CN118956112B - Infrared absorbing film and preparation method thereof - Google Patents
Infrared absorbing film and preparation method thereof Download PDFInfo
- Publication number
- CN118956112B CN118956112B CN202411091718.6A CN202411091718A CN118956112B CN 118956112 B CN118956112 B CN 118956112B CN 202411091718 A CN202411091718 A CN 202411091718A CN 118956112 B CN118956112 B CN 118956112B
- Authority
- CN
- China
- Prior art keywords
- modified
- infrared absorbing
- infrared absorption
- parts
- absorbing film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
An infrared absorption film and a preparation method thereof belong to the technical field of infrared absorption materials. The infrared absorption film comprises, by weight, 100-110 parts of polyester resin, 10-20 parts of modified resin, 20-30 parts of infrared absorption master batch and 4-17 parts of other auxiliary agents, wherein the infrared absorption master batch comprises, by mass, 100% of total weight, 55-75% of carrier resin, 10-15% of K xWO3 and 15-30% of modified Cs yWO3, wherein 0< x <1,0< y <1, and the mass ratio of K xWO3 to modified Cs yWO3 is 1:1.5-2. The infrared absorption film has excellent heat resistance and mechanical property, can realize maximum infrared absorption property on the basis of not sacrificing visible light transmittance, and has excellent long-term stability.
Description
Technical Field
The invention belongs to the technical field of infrared absorption materials, and particularly relates to an infrared absorption film and a preparation method thereof.
Background
In recent years, with the increasing interest in environmental and energy related problems, glass films are increasingly attracting attention for heat insulation and energy conservation, not only for automotive glass films, but also for building glass windows. The glass film needs to have the characteristics of transmitting visible light and shielding infrared light, namely, needs to ensure a heat insulation effect under the condition of certain visible light transmittance, and simultaneously reduces the transmittance of infrared light wave bands (780-2500 nm) in the sunlight spectrum as much as possible.
At present, infrared absorbing materials used in films at home and abroad mainly comprise nano metals such as silicon carbide, silicon nitride nano powder, cobalt-nickel nano powder, nano graphite, fe, co, ni and the like, alloys, nano metal oxides, nano needle-shaped magnetic metal powder and the like. The unique structure of the nano metal oxide ensures that the nano metal oxide has unique performance and advantages in infrared absorption materials, but nano oxide powder is easy to agglomerate and difficult to uniformly disperse, and the infrared absorption performance is unstable and the long-term service performance is obviously reduced.
Patent CN201711396606 discloses a thermoplastic polyurethane elastomer (TPU) film with infrared absorption function and a preparation method thereof, wherein an infrared absorption substance polyaniline, polypyrrole, polycarbonate, polyvinylpyrrolidone, TPU particles and nano silicon dioxide are mixed and extruded to obtain the TPU film, the film has good flexibility and mechanical property, but the problem of uneven dispersion of the infrared absorption substance exists in physical mixing, and the infrared absorption rate is only 60-75%.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention aims to provide an infrared absorbing film and a method for preparing the same, which have excellent heat resistance and mechanical properties, and can achieve maximum infrared absorbing properties without sacrificing visible light transmittance, while having excellent long-term stability.
In order to achieve the aim, according to one aspect of the invention, an infrared absorption film is provided, which comprises, by weight, 100-110 parts of polyester resin, 10-20 parts of modified resin, 20-35 parts of infrared absorption master batch and 4-17 parts of other auxiliary agents, wherein the infrared absorption master batch comprises, by weight, 100% of total weight of the infrared absorption master batch, 55-75% of carrier resin, 10-15% of K xWO3 and 15-30% of modified Cs yWO3, wherein 0< x <1,0< y <1, and the mass ratio of K xWO3 to modified Cs yWO3 is 1:1.5-2.
In some embodiments, the polyester resin and the carrier resin are each independently selected from one or more of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate.
In some embodiments, the modified resin is polyethylene naphthalate having an intrinsic viscosity of 0.65 to 0.80dL/g.
