CN110016822B - Dye composition and preparation method thereof, conductive heating fiber and preparation method thereof, and conductive heating fabric - Google Patents
Dye composition and preparation method thereof, conductive heating fiber and preparation method thereof, and conductive heating fabric Download PDFInfo
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- CN110016822B CN110016822B CN201810015483.0A CN201810015483A CN110016822B CN 110016822 B CN110016822 B CN 110016822B CN 201810015483 A CN201810015483 A CN 201810015483A CN 110016822 B CN110016822 B CN 110016822B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/445—Use of auxiliary substances before, during or after dyeing or printing
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
- D06P1/5235—Polyalkenyl halides, e.g. PVC
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5285—Polyurethanes; Polyurea; Polyguanides
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65131—Compounds containing ether or acetal groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/673—Inorganic compounds
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Abstract
The invention relates to the field of water-based carbon nanotube/graphene dyes, and discloses a dye composition and a preparation method thereof, a conductive heating fiber and a preparation method thereof, and a conductive heating fabric, wherein the dye composition contains water-based resin, a carbon nanotube, graphene and water, and the particle sizes of the carbon nanotube and the graphene are all less than 800 nanometers. The invention also discloses a conductive heating fabric which has good conductive heating effect, excellent breaking strength and better color fastness, and meanwhile, the fabric is thermally combined with TPU, has insulating, waterproof and breathable effects and does not lose softness.
Description
Technical Field
The invention relates to the field of aqueous carbon nanotube dyes, in particular to a dye composition and a preparation method thereof, a conductive heating fiber and a preparation method thereof, and a conductive heating fabric.
Background
The disperse dye is a hydrophobic nonionic dye, generally has small molecular weight and simple structure, and can be in a uniformly dispersed state by interacting with a dispersant in an aqueous solution. Dye molecules can enter the interior of the fiber and dye with the action of hydrogen bonds and Van der Waals force and the fiber.
The carbon nanotube is a seamless nanotube formed by rolling a single-layer or multi-layer graphite sheet, and shows excellent mechanical properties and good thermal and electrical conductivity due to its unique structure and nano effect.
Graphene (Graphene) is a polymer made of carbon atoms in sp2The honeycomb plane film formed by the hybridization mode has good toughness, can be bent, and is a novel nano material which is the thinnest, the largest in strength and the strongest in electric conduction and heat conduction performance and is discovered at present.
The conductive fiber is a conductive fiber invented earlier, and the existing methods for preparing the conductive fiber by using inorganic conductive nanoparticles mainly comprise two types, namely a method for blending conductive particles and polymers, and a method for adsorbing the conductive particles by conductive polymers, but the conductive fiber obtained needs to be further improved in conductive heat generating property, resistance, strength and color fastness.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides a dye composition and a preparation method thereof, a conductive heating fiber and a preparation method thereof, and a conductive heating fabric, wherein the conductive heating fabric has an excellent conductive heating effect, excellent breaking strength and good color fastness, and meanwhile, the fabric is thermally combined with TPU (thermoplastic polyurethane), has insulating, waterproof and breathable effects, and does not lose softness.
In order to achieve the above object, a first aspect of the present invention provides a dye composition, wherein the dye composition comprises an aqueous resin, carbon nanotubes, graphene, and water, and the particle size of each of the carbon nanotubes and the graphene is 800 nm or less.
The second aspect of the present invention provides a method for preparing a dye composition, wherein the method comprises: mixing an aqueous dispersion containing carbon nanotubes and an aqueous dispersion containing graphene, an aqueous resin, an optional auxiliary agent, an optional organic solvent and water, wherein the particle sizes of the carbon nanotubes and the graphene in the aqueous dispersion containing the carbon nanotubes and the aqueous dispersion containing the graphene are both 800 nanometers or less.
The third aspect of the present invention provides a conductive heating fiber, wherein the conductive heating fiber is obtained by contact dyeing of a raw material fiber and the dye prepared by the dye composition or the dye preparation method.
The invention also provides a preparation method of the conductive heating fiber, wherein the method further comprises the steps of carrying out contact dyeing on the raw material fiber and the dye prepared by the dye composition or the preparation method of the dye, and then carrying out padding, baking, shaping and winding on the raw material fiber.
The fifth aspect of the invention provides a conductive heating fabric, wherein the conductive heating fibers or the conductive heating fibers prepared by the preparation method are woven by using warp yarns and/or weft yarns.
