CN114434926A - Intelligent refrigeration artificial leather and preparation method thereof - Google Patents

Intelligent refrigeration artificial leather and preparation method thereof Download PDF

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Publication number
CN114434926A
CN114434926A CN202011209473.4A CN202011209473A CN114434926A CN 114434926 A CN114434926 A CN 114434926A CN 202011209473 A CN202011209473 A CN 202011209473A CN 114434926 A CN114434926 A CN 114434926A
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layer
artificial leather
micro
refrigeration
intelligent refrigeration
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不公告发明人
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0068—Polymeric granules, particles or powder, e.g. core-shell particles, microcapsules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/304—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The application discloses intelligent refrigeration artificial leather which is characterized by comprising a surface layer, a heat insulation layer, a refrigeration layer and a basal layer which are sequentially arranged from outside to inside; micro-nano particles are doped in the refrigerating layer and the substrate layer; the mass percentage of the micro-nano particles in the substrate layer is 0.1-50 wt.%, and the mass percentage of the micro-nano particles in the refrigeration layer is 0.1-50 wt.%; the average emissivity of the refrigerating layer in a wave band of 8-13 mu m is more than 0.7, and the average reflectivity of the refrigerating layer in a solar wave band is more than 0.8. The intelligent refrigeration artificial leather has the advantages that through regulation and control of the internal structure of the leather, the excellent intelligent refrigeration performance is achieved, meanwhile, the good air and moisture permeable performance, the heat insulation and waterproof performance are achieved, the intelligent refrigeration artificial leather is suitable for cooling a human body, and the preparation process is simple and low in cost.

Description

Intelligent refrigeration artificial leather and preparation method thereof
Technical Field
The application relates to the technical field of radiation refrigeration, in particular to intelligent refrigeration artificial leather and a preparation method thereof.
Background
The artificial leather is a cloth-based synthetic material made by coating synthetic resin and various plastic additives on a fabric as a base. Natural leather is high in cost, difficult to produce in batches and uneven in color quality. The artificial leather substrate is prepared by using non-woven fabrics or woven fabrics, so that the defects of natural leather are overcome, the appearance and the hand feeling of the artificial leather substrate are comparable to those of the natural leather, and the artificial leather substrate is widely applied to multiple fields such as the automobile industry and the like. However, the artificial leather has poor heat dissipation performance, and the problems of damage and aging of parts and the like caused by the fact that the artificial leather covers the surface of an object and heat cannot be dissipated; and the temperature of the leather can reach 70 ℃ under the high temperature condition in summer, so that the leather has strong hot feeling and is extremely uncomfortable.
Patent document 1 discloses a heat conductive trim cover adapted for use on a seat assembly, the trim cover having a leather material layer with a top surface and a bottom surface, and heat conductive particles embedded between the top surface and the bottom surface, whereby heat is dissipated through the heat conductive particles. However, the method only regulates and controls the heat conduction coefficient of the seat component, has limited cooling effect and cannot realize the self-cooling of the leather.
Patent document 2 discloses a novel heat-conducting carpet for offices, which includes a main body, an anti-slip bottom layer, a heat-insulating layer, heat-conducting leather, a fabric layer, and a cotton thread layer. Set up even heat conduction hole in the middle of heat conduction leather layer and fabric layer, fill heat-conducting medium in heat conduction hole inside to in time scatter and disappear out the inboard heat of carpet convenient to be used for the daily heat dissipation of carpet. However, the manufacturing process of the heat-conducting leather layer is complex, the problems of heat-conducting medium encapsulation and the like are involved, and the cooling effect in the heat-conducting carpet is limited.
Patent document 3 discloses a polyvinyl chloride-based artificial leather with high infrared reflection, which is composed of a surface layer, a foam layer and a base layer. The surface layer contains black pigment mixture and can transmit infrared rays; the foam layer is composed of titanium dioxide and polyvinyl chloride resin, the substrate layer is made of polyester fibers containing titanium dioxide, and the foam layer and the substrate layer can reflect infrared rays, so that the artificial leather is cooled. However, the method cannot realize the regulation and control of solar radiation, so that large external energy is input, and the cooling performance is poor.
Patent document 4 discloses a heat-reflective artificial leather in which a heat-reflective additive is applied to raw materials for preparing a top layer, a middle layer and a bottom layer of the artificial leather, and the obtained heat-reflective artificial leather can effectively reflect infrared light in sunlight by adding the heat-reflective additive to the top layer, the middle layer and the bottom layer, thereby reducing the absorption of heat by the surface of the leather to achieve the effect of reducing the surface temperature of the leather. However, this method only blocks the input of external energy, and cannot effectively dissipate the heat on the surface of the object to the outside, thereby resulting in a limited cooling effect.
Patent document 5 discloses a breathable automatic temperature-adjusting leather and a preparation method thereof, and the breathable automatic temperature-adjusting leather sequentially comprises an automatic temperature-adjusting surface layer, a microporous breathable layer and a base fabric layer from top to bottom, wherein phase-change material microcapsules are distributed in the automatic temperature-adjusting surface layer. The characteristics of the phase-change material microcapsules are fully exerted to form the breathable sofa and cushion leather capable of automatically adjusting the temperature. However, the method for realizing temperature regulation by using the phase-change microcapsule has the defects of low doping concentration, low temperature transmission speed and the like, and has low production efficiency and complex process.
Compared with the artificial leather which has the advantages of enhancing the heat conductivity coefficient, enhancing the infrared reflection, realizing the cooling effect of the artificial leather by using the phase-change material and the like, the radiation refrigeration technology can realize the excellent cooling effect of the human skin. The radiation refrigeration technology is characterized in that through material selection and structure design, high reflectivity of an object is achieved in the wavelength range of solar radiation (0.3-2.5 microns), and high emissivity is achieved in the human body thermal radiation waveband (7-14 microns), so that heat input of a human body through solar radiation is greatly blocked, thermal radiation loss of the human body is maximized, and zero-energy-consumption cooling can be effectively achieved.
At present, there is a design of synthetic leather using controlled radiation to reduce temperature, and patent document 6 discloses a synthetic leather for tarpaulin and a preparation method thereof, wherein the synthetic leather comprises a surface layer, a refrigeration layer, a heat reflection layer, a middle layer and a matrix layer, the refrigeration layer contains refrigeration type nano particles, high radiation rate is realized in an atmospheric infrared window, the surface of the middle layer is silvered to form the heat reflection layer, and reflection of near-infrared band can be realized, thereby realizing the effect of reducing temperature. However, this method requires silvering, is complicated in preparation process, low in cost-effectiveness, and hinders the flexibility, air permeability and moisture permeability of leather.
