CN115179634A - Heat storage film and preparation method thereof - Google Patents

Heat storage film and preparation method thereof Download PDF

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Publication number
CN115179634A
CN115179634A CN202210640981.0A CN202210640981A CN115179634A CN 115179634 A CN115179634 A CN 115179634A CN 202210640981 A CN202210640981 A CN 202210640981A CN 115179634 A CN115179634 A CN 115179634A
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heat storage
layer
film
storage layer
change material
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陈彤红
许剑
赵义丽
王亚东
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China Lucky Group Corp
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China Lucky Group Corp
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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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/016—Layered products comprising a layer of metal all layers being exclusively metallic all layers being formed of aluminium or aluminium alloys
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/085—Layered products comprising a layer of metal comprising metal 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 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B15/09—Layered products comprising a layer of metal comprising metal 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 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Abstract

The invention discloses a heat storage film and a preparation method thereof. The heat storage film includes: a first support layer having a first surface; a glue layer disposed on the first surface; the second supporting layer is arranged on one side, far away from the first supporting layer, of the adhesive layer, and is provided with a second surface which is close to the adhesive layer; the heat storage layer is arranged on the second surface and comprises at least two sub heat storage layers arranged at intervals; wherein the glue layer covers the surfaces and the side faces of the at least two sub-thermal storage layers far away from the second support layer and the parts of the second surface which are not covered by the thermal storage layer. Therefore, the heat storage layer can be well sealed, the leakage of substances in the heat storage layer is prevented, and the reduction of the heat storage performance of the heat storage film is effectively avoided.

Description

Heat storage film and preparation method thereof
Technical Field
The invention relates to the field of heat management materials, in particular to a heat storage film and a preparation method thereof.
Background
The heat storage film plays a very critical role in the field of heat management, the heat storage film is arranged between a heat generating part of an electronic product and a heat releasing part to play a good role in controlling temperature, and the heat storage film also can play a role in controlling temperature in other heat generating processes.
In practical applications, the heat storage amount per unit weight of the heat storage film needs to be high, or the heat storage film with a low thickness can have a high enthalpy value. In addition, in the using process, if the phase change material in the heat storage film leaks, the heat storage performance of the heat storage film is influenced, parts around the heat storage film are polluted, and the performances of electronic products and the like are influenced.
Therefore, the heat storage film and the method for preparing the same still need to be improved.
Disclosure of Invention
The present invention aims to alleviate or solve at least to some extent at least one of the above mentioned problems. In view of the above, in one aspect of the present invention, there is provided a heat storage film, including: a first support layer having a first surface; a glue layer disposed on the first surface; the second supporting layer is arranged on one side, far away from the first supporting layer, of the adhesive layer, the second supporting layer is provided with a second surface, and the second surface is close to the adhesive layer; the heat storage layer is arranged on the second surface and comprises at least two sub heat storage layers arranged at intervals; wherein the glue layer covers the surfaces and the side faces of the at least two sub-thermal storage layers far away from the second support layer and the parts of the second surface which are not covered by the thermal storage layer. Therefore, the heat storage layer can be well sealed, the leakage of substances in the heat storage layer is prevented, and the reduction of the heat storage performance of the heat storage film is effectively avoided.
According to an embodiment of the present invention, the first support layer and the second support layer are each independently selected from a PET film, a PEN film, a polyethylene film, a polypropylene film, a polyimide film, a copper foil, or an aluminum foil, and/or the thickness of the first support layer and the thickness of the second support layer are each independently 5 μm to 50 μm. Therefore, the first supporting layer and the second supporting layer have good supporting effects, and the overall stability of the heat storage film is improved.
According to an embodiment of the present invention, the glue layer includes at least one of alkyd resin, polyurethane, polyester polyol, polyacrylate, styrene-butadiene latex, carboxylated styrene-butadiene latex, and polyvinyl alcohol; the thickness of the adhesive layer is 1-10 μm, and preferably 1-3 μm.
According to an embodiment of the invention, the thickness of the thermal storage layer is 50 μm to 200 μm. Therefore, the heat storage layer has proper thickness, and the heat storage performance of the heat storage film is improved.
According to the embodiment of the invention, the heat storage layer comprises the phase-change material, the enthalpy value of the phase-change material is 100J/g-350J/g, and preferably, the enthalpy value of the phase-change material is 170J/g-350J/g, so that the enthalpy value of the phase-change material is higher, and the heat storage performance of the heat storage film is further improved.
According to an embodiment of the present invention, the thermal storage layer further includes a curing agent and a leveling agent, wherein the curing agent includes at least one of an isocyanate curing agent, a silicic acid curing agent, a boric acid curing agent and a dialdehyde curing agent, and the leveling agent includes at least one of a polyacrylate leveling agent, a fluorocarbon-modified polyacrylate leveling agent and an alkynol leveling agent.
According to the embodiment of the invention, the heat storage layer comprises 98-99.8 parts by weight of phase change material, 0.1-1 part by weight of leveling agent and 0.1-1 part by weight of curing agent; preferably, the heat storage layer comprises 98.9-99.8 parts by weight of phase change material, 0.1-0.5 part by weight of leveling agent and 0.1-0.6 part by weight of curing agent.
According to an embodiment of the present invention, the phase change material is a microcapsule structure, a core of the microcapsule structure includes at least one of stearic acid, lauric acid, palmitic acid, erythritol, n-octadecane, n-nonadecane, n-eicosane, n-docosane, and n-octacosane, and a wall of the microcapsule structure includes at least one of melamine, urea-formaldehyde, chitosan, acrylic polymer, polyurea, polyurethane, and polyurethane-urea. Therefore, the capsule wall in the microcapsule structure can protect the phase-change material in the capsule core, and by combining the sealing effect of the glue layer, the double protection can be formed on the phase-change material, so that the overall stability of the heat storage film can be improved, and the good heat storage performance of the heat storage film can be kept.
According to an embodiment of the present invention, the microcapsule structure has a particle size of 1 to 50 μm; the surface of the capsule wall is provided with hydrophilic groups, and preferably, the particle size of the microcapsule structure is 1-30 μm. Therefore, the microcapsule structure has a proper particle size, which is beneficial to the formation of a heat storage layer; the formation of the thermal storage layer is also facilitated by the hydrophilic groups on the surface of the capsule wall.