The dye composition overcomes the defects of poor uniformity and poor dispersibility of conductive particles caused by blending conductive particles and polymers or adsorbing the conductive particles by conductive polymers in the prior art, simultaneously adopts the water dispersion containing the carbon nano tubes and the water dispersion containing the graphene, further increases the compatibility of the carbon nano tubes, the graphene and other components, can ensure that the conductive heating fabric has excellent conductive heating effect, and also has excellent breaking strength and better color fastness.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic flow diagram of a process for preparing a dye composition of the present invention;
FIG. 2 is a process diagram of the method for preparing the conductive heating fiber of the present invention;
fig. 3 is a schematic structural view of a conductive heat emitting fabric according to a preferred embodiment of the present invention;
fig. 4 is a schematic structural view of a conductive heat emitting fabric according to another preferred embodiment of the present invention;
fig. 5 is a schematic process flow diagram of the conductive heating fabric of the present invention.
Description of the reference numerals
1. Raw material fiber 2 and dye tank containing dye
3. Baking and shaping 4, and winding
First, a schematic region in which electrode copper wires are arranged in the warp direction
Indication area of flame-retardant thread arranged along warp direction
Indication area of conductive fiber arranged along weft direction
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
It should be noted that, in the dye composition of the present invention, the components included therein, for example, the components of the aqueous resin, the aqueous dispersion containing carbon nanotubes, and the aqueous dispersion containing graphene, are present separately. When the dye is used, the dye is prepared by mixing according to the method of the invention.
In a first aspect, the present invention provides a dye composition, wherein the dye composition comprises an aqueous resin, carbon nanotubes, graphene and water, and the particle size of each of the carbon nanotubes and the graphene is 800 nm or less.
Preferably, the particle size of the carbon nanotube is 400-600 nm, and the particle size of the graphene is 400-600 nm.
According to the invention, relative to 100 parts by weight of the aqueous resin, the content of the carbon nano tube is 40-60 parts by weight, and the content of the graphene is 5-25 parts by weight; preferably, the content of the carbon nanotubes is 45 to 55 parts by weight and the content of the graphene is 5 to 15 parts by weight relative to 100 parts by weight of the aqueous resin; more preferably, the carbon nanotube is included in an amount of 50 parts by weight, and the graphene is included in an amount of 10 parts by weight.
According to the invention, the weight ratio of the content of the carbon nanotubes to the content of the graphene is (1-3): 1.
according to the invention, the carbon nanotube is one or more of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube, and is preferably a multi-walled carbon nanotube. In the present invention, the source of the carbon nanotube is not particularly limited, and the carbon nanotube may be obtained commercially or prepared according to a known method, and will not be described herein again.
According to the present invention, the aqueous resin may be various aqueous resins conventional in the art, and preferably, the aqueous resin is selected from one or more of polyurethane resin, acrylic resin, fluorocarbon resin, polyester resin and polyether resin; preferably a polyurethane resin.
According to the present invention, in order to further increase the performance of the dye prepared from the dye composition, the dye composition further comprises at least one auxiliary selected from one or more of a dispersant, a defoamer and a thickener, the total content of the auxiliary being 2 to 30 parts by weight, preferably 2 to 15 parts by weight, with respect to 100 parts by weight of the aqueous resin; more preferably 5 to 10 parts by weight.
The dispersant, defoamer and thickener according to the present invention may be various dispersants, defoamers and thickeners which are conventional in the art. For example,
the dispersant is selected from aqueous dispersants, for example, one or more of BYK chemical BYK-190, X-405, and BYK 110;
the defoaming agent is selected from one or more of F111 defoaming agent, 901W and BYK 024;
the thickener is selected from one or more of a polyurethane thickener (e.g., polyurethane thickener 8w), a polyacrylate thickener, and a copolymer emulsion thickener.
The dispersant, defoamer and thickener may be in conventional amounts. Preferably, the dispersant may be used in an amount of 5 to 15 parts by weight, the defoamer may be used in an amount of 0.5 to 5 parts by weight, and the thickener may be used in an amount of 0.5 to 3 parts by weight, relative to 100 parts by weight of the aqueous resin.
More preferably, the dispersant may be used in an amount of 8 to 12 parts by weight, the defoamer may be used in an amount of 0.8 to 3 parts by weight, and the thickener may be used in an amount of 0.8 to 1.2 parts by weight, relative to 100 parts by weight of the aqueous resin.