In some embodiments, the modified Cs yWO3 is Cs yWO3 with polyvinylpyrrolidone coated on the surface, and the mass ratio of polyvinylpyrrolidone in the modified Cs yWO3 is 3-5%.
In some embodiments, the other adjuvants include any one or more of antioxidants, ultraviolet light absorbers, lubricants.
According to another aspect of the present invention, there is also provided a method for preparing the above infrared absorbing film, comprising the steps of:
(1) Adding tungsten chloride and potassium acetate into ethanol according to a molar ratio of 2:1, carrying out ultrasonic treatment and stirring until the tungsten chloride and the potassium acetate are fully dissolved, reacting for 20-24 hours at 180-190 ℃, centrifuging and drying after the reaction is finished to obtain K xWO3, adding Cs yWO3 into ethanol for ball milling, adding an ethanol solution of polyvinylpyrrolidone, stirring uniformly, carrying out ultrasonic treatment, centrifuging and drying a dispersion liquid after ultrasonic treatment to obtain modified Cs yWO3, mixing the K xWO3, the modified Cs yWO3 and carrier resin uniformly according to a proportion, and then sending the mixture to a double-screw extruder for melt extrusion granulation and drying to obtain the infrared absorption master batch;
(2) Uniformly mixing the infrared absorption master batch, the polyester resin, the modified resin and other auxiliary agents in the step (1) according to a proportion, sending the mixture to a double-screw extruder for melt mixing, and extruding the mixture to form a film to obtain the infrared absorption film.
In some embodiments, in step (1), the concentration of tungsten chloride in ethanol is 13-15mg/mL.
In some embodiments, in step (1), the mass ratio of Cs yWO3 to polyvinylpyrrolidone is 100:6-10.
In some embodiments, in step (2), the extrusion temperature is 270-290 ℃ and the extrusion pressure is 4-6MPa.
According to another aspect of the present invention, there is also provided an infrared absorbing film as described above or an infrared absorbing film produced according to the above production method for use in a glass film.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, K xWO3 and modified Cs yWO3 are mixed at first, and the optimal adding proportion of the two substances is further found, so that an infrared absorption master batch with excellent performance is prepared, and then the master batch is added into polyester resin and a certain amount of modified resin, so that an infrared absorption film is obtained. The film has excellent heat resistance and mechanical properties, and can achieve maximum infrared absorption performance without sacrificing visible light transmittance, while having excellent long-term stability.
(2) The infrared absorption film has simple preparation method and good application prospect.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
Herein, when embodiments or examples are described, it should be understood that they are not intended to limit the invention to these embodiments or examples. On the contrary, all alternatives, modifications, and equivalents of the methods and materials described herein are intended to be included within the scope of the invention as defined by the appended claims.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
In the invention, the intrinsic viscosity test standard is GB/T14190-2008.
The invention provides an infrared absorption film which comprises polyester resin, modified resin, infrared absorption master batch and other auxiliary agents. In the present invention, the thickness of the infrared absorbing film is 0.02 to 0.06mm, and it is understood that the thickness may be any specific value of 0.02mm, 0.03mm, 0.04mm, 0.05mm, 0.06mm, or any value in the range of 0.02 to 0.06 mm.
In the present invention, the weight portion of the polyester resin is 100 to 110 portions, and it is understood that the weight portion may be any specific value of 100 portions, 101 portions, 102 portions, 103 portions, 104 portions, 105 portions, 106 portions, 107 portions, 108 portions, 109 portions, 110 portions, or any value in the range of 100 to 110 portions. In some embodiments, the polyester resin is selected from one or more of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate.
In the present invention, the weight portion of the modified resin is 10-20, and it is understood that the weight portion may be any specific value of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or any value in the range of 10-20. In some embodiments, the modified resin is polyethylene naphthalate having an intrinsic viscosity of 0.65 to 0.80dL/g. In the present invention, the intrinsic viscosity is a viscosity measured by dissolving a sample in a mixed solvent of phenol and tetrachloroethane in a weight ratio of 1:1 using a black-bone viscometer at 25 ℃. According to the invention, the polyester resin and a small amount of modified resin are mixed, and the optimal mixing proportion of the polyester resin and the modified resin is further found out, so that the prepared film has excellent mechanical property, heat resistance and optical property. If the content of the modified resin is low, the heat resistance and mechanical properties are insufficient, and if the content of the modified resin is high, the flexibility of the film is deteriorated.