In another aspect of the present invention, the present invention provides a method of preparing the heat storage film described above, the method of preparing the heat storage film described above comprising: intermittently coating the heat storage layer slurry on the second surface of the second supporting layer, and performing first drying treatment to form a heat storage layer, wherein the heat storage layer comprises at least two sub heat storage layers arranged at intervals; coating an adhesive on the first surface of the first support layer, and performing a second drying process to form an adhesive layer; and (3) bonding and curing the heat storage layer, the second supporting layer and the adhesive layer to form an adhesive layer, wherein the adhesive layer covers at least two surfaces and side surfaces of the sub heat storage layer far away from the second supporting layer and the part of the second surface which is not covered by the heat storage layer. Therefore, the heat storage film prepared by the method has good overall stability, and can effectively avoid adverse effects caused by substance leakage in the heat storage layer; the method is simple and convenient to operate, is beneficial to reducing the preparation cost and is beneficial to improving the yield of products.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 shows a schematic structural view of a heat storage film according to an embodiment of the present invention;
fig. 2 shows a schematic structural view of a heat storage film according to another embodiment of the present invention.
Description of the reference numerals:
10: a first support layer; 11: a first surface; 20: a glue layer; 30: a second support layer; 31: a second surface; 40: a heat storage layer; 41: a sub thermal storage layer.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
In one aspect of the present invention, the present invention provides a heat storage film, and referring to fig. 1 and 2, the heat storage film includes a first support layer 10, a glue layer 20, a second support layer 30, and a heat storage layer 40. According to an embodiment of the present invention, referring to fig. 1 and fig. 2, the first support layer 10 has a first surface 11, the glue layer 20 is disposed on the first surface 11, the second support layer 30 is disposed on a side of the glue layer 20 away from the first support layer 10, the second support layer 30 has a second surface 31, the second surface 31 is disposed adjacent to the glue layer 20, the thermal storage layer 40 is disposed on the second surface 31, the thermal storage layer 40 includes at least two sub thermal storage layers 41 disposed at intervals, and the glue layer 20 covers surfaces and side surfaces of the at least two sub thermal storage layers 41 away from the second support layer 30 and a portion of the second surface 31 that is not covered by the thermal storage layer 40. From this, the heat storage layer comprises the sub-heat storage layer that two at least intervals set up, and the glue film can cover every sub-heat storage layer and keep away from the surface and the side of second supporting layer to realize the good encapsulation to the heat storage layer, effectively avoid the material in the heat storage layer to reveal, and then can make the heat storage membrane keep higher enthalpy value.
Note that the thermal storage layer 40 includes at least two sub thermal storage layers 41 arranged at intervals, which means that the thermal storage layer 40 may include two or more sub thermal storage layers 41 arranged at intervals. According to some embodiments of the present invention, referring to fig. 1, the thermal storage layer 40 may include two sub thermal storage layers 41 arranged at intervals; according to other embodiments of the present invention, referring to fig. 2, the thermal storage layer 40 may include three sub thermal storage layers 41 arranged at intervals. Of course, the thermal storage layer 40 may include four, five or more sub thermal storage layers 41 arranged at intervals, as long as each sub thermal storage layer can be well encapsulated to prevent substance in the sub thermal storage layer from leaking.
According to the embodiment of the present invention, referring to fig. 1 and 2, an orthographic projection of the glue layer 20 on the second support layer 30 covers an orthographic projection of the heat storage layer 40 on the second support layer 30, and the edge of the first support layer 10 and the edge of the second support layer 30 may be sealed by the glue layer, whereby the structural stability and the sealing effect of the heat storage film may be further ensured.
According to the embodiment of the invention, the heat storage layer 40 comprises the phase change material, the enthalpy value of the phase change material is 100J/g-350J/g, for example, the enthalpy value of the phase change material can be 100J/g, 120J/g, 140J/g, 160J/g, 180J/g, 200J/g, 220J/g, 240J/g, 260J/g, 280J/g, 330J/g, 350J/g and the like. The inventors have found that if the enthalpy value of the phase change material per unit weight is high, a better heat storage capacity per unit thickness can be obtained, and therefore, the heat storage performance of the heat storage layer can be further improved by controlling the enthalpy value of the phase change material to the above range, and further, the overall performance of the heat storage film can be further improved. According to some embodiments of the invention, the enthalpy value of the phase change material is 170J/g-350J/g, thereby being beneficial to further improving the heat storage performance of the heat storage film.
According to an embodiment of the present invention, the phase change material may be a microcapsule structure, i.e. a structure in which the core is enclosed by the wall, which corresponds to a structure in which the core material is encapsulated in the wall. According to some embodiments of the present invention, the microcapsule-structured capsule core may include at least one of stearic acid, lauric acid, palmitic acid, erythritol, n-octadecane, n-nonadecane, n-eicosane, n-docosane, and n-octacosane, that is, the microcapsule-structured capsule core may include one or more of the above materials, and the microcapsule-structured capsule wall may include at least one of melamine, urea-formaldehyde, chitosan, acrylic polymer, polyurea, polyurethane, and polyurethane-urea, that is, the microcapsule-structured capsule wall may include one or more of the above materials, so that, on one hand, the microcapsule-structured capsule wall has a better encapsulation performance, and the microcapsule-structured capsule core has a better phase change performance, and the capsule core having the phase change performance is encapsulated by the capsule wall, and then, by combining two support layers and a glue layer, secondary encapsulation of the phase change material can be achieved, double protection can be performed, leakage of the phase change material can be better prevented, and the heat storage film can be prevented from being contaminated or affected by leakage of the phase change material; on the other hand, the phase-change material can be dissolved in an aqueous solvent, so that the use of the traditional organic solvent can be avoided, and further, the harm to the production environment, the living environment and the human health caused by the use of the organic solvent is avoided; on the other hand, no adhesive is needed to be added into the heat storage layer, the heat storage layer can be formed into a film by crosslinking the capsule wall of the microcapsule structure into the film, and a thinner heat storage layer can achieve a higher enthalpy value, so that the enthalpy value of the unit weight of the heat storage film can be further improved. The enthalpy value of the microcapsule structure can be adjusted by selecting the phase change material, the mass of the capsule wall in the microcapsule structure accounting for the total mass of the microcapsule structure, and the like.
The inventor finds that the enthalpy value of the heat storage membrane is mainly related to the mass ratio of the phase change material, the integral structure is prepared by directly crosslinking the capsule wall of the phase change material microcapsule structure into a film, the addition of a large amount of adhesive is avoided, the enthalpy value of the unit weight of the slurry of the heat storage layer is improved, and the heat storage membrane can be thinner and has higher enthalpy value when being coated and formed.
