CN113411917A - Carbon nano tube transparent heating structure, preparation method and preparation device thereof - Google Patents
Carbon nano tube transparent heating structure, preparation method and preparation device thereof Download PDFInfo
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- CN113411917A CN113411917A CN202110865132.0A CN202110865132A CN113411917A CN 113411917 A CN113411917 A CN 113411917A CN 202110865132 A CN202110865132 A CN 202110865132A CN 113411917 A CN113411917 A CN 113411917A
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 51
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/02—Details
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/02—Details
- H05B3/03—Electrodes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
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Abstract
The invention discloses a carbon nano tube transparent heating structure, a preparation method and a preparation device thereof, wherein a first bonding layer and a second bonding layer are respectively arranged on the connecting surface of a first substrate and a second substrate, a single-walled carbon nano tube conductive coating is arranged on the first bonding layer, the single-walled carbon nano tube conductive coating is fixed between the first substrate and the second substrate through the first bonding layer and the second bonding layer, the first bonding layer and the second bonding layer are mutually bonded through a transparent conductive coating network, parallel electrodes are arranged on two sides of the single-walled carbon nano tube conductive coating, and copper foils are arranged on the parallel electrodes. The problem of easy interlayer peeling caused by poor adhesion between the heating layer and the base material or poor cohesion of the heating layer in the prior art is solved. The problem of among the prior art copper foil burr easily will generate heat the layer and pierce through is solved. The problem of copper foil and silver thick liquid electrode virtual connection in the current product is improved.
Description
Technical Field
The invention relates to the technical field of heating, in particular to a carbon nano tube transparent heating structure, a preparation method and a preparation device thereof.
Background
The electro-thermal technology is a technology for converting electric energy into thermal energy by applying a certain voltage to an object having a certain resistance. Recently, under the national policies of "carbon peak reaching" and "carbon neutralization", more strict control measures are implemented on the carbon dioxide emission in various places, and various electric energy substitute products, such as electric floor heating, electric wall heating, electric furnaces, electric heaters and the like, emerge in the market. Wherein the product receives the favor in market with the electric floor heating that the electric heat membrane represented, compares with traditional hot-water heating, and electric heat membrane floor heating has that heat conversion efficiency is high, paves a great deal of advantages such as simple and convenient, need not follow-up maintenance.
But simultaneously, because the technical threshold of electric heat membrane product is lower relatively, and the product quality on the market is uneven, and many products take place various quality safety problems after putting into the market, like fire, power decay etc. not only bring the loss for people's personal and property safety, still seriously influenced the development of trade.
The heating material of the electrothermal film product mainly comprises carbon crystals (short-fiber carbon fibers), graphene, graphite, multi-walled carbon nanotubes and the like. The problems existing in the prior art are mainly as follows: 1. the adhesion between the heating slurry and the base material is insufficient, so that water vapor can permeate and the coating can crack after long-term use; 2. the quality of the packaging adhesive layer is greatly different; 3. the heating structure in the prior art has defects, and the packaging glue layer is not enough for packaging the whole structure. The above problems play a key role in the safety and service life of the product.
In addition, the outward appearance of current electric heat membrane is black or opaque, uses as internal heating usually, if use in the lower floor of floor, ceramic tile, wallboard, can't use as the top layer decorative layer, has further influenced the thermal conversion efficiency of whole product.
Disclosure of Invention
The invention aims to provide a carbon nano tube transparent heating structure, a preparation method and a preparation device thereof, wherein the heating structure is safe, stable and transparent.
In order to achieve the purpose, the invention provides the following technical scheme:
the carbon nanotube transparent heating structure comprises a first substrate, a single-walled carbon nanotube conductive coating and a second substrate, wherein a first bonding layer and a second bonding layer are respectively arranged on the connecting surface of the first substrate and the second substrate, the single-walled carbon nanotube conductive coating is arranged on the first bonding layer, the single-walled carbon nanotube conductive coating is fixed between the first substrate and the second substrate through the first bonding layer and the second bonding layer, the first bonding layer and the second bonding layer are mutually bonded through a transparent conductive coating network, parallel electrodes are arranged on two sides of the single-walled carbon nanotube conductive coating, copper foils are arranged on the parallel electrodes, the copper foils and the parallel electrodes are arranged along the length direction of the single-walled carbon nanotube conductive coating, and the edges of the copper foils and the parallel electrodes are not more than the edges of the first bonding layer and the second bonding layer.