In conclusion, the existing artificial leather can not provide effective cooling for human skin, and has the defects of insufficient air permeability and comfort, complex method and process and high cost. Therefore, an intelligent refrigeration artificial leather is lacked, and the excellent intelligent refrigeration performance is achieved, and meanwhile, the good air and moisture permeable, heat insulation and waterproof performances are achieved through regulating and controlling the internal structure of the leather, so that the artificial leather is suitable for cooling a human body.
Documents of the prior art
Patent document 1 US10093208B2 publication document
Patent document 2 CN109610187A publication
Patent document 3 CN101624783B publication document
Patent document 4 CN107237163B publication document
Patent document 5 CN106218090A publication
Patent document 6 CN110205831A publication
Disclosure of Invention
In order to overcome the defects that the existing artificial leather cannot be intelligently refrigerated and is not comfortable enough, the intelligent refrigerating artificial leather and the preparation method thereof are provided, and by regulating and controlling the internal structure of the leather, the excellent intelligent refrigerating performance is achieved, and meanwhile, the artificial leather has good air and moisture permeability, heat insulation and waterproof performances and is suitable for cooling a human body. The intelligent refrigeration artificial leather is simple in preparation process and low in cost.
The specific technical scheme of the application is as follows:
1. an intelligent refrigeration artificial leather is characterized in that,
the thermal insulation layer is arranged on the surface layer;
micro-nano particles are doped in the refrigerating layer and the substrate layer.
2. The intelligent refrigeration artificial leather is characterized in that the substrate layer is a fabric comprising a polymer substrate and micro-nano particles, and the micro-nano particles are uniformly dispersed in the polymer substrate.
3. The intelligent refrigeration artificial leather according to item 1 or 2, wherein the fabric is a non-woven fabric or a woven fabric.
4. The intelligent refrigeration artificial leather is characterized in that the refrigeration layer comprises a polymer substrate and micro-nano particles, and the micro-nano particles are uniformly dispersed in the polymer substrate.
5. The intelligent refrigeration artificial leather according to any one of the items 1 to 4, wherein the heat insulation layer is a microporous structure film which comprises a polymer substrate.
6. The intelligent refrigeration artificial leather according to any one of the items 1 to 5, wherein the surface layer is a film comprising a polymer substrate.
7. The intelligent refrigeration artificial leather is characterized in that the material of the base layer and the refrigeration layer polymer base is selected from the following materials: one or more of polylactic acid (PLA), polymethyl methacrylate (PMMA), polypropylene (PP), Polyamide (PA), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), Polystyrene (PS), polyvinyl alcohol (PVA), Polyurethane (PU) and Polyacrylonitrile (PAN).
8. The intelligent refrigeration artificial leather according to any one of claims 1 to 7, wherein the material of the thermal insulation layer and the polymer substrate of the surface layer is a material with high infrared transmittance;
preferably, the material of high infrared transparency is selected from: one or more of Polyethylene (PE), Polyamide (PA) and fluorocarbon resin.
9. The intelligent refrigeration artificial leather according to any one of the items 1 to 8, wherein the micro-nano particles are selected from the group consisting of: titanium dioxide (TiO)2) Silicon dioxide (SiO)2) Silicon carbide (SiC), nitridingSilicon (Si)3N4) Zinc oxide (ZnO), aluminum oxide (Al)2O3) Boron Nitride (BN), magnesium oxide (MgO), barium sulfate (BaSO)4) Barium carbonate (BaCO)3) And aluminum silicate (Al)2SiO5) One or more than two of them.
10. The intelligent refrigeration artificial leather is characterized in that the particle size of the micro-nano particles is 0.03-25 μm, preferably 0.1-10 μm.
11. The intelligent refrigeration artificial leather according to any one of items 1 to 10, wherein the mass percentage of the micro-nano particles in the base layer is 0.1 wt.% to 50 wt.%, preferably 20 wt.% to 40 wt.%.
12. The intelligent refrigeration artificial leather according to any one of items 1 to 11, wherein the mass percentage of the micro-nano particles in the refrigeration layer is 0.1 wt.% to 50 wt.%, preferably 20 wt.% to 40 wt.%.
13. The intelligent refrigeration artificial leather according to any one of items 1 to 12, wherein the average emissivity of the refrigeration layer in a 8-13 μm waveband is greater than 0.7.
14. The intelligent refrigeration artificial leather according to any one of items 1 to 13, wherein the average reflectivity of the refrigeration layer in the solar wave band is greater than 0.8.
15. The intelligent refrigeration artificial leather is characterized in that micropores of the heat insulation layer are formed by a pore-foaming agent, the pore diameter of the micropores is 0.1-15 μm, preferably 0.1-0.2 μm, and the porosity of the heat insulation layer is 60-90%.
16. The intelligent refrigeration artificial leather according to any one of items 1 to 15, wherein the pore-foaming agent comprises: one or more of micron-sized wood powder, calcium carbonate powder, ammonium bicarbonate powder, modified cellulose powder, starch, superfine wool powder, superfine silk powder and sodium chloride powder.
17. The intelligent refrigeration artificial leather according to any one of items 1-16, wherein in the thermal insulation layer, the mass of the pore-forming agent forming the micropores is 1-5 wt.% of the mass of the polymer substrate in the thermal insulation layer.
18. The intelligent refrigeration artificial leather according to any one of items 1 to 17, wherein the thermal conductivity of the thermal insulation layer is 0.03 to 0.1W/m-K, preferably 0.03 to 0.05W/m-K.
19. The intelligent refrigeration artificial leather according to any one of the items 1 to 18, wherein the surface layer hydrophobic angle is 120-175 °.
20. The intelligent refrigeration artificial leather of any one of claims 1-19, wherein the surface layer comprises a pigment comprising titanium dioxide (TiO)2) Prussian Blue (PB), iron oxide (Fe)2O3) Silicon (Si) and perylene black pigment.
21. The intelligent refrigeration artificial leather according to any one of claims 1 to 20, wherein the artificial leather is produced by a direct coating method, a transfer coating method, a calendering lamination method or an extrusion lamination method.
22. A method for preparing intelligent refrigerating artificial leather according to any one of items 1 to 21, which comprises the following steps:
mixing the micro-nano particles and a polymer substrate material, and then spinning and weaving to obtain a substrate layer;
forming a refrigerating layer on the substrate layer, wherein the refrigerating layer is obtained by mixing a polymer substrate material and micro-nano particles;
mixing a polymer substrate material and a pore-foaming agent, coating the mixture above the refrigerating layer, and removing the pore-foaming agent to form a heat insulation layer;
and forming a surface layer containing a polymer substrate material on the heat insulation layer to obtain the intelligent refrigeration artificial leather.