According to some embodiments of the present invention, the particle size of the microcapsule structure may be 1 μm to 50 μm, for example, 1 μm, 2 μm, 3 μm, 5 μm, 7 μm, 9 μm, 12 μm, 15 μm, 18 μm, 21 μm, 24 μm, 27 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, etc., and the inventors found that if the particle size of the microcapsule structure is too small, for example, the particle size of the microcapsule structure is less than 1 μm, the enthalpy value of the microcapsule structure is significantly reduced, thereby affecting the heat storage performance of the heat storage film; if the particle size of the microcapsule structure is too large, for example, the particle size of the microcapsule structure is larger than 50 μm, the microcapsule structure is easy to precipitate, and the storage stability of the slurry of the heat storage layer is reduced; in the invention, the particle size of the microcapsule structure is controlled within the particle size range, so that the stability of the slurry of the heat storage layer can be ensured, and the obtained heat storage layer has a higher enthalpy value. According to some embodiments of the present invention, the particle size of the microcapsule structure may be 1 μm to 30 μm, thereby further ensuring the stability of the slurry of the thermal storage layer and enabling the thermal storage layer to have a higher enthalpy value.
According to some embodiments of the present invention, the surface of the wall of the microcapsule structure may have a hydrophilic group, and the hydrophilic group may include at least one of amino group, imino group, hydroxyl group, and carboxyl group, thereby facilitating dispersion of the microcapsule structure in an aqueous solvent, facilitating faster preparation of a thermal storage layer slurry, facilitating reduction of production time, and reducing production cost; moreover, the microcapsule structure is dispersed in the aqueous solvent, which is more beneficial to environmental protection and human health.
According to some embodiments of the present invention, the thermal storage layer 40 may further include a curing agent and a leveling agent, so that the addition of the leveling agent is beneficial to improving the flatness of the thermal storage layer, and the addition of the curing agent can improve the bonding strength between the thermal storage layer and the supporting layer and the adhesive layer, and can enhance the interaction force among the microcapsule particles, thereby being beneficial to improving the film forming property of the slurry of the thermal storage layer.
According to some embodiments of the present invention, the curing agent may include at least one of an isocyanate-based curing agent, a silicic acid-based curing agent, a boric acid-based curing agent, a dialdehyde-based curing agent, and the like, whereby the flatness of the thermal storage layer may be further improved.
According to some embodiments of the present invention, the leveling agent may include at least one of a polyacrylate type leveling agent, a fluorocarbon-modified polyacrylate type leveling agent, an acetylene alcohol type leveling agent, and the like. Therefore, the bonding strength of the heat storage layer, the supporting layer and the adhesive layer can be further improved, and the film forming property of the heat storage layer slurry can be further improved.
According to an embodiment of the present invention, the thermal storage layer may include 98 to 99.8 parts by weight of the phase change material, 0.1 to 1 part by weight of the leveling agent, and 0.1 to 1 part by weight of the curing agent. Therefore, the heat storage layer has better flatness and higher enthalpy value, and the heat storage layer has higher bonding force with the supporting layer and the adhesive layer, and higher bonding strength, so that the heat storage membrane has higher enthalpy value and good stability. The inventor finds that if the proportion of the phase-change material in the heat storage layer is too small, the enthalpy value of the heat storage layer is relatively low, the heat storage performance of the heat storage film is relatively poor, and the enthalpy value of the heat storage layer is correspondingly increased along with the increase of the proportion of the phase-change material; if the using amount of the leveling agent is too small, the effect of the leveling agent on improving the flatness of the heat storage layer is not obvious; if the consumption of the curing agent is too little or too much, the film forming property of the heat storage layer and the bonding strength of the heat storage layer, the supporting layer and the adhesive layer can cause adverse effects; according to the invention, by controlling the components of the heat storage layer to be the component distribution ratio, the feasibility of the preparation process of the heat storage layer and the enthalpy value of the heat storage layer are improved. According to the embodiment of the invention, the heat storage layer can comprise 98.9-99.8 parts by weight of the phase change material, 0.1-0.5 part by weight of the leveling agent and 0.1-0.6 part by weight of the curing agent, so that the enthalpy value of the heat storage layer can be improved, and the feasibility of the preparation process of the heat storage layer and the enthalpy value of the heat storage layer can be further improved.
According to the embodiment of the present invention, referring to fig. 1, the thickness d4 of the thermal storage layer 40 may be 50 μm to 200 μm, for example, 50 μm, 75 μm, 100 μm, 120 μm, 150 μm, 180 μm, 200 μm, etc., the inventors found that if the thickness of the thermal storage layer is too small, for example, less than 50 μm, the enthalpy value of the thermal storage film is easily caused to be low, and the heat storage amount of the thermal storage film is difficult to satisfy the heat storage requirement of electronic products or devices; if the thickness of the heat storage layer is too large, for example, more than 200 μm, on one hand, the slurry of the heat storage layer is not easy to dry after coating, which easily results in too long drying time, low production efficiency and difficult realization of continuous coating and rolling; on the other hand, an excessively thick heat storage layer has relatively high rigidity, and the heat storage layer is easily broken when being coated and rolled, so that the yield of the product is remarkably reduced. According to the invention, the thickness of the heat storage layer is controlled within the thickness range, so that the heat storage layer has a higher enthalpy value, and the heat storage performance of the heat storage film is further improved; the feasibility of the preparation process can be ensured, and the production efficiency and the yield of products are improved.
According to some embodiments of the present invention, the thickness d4 of the thermal storage layer 40 may be 50 μm to 100 μm, for example, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 97 μm, 100 μm, and the like, so that the thermal storage film can further achieve high efficiency and continuity of production while ensuring good thermal storage performance, and further improve the yield of products.
According to the embodiment of the invention, the first support layer 10 and the second support layer 30 can be respectively and independently selected from a PET film (polyethylene terephthalate film), a PEN film (polyethylene naphthalate film), a polyethylene film, a polypropylene film, a polyimide film, a copper foil or an aluminum foil, so that both the first support layer and the second support layer have certain support performance, and the bonding adhesive layer can form good sealing performance on the heat storage layer, thereby being beneficial to improving the overall stability of the heat storage layer. Of course, the material of the first supporting layer 10 and the material of the second supporting layer 30 may be the same or different, and those skilled in the art may select and set the materials according to actual needs, as long as the first supporting layer and the second supporting layer may have a better supporting effect, and the heat storage layer is sealed well by the adhesive layer.
According to an embodiment of the present invention, referring to fig. 1, the thickness d1 of the first support layer 10 and the thickness d3 of the second support layer 30 may be each independently 5 μm to 50 μm, for example, the thickness d1 of the first support layer 10 may be 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm, etc., and the thickness d3 of the second support layer 10 may also be 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, or 50 μm, etc. The inventors have found that if the thickness of the support layer (first support layer or second support layer) is too thin, e.g. less than 5 μm, the mechanical strength of the support layer is relatively poor, which may lead to leakage of the phase change material during use due to damage of the support layer; however, if the thickness of the supporting layer is too thick, for example, greater than 50 μm, the too thick supporting layer may affect the heat conduction during the use of the heat storage film, and affect the practical use performance of the heat storage film. According to the invention, the first supporting layer and the second supporting layer are controlled to be in the thickness ranges respectively and independently, so that the supporting layer has higher mechanical strength, and the supporting layer can be ensured not to generate overhigh thermal resistance, thereby greatly reducing the risk of phase-change material leakage caused by the damage of the supporting layer, and ensuring that heat can be transferred to the phase-change material more quickly.