According to the invention, the dye composition also comprises an organic solvent which has the functions of enhancing the compatibility of the aqueous resin and the carbon nano tube and the graphene and reducing the surface tension of the whole system as a cosolvent. For example, the organic solvent may be one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol methyl ether and ethylene glycol phenyl ether, preferably ethylene glycol butyl ether.
The amount of the organic solvent used is not particularly limited as long as the dye easily wets the fibers. Specifically, the content of the organic solvent is 1 to 10 parts by weight relative to 100 parts by weight of the aqueous resin; preferably, the organic solvent is contained in an amount of 1 to 5 parts by weight with respect to 100 parts by weight of the aqueous resin.
In a second aspect, the present invention provides a process for preparing the dye composition described above, which comprises: mixing an aqueous dispersion containing carbon nanotubes and an aqueous dispersion containing graphene, an aqueous resin, an optional auxiliary agent, an optional organic solvent and water, wherein the particle sizes of the carbon nanotubes and the graphene in the aqueous dispersion containing the carbon nanotubes and the aqueous dispersion containing the graphene are both 800 nanometers or less.
Preferably, the particle size of the carbon nanotube is 400-600 nm, and the particle size of the graphene is 400-600 nm.
According to the present invention, the method for mixing the dye composition of the present invention with water is not particularly limited, and may be various mixing methods in the art, and preferably, in the present invention, the preparation process of the aqueous dispersion containing carbon nanotubes and the aqueous dispersion containing graphene comprises the following steps:
(1) grinding and mixing the carbon nano tube and water to obtain an aqueous dispersion liquid with the carbon nano tube content of 5-15 wt%;
(2) grinding and mixing graphene and water to obtain an aqueous dispersion with the graphene content of 1-10 wt%;
(3) and (3) uniformly mixing the aqueous dispersions obtained in the step (1) and the step (2).
The inventors of the present invention have found, in the course of their research, that the use of the aqueous dispersion containing carbon nanotubes and the aqueous dispersion containing graphene in combination can significantly improve the dispersibility, conductivity, stability, color fastness, and the like of the resulting dye. Therefore, according to a preferred embodiment of the present invention, the aqueous dispersion containing carbon nanotubes and the aqueous dispersion containing graphene are used in combination with the aqueous resin, and the effects are excellent. Wherein, in the dye composition, the aqueous dispersion containing carbon nanotubes, the aqueous dispersion containing graphene, and the aqueous resin may be present separately. Preferably, for the convenience of proportioning, the components of the dye composition are stored according to a certain proportion, for example, the weight ratio of the aqueous dispersion containing the carbon nanotubes to the aqueous dispersion containing the graphene is (1-3): 1, preferably, the weight ratio of the aqueous dispersion containing carbon nanotubes to the aqueous dispersion containing graphene is (1.5-2.5): 1, more preferably, the weight ratio of the aqueous dispersion containing carbon nanotubes to the aqueous dispersion containing graphene is (1.8-2.5): 1, most preferably, the weight ratio of the aqueous dispersion containing carbon nanotubes to the aqueous dispersion containing graphene is 5: 2.
according to the present invention, the aqueous dispersion containing carbon nanotubes may contain: 100 parts by weight of water, 5 to 15 parts by weight of carbon nanotubes, preferably 6 to 14 parts by weight of carbon nanotubes, more preferably 8 to 12 parts by weight of carbon nanotubes; most preferably, 12 parts by weight of carbon nanotubes; the aqueous dispersion containing graphene may contain: 100 parts by weight of water, 1-10 parts by weight of graphene, preferably 2-9 parts by weight of graphene, more preferably 3-8 parts by weight of graphene; most preferably 5.5 parts by weight of graphene.
The method for preparing the aqueous dispersion containing graphene is also not particularly limited in the present invention, and for example, commercially available water-soluble graphene may be mixed with water in the above ratio. However, in order to further improve the electrothermal performance, the adhesion stability and the color fastness of the obtained dye, it is preferable that the graphene-containing aqueous dispersion is prepared by the following method:
(1) treating graphite oxide under the conditions of vacuum degree of-0.1 MPa to 0MPa and temperature of 180 ℃ and 220 ℃ for 40-55 hours;
(2) mixing the material obtained in the step (1) with water, refluxing for 40-60 hours at 80-120 ℃, and then carrying out solid-liquid separation on the obtained refluxed material to obtain water-soluble graphene; preferably, the amount of water is 150-220mL based on 10g of graphite oxide.