Furthermore, the carbon nano tube in the single-walled carbon nano tube conductive coating is a single-walled carbon nano tube, the tube diameter is 0.6-2 nm, the length is 0.1-100 um, the light transmittance of the single-walled carbon nano tube conductive coating is 70-90%, the porosity is 15-45%, and the surface resistance is 300-1500 omega.
Furthermore, adhesive force bonding resin is not used in the single-walled carbon nanotube conductive coating, adhesion is formed between the high specific surface area of the single-walled carbon nanotube and the first base material, the width of the single-walled carbon nanotube coating is 300-1000 mm, and the distance between the edge of the single-walled carbon nanotube coating and the edge of the first base material is 20-35 mm, so that the insulation property of a packaged product is ensured.
Further, the construction process of the single-wall carbon nano coating is micro-concave coating, the used micro-concave roller is a 75-mesh twill micro-concave roller, and the inking amount of the wet coating is 40-60 g/m2。
Further, the parallel electrodes are silver paste electrodes, silver paste can be well bonded with the first base material through the carbon nanotube network, the construction process of the silver paste electrodes is one of micro-concave coating, screen printing and the like, the micro-concave coating is preferred, the width of the silver paste electrodes is 8-15 mm, the silver paste electrodes can be coated in a full mode or in a patterned mode, and the patterned printing mode is preferred in cost consideration.
Further, the copper foil is arranged on the parallel electrodes, the copper foil comprises a copper foil, a nickel-plated copper foil, a silver-plated copper foil and an aluminum foil, the silver-plated copper foil is preferred, the width of the copper foil is 8-15 mm, the thickness of the copper foil is 18-50 um, the copper foil is close to the edges of the first substrate and the second substrate, the copper foil and the parallel electrodes are arranged in a staggered mode, and the lap joint area of the parallel electrodes and the copper foil is 2/3-1/2 of the copper foil.
It should be noted that, in order to ensure the safety and reliability of the product, the edge of the copper foil cannot be directly lapped on the single-walled carbon nanotube coating, so as to prevent the cutting burr on the edge of the copper foil from cutting the carbon nanotube coating, which leads to the risk of sparking caused by too high local resistance.
Furthermore, the surface of the copper foil is provided with a plurality of groups of hollowed holes distributed along the length of the copper foil, the holes can be in any shapes such as round, square and sporadic shapes, the distance can be adjusted according to actual conditions, the interval of each hollowed hole is 15-50 mm, the second bonding layer can be firmly bonded with the silver paste electrode layer through the round holes, and then the copper foil electrode is fully fixed on the surface of the silver paste.
Further, the second bonding layer is coated on the surface of a second substrate in a precise coating mode, and then is laminated with the first substrate coated with the carbon nanotube transparent conductive coating and the silver paste through laminating equipment, and the copper foil is placed between the bonding layer and the silver paste during laminating.
In the process of lamination, the bonding layer coated on the surface of the second substrate can be directly bonded with the first substrate through the voids of the single-walled carbon nanotube network, and after curing, the first bonding layer and the second bonding layer are formed on both sides of the conductive film.
Further, first tie coat and second tie coat material include that PUR hot melt adhesive, UV photocuring type structure glue, no solvent glue, and preferred UV photocuring glues, and especially preferred no solvent glue, the thickness of tie coat is 20 ~ 50um, and the thickness homogeneity is 5 um.
Further, the adhesive layer is coated on the surface of the second substrate by a precision coating method, which is one of a micro-concave method, a comma knife method, a slit method, and the like, but is not limited thereto.
Further, the first base material and the second base material are combined through a combining press roll, the pressure of the combining press roll is 150-250 kg/cm2, and the combining temperature is 50-90 ℃. The temperature can soften the adhesive layer, has certain fluidity, and applies certain pressure to enable the UV light-cured structural adhesive on the second substrate to penetrate through the carbon nano tube transparent conductive film to be bonded with the first substrate.
Further, first substrate and second substrate material are any one of PET, PVC, PC, PMMA, TPU film, because of PC has better shock resistance, fire resistance and temperature toleration, therefore preferred PC material, the thickness of first substrate and second substrate is 50 ~ 200um, preferred 125 um.
Furthermore, the first substrate and the second substrate need to be subjected to corona treatment before being coated with the carbon nanotubes and the bonding layer so as to improve the surface energy of the substrate surface.
