阅读说明：本技术 一种导电发热印花织物的制备方法及其产品和应用 (Preparation method of conductive heating printed fabric, product and application thereof ) 是由 邵怡沁 陈慰来 宋倩倩 于 2021-09-28 设计创作，主要内容包括：本发明供了一种导电发热印花织物的制备方法及其产品和应用,包括以下步骤：1)、采用三维制造技术织造针织物作为三维间隔针织层：a、通过经纬交织制成表面层,将两层表面层作为一组；b、通过连接纱在两层表面层之间交替钩连形成往复折回连接形态,通过往复折回连接形态在两层表面层之间形成中空间隙,通过中空间隙使正反两表面层间距增大,形成三维空间形态的双层面料；2)、采用石墨烯和/或碳纳米管作为导电基本材料,制备出导电印花浆；3)、将导电印花浆通过喷墨印花的方式,在三维间隔针织层表面有选择性地形成导电通路图案,通过控制喷涂压力及织物的孔隙率来控制导电印花浆的浸润程度,从而控制电导率和发热功效。(The invention provides a preparation method of a conductive heating printed fabric, a product and an application thereof, and the preparation method comprises the following steps: 1) and weaving the knitted fabric as a three-dimensional interval knitting layer by adopting a three-dimensional manufacturing technology: a. the surface layer is made by warp and weft interweaving, and the two surface layers are used as a group; b. the connecting yarns are alternately hooked between the two surface layers to form a reciprocating folding connecting form, a hollow gap is formed between the two surface layers through the reciprocating folding connecting form, and the distance between the front surface layer and the back surface layer is increased through the hollow gap to form the double-layer fabric in a three-dimensional space form; 2) preparing conductive printing paste by using graphene and/or carbon nano tubes as conductive basic materials; 3) and selectively forming a conductive path pattern on the surface of the three-dimensional interval knitted layer by using the conductive printing paste in an ink-jet printing mode, and controlling the infiltration degree of the conductive printing paste by controlling the spraying pressure and the porosity of the fabric so as to control the conductivity and the heating effect.)

1. The preparation method of the conductive heating printed fabric is characterized by comprising the following steps of:

1) and weaving the knitted fabric as a three-dimensional interval knitting layer by adopting a three-dimensional manufacturing technology:

a. the surface layer is made by warp and weft interweaving, and the two surface layers are used as a group;

b. the connecting yarns are alternately hooked between the two surface layers to form a reciprocating folding connecting form, a hollow gap is formed between the two surface layers through the reciprocating folding connecting form, and the distance between the front surface layer and the back surface layer is increased through the hollow gap to form the double-layer fabric in a three-dimensional space form;

2) preparing conductive printing paste by using graphene and/or carbon nano tubes as conductive basic materials;

3) selectively forming conductive path patterns on the surface of the three-dimensional interval knitted layer by using the conductive printing paste in an ink-jet printing mode, and controlling the infiltration degree of the conductive printing paste by controlling the spraying pressure and the porosity of the fabric so as to control the conductivity and the heating effect;

4) and drying the sprayed three-dimensional interval knitted layer to finally realize the conductive heating fabric.

2. The method of manufacturing a conductive heat emitting printed fabric according to claim 1, wherein in the step 1) b, the connecting yarn is reciprocatingly hooked between the warp direction reinforcing yarns of the two surface layers by the knitting machine, thereby enlarging a gap between the two surface layers.

3. The method for preparing the conductive heat emitting printed fabric according to claim 1, wherein in the step 2), the method for preparing the conductive printing paste comprises the steps of:

a. mixing graphene and/or carbon nano tubes with an ethylene, acetone and toluene dichloride organic solvent, and ultrasonically stirring and dispersing at room temperature to obtain a conductive mixed solution;

b. the conductive mixed liquid is mixed with the water-based resin, so that the adhesion performance of the conductive slurry and the surface of the fabric is improved.

4. The method for preparing a conductive heat emitting printed fabric according to claim 1, wherein in the step 2), a conductive base material containing graphene and/or carbon nanotubes may be further added with a conductive metal to form a mixed conductive material.

5. The method for preparing the conductive heating printed fabric according to claim 1, wherein in the step 3), the conductive printing paste is sprayed on the surface of the three-dimensional spaced knitted layer according to the set transverse and longitudinal conductive paths by an intelligent electric control spraying device, the nozzle pressure is controlled during the spraying process, and the thickness of the conductive printing paste penetrating into the fabric is controlled according to the set by utilizing the porosity of the fabric.