In the present invention, the weight portion of the infrared absorbing master batch is 20 to 35 portions, and it is understood that the weight portion may be any specific value of 20 portions, 21 portions, 22 portions, 23 portions, 24 portions, 25 portions, 26 portions, 27 portions, 28 portions, 29 portions, 30 portions, 31 portions, 32 portions, 33 portions, 34 portions, 35 portions, or any value in the range of 20 to 35 portions. In some embodiments, the infrared absorption master batch comprises, by weight, 100% of the total weight, 55-75% of a carrier resin, 10-15% of K xWO3 and 15-30% of modified Cs yWO3, wherein 0< x <1,0< y <1. In some embodiments, x=0.3 and y=0.33. In some embodiments, the mass ratio of K xWO3 to modified Cs yWO3 is 1:1.5-2, it being understood that the mass ratio may be any specific value of 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, or any value in the range of 1:1.5-2. According to the invention, the mass ratio of the K xWO3 to the modified Cs yWO3 is controlled, so that the comprehensive optical performance of the master batch can be further regulated, the synergistic effect of the two substances is exerted to the maximum extent, and the maximum infrared absorption performance is realized on the basis of not sacrificing the visible light transmittance.
In the present invention, the mass fraction of the carrier resin in the infrared absorbing master batch is 55 to 75% based on 100% by mass of the total mass, and it is understood that the mass fraction may be any specific value of 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75% or any value in the range of 55 to 75%. In some embodiments, the carrier resin is selected from one or more of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate.
In the invention, the mass fraction of K xWO3 in the infrared absorption master batch is 10-15% according to the total mass percentage of 100%, and it is understood that the mass fraction can be any specific value of 10%, 11%, 12%, 13%, 14% and 15% or any value in the range of 10-15%. In some embodiments, the K xWO3 has an average aspect ratio of 13-15. The K xWO3 with the length-diameter ratio can ensure higher carrier fluid concentration, thereby improving infrared absorption performance.
In the present invention, the mass fraction of the modified Cs yWO3 in the infrared absorption master batch is 15-30% based on 100% of the total mass, and it is understood that the mass fraction may be any specific value of 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% or any value in the range of 15-30%. In some embodiments, the modified Cs yWO3 is Cs yWO3 with polyvinylpyrrolidone coated on the outer surface, and the mass ratio of polyvinylpyrrolidone in the modified Cs yWO3 is 3-5%. In some embodiments, the particle size of the modified Cs yWO3 is 140-160nm, it being understood that the particle size may be any particular value of 140nm, 142nm, 144nm, 146nm, 148nm, 150nm, 152nm, 154nm, 156nm, 158nm, 160nm, or any value in the range of 140-160 nm.
According to the invention, the polyvinyl pyrrolidone modified Cs yWO3 with specific content is used, and the mass ratio of the polyvinyl pyrrolidone in the modified Cs yWO3 is further adjusted, so that the obtained modified Cs yWO3 can be compatible with long-term dispersion stability and excellent infrared absorption performance. If the mass ratio of polyvinylpyrrolidone in the modified Cs yWO3 is low, the improvement of dispersion stability is not obvious, and if the mass ratio of polyvinylpyrrolidone in the modified Cs yWO3 is high, the dispersion stability is also reduced, and the infrared absorption performance is also obviously reduced.