After the carbon nano tube transparent heating structure is subjected to accelerated aging for 360 hours under the voltage of 1.35 times and tested for 168 hours under the aging conditions of 85 ℃ and 85% RH, the power attenuation is only 0.5-1%, which is far lower than the requirement of the industry standard of +/-10%.
In one embodiment, the composite structure is subjected to a photo-curing crosslinking reaction with energy of 300-1500 mJ/cm 2.
Further, the peel force between the first substrate and the second substrate after the photo-curing treatment is > 2 kgf/inch.
Further, the photocurable bonding layer has a wet and heat resistance, and an interlayer peel force of > 2kgf/inch after aging test at 85 ℃ and 85% RH humidity for 168 hours.
The preparation method of the carbon nano tube transparent heating structure comprises the following steps: step 1, after corona treatment is carried out on a first base material, single-walled carbon nanotube conductive liquid is coated on the surface of the first base material, and a wet coating is baked for 3-5 min at a high temperature of 60-120 ℃ to obtain a transparent conductive carbon nanotube coating;
and 5, curing and crosslinking the combined product by a UVHg lamp to form a product with a transparent heating structure.
Carbon nanotube transparent heating structure preparation facilities, including first unreeling line, second unreeling line and third unreeling line, first unreeling line is including the first roll of unreeling, first scribbling leftover of bolt of cloth, first oven, second that set gradually and scribble leftover of bolt of cloth and second oven, the second unreels the line and scribbles the leftover of bolt of cloth including the second that sets gradually unreels the roll and the third, the third unreels the line and includes third and fourth unreeling roller, first, second, third unreel the line and pass through the compound compression roller pressfitting of second substrate and second with three group's materials, roll up through the wind-up roll, the wind-up roll front end is equipped with curing device, curing device carries out the UV solidification to the material of pressfitting.
Furthermore, the device also comprises a tension system and a deviation rectifying system.
The first unwinding roller is used for discharging a first substrate and is provided with an automatic material changing and receiving device.
First scribble the leftover of bolt of cloth and be used for scribbling single-walled carbon nanotube conductive coating on first substrate, scribble the leftover of bolt of cloth and be one of little concave, reticulation, slit, scribble the leftover of bolt of cloth and set up silo and automatic cycle feeding system, set up tertiary filter equipment in the circulation system, place 30um, 15um and 5umPP respectively and melt the filter core.
The first drying oven is arranged on two layers, the length of the first drying oven is 15-20 meters, 3-4 sections are provided, and the preferable temperature is set to be 70 ℃, 90 ℃, 120 ℃ and 80 ℃. The inside air supply and exhaust device that sets up of oven, the totality is little negative pressure, and the air supply is the clean air after just imitating, well effect, high efficiency filtration, and the heating method can be for the conduction oil heating, also can be for electric heating.
Furthermore, the first coating head and the first drying oven have a height difference so as to ensure that the leveling angle of the first base material before entering the drying oven is about 30-45 degrees.
The second is scribbled the leftover of bolt of cloth and is set up in being less than first oven exit position, and the coating mode is slightly concave, and the particular position of slightly concave roller is provided with silver thick liquid electrode pattern, corresponds that slightly concave roller pattern department sets up respectively and sets up a silver thick liquid groove for supply with silver thick liquid, and set up manual feeding device.
The second oven is arranged at the same height as the first oven, the length of the second oven is about 10-15 meters, and the set temperature is 150 ℃.
The second unwinding roller is positioned at the tail end of the equipment and used for discharging the second substrate, and an automatic material changing and receiving device is arranged.
The third coating head is used for coating the UV light-cured adhesive, the coating mode is one of micro-concave, comma scraper and slit, and the coating area is full coating.
Furthermore, a deviation correcting device is arranged behind the third coating head and used for correcting the position of the first base material.
Furthermore, the third coating head is arranged in a yellow light area to avoid the influence of ultraviolet rays on the coating.
The third unwinding roller and the fourth unwinding roller are used for unwinding copper foil, the unwinding device is arranged between the first substrate and the second substrate, and the unwinding device is arranged at a position 1.5-2.5 cm close to the edge of the substrate in the horizontal direction.
The laminating press roller is arranged at the intersection of the first base material, the second base material and the copper foil, one of the first laminating press roller and the second laminating press roller is made of rubber, the other one of the first laminating press roller and the second laminating press roller is made of mirror surface stainless steel, the stainless steel mirror surface roller is of a double-layer structure, the interior of the stainless steel mirror surface roller can be heated through heat conduction oil, and the diameters of the rubber press roller and the stainless steel roller are 300-800 mm.