6. The method for preparing a conductive heat emitting printed fabric according to claim 1, wherein in the step 4), the drying operation comprises room temperature drying, low temperature freeze drying or high temperature drying.

7. The preparation method of the conductive heating printed fabric as claimed in claim 1, wherein the three-dimensional spacing knitted layer is woven by any one of terylene, cotton, aramid, glass fiber, polyamide, 30% stainless steel fiber and carbon fiber.

8. The preparation method of the conductive heating printed fabric as claimed in claim 1, wherein the three-dimensional spacing knitted layer is mixed and woven by adopting at least two materials of terylene, cotton, aramid fiber, glass fiber, polyamide, 30% stainless steel fiber and carbon fiber.

9. An electroconductive heat-emitting printed fabric, characterized in that it is produced by the process according to any one of claims 1 to 8.

10. The conductive heating printed fabric according to claim 9 is used alone as a conductive heating material or is compounded with other materials to prepare an intelligent heat-insulating conductive heating material.

Technical Field

The invention belongs to the technical field of textiles, and relates to a functional fabric, in particular to a preparation method of a conductive heating printed fabric, a product and an application thereof.

Background

At present, wearable conductive heating equipment based on textiles receives more and more extensive attention from people due to the application of the wearable conductive heating equipment in the aspects of intelligent energy and the like. With the development of wearable electronic textile technology, attempts are being made to develop joule conductive heat generating textiles using conductive flexible materials. The textile material with the conductive heating function has the characteristics of good flexibility, light and thin texture, simple and convenient preparation method, good interface combination and the like, so that the textile material with the conductive heating function becomes the most promising material for wearable conductive heating equipment.

The electric heating textile is a general name of a textile which realizes heating by driving a heating element embedded in the textile to work by electric energy. The electric heating device mainly comprises a power supply, a temperature control part, a circuit protection part, a heating element and the like, which are connected with each other through leads, and the electric energy is converted into heat energy after being electrified to achieve the effect of heating and keeping warm. However, the current domestic and foreign research on electric heating elements mainly includes three aspects of conductive heating metal wires, conductive heating films and conductive heating fabrics, wherein the conductive heating metal wires are hard in material, poor in folding resistance and poor in comfort; the conductive heating film has low production cost and long service life, but has poor air permeability and low flexibility. The conductive heating fabric prepared from the organic heating material is easy to break in the weaving process due to high brittleness, so that the stability of the conductive heating fabric is poor. Meanwhile, the heat utilization rate of the conductive heating fabric is generally low.

Disclosure of Invention

The invention aims to solve the problems in the prior art, and provides a preparation method of a conductive heating printed fabric, a product and application thereof, wherein the preparation method adopts the combination of fabric with three-dimensional gaps and the wetting degree of conductive slurry to regulate and control the conductivity and the heating effect.

The purpose of the invention can be realized by the following technical scheme: a preparation method of a conductive heating printed fabric comprises the following steps:

1) and weaving the knitted fabric as a three-dimensional interval knitting layer by adopting a three-dimensional manufacturing technology:

a. the surface layer is made by warp and weft interweaving, and the two surface layers are used as a group;

b. the connecting yarns are alternately hooked between the two surface layers to form a reciprocating folding connecting form, a hollow gap is formed between the two surface layers through the reciprocating folding connecting form, and the distance between the front surface layer and the back surface layer is increased through the hollow gap to form the double-layer fabric in a three-dimensional space form;

2) preparing conductive printing paste by using graphene and/or carbon nano tubes as conductive basic materials;

3) selectively forming conductive path patterns on the surface of the three-dimensional interval knitted layer by using the conductive printing paste in an ink-jet printing mode, and controlling the infiltration degree of the conductive printing paste by controlling the spraying pressure and the porosity of the fabric so as to control the conductivity and the heating effect;

4) and drying the sprayed three-dimensional interval knitted layer to finally realize the conductive heating fabric.

In the above method for manufacturing the conductive heat-generating printed fabric, in step 1) b, the connecting yarn is hooked to the warp-wise reinforcing yarns of the two surface layers in a reciprocating manner by the knitting machine, so that the gap between the two surface layers is enlarged.

In the above method for preparing the conductive heating printed fabric, in the step 2), the method for preparing the conductive printing paste comprises the following steps:

a. mixing graphene and/or carbon nano tubes with an ethylene, acetone and toluene dichloride organic solvent, and ultrasonically stirring and dispersing at room temperature to obtain a conductive mixed solution;

b. the conductive mixed liquid is mixed with the water-based resin, so that the adhesion performance of the conductive slurry and the surface of the fabric is improved.