In the invention, the weight part of the other auxiliary agent is 4-17 parts, preferably 5-15 parts. In some embodiments, the other adjuvants include any one or more of antioxidants, ultraviolet light absorbers, lubricants. In some embodiments, the antioxidant is a compound of antioxidant 1010 and antioxidant 168 in a weight ratio of 1:1-2. In some embodiments, the ultraviolet light absorber is 1-5 parts by weight, and in some embodiments, the ultraviolet light absorber is a benzotriazole ultraviolet light absorber. In some embodiments, the lubricant comprises 2-7 parts by weight, and in some embodiments, the lubricant comprises one or more of stearic acid, pentaerythritol ester, oxidized wax, white oil, zinc stearate, calcium stearate.
According to another aspect of the present invention, there is also provided a method for preparing the above infrared absorbing film, comprising the steps of:
(1) Adding tungsten chloride and potassium acetate into ethanol according to a molar ratio of 2:1, carrying out ultrasonic treatment and stirring until the tungsten chloride and the potassium acetate are fully dissolved, reacting for 20-24 hours at 180-190 ℃, centrifuging and drying after the reaction is finished to obtain K xWO3, adding Cs yWO3 into ethanol for ball milling, adding an ethanol solution of polyvinylpyrrolidone, stirring uniformly, carrying out ultrasonic treatment, centrifuging and drying a dispersion liquid after ultrasonic treatment to obtain modified Cs yWO3, mixing the K xWO3, the modified Cs yWO3 and carrier resin uniformly according to a proportion, and then sending the mixture to a double-screw extruder for melt extrusion granulation and drying to obtain the infrared absorption master batch;
(2) Uniformly mixing the infrared absorption master batch, the polyester resin, the modified resin and other auxiliary agents in the step (1) according to a proportion, sending the mixture to a double-screw extruder for melt mixing, and extruding the mixture to form a film to obtain the infrared absorption film.
In the invention, in the step (1), tungsten chloride and potassium acetate are added into ethanol according to the mol ratio of 2:1, and are subjected to ultrasonic treatment and stirring until the tungsten chloride and the potassium acetate are fully dissolved, the tungsten chloride and the potassium acetate react for 20 to 24 hours at 180 to 190 ℃, and the tungsten chloride and the potassium acetate are centrifuged and dried after the reaction is finished, so that the K xWO3 is obtained. In some embodiments, in step (1), the concentration of tungsten chloride in ethanol is 13-15mg/mL. The microcosmic size of the obtained K xWO3 can be effectively regulated and controlled by controlling the concentration of the tungsten chloride, so that effective coordination of the K xWO3 and the modified Cs yWO3 is ensured.
In the invention, in the step (1), cs yWO3 is added into ethanol for ball milling, ethanol solution of polyvinylpyrrolidone is added, stirring is uniform, ultrasonic treatment is carried out, and dispersion liquid after ultrasonic treatment is centrifuged and dried, thus obtaining the modified Cs yWO3. In the present invention, the ethanol solution of polyvinylpyrrolidone refers to a solution obtained by dissolving a certain amount of polyvinylpyrrolidone in a certain amount of ethanol. In some embodiments, the ball milling time may be 2-4 hours. In some embodiments, the agitation time may be 1-2 hours. In some embodiments, the time of the sonication may be from 0.5 to 1h. In some embodiments, the mass ratio of Cs yWO3 to polyvinylpyrrolidone is 100:6-10, it being understood that the mass ratio may be any specific value of 100:6, 100:6.5, 100:7, 100:7.5, 100:8, 100:8.5, 100:9, 100:9.5, 100:10 or any value in the range of 100:6-10.
In the invention, in the step (1), the K xWO3, the modified Cs yWO3 and the carrier resin are mixed uniformly according to a proportion, and then the mixture is sent to a double-screw extruder for melt extrusion granulation and drying, so that the infrared absorption master batch is obtained. In some embodiments, the twin screw extruder has a rotational speed of 100-500r/min, it being understood that the rotational speed may be any particular value of 100r/min, 150r/min, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, or any value in the range of 100-500 r/min. In some embodiments, the temperature of the screw zones of the twin screw extruder is 180-230 ℃, it being understood that the temperature may be any particular value of 180 ℃, 185 ℃, 190 ℃, 195 ℃,200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃ or any value in the range of 180-230 ℃.