Furthermore, the first base material, the second base material and the two laminating press rollers have wrap angles of more than 30 degrees, so that no bubbles are generated during lamination.
Furthermore, the laminating pressure can be adjusted by the air pressure of the air cylinder, and the general laminating pressure is 150-250 kg/cm 2.
The curing device is arranged on one side of the product after the lamination, and is about 30-100 mm away from the film; the energy range of the UV light is 200-1000 mJ/cm2, the UV lamp can also be one of a high-pressure Hg lamp, an electrodeless lamp, a halogen lamp and an LED lamp, and a reflecting cover and an exhaust device are arranged.
The winding roller is used for winding and collecting the cured product;
the tension system and the deviation rectifying system are used for controlling the coating and laminating quality of the film.
Compared with the prior art, the carbon nanotube transparent heating structure has higher reliability;
the adhesive layer has enhanced fluidity at high temperature and high pressure, can penetrate through the carbon nanotube network to tightly bond the first substrate and the second substrate, and overcomes the problem of easy interlayer peeling caused by poor adhesion between the heating layer and the substrate or poor cohesion of the heating layer in the prior art;
by adjusting the relative position of the copper foil electrode and the silver paste electrode, the problem that the heating layer is easily pierced by the burrs of the copper foil in the prior art is solved;
the copper foil is hollowed in a local area, so that the bonding layer is bonded with the silver paste electrode through the copper foil, and the problem of virtual connection between the copper foil and the silver paste electrode in the existing product is solved;
meanwhile, the invention also provides a method and a device for preparing the carbon nano tube transparent heating structure, the method and the device are simple and easy to implement, the finished heating film can be prepared at one time, and the first pass rate and the yield of products are greatly improved.
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 without limiting the invention in which:
FIG. 1 is a schematic diagram of a longitudinal cross-sectional structure of a carbon nanotube transparent heating structure;
FIG. 2 is a schematic cross-sectional structure diagram of a carbon nanotube transparent heating structure;
FIG. 3 is a flow chart of the preparation of the carbon nanotube transparent heating structure;
fig. 4 is a diagram of a manufacturing apparatus of the carbon nanotube transparent heating structure.
In the drawings:
1. a first substrate; 11. a second substrate; 2. a first adhesive layer; 21. a second adhesive layer; 3. a single-walled carbon nanotube conductive coating; 4. parallel electrodes; 5. copper foil; 6. a first unwinding roller; 7. a first coating head; 8. a first oven; 9. a second coating head; 10. a second oven; 11. a first composite press roll; 12. Third and fourth unwinding rollers; 13. a second composite press roll; 14. a third coating head; 15. a curing device; 16. a second unwinding roller; 17. and (7) winding the roller.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-4, the present invention provides a technical solution: carbon nanotube transparent heating structure, including first substrate 1, single-walled carbon nanotube conductive coating 3 and second substrate 11, first substrate 1 and 11 connection face of second substrate are equipped with first tie coat 2 and second tie coat 21 respectively, single-walled carbon nanotube conductive coating 3 is arranged in on first tie coat 2, single-walled carbon nanotube conductive coating 3 is fixed between first substrate 1 and second substrate 11 through first tie coat 2 and second tie coat 21, first tie coat 2 and second tie coat 21 bond each other through transparent conductive coating network, 3 both sides of single-walled carbon nanotube conductive coating are equipped with parallel electrode 4, be equipped with copper foil 5 on parallel electrode 4, copper foil 5 and parallel electrode 4 lay along 3 length direction of single-walled carbon nanotube conductive coating, and copper foil 5 and parallel electrode 4 edge are no longer than first tie coat 2 and second tie coat 21 edge.