According to an embodiment of the present invention, referring to fig. 1, the thickness d1 of the first support layer 10 and the thickness d3 of the second support layer 30 may be respectively and independently 6 μm to 12 μm, such as 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, and the like, so that the negative effect of the increase in the thickness of the two support layers on the thermal conduction may be further reduced on the basis of ensuring that the support layers have good mechanical strength.
In the invention, the adhesive layer 20 firmly bonds the heat storage layer 40 with the first support layer 10 and the third support layer 30, so that the above structures are combined to form a heat storage film, and the adhesive layer 20 can cover the surface and the side surface of the heat storage layer 40 far away from the second support layer 30, so as to form a good package for the heat storage layer 40, thereby avoiding leakage of substances in the heat storage layer 40.
According to an embodiment of the present invention, the adhesive layer 20 may include at least one of alkyd resin, polyurethane, polyester polyol, polyacrylate, styrene-butadiene latex, carboxylated styrene-butadiene latex, polyvinyl alcohol, and the like. The materials have good bonding performance, and can firmly combine the heat storage layer, the first supporting layer and the second supporting layer; and the materials are all water-based adhesives, so that the use of organic solvents can be further avoided, and the pollution to the environment and the harm to the health of a human body in the production and use processes of the heat storage film are greatly reduced. However, those skilled in the art may select other suitable materials to form the glue layer according to actual needs.
According to some embodiments of the present invention, the thickness d2 of the glue layer 20 may be 1 μm to 10 μm, for example, may be 1 μm, 1.7 μm, 2 μm, 3 μm, 3.5 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, and the like. The inventors found that if the thickness of the adhesive layer is too thin, for example, less than 1 μm, the adhesive layer is difficult to perform a good bonding function, which may result in a reduction in the yield of the product; on the other hand, if the total thickness of the heat storage film is constant, the thickness of the heat storage layer needs to be correspondingly reduced if the thickness of the adhesive layer is increased, so that the heat storage performance of the heat storage film is correspondingly reduced. According to the invention, by controlling the thickness of the adhesive layer within the thickness range, the adhesive layer can be ensured to have better bonding strength, and the heat storage performance of the heat storage film can not be obviously reduced.
According to some embodiments of the present invention, referring to fig. 1, the thickness d2 of the adhesive layer 20 may be 1 μm to 3 μm, so that on the basis of ensuring the adhesive strength of the adhesive layer, the negative effect of the increase in the thickness of the adhesive layer on the heat storage performance of the heat storage film may be further reduced, thereby further improving the overall performance of the heat storage film.
In summary, the heat storage film proposed by the present invention has the following advantages: 1. the heat storage layer sets up to the sub heat storage layer that two at least intervals set up, and the glue film is kept away from the surface and the side of second supporting layer to the heat storage layer and all can carry out good encapsulation to avoid the material in the heat storage layer to reveal, and then make the heat-retaining membrane keep good heat storage performance. 2. According to the invention, an integrated structure with good bonding strength is formed between the heat storage film and the supporting layer through the adhesive layer, so that the uniformity of heat storage of each part of the heat storage film can be better ensured. 3. The heat storage film can be applied to heating components related to a new energy lithium ion battery in the production or application process, the heat generated by the heating components is led out, and the heat is stored and released in the environment lower than the phase change temperature to achieve heat balance, so that the adverse effect on the service life caused by the overhigh local temperature of the heating components can be prevented, and the safety coefficient in the production or use process can be improved. 4. The heat storage film provided by the invention has potential application prospect for assisting heat dissipation of the electronic equipment or the processor outside the electronic equipment or the processor. 5. The heat storage film has good flexibility and can be applied to scenes needing to be wound. 6. Due to the design of the sub heat storage layer, the heat storage film with the length of meters can have a smaller axial diameter, and the production and the storage are more convenient.
In another aspect of the present invention, the present invention provides a method of preparing the aforementioned heat storage film, comprising the steps of:
s100: and intermittently coating the thermal storage layer slurry on the second surface of the second support layer, and performing a first drying process to form the thermal storage layer.
In this step, a thermal storage layer slurry is intermittently coated on the second surface 31 of the second support layer 30, and a first drying process is performed to form the thermal storage layer 40, wherein the thermal storage layer 40 includes at least two sub thermal storage layers 41 arranged at intervals. As a method of applying the thermal storage layer slurry, three-roll coating, slot coating, slide extrusion coating, gravure coating, micro gravure coating, or the like may be used, and the thermal storage layer slurry may be intermittently applied to the second surface of the second support layer by performing intermittent coating using one or more of the above-described coating methods.
According to embodiments of the present invention, the thermal storage layer slurry may be an aqueous slurry. Therefore, water can be used as a solvent, the use of an organic solvent can be avoided, and the negative influence of the organic solvent on the environment and the human health is further avoided.
According to the embodiment of the present invention, the temperature of the first drying treatment may be 50 to 80 ℃, for example, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or the like, and the time of the first drying treatment may be 1 to 3min, for example, 1min, 1.5min, 2min, 2.5min, 3min or the like. Thus, the heat storage layer slurry coated on the surface of the second support layer can form the heat storage layer.
According to an embodiment of the present invention, the thermal storage layer slurry may include a phase-change material, a curing agent, a leveling agent, and the like, and the structure and the material of the phase-change material, the specific material of the curing agent, the specific material of the leveling agent, and the contents of the phase-change material, the curing agent, the leveling agent, and the like in the thermal storage layer are all described in detail above and are not described herein again. According to some embodiments of the invention, the thermal storage layer slurry may be formed by: weighing the phase-change material aqueous suspension and the leveling agent according to the mass ratio, placing the aqueous suspension and the leveling agent in a stirrer, stirring and mixing, adding the weighed curing agent in the stirring process, and uniformly stirring to obtain the heat storage layer slurry. The aqueous phase change material suspension is a mixture obtained by dispersing a phase change material in water using water as a solvent.
In addition, the thickness of the thermal storage layer has been described in detail above, and is not described herein again.
Before the thermal storage layer slurry is coated on the second support layer, corona treatment may be performed on the second support layer to facilitate the coating of the thermal storage layer slurry.
S200: an adhesive is coated on the first surface of the first support layer, and a second drying process is performed to form an adhesive layer.
In this step, an adhesive is coated on the first surface 11 of the first support layer 10, and a second drying process is performed to form an adhesive layer. It should be noted that the adhesive includes a bonding material and a solvent, wherein according to an embodiment of the present invention, the bonding material may include at least one of alkyd resin, polyurethane, polyester polyol, polyacrylate, styrene-butadiene latex, carboxylic styrene-butadiene latex, polyvinyl alcohol, and the like, and the solvent may be water, and the bonding material is dissolved in the solvent water to facilitate coating of the adhesive.