The surface tension of the conductive mixed liquid is between 30 and 50 mN/m; the viscosity is 1 to l0Pa s, preferably 4 pas or more. The aperture of the nozzle is 50 μm, and the average particle size of the conductive paste system is less than 0.5 μm.

In the above method for preparing the conductive heat-generating printed fabric, in step 2), a conductive base material containing graphene and/or carbon nanotubes may further be added with a conductive metal to form a mixed conductive material.

In the preparation method of the conductive heating printed fabric, in the step 3), the conductive printing paste is sprayed on the surface of the three-dimensional spaced knitted layer according to the set transverse and longitudinal conductive paths by intelligent electric control spraying equipment, the pressure of a nozzle is controlled in the spraying process, and the thickness of the conductive printing paste penetrating into the fabric is controlled according to the set porosity of the fabric.

In the above method for preparing the conductive heat-generating printed fabric, in step 4), the drying operation includes room temperature drying, low temperature freeze drying or high temperature drying.

In the preparation method of the conductive heating printed fabric, the three-dimensional interval knitted layer is woven by any one of terylene, cotton, aramid fiber, glass fiber, polyamide, 30% stainless steel fiber and carbon fiber.

In the preparation method of the conductive heating printed fabric, the three-dimensional interval knitted layer is mixed and woven by adopting at least two materials of terylene, cotton, aramid fiber, glass fiber, polyamide, 30% stainless steel fiber and carbon fiber.

The conductive heating printed fabric is prepared according to the method.

The conductive heating printed fabric is independently used as a conductive heating material or is compounded with other materials to prepare the intelligent heat-insulating conductive heating material.

Compared with the prior art, the preparation method of the conductive heating printed fabric, the product and the application thereof have the following advantages:

1. the invention provides a preparation method of a conductive heating printed fabric, wherein the conductive material utilizes the excellent characteristics of high thermal conductivity, electron mobility and the like of graphene and carbon nano tubes to enhance the conductive heating performance of the fabric.

2. The invention provides a preparation method of a conductive heating printed fabric, which is prepared by ink-jet printing, so that the product has the characteristics of high forming speed, flexible pattern, adjustable conductive material, suitability for personalized production, low environmental protection energy consumption and the like, and is suitable for industrial production.

3. The invention provides a conductive heating printed fabric, which takes a three-dimensional weft-knitted or warp-knitted spacer fabric as a matrix, has good compression resilience, compact structure, light weight and good flexibility, and is beneficial to the utilization efficiency of the conductive heating fabric because the spacer fabric is internally provided with an intermediate air layer.

4. The invention provides a conductive heating printed fabric which has high conductive heating performance and controllability of setting resistance form and resistance value, so that the conductivity and the heating effect are controlled. Has wide application prospect in the fields of medical health care textiles and intelligent textiles.

Drawings

Fig. 1 is a schematic structural view of the conductive heat-emitting printed fabric of the present invention.

In the figure, 1, weft reinforcement yarn; 2. a warp-wise reinforcing yarn; 3. connecting yarns; 4. and (4) a conductive printing layer.

Detailed Description

The following are specific embodiments of the present invention and are further described with reference to the drawings, but the present invention is not limited to these embodiments.

As shown in fig. 1, the conductive heating printed fabric comprises three-dimensional spacing knitted layers, the three-dimensional spacing knitted layers comprise two surface layers which are arranged in parallel, the two surface layers are connected through a connecting layer, the connecting layer is provided with connecting yarns 3, the connecting yarns 3 are alternately hooked between the two surface layers to form a connecting path in a reciprocating folding back shape, the surface layers are coated with conductive printed layers 4, a transverse conductive path and a longitudinal conductive path are arranged in the conductive printed layers 4, and the conductive printed layers 4 are provided with conductive resistors with different permeation thicknesses.

The surface layer has a weave structure of any one of a rib weave, a loop weave, a plated stitch, and a warp flat weave.

The organizational structure of superficial layer is the warp flat tissue, and the superficial layer includes latitudinal direction reinforcing yarn 1 and warp direction reinforcing yarn 2, and latitudinal direction reinforcing yarn 1 is horizontal arrangement, and warp direction reinforcing yarn 2 is vertical arrangement, and latitudinal direction reinforcing yarn 1 and warp direction reinforcing yarn 2 looks vertical cross weave.

The connecting yarns 3 hook the warp-wise reinforcing yarns 2.

A hollow gap is clamped in the connecting layer between the two surface layers. The space between the front surface layer and the back surface layer is increased through the hollow gap, and the double-layer fabric with a three-dimensional space form is formed.