More preferably, in the step (2), the method for preparing the graphene-containing aqueous dispersion further comprises: and carrying out solid-liquid separation on the obtained water-soluble graphene under the condition that the vacuum degree is-0.1 MPa to 0MPa, and cleaning and dissolving a solid obtained after the solid-liquid separation by using acetone, wherein the using amount of the acetone is preferably 150-300mL relative to 10g of graphite oxide. The solid-liquid separation method may be any of various conventional solid-liquid separation methods, and for example, it may be filtration, and the filtration preferably uses a cellulose filter membrane having a pore size of 0.22 to 0.45. mu.m.
Wherein, the vacuum degree of-0.1 MPa means that the environmental pressure in the process of preparing the graphene water dispersion liquid is close to the vacuum state.
According to the present invention, in the step (1), after the milling and mixing, the carbon nanotubes are aggregated in the dispersion liquid to form carbon nanotube micelles, preferably, the average particle size of the carbon nanotube micelles is 0.3-1.0 μm, more preferably 0.5-0.7 μm, and the aspect ratio L/D of the carbon nanotube micelles can be 200-.
The conditions for the above-mentioned grinding are not particularly limited, and may be those conventional in the art. For example, the temperature of the polishing may be room temperature, e.g., 10-35 deg.C, the polishing rate may be 1500-.
As shown in fig. 1, specifically, the preparation method of the dye composition comprises the following steps:
(1) grinding and mixing the carbon nano tube and water to obtain water dispersion containing the carbon nano tube;
(2) grinding and mixing graphene and water to obtain a graphene-containing aqueous dispersion;
(3) uniformly mixing the aqueous dispersions obtained in the step (1) and the step (2);
(4) mixing the mixed water dispersion liquid obtained in the step (3) with an aqueous resin, an optional auxiliary agent, an optional organic solvent and water.
Among them, in the present invention, it is preferable that the method is performed under stirring conditions including: the stirring rate was 200 and 800 rpm.
In a third aspect, the present invention provides a conductive heating fiber, wherein the conductive heating fiber is obtained by contact dyeing of a raw material fiber and the dye prepared by the dye composition or the preparation method of the dye composition.
In a fourth aspect, the present invention provides a method for preparing the above conductive heat-generating fiber, wherein the method further comprises the steps of padding, baking, shaping and winding after the raw material fiber is subjected to contact dyeing with the above dye composition or the dye prepared by the above method for preparing the dye composition.
The method for contacting the raw fiber with the dye of the present invention is not particularly limited, and the present invention preferably produces the conductive heat-generating fiber using a monofilament sizing apparatus. As shown in fig. 2, specifically, a raw material fiber 1 is prepared, a dye is placed in a size tank 2, a single fiber is pulled to enter the size tank for multi-stage rolling dyeing, the redundant dye is extruded by the cooperation of roller mechanical extrusion and ultrasonic vibration, then the obtained product enters an oven for drying, roasting and shaping 3, and finally the obtained product is wound 4. Wherein, in the padding process, the tension of the raw material fiber is 1-4N; in the baking and shaping process, the temperature of the oven is 70-100 ℃, preferably 75-80 ℃; in the winding process, the linear speed of the conductive heating fiber is 25-35 m/min.
The conductive fiber is prepared by the monofilament sizing machine equipment, so that the stability of the resistance value of the prepared conductive fiber can be further improved.
According to the invention, the volume ratio of the amount of the raw material fiber to the amount of the dye is 1: (20-40).
In a fifth aspect, the invention provides a conductive heating fabric, wherein the conductive heating fiber or the conductive heating fiber prepared by the preparation method is woven by using the conductive heating fiber as warp and/or weft.
According to the invention, the conductive heating fabric further comprises a fabric electrode, the fabric electrode comprises a fabric electrode body and an electric connecting piece, the electric connecting piece is fixed on the fabric electrode body, and the fabric electrode body is the conductive heating fabric.
According to the invention, the electrical connection comprises electrode copper wires and electrically conductive fibres, and the electrode copper wires and the electrically conductive fibres are arranged in contact.