23. The method of item 22, wherein,
in the step of forming the refrigerating layer, a polymer substrate material and micro-nano particles are mixed to obtain a refrigerating layer coating agent, the refrigerating layer coating agent is coated on the substrate layer, and after plasticizing, the refrigerating layer is formed on the substrate layer.
24. The method of item 22, wherein,
in the step of forming the refrigerating layer, a polymer base material and micro-nano particles are mixed to obtain a refrigerating layer coating agent, the refrigerating layer coating agent is coated on a steel belt, semi-gelation is carried out to obtain a semi-gelation refrigerating layer coating agent, the base layer is attached to the semi-gelation refrigerating layer coating agent, after plasticization, the refrigerating layer is formed on the base layer, and the refrigerating layer attached to the base layer is peeled from the steel belt.
25. The method of item 22, wherein,
in the step of forming the refrigerating layer, a polymer substrate material and the micro-nano particles are mixed and mixed, then the mixture is rolled to obtain a film-shaped refrigerating layer, and the refrigerating layer and the substrate layer are attached together to form the refrigerating layer on the substrate layer.
26. The method of item 22, wherein,
in the step of forming the refrigerating layer, a polymer substrate and the micro-nano particles are mixed, mixed and plasticated, the plasticated materials are extruded into a film-shaped refrigerating layer, and the refrigerating layer and the substrate layer are attached together to form the refrigerating layer on the substrate layer.
27. The method according to any one of items 22 to 26, wherein in the step of forming the surface layer, a polymer base material is applied to the surface of the thermal insulation layer to form the surface layer on the thermal insulation layer, so that the intelligent refrigeration artificial leather is obtained.
28. The method according to any one of items 22 to 26, wherein in the step of forming the surface layer, the polymer base material is extruded into a film shape, the film-shaped polymer base material is attached to the heat insulating layer, and the surface layer is formed on the heat insulating layer, so that the intelligent refrigeration artificial leather is obtained.
Effect of application
(1) The intelligent refrigeration artificial leather realizes that the average emissivity at a wave band of 8-13 mu m is greater than 0.7 by selecting polymer substrate materials of each layer, and the average reflectivity at a wave band of sunlight is greater than 0.8 by introducing micro-nano particles at the substrate layer and the refrigeration layer, so that the day and night radiation refrigeration effect suitable for cooling human skin is achieved.
(2) According to the intelligent refrigeration artificial leather, the heat insulation layer is arranged between the surface layer and the refrigeration layer, the heat conductivity coefficient of the heat insulation layer is preferably 0.03-0.05W/m.K, the heat of the surface layer is prevented from being transferred to the interior of the leather, and the heat insulation layer and the refrigeration layer are matched to act together, so that the integral temperature of the artificial leather is effectively controlled.
(3) According to the intelligent refrigeration artificial leather, the polymer substrate materials of the surface layer and the heat insulation layer are high infrared transparency materials, and human body radiation can be well transmitted to the external environment in a wave band of 8-13 microns.
(4) The utility model provides an intelligent refrigeration artificial leather, the quality percentage content of the micro-nano granule of stratum basale and refrigeration layer is 0.1 wt.% -50 wt.%, and micro-nano granule's doping concentration is high, and the scope is wide, can more effectively block solar radiation energy input to maximize infrared radiation heat output has excellent intelligent refrigeration performance, effective control artificial leather bulk temperature.
(5) According to the intelligent refrigeration artificial leather, the particle size of the micro-nano particles is 0.03-25 mu m, the particle size can achieve an excellent radiation refrigeration effect in the range, and human body heat management is effectively achieved.
(6) The preparation method of the intelligent refrigeration artificial leather is simple, is compatible with the existing process, and can realize industrial preparation.
Drawings
Fig. 1 is a schematic structural view of an intelligent refrigerating artificial leather according to an embodiment of the present application.
FIG. 2 shows the TiO doped intelligent refrigeration artificial leather refrigeration layer with different thicknesses according to one embodiment of the present application2Schematic representation of solar radiation reflectivity.
FIG. 3 shows the TiO doped intelligent refrigeration artificial leather layer with different thickness according to one embodiment of the present application2Schematic diagram of infrared emissivity.
Fig. 4 is a diagram illustrating the intelligent refrigeration effect of the intelligent refrigeration artificial leather refrigeration layer in one day under different thicknesses according to one embodiment of the application.
Description of the symbols
1 base layer 2 refrigeration layer
3 insulating layer 4 surface layer
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application. In addition, the technical features mentioned in the embodiments of the present application described below may be combined with each other as long as they do not conflict with each other.
The meaning of the terms herein are as follows:
the purpose of self-cooling is achieved by radiating heat exchange, namely discharging self heat to the outer space with the temperature close to absolute zero through an atmospheric window in the form of 8-13 mu m electromagnetic waves, and the cooling mode of completely radiating and releasing the heat to the space is generally called as radiation cooling.
The intelligent refrigeration mainly refers to a cooling mode based on a passive radiation refrigeration principle, and the leather can realize intelligent refrigeration on the premise of no need of external intervention and energy input.
"average emissivity", the ratio of the emissivity of an object to the emissivity of a black body at the same temperature, is referred to as the emissivity or blackness of the object, also known as emissivity, specific emissivity. This is for all wavelengths and therefore shall be referred to as total emissivity, often simply emissivity; the average emissivity is a weighted average of emissivity of each wavelength in a specified waveband (4-16 μm in this case), the weight is blackbody radiation intensity, and the average emissivity is obtained by FTIR test, and the formula is:
Figure BDA0002758330440000081
wherein is ep_avgFinger flatEmissivity of homogeneity, IbbAnd (lambda) refers to the intensity of blackbody radiation, and epsilon (lambda) refers to the emissivity of the object at different wavelengths.
"average reflectance", the percentage of radiant energy reflected by an object to the total radiant energy, called reflectance, means the weighted average of the reflectance at each wavelength within a specified band (0.4-2.5 μm), the weight being the intensity of solar radiation, and the average reflectance is measured by a UV-VIS-NIR spectrophotometer, and the formula is:
Figure BDA0002758330440000082
in the formula, Rp_avgMean average reflectance, Isun(λ) refers to the intensity of solar radiation, and R (λ) refers to the reflectivity of the object at different wavebands.
The term "infrared transmittance" refers to the percentage of infrared energy transmitted by an object to the total incident infrared light, and the transmittance of the structure referred to in this application in the infrared band is more than 80%.