According to the embodiment of the present invention, the coating adhesive may be one or more of three-roll coating, slot coating, slide extrusion coating, gravure coating, micro-gravure coating, etc., as long as a smooth and uniform coating layer can be formed.
According to the embodiment of the invention, the temperature of the second drying treatment may be 30 ℃ to 80 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and the like, and the time of the second drying treatment may be 2min to 15min, for example, 2min, 5min, 8min, 10min, 12min, 15min and the like, so that the solvent in the adhesive can be removed by the second drying treatment, and the adverse effect of water or other solvents existing in the adhesive layer in the subsequent treatment process on the performance of the heat storage film can be avoided.
The specific material and thickness of the first supporting layer have been described in detail above, and are not described herein again.
It should be noted that before the adhesive is applied to the first support layer, the first support layer may be subjected to corona treatment to facilitate the application of the adhesive.
S300: and (3) bonding and curing the heat storage layer, the second supporting layer and the adhesive layer to form an adhesive layer, wherein the adhesive layer covers the surfaces and the side surfaces of the at least two sub heat storage layers far away from the second supporting layer and the part of the second surface which is not covered by the heat storage layer.
After forming the adhesive layer on the first surface 11 of the first support layer 10 and forming the thermal storage layer 40 on the second surface 31 of the second support layer 30, the thermal storage layer 40 is bonded to the second support layer 30 and the adhesive layer and cured to form the adhesive layer 20, and the adhesive layer 20 covers the surfaces and the side surfaces of the at least two sub thermal storage layers 41 away from the second support layer 30 and the portions of the second surface 31 not covered by the thermal storage layer 40, as shown in fig. 1 and 2. It will be appreciated by those skilled in the art that the adhesive may also bond the edges of the first and second support layers when bonding.
According to embodiments of the present invention, the bonding of the thermal storage layer with the second support layer and the adhesive layer may be performed under certain temperature and pressure conditions, and according to some embodiments of the present invention, the temperature may be 40 to 80 ℃ and the pressure may be 0.1 to 0.8MPa, thereby achieving a firm bonding.
According to the embodiment of the present invention, the temperature of the aging may be 40 to 80 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and the like, and the time of the aging may be 24 hours, 36 hours, 48 hours, 60 hours, 72 hours and the like. Therefore, the curing is performed under the conditions, so that the adhesive property of the adhesive layer is stronger, and the adhesive effect on the supporting layer and the packaging effect on the heat storage layer are further improved.
The heat storage film prepared by the method has all the characteristics and advantages of the heat storage film; and the operation is simple and convenient, the preparation cost is reduced, and the yield is improved.
The present invention is illustrated below by specific examples, and it will be understood by those skilled in the art that the following specific examples are for illustrative purposes only and do not limit the scope of the present invention in any way. In addition, in the following examples, materials and equipment used are commercially available unless otherwise specified. If in the following examples, specific treatment conditions and treatment methods are not explicitly described, the treatment may be performed using conditions and methods well known in the art.
Example 1
In the heat storage film of this embodiment, the first support layer and the second support layer are both PET films, the thicknesses of the first support layer and the second support layer are both 5 μm, the thickness of the heat storage layer is 120 μm, and the thickness of the adhesive layer is 1 μm.
The heat storage layer of the embodiment comprises the following components in effective parts by mass: 99wt% of phase change material with a microcapsule structure (urea formaldehyde resin is used as a capsule wall and n-eicosane is used as a capsule core), 0.5wt% of flatting agent (BYK-381), and 0.5wt% of curing agent ethyl orthosilicate.
After the components are taken according to respective proportions, the steps for preparing the heat storage film are as follows:
(1) Firstly, weighing the phase change material aqueous suspension and the flatting agent with the microcapsule structure according to the formula dosage, stirring and mixing the phase change material aqueous suspension and the flatting agent by adopting a top-mounted stirrer, wherein the stirring speed is 300rpm, adding weighed ethyl orthosilicate during the stirring process, and mixing and stirring for 60min to obtain heat storage layer slurry. Wherein the solid content of the thermal storage layer slurry is 50.3%, and the solvent is pure water (the solvent is from the phase-change material aqueous suspension).
(2) And intermittently coating the heat storage layer slurry on a PET (polyethylene terephthalate) film (a second supporting layer) which is subjected to corona treatment and has the thickness of 5 mu m by adopting a coating process of strip-and-seam coating, and drying to obtain the heat storage layer.
(3) Coating a coating liquid for composite glue consisting of acrylate adhesive and crosslinking agent on another PET film (first support layer) which is subjected to corona treatment and has the thickness of 5 microns by adopting a micro-gravure coating process, directly compounding the PET film with a heat storage layer at 80 ℃ and the pressure of 0.1MPa without rolling after drying, and then curing for 72 hours at 40 ℃ to obtain the finished heat storage film.
Example 2
In the heat storage film of the embodiment, the first supporting layer and the second supporting layer are both polyethylene films, the thicknesses of the first supporting layer and the second supporting layer are both 12 μm, the thickness of the heat storage layer is 180 μm, and the thickness of the adhesive layer is 3 μm.
The heat storage layer of the embodiment comprises the following components in parts by mass: 98wt% of phase change material with a microcapsule structure (the capsule wall is made of polyurethane, and the capsule core is made of octacosane), 1wt% of flatting agent (BYK-20990) and 1wt% of curing agent propyl orthosilicate.
After the components are taken according to respective proportions, the steps for preparing the heat storage film are as follows:
(1) Firstly, weighing the phase change material aqueous suspension and the flatting agent with the microcapsule structure according to the formula dosage, stirring and mixing the phase change material aqueous suspension and the flatting agent by adopting a top-mounted stirrer, wherein the stirring speed is 300rpm, adding the weighed propyl orthosilicate during the stirring process, and mixing and stirring for 60min to obtain the heat storage layer slurry. Wherein the solid content of the heat storage layer slurry is 40.9%, and the solvent is purified water.
(2) And (3) intermittently coating the slurry of the heat storage layer on a polyethylene film (a second supporting layer) by adopting a coating process of strip and seam coating, and drying to obtain the heat storage layer.
(3) Coating a coating liquid for composite glue consisting of a polyester adhesive and a crosslinking agent on another polyethylene film (a first support layer) by adopting a micro-gravure coating process, directly compounding the coating liquid with the heat storage layer at 70 ℃ and 0.3MPa without rolling after drying, and curing for 60 hours at 50 ℃ to obtain the finished heat storage film.