Preferably, the electrode copper wires are arranged along a warp direction, and the conductive fibers are arranged along a weft direction.
More preferably, the flame-retardant threads may also be arranged in the warp direction.
Preferably, the density of the electrode copper wires is 15-25/cm, and the density of the conductive fibers is 5-15/cm.
According to the invention, the total cross-sectional area of the electrode copper wires accounts for 1-2% of the total cross-sectional area of the fabric electrode body; the total cross-sectional area of the conductive fibers accounts for 98-99% of the total cross-sectional area of the fabric electrode body.
Specifically, according to a preferred embodiment of the present invention, the method for arranging the electrode in the manufacturing process of the electrically and thermally conductive fabric is, for example, as shown in fig. 3, wherein (i) the electrode copper wires are arranged in the warp direction; a schematic area in which the flame-retardant threads are arranged along the warp direction; thirdly, a schematic area in which the conductive fibers are arranged along the weft direction; the method further includes subjecting the electrode portion to an electrode treatment, and for example, the fabric electrode may be coated with a conductive paste or the like to enhance conductivity.
In addition, according to another preferred embodiment of the present invention, the process flow of preparing the electrically and thermally conductive fabric may further include thermally laminating the electrically and thermally conductive fabric with rubber, for example, as shown in fig. 4, preferably, the rubber is thermoplastic polyurethane elastomer rubber (TPU). Therefore, TPU thermal cladding is carried out on the outer side of the electric and heat conducting fabric, so that the effects of insulation, water resistance and ventilation can be achieved, and the softness performance is not lost.
And, more particularly, in another preferred embodiment of the present invention, the process flow for preparing the electrically and thermally conductive fabric is, for example, as shown in fig. 5, that is, the process flow for preparing the electrically and thermally conductive fabric includes the following steps:
(1) typesetting: designing and typesetting the warp yarns, the weft yarns and the fabric structure;
(2) weaving: taking the conductive heating fiber as warp and/or weft, weaving according to the fabric structure designed in the step (1);
(3) electrode treatment: taking the woven fabric in the step (2) as an electrode body, and fixing the electric connecting piece on the fabric electrode body;
(4) insulating and waterproofing treatment: thermally laminating the conductive heating woven fabric subjected to the electrode treatment in the step (3) with TPU;
(5) cutting: and cutting into required sizes according to the requirements.
The dye composition disclosed by the invention simultaneously adopts the water dispersion containing the carbon nano tubes and the water dispersion containing the graphene, the compatibility of the carbon nano tubes with the graphene and other components is further increased, the conductive heating fabric disclosed by the invention has an excellent conductive heating effect, and in addition, the conductive heating fabric also has excellent breaking strength and better color fastness, and meanwhile, the fabric is thermally combined with TPU, so that the conductive heating fabric has insulating, waterproof and breathable effects and does not lose the softness.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
multiwall carbon nanotubes are commercially available from tiannai technology under the designation 7010.
Graphene powder is commercially available from carbon american technology, cat # graphene powder G250.
The planetary grinder is available from Beijing hong Rui Tian Wei science and technology, Inc., model number KQM-X4.
The method for measuring the morphological parameters of the carbon nano tube is characterized by a transmission electron microscope and a scanning electron microscope.
The method for measuring the average particle size of the carbon nanotube micelle is a laser particle size analysis method.
The resistance value of the conductive fiber was measured according to voltammetry, and the resistance value and standard deviation were measured.
The elongation at break of the conductive fiber is determined according to GB/T3916-2013.
The breaking strength of the conductive fibers was determined in accordance with GB/T3916-2013.
The fiber density of the conductive fibers was determined in accordance with GB/T14335-.
The dry crockfastness of the conductive fibers was determined in accordance with GB/T3920-.
The dry-cleaning color fastness of the conductive fibers is determined in accordance with GB/T5711-.
Example 1
This example illustrates the dye composition of the present invention and its preparation.
Grinding and mixing the multi-walled carbon nanotubes with water to obtain a dispersion liquid with the content of the multi-walled carbon nanotubes of 10 weight percent; grinding and mixing graphene and water to obtain a dispersion liquid with the graphene content of 5 wt%; mixing 50g of aqueous dispersion containing multi-walled carbon nanotubes and 20g of aqueous dispersion containing graphene with 16g of water and 1.0g of ethylene glycol butyl ether, stirring at the rotating speed of 200rpm for 20min, adding 10g of aqueous polyurethane emulsion 3218BTN, adding 0.5g of defoaming agent F111, 1g of dispersing agent BYK-190 and 0.1g of thickening agent 8w, stirring at the rotating speed of 400rpm for 90min, and discharging; thus obtaining the dye composition A1 of the invention.