The three-dimensional interval knitting layer is a three-dimensional interval warp knitting fabric or a three-dimensional interval weft knitting fabric.

The weaving material adopted by the three-dimensional interval knitting layer adopts the following two schemes:

according to the first scheme, the three-dimensional interval knitted layer is any one fabric of terylene, cotton, aramid fiber, glass fiber, polyamide, 30% stainless steel fiber and carbon fiber.

And in the second scheme, the three-dimensional interval knitting layer is a mixed fabric of at least two of terylene, cotton, aramid fiber, glass fiber, polyamide, 30% stainless steel fiber and carbon fiber.

The conductive printing layer 4 is a mixture layer of graphene and/or carbon nanotubes and conductive metal.

The following are examples of several preparation methods of the conductive heating printed fabric:

example 1: carbon nanotube printed polyester fiber conductive heating fabric

Step one, manufacturing a three-dimensional polyester fiber spacer fabric, which comprises the following specific operations:

the weaving technology is used for weaving three-dimensional fabrics as framework materials, and the framework materials are woven by a double-needle bed circular knitting machine. The upper layer tissue and the lower layer tissue of the weft-knitted spacer fabric are tucked on a cylinder needle through spacer yarns, loops are knitted on a dial needle, the spacer yarns are tucked on the cylinder needle, and the cylinder needle is tucked. The spacing yarn weaves alternately on the dial and the needle cylinder, travels in the upper and lower surface layers in a tucking or looping mode, and is regularly connected with the upper and lower surface layers to form the fabric with an intermediate air layer. The connecting line is made of monofilament, such as polyester with higher bending rigidity, and the two surface layers are supported and separated to form the elastic spacer fabric with thickness and more air storage capacity.

Step two, preparing the conductive slurry, which comprises the following specific operations:

4.5g of carboxylated carbon nanotubes are added into a beaker for wetting treatment, and then 0.6g of 3-sulfopropyl tetradecyl dimethyl betaine and 0.45g of polyoxyethylene dodecyl sulfonic ether are sequentially added as chemical dispersants to replace air and moisture on the surface of the carbon nanotubes, and are mixed with quantitative water to prepare 150mL of mixed solution. And (3) putting the beaker filled with the mixed solution into an ultrasonic cleaner for grinding and oscillation, so that the wet carbon nano tubes become independent micro particles. Wherein, the ultrasonic time is 3h, the ultrasonic temperature is 30 ℃, and the ultrasonic frequency is 40kHz, undissolved carbon nano tube monomers are not seen at the bottom of the beaker finally, the solution is uniformly mixed, and the solution is kept for a long time without precipitation, so that the required uniform carbon nano tube solution is prepared.

Step three, ink-jet printing of the conductive paste comprises the following specific operations:

the polyester fabric was padded with a pre-treatment solution (mangle ratio of 80%) on a padder and then dried at 110 ℃ for 3 min. Performing ink-jet printing on the fabric by using the carbon nanotube slurry synthesized in the step two on an ink-jet printer, and then drying for 3min at 110 ℃; then treating for a certain time (30s-120s) at a certain temperature (150-. The relation of the surface heating temperature of the heating sample under different voltages along with the change of the voltage is tested, and the optimal conductive heating effect is obtained as follows: the power voltage is 9V, the heating temperature can be maintained at 38.3 ℃, and the surface heating temperature of the sample after low-voltage heating can meet the warm-keeping requirement of a human body.

Example 2: graphene printed three-dimensional warp-knitted conductive heating fabric

Step one, weaving a three-dimensional warp knitted fabric as a framework material by adopting a three-dimensional weaving technology, and comprising the following steps of:

the method is characterized in that six guide bars are adopted to weave on a double-needle bed warp knitting machine, the six guide bars are GB1, GB2, GB3, GB4, GB5 and GB6 in sequence, and the method comprises the following steps: the guide bars GB1 and GB2 penetrate into the upper surface layer yarns, the guide bars GB5 and GB6 penetrate into the lower surface layer yarns, and the guide bars GB3 and GB4 penetrate into the space yarns, which are both positive let-off; the upper surface layer of the fabric is knitted by guide bars GB1 and GB2, and the lower surface layer of the fabric is knitted by guide bars GB5 and GB6, which are normal yarn feeding; the spacer filaments are woven from guide bars GB3, GB 4.