Example 3
In the heat storage film of this embodiment, the first support layer is a polypropylene film, the thickness of the first support layer is 15 μm, the second support layer is a polyimide film, the thickness of the second support layer is 50 μm, the thickness of the heat storage layer is 200 μm, and the thickness of the adhesive layer is 10 μm.
The heat storage layer of the embodiment comprises the following components in parts by mass: 99.8wt% of phase change material with a microcapsule structure (the capsule wall of the phase change material is polyurea, and the capsule core of the phase change material is lauric acid), 0.1wt% of flatting agent (BYK-20990) and 0.1wt% of curing agent isocyanate.
After the components are taken according to respective proportions, the steps for preparing the heat storage film are as follows:
(1) Firstly, weighing the phase change material aqueous suspension and the flatting agent with the microcapsule structure according to the formula dosage, stirring and mixing the phase change material aqueous suspension and the flatting agent by adopting a top-placed stirrer, wherein the stirring speed is 300rpm, adding weighed isocyanate during the stirring process, and mixing and stirring for 60min to obtain the heat storage layer slurry. Wherein the solid content of the heat storage layer slurry is 45.7%, and the solvent is purified water.
(2) And (3) intermittently coating the heat storage layer slurry on a polyimide film (a second supporting layer) by adopting a coating process of strip and seam coating, and drying to obtain the heat storage layer.
(3) Coating a coating liquid for composite glue consisting of acrylate adhesives and cross-linking agents on a polypropylene film (a first support layer) by adopting a micro-gravure coating process, directly compounding the coating liquid with a heat storage layer at 80 ℃ and 0.5MPa without rolling after drying, and then curing for 24 hours at 60 ℃ to obtain the finished heat storage film.
Example 4
In the heat storage film in this embodiment, the first support layer is a polypropylene film, the thickness of the first support layer is 20um, the second support layer is a polyimide film, the thickness of the second support layer is 30um, the thickness of the heat storage layer is 150 μm, and the thickness of the adhesive layer is 2.5um.
The heat storage layer of the embodiment comprises the following components in parts by mass: 98.8wt% of phase-change material with a microcapsule structure (the capsule wall is acrylate, and the capsule core is n-docosane), 0.6wt% of flatting agent (Shanghai Semiflu DS-960E) and 0.6wt% of curing agent boric acid.
After the components are taken according to respective proportions, the steps for preparing the heat storage film are as follows:
(1) Firstly, weighing the phase change material aqueous suspension and the flatting agent with the microcapsule structure according to the formula dosage, stirring and mixing the phase change material aqueous suspension and the flatting agent by using a top-mounted stirrer, wherein the stirring speed is 300rpm, adding weighed boric acid during the stirring process, and mixing and stirring for 60min to obtain heat storage layer slurry. Wherein the solid content of the heat storage layer slurry is 50.2%, and the solvent is purified water.
(2) And (3) intermittently coating the heat storage layer slurry on a polyimide film (a second supporting layer) by adopting a coating process of strip and seam coating, and drying to obtain the heat storage layer.
(3) Coating a coating liquid for composite glue consisting of acrylate adhesives and cross-linking agents on a polypropylene film (a first support layer) by adopting a micro-gravure coating process, directly compounding the coating liquid with a heat storage layer at 80 ℃ and 0.5MPa without rolling after drying, and curing for 24 hours at 60 ℃ to obtain the finished heat storage film.
Example 5
In the heat storage film of this embodiment, the first support layer and the second support layer are both copper foils, the thicknesses of the first support layer and the second support layer are both 20 μm, the thickness of the heat storage layer is 150 μm, and the thickness of the adhesive layer is 3.5 μm.
The heat storage layer of the embodiment comprises the following components in parts by mass: 99.5wt% of phase change material (the capsule wall is polyurethane, and the capsule core is stearic acid), 0.1wt% of flatting agent (Shanghai Seifen DS-960E), and 0.4wt% of curing agent isocyanate.
After the components are taken according to respective proportions, the steps for preparing the heat storage film are as follows:
(1) Firstly, weighing the phase change material aqueous suspension and the flatting agent with the microcapsule structure according to the formula dosage, stirring and mixing the phase change material aqueous suspension and the flatting agent by adopting a top-placed stirrer, wherein the stirring speed is 300rpm, adding weighed isocyanate during the stirring process, and mixing and stirring for 60min to obtain the heat storage layer slurry. Wherein the solid content of the heat storage layer slurry is 59.7%, and the solvent is purified water.
(2) And (3) intermittently coating the heat storage layer slurry on a copper foil (a second supporting layer) by adopting a coating process of strip and seam coating, and drying to obtain the heat storage layer.
(3) The composite adhesive composed of the acrylate adhesive and the crosslinking agent is coated on another copper foil (a first supporting layer) by adopting a micro-gravure coating process, is directly compounded with the heat storage layer at 80 ℃ and 0.5MPa without rolling after being dried, and is cured for 24 hours at 60 ℃ to obtain the finished heat storage film.
Example 6
In the heat storage film of this embodiment, the first support layer and the second support layer are both aluminum foils, the thicknesses of the first support layer and the second support layer are both 20 μm, the thickness of the heat storage layer is 200 μm, and the thickness of the adhesive layer is 2 μm.
The heat storage layer of the embodiment comprises the following components in parts by mass: 99.4wt% of phase change material (the capsule wall is chitosan, and the capsule core is n-docosane), 0.4wt% of flatting agent (Shanghai Seifei DS-960E) and 0.2 wt% of curing agent isocyanate.
After the components are taken according to respective proportions, the steps for preparing the heat storage film are as follows:
(1) Firstly, weighing the phase change material aqueous suspension and the flatting agent with the microcapsule structure according to the formula dosage, stirring and mixing the phase change material aqueous suspension and the flatting agent by adopting a top-placed stirrer, wherein the stirring speed is 300rpm, adding weighed isocyanate during the stirring process, and mixing and stirring for 60min to obtain the heat storage layer slurry. Wherein the solid content of the heat storage layer slurry is 55.6%, and the solvent is purified water.
(2) And (3) intermittently coating the heat storage layer slurry on an aluminum foil (a second supporting layer) by adopting a coating process of strip-and-seam coating, and drying to obtain the heat storage layer.
(3) Coating a coating liquid for composite glue consisting of acrylate adhesives and cross-linking agents on another aluminum foil (a first supporting layer) by adopting a micro-gravure coating process, directly compounding the coating liquid with a heat storage layer at 40 ℃ and 0.5MPa without rolling after drying, and curing for 24 hours at 60 ℃ to obtain the finished heat storage film.
Example 7
In the heat storage film of this embodiment, the first support layer and the second support layer are both PET films, the thicknesses of the first support layer and the second support layer are both 5 μm, the thickness of the heat storage layer is 50 μm, and the thickness of the adhesive layer is 1 μm.