Example 2
This example illustrates the dye composition of the present invention and its preparation.
The preparation of dye composition a2 was carried out according to the method described in example 1, except that the dispersion of multiwall carbon nanotubes was 8% by weight multiwall carbon nanotubes; a graphene dispersion having a graphene content of 4 wt%; thus obtaining the dye composition A2 of the invention.
Example 3
This example illustrates the dye composition of the present invention and its preparation.
Dye composition a3 was prepared as described in example 1, except that a multiwall carbon nanotube dispersion having a single wall carbon nanotube content of 9 wt% was added; the graphene dispersion liquid with the graphene content of 3 wt% is prepared by replacing 3218BTN of the aqueous polyurethane emulsion with an equivalent amount of acrylic resin; thus obtaining the dye composition A3 of the invention.
Example 4
This example illustrates the dye composition of the present invention and its preparation.
The preparation of dye composition a4 was carried out as described in example 1, except that 55g of the aqueous dispersion containing multiwalled carbon nanotubes and 25g of the aqueous dispersion containing graphene were mixed with 16g of water and 0.1g of butyl diglycol ether, stirred at 150rpm for 30min, then 10g of the aqueous polyurethane emulsion 3218BTN was added, as well as 0.5g of defoamer 901W, 1g of dispersant X-405 and 0.3g of polyacrylate thickener; thus obtaining the dye composition A4 of the invention.
Example 5
This example illustrates the dye composition of the present invention and its preparation.
Dye composition A5 was prepared as described in example 1, except that 60g of the aqueous dispersion containing double-walled carbon nanotubes and 30g of the aqueous dispersion containing graphene were mixed with 16g of water and 0.8g of propylene glycol methyl ether, stirred at 150rpm for 30min, 10g of fluorocarbon resin was added, and 0.3g of defoamer BYK024, 1.5g of dispersant BYK110 and 0.2g of copolymer emulsion thickener were added; thus obtaining the dye composition A5 of the invention.
Example 6
This example illustrates the dye composition of the present invention and its preparation.
The dye composition A6 was prepared according to the method described in example 1, except that the materials in the examples were directly mixed at once in accordance with the proportions thereof; thus obtaining the dye composition A6 of the invention.
Comparative example 1
The dye composition D1 was prepared according to the method described in example 1, except that the weight ratio of the aqueous dispersion of multiwall carbon nanotubes (40g) to the aqueous dispersion of graphene (10g) was 4: 1; thus, dye composition D1 according to the invention was obtained.
Comparative example 2
The preparation of dye composition D2 was carried out as described in example 1, with the exception that no graphene dispersion was added; thus, dye composition D2 according to the invention was obtained.
Comparative example 3
The preparation of dye composition D3 was carried out as described in example 1, except that no carbon nanotube dispersion was added; thus, dye composition D3 according to the invention was obtained.
Comparative example 4
The preparation of dye composition D4 was carried out according to the method described in example 1, except that the dispersion of multiwall carbon nanotubes was 3% by weight multiwall carbon nanotubes; a graphene dispersion having a graphene content of 2 wt%; thus, dye composition D4 according to the invention was obtained.
Comparative example 5
The preparation of dye composition D5 was carried out as described in example 1, except that 20g of the aqueous dispersion containing multiwalled carbon nanotubes and 20g of the aqueous dispersion containing graphene were mixed with 10g of water and 1.5g of butyl cellosolve, stirred at 200rpm for 60min, then 50g of the aqueous polyurethane emulsion 3218BTN was added, as well as 0.5g of defoamer F111, 3g of dispersant BYK-190 and 20g of polyurethane thickener 8 w; thus, dye composition D5 according to the invention was obtained.
Application example
(1) Conductive heating fiber
The raw material fiber is in contact dyeing with the prepared dyes A1-A6 and D1-D5, and then is padded, baked, shaped and wound to obtain conductive heating fibers F1-F6 and FD1-FD 5; wherein the volume ratio of the raw material fiber to the dye is 1: 30.
wherein, the technological parameters of the single yarn sizing machine are shown in the table 1.