The carbon nano tube in the single-walled carbon nano tube conductive coating 3 is a single-walled carbon nano tube, the tube diameter is 0.6-2 nm, the length is 0.1-100 um, the light transmittance of the single-walled carbon nano tube conductive coating 3 is 70-90%, the porosity is 15-45%, the surface resistance is 300-1500 omega, adhesive bonding resin is not used in the single-walled carbon nano tube conductive coating, adhesion is formed between the high specific surface area of the single-walled carbon nano tube and a first base material, the width of the single-walled carbon nano tube coating is 300-1000 mm, the distance between the edge of the single-walled carbon nano tube coating and the edge of the first base material is 20-35 mm, so that the insulativity of a packaged product is ensured, the construction process of the single-walled carbon nano coating is micro-concave coating, the used micro-concave roller is a 75-mesh micro-concave roller, and the ink amount of a wet coating is 40-60 g/m2。
The conductive coating 3 of single-walled carbon nanotubes forms an attachment to the first substrate 1 by means of the high specific surface area of the single-walled carbon nanotubes.
The parallel electrode 4 is a silver paste electrode, silver paste can be well bonded with the first substrate through the carbon nanotube network, the construction process of the silver paste electrode is one of micro-concave coating, screen printing and the like, the micro-concave coating is preferred, the width of the silver paste electrode is 8-15 mm, the silver paste electrode can be coated in a full mode and can be coated in a patterning mode, and the cost is considered to be the preferred patterning printing mode.
The copper foil 5 is arranged on the parallel electrode 4, the copper foil 5 comprises a copper foil, a nickel-plated copper foil, a silver-plated copper foil and an aluminum foil, the copper foil 5 is close to the edges of the first base material 1 and the second base material 11, the width of the copper foil 5 is 8-15 mm, the thickness of the copper foil 5 is 18-50 um, the copper foil 5 and the parallel electrode 4 are arranged in a staggered mode, and the overlapping area of the parallel electrode 4 and the copper foil 5 is 2/3-1/2 of the copper foil 5.
The multiple groups of hollowed holes distributed along the length of the copper foil 5 are formed in the surface of the copper foil, the interval of each hollowed hole is 15-50 mm, the holes can be in any shape such as circular, square and sporadic shapes, the distance can be adjusted according to actual conditions, the interval of each hollowed hole is 15-50 mm, the second bonding layer 21 can be firmly bonded with the 4 silver paste electrodes through the round holes, the copper foil electrodes are fully fixed on the surfaces of the silver pastes, the second bonding layer is coated on the surfaces of the second substrates in a precise coating mode and then is combined with the first substrates coated with the carbon nanotube transparent conductive coatings and the silver pastes through the combining equipment, and the copper foil is placed between the bonding layer and the silver pastes when the copper foil is combined.
In the process of lamination, the bonding layer coated on the surface of the second substrate can be directly bonded with the first substrate through the voids of the single-walled carbon nanotube network, and after curing, the first bonding layer and the second bonding layer are formed on both sides of the conductive film.
Further, the adhesive layer is coated on the surface of the second substrate by a precision coating method, which is one of a micro-concave method, a comma knife method, a slit method, and the like, but is not limited thereto.
Further, the first base material 1 and the second base material 11 are combined through a combining press roll, the pressure of the combining press roll is 150-250 kg/cm2, and the combining temperature is 50-90 ℃. The temperature can soften the adhesive layer, and the adhesive layer has certain fluidity, and simultaneously, a certain pressure is applied, so that the UV light-cured structural adhesive on the second substrate 11 can penetrate through the carbon nano tube transparent conductive film to be bonded with the first substrate.
Further, the first substrate 1 and the second substrate 11 are subjected to corona treatment before coating the carbon nanotubes and the adhesive layer to increase the surface energy of the substrate surface.
After the carbon nano tube transparent heating structure is subjected to accelerated aging for 360 hours under the voltage of 1.35 times and tested for 168 hours under the aging conditions of 85 ℃ and 85% RH, the power attenuation is only 0.5-1%, which is far lower than the requirement of the industry standard of +/-10%.
In one embodiment, the composite structure is subjected to a photo-curing crosslinking reaction with energy of 300-1500 mJ/cm 2.
Further, the peel force between the first substrate and the second substrate after the photo-curing treatment is > 2 kgf/inch.
Further, the photocurable bonding layer has a wet and heat resistance, and an interlayer peel force of > 2kgf/inch after aging test at 85 ℃ and 85% RH humidity for 168 hours.
Carbon nanotube transparent heating structure preparation facilities, including first unreeling line, second unreeling line and third unreeling line, first unreeling line is including the first roll 6 of unreeling that sets gradually, first scribbles leftover of bolt of cloth 7, first oven 8, leftover of bolt of cloth 9 and second oven 10 are scribbled to the second, the second unreels the line and is including the second that sets gradually unreel the roller 16 and the leftover of cloth 14 is scribbled to the third, the third unreels the line and includes third and fourth unreel roller 12, first, second, three unreel the line with three group's materials through the pressfitting of second substrate 11 and the compound compression roller 13 of second, roll up through wind-up roll 17, wind-up roll 17 front end is equipped with solidification equipment 15, solidification equipment 15 carries out the UV solidification to the material of pressfitting.