The term "hydrophobic angle" refers to an angle of more than 90 ° from the solid-liquid interface to the gas-liquid interface through the interior of the liquid at the intersection of the solid, liquid and gas, at which point the solid surface is hydrophobic, i.e., the liquid does not readily wet the solid and readily migrates over the surface. The detection method of the hydrophobic angle in the application is a maximum height method of the liquid drop.
The application provides an intelligent refrigeration artificial leather, which is characterized in that,
the thermal insulation layer is arranged on the surface layer;
micro-nano particles are doped in the refrigerating layer and the substrate layer.
In one embodiment, the intelligent refrigeration artificial leather of the present application is shown in fig. 1, and comprises a surface layer 4, a refrigeration layer 3, a thermal insulation layer 2 and a substrate layer 1 from outside to inside (i.e., "from bottom to top" in the figure).
In a specific embodiment, the substrate layer is a non-woven fabric or a woven fabric comprising a polymer substrate and micro-nano particles, and the micro-nano particles are uniformly dispersed in the polymer substrate; the refrigeration layer comprises a polymer substrate and micro-nano particles, the micro-nano particles are uniformly dispersed in the polymer substrate, and the surface layer is a film and comprises the polymer substrate.
In one embodiment, the thermal insulation layer is a microporous structure film, which includes a polymer substrate and does not contain micro-nano particles. The pores of the thermal insulation layer are formed by a porogen, the pore diameter of the pores is 0.1-15 μm, such as 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm, 10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm, 12.5 μm, 13 μm, 13.5 μm, 14 μm, 14.5 μm, 15 μm, etc., preferably 0.1-0.2 μm, the porosity of the thermal insulation layer is 60-90%, such as 60%, 62%, 64%, 66%, 68%, 70%, 72%, 76%, 80% -80%, 80% and the like. And after the micropores are formed, dissolving the pore-foaming agent by using a solvent so as to remove the pore-foaming agent. In one embodiment, the solvent may be water, hydrochloric acid, acetic acid, NMMO solvent, DMSO solvent.
The detection method of the pore diameter of the micropores is a section direct observation method, the pore diameter of the micropores is obtained through direct observation of an electron microscope, for example, the average pore diameter is obtained through observing the surface of the material and 100 pores on the section by a scanning electron microscope.
And cutting experimental leather with a certain area on the leather for detection of the porosity of the thermal insulation layer, soaking the experimental leather into water after weighing, taking out the experimental leather after 24 hours, wiping the experimental leather with filter paper, and weighing again. Calculating porosity as formula
Figure BDA0002758330440000091
Shown in the formula, wherein W1G, experimental leather dry mass; w is a group of2The experimental leather quality after 24 hours; s is the area of experimental leather; d is the thickness of the experimental leather; ρ is the immersion liquid density (with deionized water).
In one embodiment, the porogen may comprise: one or more of micron-sized wood powder, calcium carbonate powder, ammonium bicarbonate powder, calcium carbonate powder, modified cellulose powder, starch, superfine wool powder, superfine silk powder and sodium chloride powder.
In a specific embodiment, the mass of porogen forming the micropores in the thermal insulation layer is 1 wt.% to 5 wt.%, e.g., may be 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, etc., of the mass of polymer in the thermal insulation layer. The thermal conductivity of the thermal insulation layer is 0.03 to 0.1W/mK, and may be, for example, 0.03W/mK, 0.04W/mK, 0.05W/mK, 0.06W/mK, 0.07W/mK, 0.08W/mK, 0.09W/mK, 0.1W/mK, or the like, preferably 0.03 to 0.05W/mK. The thermal conductivity of the thermal insulation layer is related to the content of the pore-foaming agent, the higher the content of the pore-foaming agent in the polymer is, the smaller the thermal conductivity is, the external heat can be more effectively prevented from being transferred to the inside of the leather, and the integral temperature of the artificial leather can be more effectively controlled. The detection method of the heat conductivity coefficient of the heat insulation layer is a steady-state hot plate method.
In one embodiment, the surface layer further comprises: the base material solvent is used for dissolving the base material so as to better coat the base material on the surface of the leather.
In one embodiment, the insulation layer further comprises: one or both of a plasticizer and a stabilizer.
In one embodiment, the refrigeration layer further comprises: one or more of a filler, a plasticizer and a stabilizer.
In one embodiment, the base material solvent may be selected from one or two or more of: toluene, trichloroethylene, tetralin, decalin, petroleum ether, mineral oil and paraffin, ethylene glycol, chlorohydrin, propylene glycol and zinc chloride in methanol; the plasticizer is not particularly limited, and may be selected from, for example, one or two or more of the following: dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl terephthalate (DOTP), dinonyl phthalate (DNP), diisodecyl phthalate (DIDP), Butyl Benzyl Phthalate (BBP), dioctyl adipate (DOA), di-n-butyl sebacate (DBS), dioctyl sebacate (DOS), butyl stearate, epoxidized soybean oil, etc.; the stabilizer is not particularly limited, and may include, for example, a heat stabilizer and a light stabilizer, and the heat stabilizer may be selected from one or two or more of the following: zinc maleopimaric acid, zinc stearate, tribasic lead sulfate, dibasic lead sulfate, barium stearate, organic tin and the like, wherein the light stabilizer is benzotriazole UVA-2 or UV-32; the filler is not particularly limited, and may be selected from, for example, one or two or more of the following: acrylic resin, polyurethane, calcium carbonate, and the like.
In one embodiment, the surface layer, the thermal insulation layer, and the refrigeration layer may each contain a pigment, the pigment is not particularly limited, and preferably the pigment is a pigment of high infrared transparency, for example, the pigment may include titanium dioxide (TiO)2) Prussian Blue (PB), iron oxide (Fe)2O3) One or more than two of silicon (Si) and perylene black pigment. The pigment with high infrared transparency is selected, so that the intelligent refrigeration artificial leather can well transmit human body radiation to the external environment in a wave band of 8-13 mu m to the maximum extent.
In one embodiment, the material of the base layer, the refrigeration layer polymer base may be selected from: one or more of polylactic acid (PLA), polymethyl methacrylate (PMMA), polypropylene (PP), Polyamide (PA), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), Polystyrene (PS), polyvinyl alcohol (PVA), Polyurethane (PU) and Polyacrylonitrile (PAN).
In one embodiment, the thermal insulation layer and the surface layer polymer substrate material are high infrared transparency materials, and the high infrared transmittance materials can be selected from: one or more of Polyethylene (PE), Polyamide (PA) and fluorocarbon resin. The material with high infrared transparency is selected as the polymer substrate, so that the intelligent refrigeration artificial leather can transmit human body radiation to the external environment in a wave band of 8-13 mu m to the maximum extent.