TABLE 1
| Important parameters | Numerical value |
| Prebaking temperature | 90℃ |
| Oven temperature | 80℃ |
| Yarn tension | 2.2 |
| Linear velocity | 30m/min |
(2) Weaving the conductive heating fibers F1-F6 and FD1-FD5 prepared in the step (1) as warp yarns and/or weft yarns to form conductive heating fabrics C1-C6 and CD1-CD 5;
the conductive heating fabric is characterized in that an electric connecting piece is further fixed on the conductive heating fabric, the electric connecting piece comprises an electrode copper wire and conductive fibers, and the electrode copper wire and the conductive fibers are arranged in a contact mode; the electrode copper wires are arranged along the warp direction, and the conductive fibers are arranged along the weft direction; the density of the electrode copper wires is 20 pieces/cm, and the density of the conductive fibers is 10 pieces/cm;
wherein the total cross-sectional area of the electrode copper wires accounts for 1.5% of the total cross-sectional area of the fabric electrode body; the total cross-sectional area of the conductive fibers accounts for 98.5% of the total cross-sectional area of the fabric electrode body;
and coating conductive adhesive on the fabric electrode, and thermally laminating the conductive heating fabric and the thermoplastic polyurethane elastomer rubber.
Test example
The conductive heat emitting fabrics C1-C6 and CD1-CD5 prepared above were subjected to a performance test in which:
measuring the resistance value of the conductive fiber according to a voltammetry method;
determining the breaking elongation of the conductive fiber according to GB/T3916-2013;
the breaking strength of the conductive fiber is measured according to GB/T3916-2013;
determining the fiber density of the conductive fiber according to GB/T14335-;
determining the dry rubbing color fastness of the conductive fiber according to GB/T3920-1997;
the dry-cleaning color fastness of the conductive fibers was determined according to GB/T5711-.
The results are shown in Table 2.
TABLE 2
From the above data, it can be seen that, with the dye composition of the present invention, and with the component contents, the specific concentration of the aqueous dispersion of the carbon nanotubes and the aqueous dispersion containing graphene, and the specific ratio of the aqueous dispersion of the carbon nanotubes and the aqueous dispersion containing graphene defined in the present invention, and with the aqueous dispersion containing carbon nanotubes and the aqueous dispersion containing graphene, the compatibility of the carbon nanotubes with graphene and other components is further increased, so that the conductive heating fabric of the present invention has excellent conductive heating effect, excellent breaking strength and good color fastness, and at the same time, the fabric is thermally combined with TPU, so that the fabric has insulating, waterproof and air permeable effects, and does not lose softness.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (21)
1. The conductive heating fiber is characterized in that the conductive heating fiber is obtained by padding, baking, shaping and winding after raw material fibers and a dye composition are in contact dyeing; wherein the volume ratio of the raw material fiber to the dye is 1: (20-40); in the padding process, the tension of the raw material fiber is 1-4N;
the dye composition contains water-based resin, carbon nanotubes, graphene and water, wherein the particle sizes of the carbon nanotubes and the graphene are both less than 800 nanometers; wherein, relative to 100 parts by weight of the aqueous resin, the content of the carbon nano tube is 40-60 parts by weight, and the content of the graphene is 5-25 parts by weight.
2. The conductive heat-generating fiber according to claim 1, wherein the content of the carbon nanotube is 45 to 55 parts by weight and the content of the graphene is 5 to 15 parts by weight with respect to 100 parts by weight of the aqueous resin.
3. The conductive heat-generating fiber according to claim 1 or 2, wherein the carbon nanotube is one or more of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube.
4. The conductive heat-generating fiber according to claim 1 or 2, wherein the aqueous resin is selected from one or more of polyurethane resin, acrylic resin, fluorocarbon resin, polyester resin, and polyether resin.
5. The conductive heat-generating fiber according to claim 4, wherein the aqueous resin is a polyurethane resin.
6. The conductive heat-generating fiber according to claim 1, wherein the dye composition further comprises at least one auxiliary selected from one or more of a dispersant, a defoamer and a thickener, the auxiliary being contained in a total amount of 2 to 30 parts by weight with respect to 100 parts by weight of the aqueous resin.
7. The conductive heat emitting fiber according to claim 6, wherein the dispersant is selected from one or more of aqueous dispersants BYK-190, X-405, and BYK 110;
the defoaming agent is selected from one or more of F111 defoaming agent, 901W and BYK 024;
the thickener is selected from polyacrylate thickener and/or copolymer emulsion thickener.