Step two, preparing the conductive slurry, which comprises the following specific operations:

graphite powder is firstly oxidized and centrifuged, sodium dodecyl benzene sulfonate is used as a stabilizer, and supernatant liquid is taken for ink-jet printing. After the preparation, the film was annealed at a high temperature of 500 ℃ for 2 hours in the air, and the resistance was measured to be 270. omega. Further, the graphene conductive agent is repeatedly pressed with a roller when it is prepared. After pressing, a tight conductive network is formed between the graphene layers to improve the conductivity of the ink. The effect is better if 3-butyl-1-methylimidazolium chloride is used as a dispersant and the concentration of graphene is increased by evaporation and concentration.

Step three, ink-jet printing of the conductive paste comprises the following specific operations:

graphene oxide is dispersed in a solvent, and a reduction reaction is required after printing. And (3) flatly laying the cut fabric under a spray head, carrying out ink-jet printing on the graphene prepared in the step two, repeating the process for 1, 2, 3, 4 and 5 times to obtain conductive printing coatings with different thicknesses, and then placing the obtained GO-printed fabric in an oven at 80 ℃ for drying for 15 min. Weighing a certain amount of reducing agent, preparing the reducing agent into solutions with different concentrations, placing the solutions in a water bath condition at 90 ℃ for reduction for 1, 2, 4, 6 and 12 hours respectively, and drying the graphene cotton fabric obtained by reduction in an oven at 80 ℃ for 15 min. The surface resistance of the heating fabric obtained by testing the conductivity of the fabric is 4k/cm, and the heating performance of the fabric is good when the voltage interval between two ends of the fabric is 20-24V, and reaches about 70 ℃.

Example 3: graphene/carbon nanotube mixed printed fabric

Step one, weaving a three-dimensional warp knitted fabric as a framework material by adopting a three-dimensional weaving technology, and the method comprises the following specific operations:

the method comprises the steps of utilizing 1, 2 and 3 guide bars in front of a Raschel double-needle bed warp knitting machine and 1, 2 and 3 guide bars behind the Raschel double-needle bed warp knitting machine to respectively complete the knitting of an upper surface layer and a lower surface layer of a three-dimensional fabric on two needle beds, then alternately knitting a yarn guide on the front needle bed and the rear needle bed to form loops, connecting the two knitted surface layers to complete the knitting of the three-dimensional fabric, and changing the thickness of the three-dimensional fabric by adjusting the distance between the front needle bed and the rear needle bed. When weaving, the high-grade quilting product can be woven by adding fluffy yarn between the front and back fabrics and matching with computer jacquard equipment. The double-faced fabric with jacquard effect on both front and back can be woven by adopting a double-faced needle selection electronic jacquard knitting machine.

Step two, preparing the conductive slurry, which comprises the following specific operations:

the preparation method comprises the following steps of adding a certain amount of carbon nano tubes into 25 parts of water-soluble acrylic resin, 15 parts of water-soluble graphene powder, 30 parts of deionized water, 5 parts of an auxiliary agent, 1 part of a coloring agent, 0.5 part of a dispersing agent, 2 parts of an epoxy silane coupling agent and the like, and preparing and calculating all materials according to mass percentage. And (3) adding the water-soluble acrylic resin into deionized water, and stirring to add the water-soluble graphene powder. And then gradually adding the auxiliary agent to obtain the pre-dispersed material, wherein the stirring speed is 1300 r/min. Standing the stirred intermediate material for 20min, filtering to remove excessive water, and grinding the obtained mixed slurry until the fineness is below 10 μm. And filtering the ground material to obtain the water-soluble graphene carbon nanotube conductive slurry.

Step three, ink-jet printing of the conductive paste comprises the following specific operations:

mixing water-soluble polyurethane with distilled water, and performing ultrasonic treatment for 30min (setting parameters of an ultrasonic machine to be 600W and 40kHz) to fully and uniformly mix the water-soluble polyurethane and the distilled water. Fully emulsifying the graphene carbon nanotube slurry by using a homogenizer, adding the solution obtained in the previous step, and carrying out ultrasonic treatment for 1 hour again. The finally obtained mixed liquid is used for processing the fabric for multiple times in an ink-jet printing mode, and the ink-jet pressure parameters in the experiment are set as follows: the pressure was set at 1MPa, the liquid flow rate of the solution was 0.3mL/cm2, and the treatment time was 3 seconds each. And finally, drying to obtain the graphene carbon nanotube conductive heating functional textile with different graphene carbon nanotube/water-soluble polyurethane ratios. The test result shows that the conductive heating fabric with better effect can be quickly increased to the steady-state temperature of 48.6 ℃ within 40s under the condition of the direct current voltage applied to 10V.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Although weft-reinforcing yarns 1 are used more herein; warp-wise reinforcing yarns 2; a connecting yarn 3; conductive print layer 4, etc., but does not exclude the possibility of using other terms. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.