In one embodiment, the micro-nano particles may be selected from: titanium dioxide (TiO)2) Silicon dioxide (SiO)2) Silicon carbide (SiC) and silicon nitride (Si)3N4) Zinc oxide (ZnO), aluminum oxide (Al)2O3) Boron Nitride (BN), magnesium oxide (MgO), barium sulfate (BaSO)4) Barium carbonate (BaCO)3) And aluminum silicate (Al)2SiO5) One or more than two of them.
In a specific embodiment, the micro-nano particles have a particle size of 0.03 μm to 25 μm, preferably 0.1 μm to 10 μm, and may be, for example, 0.03 μm, 0.1 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, etc. In the application, the particle size of the micro-nano particles refers to an average particle size obtained by an electron microscope detection method, specifically is a D50 median size, and for example, the D50 median size is obtained by observing 300 particles.
In a specific embodiment, the mass percentage of the micro-nano particles in the base layer is 0.1 wt.% to 50 wt.%, preferably 20 wt.% to 40 wt.%, and may be, for example, 0.1 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, 35 wt.%, 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, 41 wt.%, 42 wt.%, 44 wt.%, 46 wt.%, 47 wt.%, 46 wt.%, or 40 wt.% 50 wt.%, etc. The mechanical property of the substrate layer can be reduced if the mass percentage of the micro-nano particles is too high, the mass percentage of the micro-nano particles of the substrate layer is controlled to be within the range of 0.1-50 wt.%, and finally the manufactured artificial leather is high in average reflectivity, high in tensile strength and high in elongation at break, and meanwhile, excellent optical property and mechanical property are obtained.
In a specific embodiment, the micro-nano particles in the refrigeration layer have a mass percentage of 0.1 wt.% to 50 wt.%, preferably 20 wt.% to 40 wt.%, for example, 0.1 wt.%, 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, 21 wt.%, 22 wt.%, 23 wt.%, 24 wt.%, 25 wt.%, 26 wt.%, 27 wt.%, 28 wt.%, 29 wt.%, 30 wt.%, 31 wt.%, 32 wt.%, 33 wt.%, 34 wt.%, 35 wt.%, 36 wt.%, 37 wt.%, 38 wt.%, 39 wt.%, 40 wt.%, 41 wt.%, 42 wt.%, 44 wt.%, 47 wt.%, 46 wt.%, or 40 wt.% 50 wt.%, etc. The mechanical property of the refrigerating layer can be reduced if the mass percentage of the micro-nano particles is too high, the mass percentage of the micro-nano particles of the refrigerating layer is controlled to be in the range of 0.1-50 wt.%, and finally the manufactured artificial leather is high in average reflectivity, high in tensile strength and high in elongation at break, and meanwhile, excellent optical property and mechanical property are obtained.
In this application, the micro-nano particle mass percentage in the stratum basale with the micro-nano particle mass percentage in the refrigeration layer can be the same, also can be different. The base layer and the refrigeration layer can be the same in type or different in type. The polymer base materials of the base layer and the refrigerating layer can be the same or different. The heat insulation layer and the surface layer polymer substrate can be made of the same material or different materials.
The doping concentration of the substrate layer and the micro-nano particles of the refrigerating layer is high, the range is wide, solar radiation energy input can be effectively blocked, infrared radiation heat output is maximized, excellent intelligent refrigerating performance is achieved, and the overall temperature of the artificial leather is effectively controlled.
In a specific embodiment, the average emissivity of the refrigeration layer in the 8-13 μm band is greater than 0.7, and may be, for example, 0.7, 0.72, 0.74, 0.76, 0.78, 0.8, 0.82, 0.84, 0.86, 0.88, 0.9, 0.92, 0.94, 0.96, 0.98, etc.; the average reflectivity of the refrigeration layer in the sunlight wave band is more than 0.8, for example, 0.7, 0.72, 0.74, 0.76, 0.78, 0.8, 0.82, 0.84, 0.86, 0.88, 0.9, 0.92, 0.94, 0.96 and the like, thereby realizing excellent intelligent refrigeration effect.
In a specific embodiment, the thickness of the refrigeration layer is greater than 5 μm, specifically 5 μm, 10 μm, 20 μm, 30 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 500 μm, 550 μm, 600 μm, 650 μm, 700 μm, etc., preferably greater than 300 μm.
In a particular embodiment, the surface layer has a hydrophobic angle of 120 ° to 175 °, for example 120 °, 125 °, 130 °, 135 °, 140 °, 145 °, 150 °, 155 °, 160 °, 165 °, 170 °, 175 °, and the like.
The surface layer mainly plays the roles of hydrophobicity, protection and beauty.
The application also provides a preparation method of the intelligent refrigeration artificial leather, which is characterized by comprising the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, and then spinning and weaving to obtain a substrate layer;
(2) forming a refrigerating layer on the substrate layer, wherein the refrigerating layer is obtained by mixing a polymer substrate material and micro-nano particles;
(3) mixing a polymer substrate material and a pore-foaming agent, coating the mixture above the refrigerating layer, and removing the pore-foaming agent to form a heat insulation layer;
(4) and forming a surface layer containing a polymer substrate material on the heat insulation layer to obtain the intelligent refrigeration artificial leather.
In one embodiment, the intelligent refrigeration artificial leather can be prepared by a direct coating method, and the method comprises the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, and spinning and weaving the mixture in sequence to obtain a substrate layer;
(2) mixing a polymer substrate material and micro-nano particles to obtain a refrigerating layer coating agent, coating the refrigerating layer coating agent on the substrate layer, and plasticizing to form a refrigerating layer on the substrate layer;
(3) mixing a polymer substrate material and a pore-forming agent, coating the mixture above the refrigerating layer, and removing the pore-forming agent, namely forming a heat insulation layer with a microporous structure on the refrigerating layer;
(4) and coating the polymer substrate material on the surface of the heat insulation layer to form a surface layer on the heat insulation layer, so as to obtain the intelligent refrigeration artificial leather.
In one embodiment, the intelligent refrigeration artificial leather can be prepared by a direct coating method, and the method comprises the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, spinning to obtain composite fibers, and weaving the composite fibers into a fabric as a substrate layer;
(2) uniformly mixing a polymer substrate material, micro-nano particles, a plasticizer, a stabilizer and a filler to obtain a refrigerating layer coating agent, unreeling the fabric of the substrate layer, coating the refrigerating layer coating agent on the fabric by using a scraper after pretreatment, and forming a refrigerating layer on the substrate layer after plasticizing;
(3) uniformly mixing a polymer substrate material, a plasticizer, a stabilizer and a pore-forming agent, coating the mixture above a refrigerating layer, and removing the pore-forming agent through a solvent to form a heat insulation layer with a microporous structure on the refrigerating layer;
(4) uniformly mixing a substrate material solvent and a polymer substrate material, adding a pigment, mixing to form a surface treatment agent, coating the surface treatment agent on the surface of a heat insulation layer, heating and drying to form a surface layer on the heat insulation layer, and cooling to obtain the intelligent refrigeration artificial leather.