The heat storage layer of the embodiment comprises the following components in effective parts by mass: 99.8wt% of phase change material with a microcapsule structure (the capsule wall of the phase change material is polyurethane resin, and the capsule core of the phase change material is n-eicosane), 0.1wt% of flatting agent (BYK-381), and 0.1wt% of isocyanate curing agent.
After the components are taken according to respective proportions, the steps for preparing the heat storage film are as follows:
(1) Firstly, weighing the phase change material aqueous suspension and the flatting agent with the microcapsule structure according to the formula dosage, stirring and mixing the phase change material aqueous suspension and the flatting agent by adopting a top-mounted stirrer, wherein the stirring speed is 300rpm, adding the weighed isocyanate curing agent in the stirring process, and mixing and stirring for 30min to obtain the heat storage layer slurry. Wherein the solid content of the heat storage layer slurry is 49.6%, and the solvent is purified water.
(2) And intermittently coating the heat storage layer slurry on a PET (polyethylene terephthalate) film (a second supporting layer) which is subjected to corona treatment and has the thickness of 5 mu m by adopting a coating process of strip-and-seam coating, and drying to obtain the heat storage layer.
(3) Coating a coating liquid for composite glue consisting of acrylate adhesive and crosslinking agent on another PET film (first support layer) which is subjected to corona treatment and has the thickness of 5 microns by adopting a micro-gravure coating process, directly compounding the PET film with a heat storage layer at 80 ℃ and the pressure of 0.1MPa without rolling after drying, and then curing for 72 hours at 40 ℃ to obtain the finished heat storage film.
Comparative example 1
Comparative example 1 differs from example 4 only in that the thermal storage layer slurry was continuously coated, and other parameters were the same as in example 4.
Comparative example 2
Comparative example 2 differs from example 4 only in that boric acid was not added to the thermal storage layer slurry, the ratio of the mass of the phase-change material to the mass of the leveling agent in comparative example 2 was kept the same as the ratio of the mass of the phase-change material to the mass of the leveling agent in example 4, and other parameters were the same as in example 4.
Comparative example 3
The heat storage layer in comparative example 3 comprises the following components in parts by mass: 90.0wt% of phase-change material with a microcapsule structure (the capsule wall of the phase-change material is acrylate, and the capsule core of the phase-change material is n-docosane), 8.8wt% of acrylate adhesive, 0.6wt% of flatting agent (Shanghai Seifei DS-960E), and 0.6wt% of curing agent boric acid.
Comparative example 3 is different from example 4 in the formulation of the thermal storage layer slurry, and other parameters are the same as those of example 4.
(1) Weighing the phase change material aqueous suspension with the microcapsule structure, the acrylate adhesive and the flatting agent according to the formula dosage, stirring and mixing the phase change material aqueous suspension, the acrylate adhesive and the flatting agent by using a top-mounted stirrer, wherein the stirring speed is 300rpm, adding weighed boric acid during stirring, mixing and stirring for 60min to obtain heat storage layer slurry, the solid content of the heat storage layer slurry is 40.7%, and the solvent is purified water.
(2) And (3) intermittently coating the heat storage layer slurry on a polyimide film (a second supporting layer) by adopting a coating process of strip and seam coating, and drying to obtain the heat storage layer.
(3) Coating a coating liquid for composite glue consisting of acrylate adhesives and cross-linking agents on a polypropylene film (a first support layer) by adopting a micro-gravure coating process, directly compounding the coating liquid with a heat storage layer at 80 ℃ and 0.5MPa without rolling after drying, and curing for 24 hours at 60 ℃ to obtain the finished heat storage film.
Comparative example 4
Comparative example 4 differs from example 4 only in that the bond line thickness is 10 μm, and other parameters are the same as in example 4.
Comparative example 5
Comparative example 5 is different from example 4 only in that the first and second support layers each have a thickness of 50 μm and other parameters are the same as those of example 4.
The heat storage films obtained in examples 1 to 7 and comparative examples 1 to 5 were tested for curl resistance, cycle performance, and adhesive strength (peel force) of the heat storage layer to the support layer (first support layer or second support layer), and the test results are shown in table 1.
The test and evaluation method of the performance is as follows:
1. peeling force testing method
The method comprises the steps of cutting a heat storage film into a sample strip to be tested with the width of 25cm and the length of 20cm, adhering a 3M double-faced adhesive tape to the surface, far away from a heat storage layer, of a second supporting layer, adhering the sample strip to be tested to a hard base material which is as wide as the sample strip and is not easy to deform through the 3M double-faced adhesive tape, wherein the adhesion length is 8 cm-10 cm, fixing one end, which is not adhered with the heat storage film, of the hard base material on a lower clamp by adopting a 103B type electronic tensile machine designed and manufactured by Shenzhen Wanke test equipment Limited company, of the hard base material, fixing one end, which is not adhered with the heat storage film, of the hard base material on an upper clamp, forming an angle of 180 degrees with the hard base material through the heat storage film, starting a measuring program, and carrying out parallel measurement for 3 times to obtain an average value, wherein the required result is obtained.
2. Curl test method
The curl test is carried out by the mandrel method: with reference to the GB/T1731-93 standard, this is carried out on a flexibility tester consisting of 7 steel mandrels of different diameters fixed to a base. During testing, the coating and the base material are stressed and deformed, and then whether the four layers are layered or not is observed. If there is no delamination of the four layers, good adhesion is indicated. The heat storage film is drawn back and forth 5 times by using a 1mm shaft rod, the curling resistance of the heat storage film is evaluated, and good curling is shown if no reticulate pattern, crack or peeling phenomenon is generated.
3. Enthalpy loss rate test method
And (3) placing the heat storage film in a circulating oven, circularly heating the heat storage film to 80 ℃, keeping the temperature for 30min, then cooling the heat storage film to 25 ℃, and keeping the temperature for 30min. And comparing the enthalpy values of the heat storage membranes before and after circulation for 500 times, and obtaining the loss value of the enthalpy value through the circulation test, so that the service life of the product can be tested.