In the step (2), the infrared absorption master batch, the polyester resin, the modified resin and other auxiliary agents are mixed uniformly according to a proportion, and are sent to a double-screw extruder for melt mixing, and then are extruded to form a film, so that the infrared absorption film is obtained. In some embodiments, the extrusion temperature is 270-290 ℃, it being understood that the temperature may be any particular value of 270 ℃, 275 ℃, 280 ℃, 285 ℃, 290 ℃, or any value in the range of 270-290 ℃. In some embodiments, the extrusion pressure is 4-6MPa.
According to another aspect of the present invention, there is also provided the use of the above infrared absorbing film or the infrared absorbing film produced according to the above production method in a glass film.
The present invention will be described in detail by examples. It should be understood that the following examples are illustrative only and are not intended to limit the invention.
Unless otherwise specified, the raw materials in the examples and comparative examples of the present invention are all obtained from the general market, and specific information is as follows:
Polyethylene terephthalate with an intrinsic viscosity of 0.65dL/g, from Japanese, polybutylene terephthalate with an intrinsic viscosity of 0.9dL/g, from Toli Co., ltd, modified resin with an intrinsic viscosity of 0.75dL/g, from Japanese, polyvinylpyrrolidone with a chemical Co., ltd, tungsten chloride, potassium acetate, ethanol with a chemical Co., ltd, from Allatin, cs yWO3:30-50 nm, y=0.33, from Zhejiang, from Titania micro new materials Co., ltd, antioxidant 1010 and antioxidant 168 in a 1:1 ratio, ultraviolet absorber UV-326, from Nanjing Hua Liming chemical Co., ltd, and lubricant stearic acid, from Allatin.
Example 1
The infrared absorption film comprises, by weight, 100 parts of polyethylene terephthalate, 10 parts of polyethylene naphthalate, 20 parts of infrared absorption master batch, 5 parts of an antioxidant, 4 parts of an ultraviolet absorber and 5 parts of a lubricant, wherein the infrared absorption master batch comprises, by mass, 100% of total weight, 70% of polyethylene terephthalate, 10% of K xWO3 and 20% of modified Cs yWO3, and x=0.3 and y=0.33.
The preparation method of the infrared absorption film comprises the following steps:
(1) Adding 8g of tungsten chloride and 0.1g of potassium acetate into 0.6L of ethanol, carrying out ultrasonic treatment and stirring until the tungsten chloride and the potassium acetate are fully dissolved, reacting for 24 hours at 180 ℃, centrifuging after the reaction is finished, drying for 24 hours at 60 ℃ to obtain K xWO3, adding 100gCs yWO3 into 80mL of ethanol, carrying out ball milling for 2 hours, adding 10mL of ethanol solution dissolved with 10g of polyvinylpyrrolidone, stirring for 1 hour until the solution is uniform, carrying out ultrasonic treatment for 1 hour, centrifuging the dispersion after ultrasonic treatment, drying for 24 hours at 60 ℃ to obtain modified Cs yWO3, mixing 5g of K xWO3, 10g of modified Cs yWO3 and 35g of polyethylene terephthalate uniformly, and then carrying out melt extrusion granulation by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 500r/min, and the extrusion temperature in a screw of the double-screw extruder is respectively 180-190 ℃ in a first region, 190-210 ℃ in a second region, 190-210 ℃ in a third region, and 190-210 ℃ in a fourth region, and drying for 70 ℃ in a fifth region, so as to obtain infrared absorption granules;
(2) Uniformly mixing 20g of the infrared absorption master batch in the step (1), 100g of polyethylene terephthalate, 10g of polyethylene naphthalate, 5g of antioxidant, 4g of ultraviolet light absorber and 5g of lubricant, and sending the mixture to a double-screw extruder for melt mixing, and extruding the mixture to form a film at the temperature of 290 ℃ and the pressure of 4MPa to obtain the infrared absorption film.