Furthermore, the device also comprises a tension system and a deviation rectifying system.
The first unwinding roller is used for discharging a first substrate and is provided with an automatic material changing and receiving device.
First scribble the leftover of bolt of cloth and be used for scribbling single-walled carbon nanotube conductive coating on first substrate, scribble the leftover of bolt of cloth and be one of little concave, reticulation, slit, scribble the leftover of bolt of cloth and set up silo and automatic cycle feeding system, set up tertiary filter equipment in the circulation system, place 30um, 15um and 5umPP respectively and melt the filter core.
The first drying oven is arranged on two layers, the length of the first drying oven is 15-20 meters, 3-4 sections are provided, and the preferable temperature is set to be 70 ℃, 90 ℃, 120 ℃ and 80 ℃. The inside air supply and exhaust device that sets up of oven, the totality is little negative pressure, and the air supply is the clean air after just imitating, well effect, high efficiency filtration, and the heating method can be for the conduction oil heating, also can be for electric heating.
Further, the first coating head 7 and the first drying oven 8 have a height difference so as to ensure that the leveling angle of the first base material before entering the drying oven is about 30-45 degrees.
The second is scribbled leftover of bolt of cloth 9 and is set up in being less than 8 exit positions of first oven, and the coating mode is slightly concave, and the particular position of slightly concave roller is provided with silver thick liquid electrode pattern, corresponds that slightly concave roller pattern department sets up respectively and sets up a silver thick liquid groove for supply with silver thick liquid, and set up manual feeding device.
The second oven 10 is arranged at the same height as the first oven 8, the length of the second oven is about 10-15 meters, and the temperature is set to be 150 ℃.
The second unwinding roller 16 is located at the tail end of the equipment and used for discharging the second substrate 11, and an automatic material changing and receiving device is arranged.
The third coating head 14 is used for coating the UV light curing adhesive in one of a micro-concave, comma blade, and slit, and the coating area is full coating.
Furthermore, a deviation correcting device should be arranged behind the third coating head 14 for correcting the position of the first substrate 1.
Further, the third coating head 14 should be located in the yellow region to avoid the influence of ultraviolet rays on the coating.
The third unwinding roller 12 and the fourth unwinding roller 12 are used for unwinding the copper foil 5, the unwinding device is arranged between the first substrate 1 and the second substrate 11, and the unwinding device is arranged at a position 1.5-2.5 cm close to the edge of the substrate in the horizontal direction.
The laminating press roller is arranged at the intersection of the first base material 1, the second base material 11 and the copper foil 5, one of the press rollers of the first laminating press roller 11 and the second laminating press roller 13 is made of rubber, the other press roller is made of mirror surface stainless steel, the stainless steel mirror surface roller is of a double-layer structure, heat can be conducted through heat conduction oil inside the stainless steel mirror surface roller, and the diameters of the rubber press roller and the stainless steel roller are 300-800 mm.
Further, the first base material 1 and the second base material 11 and the two laminating press rollers have wrap angles of more than 30 degrees, so that no bubbles are generated during attaching.
Furthermore, the laminating pressure can be adjusted by the air pressure of the air cylinder, and the general laminating pressure is 150-250 kg/cm 2.
The curing device 15 is arranged on one side of the product after the lamination, and is about 30-100 mm away from the film; the energy range of the UV light is 200-1000 mJ/cm2, the UV lamp can also be one of a high-pressure Hg lamp, an electrodeless lamp, a halogen lamp and an LED lamp, and a reflecting cover and an exhaust device are arranged.
And the winding roller 17 is used for winding and collecting the solidified product.
The tension system and the deviation rectifying system are used for controlling the coating and laminating quality of the film.
Example 1:
And 2, coating silver paste electrodes inwards on the edges of the carbon nano tube conductive coating, wherein the baking temperature is 150 ℃ and the baking time is 2 min.
And 3, coating the whole surface of the 125umPET second substrate with a UV (ultraviolet) light curing adhesive.