8. The conductive heat emitting fiber according to claim 1 or 7, wherein the dye composition further comprises an organic solvent in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the aqueous resin.
9. The conductive heat-generating fiber according to claim 8, wherein the organic solvent is one or more of ethylene glycol butyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, and ethylene glycol phenyl ether.
10. The conductive heat-emitting fiber according to claim 1, wherein the dye composition is prepared by a method comprising: mixing an aqueous dispersion containing carbon nanotubes and an aqueous dispersion containing graphene, an aqueous resin, an optional auxiliary agent, an optional organic solvent and water, wherein the aqueous dispersions containing the carbon nanotubes and the aqueous dispersion containing the graphene are mixed; wherein the aqueous dispersion containing carbon nanotubes comprises: 100 parts by weight of water, 5-15 parts by weight of carbon nanotubes; the aqueous dispersion containing graphene contains: 100 parts by weight of water, 1-10 parts by weight of graphene; the weight ratio of the aqueous dispersion containing the carbon nano tubes to the aqueous dispersion containing the graphene is (1-3): 1.
11. the conductive heating fiber according to claim 10, wherein the aqueous dispersion containing carbon nanotubes and the aqueous dispersion containing graphene are prepared by a process comprising:
(1) grinding and mixing the carbon nano tube and water to obtain an aqueous dispersion liquid with the carbon nano tube content of 5-15 wt%;
(2) grinding and mixing graphene and water to obtain an aqueous dispersion with the graphene content of 1-10 wt%;
(3) and (3) uniformly mixing the aqueous dispersions obtained in the step (1) and the step (2).
12. The conductive heat-generating fiber according to claim 1,
in the baking and shaping process, the temperature of an oven is 70-100 ℃;
in the winding process, the linear speed of the conductive heating fiber is 25-35 m/min.
13. A conductive heat-generating fabric, characterized in that the conductive heat-generating fiber according to any one of claims 1 to 12 is woven as warp and/or weft.
14. The fabric as claimed in claim 13, wherein the conductive heat generating fabric is a fabric electrode body, the fabric electrode body and the electrical connection member constitute a fabric electrode, and the electrical connection member is fixed to the fabric electrode body.
15. The fabric of claim 14, wherein the electrical connections comprise electrode copper wires and conductive fibers, and the electrode copper wires and the conductive fibers are arranged in contact.
16. The fabric of claim 15, wherein the electrode copper wires are arranged in a warp direction and the conductive fibers are arranged in a weft direction.
17. The fabric according to claim 15 or 16, wherein the density of the electrode copper wires is 15-25 wires/cm and the density of the conductive fibers is 5-15 wires/cm.
18. The fabric of claim 17, wherein the total cross-sectional area of the electrode copper wires is between 1% and 2% of the total cross-sectional area of the fabric electrode body; the total cross-sectional area of the conductive fibers accounts for 98-99% of the total cross-sectional area of the fabric electrode body.
19. The fabric of claim 14, wherein the fabric electrode is coated with a conductive glue.
20. The fabric according to claim 13 or 14, wherein the conductive heat emitting fabric is heat-laminated with rubber.
21. The fabric of claim 20, wherein the rubber is a thermoplastic polyurethane elastomer rubber.
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| CN111287003B (en) * | 2020-03-30 | 2022-09-09 | 新材料与产业技术北京研究院 | Water-based graphene PTC conductive dye, preparation method thereof and conductive fiber treated by dye |
| CN112981940A (en) * | 2021-02-08 | 2021-06-18 | 浙江日方纳米生物技术有限公司 | Carbon nanotube-graphene conductive fiber |
| CN112981939A (en) * | 2021-02-08 | 2021-06-18 | 新材料与产业技术北京研究院金华分院 | Preparation method of carbon nanotube-graphene conductive fiber |
| CN114411433A (en) * | 2021-12-28 | 2022-04-29 | 晋江市维盛织造漂染有限公司 | Organic dye for dyeing fabric and preparation method thereof |
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| CN105017831A (en) * | 2014-04-18 | 2015-11-04 | 新材料与产业技术北京研究院 | Composition for water-based electric heating nano paint, water-based electric heating nano paint as well as preparation method and application of water-based electric heating nano paint |
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