Example 2
The infrared absorption film comprises, by weight, 110 parts of polybutylene terephthalate, 20 parts of polyethylene naphthalate, 30 parts of an infrared absorption master batch, 5 parts of an antioxidant, 4 parts of an ultraviolet light absorber and 7 parts of a lubricant, wherein the infrared absorption master batch comprises, by mass, 100% of the total weight of the infrared absorption master batch, 55% of polybutylene terephthalate, 15% of K xWO3 and 30% of modified Cs yWO3, and x=0.3 and y=0.33.
The preparation method of the infrared absorption film comprises the following steps:
(1) Adding 8g of tungsten chloride and 0.1g of potassium acetate into 0.55L of ethanol, carrying out ultrasonic treatment and stirring until the tungsten chloride and the potassium acetate are fully dissolved, reacting for 20h at 190 ℃, centrifuging after the reaction is finished, drying for 24h at 60 ℃ to obtain K xWO3, adding 100gCs yWO3 into 80mL of ethanol, carrying out ball milling for 2h, adding 10mL of ethanol solution dissolved with 6g of polyvinylpyrrolidone, stirring for 1h to be uniform, carrying out ultrasonic treatment for 1h, centrifuging the dispersion liquid after ultrasonic treatment, drying for 24h at 60 ℃ to obtain modified Cs yWO3, uniformly mixing 6g of K xWO3, 12g of modified Cs yWO3 and 22g of polybutylene terephthalate, and then carrying out melt extrusion granulation by a double-screw extruder, wherein the rotating speed of the double-screw extruder is 100r/min, and the extrusion temperature in a screw of the double-screw extruder is respectively 180-190 ℃ in a first zone, 190-210 ℃ in a second zone, 190-210 ℃ in a third zone 190-210 ℃, and 70 ℃ in a fifth zone 210 ℃ in a fifth zone, and drying to obtain infrared absorption granules;
(2) Uniformly mixing 30g of the infrared absorption master batch in the step (1), 110g of polybutylene terephthalate, 20g of polyethylene naphthalate, 5g of an antioxidant, 4g of an ultraviolet absorber and 7g of a lubricant, sending the mixture to a double-screw extruder for melt mixing, and extruding the mixture to form a film at the temperature of 280 ℃ and the pressure of 6MPa to obtain the infrared absorption film.
Example 3
The infrared absorption film comprises 105 parts of polyethylene terephthalate, 15 parts of polyethylene naphthalate, 25 parts of infrared absorption master batch, 2 parts of an antioxidant, 2 parts of an ultraviolet light absorber and 4 parts of a lubricant, wherein the infrared absorption master batch comprises, by mass percent, 75% of polyethylene terephthalate, 10% of K xWO3 and 15% of modified Cs yWO3, and x=0.3 and y=0.33.
The preparation method of the infrared absorption film comprises the following steps:
(1) Adding 8g of tungsten chloride and 0.1g of potassium acetate into 0.6L of ethanol, carrying out ultrasonic treatment and stirring until the tungsten chloride and the potassium acetate are fully dissolved, reacting for 24 hours at 185 ℃, centrifuging after the reaction is finished, drying for 20 hours at 60 ℃ to obtain K xWO3, adding 100gCs yWO3 into 80mL of ethanol, carrying out ball milling for 2 hours, adding 10mL of ethanol solution dissolved with 7.5g of polyvinylpyrrolidone, stirring for 1 hour until the solution is uniform, carrying out ultrasonic treatment for 1 hour, centrifuging the dispersion liquid after ultrasonic treatment, drying for 20 hours at 60 ℃ to obtain modified Cs yWO3, mixing 6g of K xWO3, 9g of modified Cs yWO3 and 45g of polyethylene terephthalate uniformly, and then delivering the mixture to a double-screw extruder for melt extrusion granulation, wherein the rotating speed of the double-screw extruder is 300r/min, and the extrusion temperatures in the screw rods of the double-screw extruder are respectively 180 ℃ in one zone, 190 ℃ in two zone 200 ℃, 210 ℃ in four zone, 220 ℃ in five zone, and drying at 70 ℃ to obtain the infrared absorption master batch;
(2) And (3) uniformly mixing 25g of the infrared absorption master batch in the step (1), 105g of polyethylene terephthalate, 15g of polyethylene naphthalate, 2g of antioxidant, 2g of ultraviolet absorber and 4g of lubricant, and sending the mixture to a double-screw extruder for melt mixing, and extruding the mixture to form a film at the temperature of 270 ℃ and the pressure of 6MPa to obtain the infrared absorption film.