In one embodiment, the intelligent refrigeration artificial leather can be prepared by a transfer coating method, and the method comprises the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, and spinning and weaving the mixture in sequence to obtain a substrate layer;
(2) mixing a polymer substrate material and micro-nano particles to obtain a refrigerating layer coating agent, coating the refrigerating layer coating agent on a steel belt, performing semi-gelation to obtain a semi-gelation refrigerating layer coating agent, attaching the substrate layer to the semi-gelation refrigerating layer coating agent, plasticizing, forming the refrigerating layer on the substrate layer, and stripping the refrigerating layer attached to the substrate layer from the steel belt;
(3) mixing a polymer substrate material and a pore-forming agent, coating the mixture above the refrigerating layer, and removing the pore-forming agent, namely forming a heat insulation layer with a microporous structure on the refrigerating layer;
(4) and coating the polymer substrate material on the surface of the heat insulation layer to form a surface layer on the heat insulation layer, so as to obtain the intelligent refrigeration artificial leather.
In one embodiment, the intelligent refrigeration artificial leather can be prepared by a transfer coating method, and the method comprises the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, spinning to obtain composite fibers, and weaving the composite fibers into a fabric as a substrate layer;
(2) uniformly mixing a polymer substrate, micro-nano particles, a plasticizer, a stabilizer and a filler to obtain a refrigerating layer coating agent, coating the refrigerating layer coating agent on a stainless steel belt, carrying out semi-gelation, flatly pasting a pretreated substrate layer on the semi-gelled refrigerating layer coating agent to form a refrigerating layer on the substrate layer, and cooling and stripping the refrigerating layer pasted with the substrate layer from the stainless steel belt;
(3) uniformly mixing a polymer substrate material, a plasticizer, a stabilizer and a pore-forming agent, coating the mixture above a refrigerating layer, and removing the pore-forming agent through a solvent to form a heat insulation layer with a microporous structure on the refrigerating layer;
(4) uniformly mixing a substrate material solvent and a polymer substrate material, then adding a pigment and mixing to form a surface treatment agent, coating the surface treatment agent on the surface of a heat insulation layer, heating and drying to form a surface layer on the heat insulation layer, and cooling to obtain the intelligent refrigeration artificial leather.
In one embodiment, the intelligent refrigeration artificial leather can be prepared by a calendering and pasting method, and the method comprises the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, and spinning and weaving the mixture to obtain a substrate layer;
(2) mixing a polymer substrate material and the micro-nano particles, mixing, rolling the mixed material to obtain a film-shaped refrigerating layer, and attaching the refrigerating layer and the substrate layer together;
(3) mixing a polymer substrate material and a pore-forming agent, coating the mixture above the refrigerating layer, and removing the pore-forming agent, namely forming a heat insulation layer with a microporous structure on the refrigerating layer;
(4) and extruding the polymer base material into a film shape, attaching the film-shaped polymer base material to the heat insulation layer, and forming a surface layer on the heat insulation layer to obtain the intelligent refrigeration artificial leather.
In one embodiment, the intelligent refrigeration artificial leather can be prepared by a calendering and pasting method, and the method comprises the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, spinning to obtain composite fibers, and weaving the composite fibers into a fabric as a substrate layer;
(2) mixing a polymer substrate, micro-nano particles, a plasticizer, a stabilizer and a filler, then mixing, continuously passing the mixed material through a roller gap of a calender, rolling into a film-shaped refrigeration layer, and attaching the film-shaped refrigeration layer and the substrate layer together;
(3) uniformly mixing a polymer substrate material, a plasticizer, a stabilizer and a pore-forming agent, coating the mixture above a refrigerating layer, and removing the pore-forming agent through a solvent to form a heat insulation layer with a microporous structure on the refrigerating layer;
(4) uniformly mixing a substrate material solvent and a polymer substrate material, adding a pigment, mixing to form a surface treatment agent, extruding the surface treatment agent into a film shape, heating, attaching the film-shaped surface treatment agent to a heat insulation layer, and forming a surface layer on the heat insulation layer to obtain the intelligent refrigeration artificial leather.
In one embodiment, the intelligent refrigeration artificial leather can be prepared by an extrusion lamination method, and the method comprises the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, and spinning and weaving the mixture to obtain a substrate layer;
(2) mixing a polymer substrate and the micro-nano particles, mixing, plasticating, extruding the plasticated materials into a film-shaped refrigerating layer, and attaching the refrigerating layer and the substrate layer together;
(3) mixing a polymer substrate material and a pore-forming agent, coating the mixture above the refrigerating layer, and removing the pore-forming agent, namely forming a heat insulation layer with a microporous structure on the refrigerating layer;
(4) and extruding the polymer base material into a film shape, attaching the film-shaped polymer base material to the heat insulation layer, and forming a surface layer on the heat insulation layer to obtain the intelligent refrigeration artificial leather.
In one embodiment, the intelligent refrigeration artificial leather can be prepared by an extrusion lamination method, and the method comprises the following steps:
(1) mixing the micro-nano particles and a polymer substrate material, spinning to obtain composite fibers, and weaving the composite fibers into a fabric as a substrate layer;
(2) mixing a polymer substrate, micro-nano particles, a plasticizer, a stabilizer and a filler, then mixing, plasticating, extruding into a film-shaped refrigerating layer by an extruder, and attaching the substrate layer and the refrigerating layer;
(3) uniformly mixing a polymer substrate material, a plasticizer, a stabilizer and a pore-forming agent, coating the mixture above a refrigerating layer, and removing the pore-forming agent through a solvent to form a heat insulation layer with a microporous structure on the refrigerating layer;
(4) uniformly mixing a substrate material solvent and a polymer substrate material, adding a pigment, mixing to form a surface treatment agent, extruding the surface treatment agent into a film shape, heating, attaching the film-shaped surface treatment agent on a heat insulation layer, and forming a surface layer on the heat insulation layer to obtain the intelligent refrigeration artificial leather.
