high-performance pattern heating device flexible
WO2022120565A1 (en) Graphene heating ink, preparation method therefor, and application thereof
CN104031353A (en) Nano mixed type thermally conductive adhesive and processing technology thereof
CN104194631B (en) It is the coating that host coats that electrochemical capacitor shell produces to dispel the heat by graphene microchip
CN113621272B (en) Conductive ink with temperature limiting characteristic, preparation method and heating ceramic tile
CN108912845A (en) A kind of quantum dot-doped silver ink and preparation method thereof
CN111560190A (en) Preparation method of PTC graphene-based conductive ink and PTC graphene-based conductive ink

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: 20211130

RJ01 Rejection of invention patent application after publication