And 4, laminating the first base material and the second base material through a heating roller, wherein the laminating temperature is 80 ℃, the laminating pressure is 200kg/cm2, in the laminating process, two pieces of 18um copper foil with hollow holes are laminated between the first base material and the second base material, the width is 15mm, and the position of the copper foil is controlled by using deviation rectification.
And 5, curing and crosslinking the compounded product by a UVHg lamp, wherein the curing energy is 550mJ/cm2, and forming the product with a transparent heating structure.
Example 2:
And 2, coating silver paste electrodes inwards on the edges of the carbon nano tube conductive coating, wherein the baking temperature is 150 ℃ and the baking time is 2 min.
And 3, coating the whole surface of the second substrate 100umPC with the UV light curing adhesive.
And 4, laminating the first base material and the second base material through a heating roller, wherein the laminating temperature is 80 ℃, the laminating pressure is 200kg/cm2, in the laminating process, two pieces of 18um copper foil with hollow holes are laminated between the first base material and the second base material, the width is 15mm, and the position of the copper foil is controlled by using deviation rectification.
And 5, curing and crosslinking the compounded product by a UVHg lamp, wherein the curing energy is 550mJ/cm2, and forming the product with a transparent heating structure.
Comparative example 1:
comparative example 1 is identical to example 1 except that the first substrate surface is coated with a multi-walled carbon nanotube conductive dispersion.
Comparative example 2:
comparative example 2 is identical to example 1 in step, except that the first substrate surface is coated with a transparent monolayer graphene conductive dispersion.
Comparative example 3:
comparative example 3 is identical to example 1 in step, except that no heat application was used in step 4.
Comparative example 4:
comparative example 4 was identical to example 1 except that a copper foil without a via hole was used in step 4.
Comparative example 5:
comparative example 5 is essentially identical to example 1 except that step 3 is eliminated, a second substrate having an EVA hot melt adhesive coating on its surface is used directly, and UV light curing is eliminated in step 4.
And (3) performance testing:
the anti-static PMMA plates prepared by the experimental groups 1-2 and the comparative groups 1-5 are subjected to various performance index evaluations, and the evaluation results are shown in Table 1:
TABLE 1
According to the test data of the experimental group and the comparative group, the single-walled carbon nanotube transparent conductive coating is adopted as the heating coating, so that the stability of the heating structure can be obviously improved.
The surfaces of the embodiment 1 and the embodiment 2 are selected from different suitable base materials, the structural stability of the product is not obviously influenced, and in practical application, the base materials can be selected by comprehensively considering the factors of temperature resistance, flame retardance, impact resistance, cost and the like of the product.
The comparative example 1 selects the multi-walled carbon nanotube coating as the heating layer, the structural stability of the multi-walled carbon nanotube coating is poor, the multi-walled carbon nanotube network is compact and is a pure black opaque coating, the UV bonding layer cannot penetrate through the carbon nanotube coating to be bonded with the first base material, and the interlayer peeling force is influenced by the adhesive force between the carbon nanotube coating and the first base material.
Although the single-layer graphene coating selected in comparative example 2 has a certain light transmittance, the adhesive cannot penetrate through the graphene coating and is bonded with the first substrate due to the fact that the microstructure of the single-layer graphene coating has no pore structure, and the interlayer peeling force of the single-layer graphene coating is also obviously affected.
Comparative example 3 experimental results show that the bonding of the UV bonding layer to the first substrate in the lamination process needs to be performed under appropriate temperature conditions, and when a certain temperature is reached, the bonding layer has certain fluidity and can penetrate through the single-walled carbon nanotube network more easily through capillary action.
In comparative example 4, the copper foil without the hollow hole is used, and the virtual connection exists between the copper foil and the silver paste, so that the power stability is more easily affected by moisture.
Comparative example 5 EVA Hot melt adhesive commonly used in the industry is used to replace UV bonding adhesive, the temperature resistance is obviously reduced, and the power attenuation reaches 15.9% after aging for 2h at 100 ℃.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The carbon nanotube transparent heating structure is characterized by comprising a first substrate (1), a single-walled carbon nanotube conductive coating (3) and a second substrate (11), wherein a first bonding layer (2) and a second bonding layer (21) are respectively arranged on the connecting surface of the first substrate (1) and the second substrate (11), the single-walled carbon nanotube conductive coating (3) is arranged on the first bonding layer (2), the single-walled carbon nanotube conductive coating (3) is fixed between the first substrate (1) and the second substrate (11) through the first bonding layer (2) and the second bonding layer (21), the first bonding layer (2) and the second bonding layer (21) are mutually bonded through a transparent conductive coating network, parallel electrodes (4) are arranged on two sides of the single-walled carbon nanotube conductive coating (3), copper foils (5) are arranged on the parallel electrodes (4), and the copper foils (5) and the parallel electrodes (4) are arranged along the length direction of the single-walled carbon nanotube conductive coating (3) And the edges of the copper foil (5) and the parallel electrode (4) do not exceed the edges of the first bonding layer (2) and the second bonding layer (21).