The intelligent refrigeration artificial leather is characterized in that a surface layer, a heat insulation layer, a refrigeration layer and a substrate layer are sequentially arranged from outside to inside, the types of polymer substrate materials of the layers and the types, particle sizes and percentage contents of micro-nano particles added into the layers are respectively controlled, the average emissivity at a wave band of 8-13 mu m is greater than 0.7 and can be as high as 0.85; the average reflectivity in the sunlight wave band is more than 0.8 and even can reach 0.95; the heat conductivity coefficient of the heat insulation layer can reach 0.03-0.05W/m.K; the tensile strength of the leather is more than 2.5MPa, even can be as high as 6.5 MPa; the elongation at break of the leather is more than 200 percent and even can reach 550 percent. The finally prepared intelligent refrigeration artificial leather has high average reflectivity and average emissivity, high tensile strength, high elongation at break and small heat conductivity coefficient, obtains excellent optical property and mechanical property, effectively realizes human body heat management and has strong practicability.
Examples
Example 1
A refrigeration layer simulation model of the intelligent refrigeration artificial leather is constructed by utilizing FDTD (fully drawn yarn) resources, PMMA (polymethyl methacrylate) is selected as a polymer substrate, and TiO (titanium dioxide) is selected as2And (3) micro-nano particles, wherein the particle size of the micro-nano particles is 550 +/-50 nm, so that simulation effect graphs of the refrigeration layers with different thicknesses are obtained. As shown in fig. 2, the solar radiation reflectivity increases with the thickness of the refrigerating layer, and then gradually approaches to saturation, so that the solar radiation reflection effect higher than 90% can be realized. As shown in FIG. 3, the infrared emissivity in the wavelength range of 4 μm to 16 μm increases with the thickness of the cooling layer and then gradually approaches saturation, and the infrared radiation effect higher than 90% can be realized. As shown in FIG. 4, the radiation refrigeration effect of the refrigeration layers with different thicknesses in 24h increases with the increase of the thickness of the refrigeration layer, when the thickness of the refrigeration layer is larger than 300 μm, the temperature in 24h is lower than the ambient temperature, and when the thickness of the refrigeration layer is 600 μm, the maximum cooling effect of 8 ℃ lower than the ambient temperature can be realized.
Example 2
The intelligent refrigerating artificial leather of the embodiment is prepared according to the following method:
(1) 300g of TiO with a particle size of 550nm2Mixing the particles and 700g of PMMA, spinning to obtain composite fibers, and weaving the composite fibers into non-woven fabric as a substrate layer;
(2) 700g of PVC and 420g of TiO with the particle size of 550nm2Uniformly mixing the particles, 210g of dioctyl phthalate (DOP), 20g of zinc stearate and 50g of calcium carbonate to obtain a refrigeration layer coating agent, and then mixing the non-woven fabric of the base layerUnreeling, after pretreatment, coating a refrigerating layer coating agent on the non-woven fabric by using a scraper, and after plasticizing, forming a refrigerating layer on the substrate layer;
(3) uniformly mixing 700g of PE, 210g of dioctyl phthalate (DOP), 20g of zinc stearate and 50g of micron-sized wood powder, coating the mixture above a refrigerating layer, and removing the micron-sized wood powder by water to form a heat insulation layer with a microporous structure on the refrigerating layer;
(4) 1000g of toluene and 700g of PE are uniformly mixed, then 300g of Prussian Blue (PB) is added and mixed to form a surface treatment agent, the surface treatment agent is coated on the surface of a heat insulation layer, heating and drying are carried out, a surface layer is formed on the heat insulation layer, and the intelligent refrigeration artificial leather is obtained after cooling.
The intelligent refrigeration artificial leather of the embodiment sequentially comprises a surface layer, a heat insulation layer, a refrigeration layer and a basal layer from outside to inside;
the substrate layer was composed of 700g of PMMA and 300g of TiO 550nm in particle size2A nonwoven fabric of particles;
the refrigerating layer comprises 700g of PVC and 420g of TiO with the grain diameter of 550nm2Granules, 210g dioctyl phthalate (DOP), 20g zinc stearate, 50g calcium carbonate;
the heat insulation layer is prepared from 700g of PE, 210g of dioctyl phthalate (DOP), 20g of zinc stearate and 50g of micron-sized wood powder, the heat insulation layer comprises 700g of PVC, 210g of dioctyl phthalate (DOP) and 20g of zinc stearate, the pore diameter of the micropores of the heat insulation layer is 0.2 mu m, and the porosity is 70%;
the surface layer comprised 700g of pe, 300g of Prussian Blue (PB) and 1000g of toluene.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.85, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 6MPa, and the elongation at break is 500%.
The method for detecting the mechanical property of the leather comprises the following steps: cutting leather into strips with the length of 15cm and the width of 1cm, testing the mechanical properties of the tensile on a microcomputer-controlled universal testing machine, measuring 2 samples in each group, and measuring the tensile distance of 5cm and the tensile speed of 100mm/min according to the standard GB/T1040-92.
Example 3
The intelligent refrigeration artificial leather of the embodiment is prepared by referring to the method of embodiment 2, and is different from embodiment 2 in that the mass percentage of the micro-nano particles in the base layer of the intelligent refrigeration artificial leather of the embodiment is 8 wt.%.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.8, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 6.5MPa, and the elongation at break is 550%.
Example 4
The intelligent refrigeration artificial leather of the embodiment is prepared by referring to the method of embodiment 2, and is different from embodiment 2 in that the mass percentage of the micro-nano particles in the base layer of the intelligent refrigeration artificial leather of the embodiment is 45 wt.%.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.9, the heat conductivity of the heat-insulating layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 4MPa, and the elongation at break is 300%.
Example 5
The intelligent refrigeration artificial leather of the embodiment is prepared by referring to the method of embodiment 2, and is different from embodiment 2 in that the mass percentage of the micro-nano particles in the refrigeration layer of the intelligent refrigeration artificial leather of the embodiment is 8 wt.%.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.8, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 6.5MPa, and the elongation at break is 550%.
Example 6
The intelligent refrigeration artificial leather of the embodiment is prepared by referring to the method of the embodiment 2, and is different from the embodiment 2 in that the mass percentage of the micro-nano particles in the refrigeration layer of the intelligent refrigeration artificial leather of the embodiment is 45 wt.%.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.9, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 5MPa, and the elongation at break is 400%.
Example 7
The intelligent refrigeration artificial leather of the embodiment is prepared by referring to the method of embodiment 2, and is different from embodiment 2 in that the mass percentage of the micro-nano particles in the refrigeration layer and the base layer of the intelligent refrigeration artificial leather of the embodiment are both 45 wt.%.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.92, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 3MPa, and the elongation at break is 250%.