Enthalpy loss rate formula: enthalpy loss after 500 cycles = 1-enthalpy after cycle/initial enthalpy
Table 1: performance test results of the heat storage films of examples 1 to 7 and comparative examples 1 to 5
Figure BDA0003682194440000141
Figure BDA0003682194440000151
As can be seen from the test data in table 1, the heat storage film samples of examples 1 to 7 had large peeling force between the heat storage layer and the support layer, high bonding strength, and good structural stability; the phenomenon of whispery cracking or peeling does not occur in the curl resistance test, and the heat storage film samples in the embodiments 1 to 7 have better curl resistance; the heat storage film samples of examples 1 to 7 all had high initial enthalpy values, and had low enthalpy loss rate after 500 cycles, good cycle stability, and long service life. Compared with example 4, comparative example 1 adopts a continuous coating mode to coat the heat storage layer slurry, which results in relatively poor packaging effect of the glue layer and the two supporting layers on the heat storage layer, so that the enthalpy loss rate of the heat storage film in comparative example 1 is higher after 500 cycles, and the stability of the heat storage film is poor. The heat storage layer slurry of comparative example 2 was not added with the curing agent boric acid, the bonding strength of the heat storage layer and the support layer was poor, and an apparent peeling phenomenon was generated, and only the initial enthalpy value was tested since the apparent peeling phenomenon occurred, and the cycle performance was not tested. Compared with example 4, the acrylic ester adhesive is added in the comparative example 3, the bonding force between the heat storage layer and the supporting layer is larger, and the enthalpy value of the heat storage film is also obviously reduced. The relatively thick glue layer of comparative example 4 results in a lower enthalpy value of the heat storage film compared to example 4, and the thickness of the two support layers is greater in comparative example 5, thus lowering the enthalpy value of the heat storage film.
In the description herein, references to the description of "one embodiment," "another embodiment," "some embodiments," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent. In addition, it should be noted that the terms "first" and "second" in this specification are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A heat storage film, comprising:
a first support layer having a first surface;
a glue layer disposed on the first surface;
the second supporting layer is arranged on one side, far away from the first supporting layer, of the adhesive layer, and is provided with a second surface which is close to the adhesive layer;
the heat storage layer is arranged on the second surface and comprises at least two sub heat storage layers arranged at intervals;
wherein the glue layer covers the surfaces and the side faces of the at least two sub-thermal storage layers far away from the second support layer and the parts of the second surface which are not covered by the thermal storage layer.
2. The heat storage film of claim 1 wherein the first support layer and the second support layer are each independently selected from the group consisting of PET film, PEN film, polyethylene film, polypropylene film, polyimide film, copper foil, and aluminum foil,
and/or the thickness of the first support layer and the thickness of the second support layer are respectively and independently 5-50 μm.
3. The heat storage film of claim 1, wherein the adhesive layer comprises at least one of alkyd, polyurethane, polyester polyol, polyacrylate, styrene-butadiene latex, carboxylated styrene-butadiene latex, and polyvinyl alcohol;
the thickness of the adhesive layer is 1-10 μm,
preferably, the thickness of the glue layer is 1-3 μm.
4. The heat storage film according to claim 1, wherein a thickness of the heat storage layer is 50 μm to 200 μm.
5. The heat storage film according to any one of claims 1 to 4, wherein the heat storage layer comprises a phase change material having an enthalpy of 100J/g to 350J/g,
preferably, the enthalpy value of the phase change material is 170J/g-350J/g.
6. The heat storage film according to claim 5, wherein the heat storage layer further comprises a curing agent and a leveling agent,
the curing agent comprises at least one of isocyanate curing agent, silicic acid curing agent, boric acid curing agent and dialdehyde curing agent, and the flatting agent comprises at least one of polyacrylate flatting agent, fluorocarbon modified polyacrylate flatting agent and alkynol flatting agent.
7. The heat storage film of claim 6, wherein the heat storage layer comprises 98-99.8 parts by weight of phase change material, 0.1-1 part by weight of leveling agent and 0.1-1 part by weight of curing agent,
preferably, the thermal storage layer comprises 98.9-99.8 parts by weight of phase change material, 0.1-0.5 part by weight of leveling agent and 0.1-0.6 part by weight of curing agent.
8. The heat storage film of claim 5, wherein the phase change material is a microcapsule structure, the core of the microcapsule structure comprises at least one of stearic acid, lauric acid, palmitic acid, erythritol, n-octadecane, n-nonadecane, n-eicosane, n-docosane, and n-octacosane, and the wall of the microcapsule structure comprises at least one of melamine, urea-formaldehyde, chitosan, acrylic polymers, polyurea, polyurethane, and polyurethane-urea.
9. The heat storage film according to claim 8, wherein the microcapsule structure has a particle size of 1 to 50 μm; the surface of the capsule wall has hydrophilic groups,
preferably, the particle size of the microcapsule structure is 1 μm to 30 μm.
10. A method of producing the heat storage film of any one of claims 1 to 9, comprising:
intermittently coating heat storage layer slurry on the second surface of the second supporting layer, and performing first drying treatment to form a heat storage layer, wherein the heat storage layer comprises at least two sub heat storage layers arranged at intervals;
coating an adhesive on the first surface of the first support layer, and performing a second drying process to form an adhesive layer;
and adhering and curing the heat storage layer, the second supporting layer and the adhesive layer to form an adhesive layer, wherein the adhesive layer covers the surface and the side surfaces of at least two sub heat storage layers far away from the second supporting layer and the part of the second surface which is not covered by the heat storage layer.
CN202210640981.0A 2022-06-07 2022-06-07 Heat storage film and preparation method thereof Pending CN115179634A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109897610A (en) * 2019-03-04 2019-06-18 苏州天脉导热科技股份有限公司 Phase-change thermal storage film and preparation method thereof
CN111097113A (en) * 2019-12-30 2020-05-05 湖南科技大学 Lining capable of adjusting space temperature in firefighter uniform and manufacturing method thereof
CN113493657A (en) * 2020-03-20 2021-10-12 深圳先进电子材料国际创新研究院 Composite phase-change material film and preparation method and application thereof
CN114157741A (en) * 2021-12-07 2022-03-08 Oppo广东移动通信有限公司 Shell, manufacturing method thereof and electronic equipment
CN216139606U (en) * 2021-06-25 2022-03-29 合肥芯能相变新材料科技有限公司 Novel phase change composite fabric and temperature-adjusting garment
CN114425898A (en) * 2022-01-13 2022-05-03 中国乐凯集团有限公司 Heat conduction and heat storage film and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109897610A (en) * 2019-03-04 2019-06-18 苏州天脉导热科技股份有限公司 Phase-change thermal storage film and preparation method thereof
CN111097113A (en) * 2019-12-30 2020-05-05 湖南科技大学 Lining capable of adjusting space temperature in firefighter uniform and manufacturing method thereof
CN113493657A (en) * 2020-03-20 2021-10-12 深圳先进电子材料国际创新研究院 Composite phase-change material film and preparation method and application thereof
CN216139606U (en) * 2021-06-25 2022-03-29 合肥芯能相变新材料科技有限公司 Novel phase change composite fabric and temperature-adjusting garment
CN114157741A (en) * 2021-12-07 2022-03-08 Oppo广东移动通信有限公司 Shell, manufacturing method thereof and electronic equipment
CN114425898A (en) * 2022-01-13 2022-05-03 中国乐凯集团有限公司 Heat conduction and heat storage film and preparation method thereof

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