2. The carbon nanotube transparent heating structure according to claim 1, wherein the carbon nanotubes in the single-walled carbon nanotube conductive coating (3) are single-walled carbon nanotubes, the tube diameter is 0.6-2 nm, the length is 0.1-100 um, the light transmittance of the single-walled carbon nanotube conductive coating (3) is 70-90%, the porosity is 15-45%, and the surface resistance is 300-1500 Ω.
3. The carbon nanotube transparent heating structure according to claim 1, wherein the single-walled carbon nanotube conductive coating (3) forms an adhesion with the first substrate (1) by the high specific surface area of the single-walled carbon nanotube.
4. The carbon nanotube transparent heating structure of claim 1, wherein the parallel electrode (4) is a silver paste electrode.
5. The carbon nanotube transparent heating structure of claim 1, wherein the copper foil (5) is disposed on the parallel electrode (4), the copper foil (5) comprises a copper foil, a nickel-plated copper foil, a silver-plated copper foil and an aluminum foil, the copper foil (5) is close to the edges of the first substrate (1) and the second substrate (11), the width of the copper foil (5) is 8-15 mm, the thickness of the copper foil is 18-50 um, the copper foil (5) and the parallel electrode (4) are arranged in a staggered manner, and the overlapping area of the parallel electrode (4) and the copper foil (5) is 2/3-1/2.
6. The carbon nanotube transparent heating structure according to claim 5, wherein the surface of the copper foil (5) is provided with a plurality of groups of hollowed-out holes distributed along the length thereof, and the spacing between every two hollowed-out holes is 15-50 mm.
7. The carbon nanotube transparent heating structure of claim 1, wherein the first bonding layer (2) and the second bonding layer (21) comprise PUR hot melt adhesive, UV light-curable structural adhesive and solvent-free adhesive, the thickness of the bonding layers is 20-50 um, and the thickness uniformity is ± 5 um.
8. The carbon nanotube transparent heating structure according to claim 1, wherein the first substrate (1) and the second substrate (11) are made of any one of PET, PVC, PC, PMMA and TPU films, and the thickness of the first substrate (1) and the thickness of the second substrate (11) are both 50-200 um.
9. The preparation method of the carbon nanotube transparent heating structure is characterized by comprising the following steps of 1, coating single-walled carbon nanotube conductive liquid on the surface of a first substrate after corona treatment, and baking a wet coating at 60-120 ℃ for 3-5 min to obtain a transparent conductive carbon nanotube coating;
step 2, coating silver paste electrodes inwards on the edges of the carbon nano tube conductive coating, and baking at the temperature of 150 ℃ for 2 min;
step 3, coating the whole surface of the second base material with a UV light curing adhesive;
step 4, the first substrate and the second substrate are combined through a heating roller, in the combining process, the copper foil with the two hollow holes is combined between the first substrate and the second substrate, and meanwhile, a deviation correcting device is used for controlling the position of the copper foil;
and 5, curing and crosslinking the combined product by a UVHg lamp to form a product with a transparent heating structure.
10. The carbon nanotube transparent heating structure preparation device is characterized by comprising a first unwinding line, a second unwinding line and a third unwinding line, wherein the first unwinding line comprises a first unwinding roller (6), a first coating head (7), a first oven (8), a second coating head (9) and a second oven (10) which are sequentially arranged, the second unwinding line comprises a second unwinding roller (16) and a third coating head (14) which are sequentially arranged, the third unwinding line comprises a third unwinding roller (12) and a fourth unwinding roller (12), the first unwinding line, the second unwinding line and the third unwinding line enable three groups of materials to be laminated through a second base material (11) and a second composite compression roller (13), the materials are wound through the winding roller (17), a curing device (15) is arranged at the front end of the winding roller (17), and the curing device (15) conducts UV curing on the laminated materials.
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