Example 8
The intelligent refrigeration artificial leather of the embodiment is prepared by referring to the method of embodiment 2, and is different from embodiment 2 in that the mass percentage of the micro-nano particles in the base layer and the refrigeration layer of the intelligent refrigeration artificial leather of the embodiment is 55 wt.%.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.95, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 1.5MPa, and the elongation at break is 150%.
Example 9
The intelligent refrigeration artificial leather of the embodiment is prepared by referring to the method of the embodiment 2, and is different from the embodiment 2 in that the particle size of the micro-nano particles of the embodiment is 15 μm.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.6, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 4.5MPa, and the elongation at break is 400%.
Example 10
The intelligent refrigerating artificial leather of the present example was manufactured by referring to the method of example 2, and is different from example 2 in that the base layer polymer substrate of the present example is PLA.
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.85, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.85, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 6MPa, and the elongation at break is 500%.
Example 11
The intelligent refrigeration artificial leather prepared by the method in the embodiment 2 is different from the intelligent refrigeration artificial leather prepared by the embodiment 2 in that the micro-nano particles of the refrigeration layer and the substrate layer are SiO2
The average emissivity of the intelligent refrigeration artificial leather in the wave band of 8-13 microns is 0.75, the average reflectivity of the intelligent refrigeration artificial leather in the solar wave band is 0.81, the thermal conductivity of the thermal insulation layer is 0.05W/m.K, the tensile strength of the intelligent refrigeration artificial leather is 6MPa, and the elongation at break is 500%.
Comparative example 1
The intelligent refrigeration artificial leather of the comparative example is prepared by referring to the method of the example 2, and the difference from the example 2 is that the base layer of the intelligent refrigeration artificial leather of the comparative example does not contain micro-nano particles.
The average emissivity of the intelligent refrigeration artificial leather of the comparative example in the wave band of 8-13 μm is 0.75, and the average reflectivity in the solar wave band is 0.4.
Comparative example 2
The intelligent refrigeration artificial leather of the present comparative example is manufactured by referring to the method of example 2, and is different from example 2 in that the intelligent refrigeration artificial leather of the present comparative example does not have a thermal insulation layer.
The artificial leather of this comparative example optical property does not receive the influence, and only internal environment temperature receives the influence, and final cooling effect receives the influence, only accomplishes the human body and is less than the cooling of ambient temperature 2 ℃.
Comparative example 3
The intelligent refrigeration artificial leather of the comparative example is prepared by referring to the method of the example 2, and is different from the example 2 in that the intelligent refrigeration artificial leather of the comparative example sequentially comprises a surface layer, a refrigeration layer, a heat insulation layer and a substrate layer from outside to inside.
This comparative example can't block outside heat outside the refrigeration layer, and only the stratum basale plays crucial intelligent refrigeration effect, and the cooling effect is far less than example 2, only accomplishes the human cooling that is less than ambient temperature 2 ℃.
Comparative example 4
The intelligent refrigeration artificial leather of the comparative example is prepared by the method of the embodiment 2, and the difference from the embodiment 2 is that the refrigeration layer of the intelligent refrigeration artificial leather of the comparative example does not contain micro-nano particles.
The average emissivity of the intelligent refrigeration artificial leather of the comparative example in the wave band of 8-13 μm is 0.75, and the average reflectivity in the solar wave band is 0.4.
The parameters and effect data for each example and comparative example are listed in table 1 below.
TABLE 1
Figure BDA0002758330440000201
Figure BDA0002758330440000211
Figure BDA0002758330440000221
It will be understood by those skilled in the art that the foregoing is merely a preferred embodiment of the present application and is not intended to limit the present application, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. An intelligent refrigeration artificial leather is characterized in that,
the thermal insulation layer is arranged on the surface layer;
micro-nano particles are doped in the refrigerating layer and the substrate layer.
2. The intelligent refrigeration artificial leather according to claim 1, wherein the substrate layer is a fabric comprising a polymer substrate and micro-nano particles, and the micro-nano particles are uniformly dispersed in the polymer substrate.
3. The intelligent refrigeration artificial leather according to claim 1 or 2, wherein the fabric is a non-woven fabric or a woven fabric.
4. The intelligent refrigeration artificial leather according to any one of claims 1 to 3, wherein the refrigeration layer comprises a polymer substrate and micro-nano particles, and the micro-nano particles are uniformly dispersed in the polymer substrate.
5. The intelligent refrigeration artificial leather according to any one of claims 1 to 4, wherein the thermal insulation layer is a microporous structure film comprising a polymer substrate.
6. The intelligent refrigerated artificial leather of any of claims 1-5 wherein the surface layer is a film comprising a polymer substrate.
7. The intelligent refrigeration artificial leather according to any one of claims 1 to 6, wherein the material of the substrate layer and the refrigeration layer polymer substrate is selected from the group consisting of: one or more of polylactic acid (PLA), polymethyl methacrylate (PMMA), polypropylene (PP), Polyamide (PA), polyethylene terephthalate (PET), polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), Polystyrene (PS), polyvinyl alcohol (PVA), Polyurethane (PU) and Polyacrylonitrile (PAN).
8. The intelligent refrigeration artificial leather according to any one of claims 1 to 7, wherein the material of the thermal insulation layer and the polymer substrate of the surface layer is a material with high infrared transparency;
preferably, the material of high infrared transparency is selected from: one or more of Polyethylene (PE), Polyamide (PA) and fluorocarbon resin.
9. The intelligent refrigeration artificial leather according to any one of claims 1 to 8, wherein the micro-nano particles are selected from the group consisting of: titanium dioxide (TiO)2) Silicon dioxide (SiO)2) Silicon carbide (SiC) and silicon nitride (Si)3N4) Zinc oxide (ZnO), aluminum oxide (Al)2O3) Boron Nitride (BN), magnesium oxide (MgO), barium sulfate (BaSO)4) Barium carbonate (BaCO)3) And aluminum silicate (Al)2SiO5) One or more than two of them.
10. The preparation method of the intelligent refrigeration artificial leather as claimed in any one of claims 1 to 9, which comprises the following steps:
mixing the micro-nano particles and a polymer substrate material, and then spinning and weaving to obtain a substrate layer;
forming a refrigerating layer on the substrate layer, wherein the refrigerating layer is obtained by mixing a polymer substrate material and micro-nano particles;
mixing a polymer substrate material and a pore-foaming agent, coating the mixture above the refrigerating layer, and removing the pore-foaming agent to form a heat insulation layer;
and forming a surface layer containing a polymer substrate material on the heat insulation layer to obtain the intelligent refrigeration artificial leather.
CN202011209473.4A 2020-11-03 2020-11-03 Intelligent refrigeration artificial leather and preparation method thereof Pending CN114434926A (en)

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