Comparative example 1
The infrared absorbing film of this comparative example was prepared in the same manner as in example 1, except that K xWO3 was not contained in the infrared absorbing master batch. The specific composition and preparation method are as follows:
The infrared absorption film comprises, by weight, 100 parts of polyethylene terephthalate, 10 parts of polyethylene naphthalate, 20 parts of infrared absorption master batch, 5 parts of an antioxidant, 4 parts of an ultraviolet absorber and 5 parts of a lubricant, wherein the infrared absorption master batch comprises, by mass, 100% of total weight, 70% of polyethylene resin and 30% of modified Cs yWO3, and y=0.33.
The preparation method of the infrared absorption film in the comparative example comprises the following steps:
(1) Adding 100gCs yWO3 to 80mL of ethanol, ball milling for 2 hours, adding 10mL of ethanol solution dissolved with 10g of polyvinylpyrrolidone, stirring for 1 hour to uniformity, carrying out ultrasonic treatment for 1 hour, centrifuging the dispersion liquid after ultrasonic treatment, drying at 60 ℃ for 24 hours to obtain modified Cs yWO3, uniformly mixing 30g of modified Cs yWO3 and 70g of polyethylene terephthalate, and then delivering to a double-screw extruder for melt extrusion granulation, wherein the rotating speed of the double-screw extruder is 300r/min, and the extrusion temperature in a screw of the double-screw extruder is respectively 180 ℃ in one region, 190 ℃ in two regions, 200 ℃ in three regions, 210 ℃ in four regions, 220 ℃ in five regions and 70 ℃ and drying to obtain the infrared absorption master batch;
(2) Step (2) of comparative example 1 corresponds to step (2) of example 1.
Comparative example 2
The infrared absorbing film of this comparative example was produced in the same manner as in example 1 except that the infrared absorbing master batch was 10 parts by weight.
Comparative example 3
The infrared absorbing film of this comparative example was produced in the same manner as in example 1 except that the infrared absorbing master batch was 40 parts by weight.
Comparative example 4
The infrared absorbing film of this comparative example was prepared in the same manner as in example 1, except that the film did not contain polyethylene naphthalate.
Performance testing
The K xWO3 and modified Cs yWO3 obtained in examples 1-3 of the present invention were characterized according to the test methods described below, and the specific characterization data are shown in Table 1.
The mass ratio of polyvinylpyrrolidone in the modified Cs yWO3 is calculated by measuring the thermal weight loss curve of the modified Cs yWO3 particles through a thermogravimetric analysis method and calculating the mass ratio of polyvinylpyrrolidone in the modified Cs yWO3 through mass loss.
Particle size of modified Cs yWO3 particle size of modified Cs yWO3 particles was analyzed using a Zetasizer3000 laser particle sizer.
Length-diameter ratio of K xWO3 the length and diameter of 50K xWO3 particles were measured respectively using a transmission electron microscope, the length-diameter ratio (length/diameter) of each K xWO3 particle was calculated respectively from the measured length and diameter, and then the average length-diameter ratio was calculated.
TABLE 1 characterization data for K xWO3 and modified Cs yWO3 in examples 1-3
The infrared absorbing films described in examples 1 to 3 and comparative examples 1 to 4 of the present invention were subjected to performance test according to the following test methods, and specific performance indexes are shown in Table 2.
Film thickness is measured by a thickness gauge.
Heat shrinkage rate according to the test of longitudinal and transverse heat shrinkage rates by using a micrometer and a blast type constant temperature drying oven under the test conditions of 150 ℃ for 30min, 3 samples were tested in each direction, and the average value was calculated. Where MD denotes the machine direction of the film and TD denotes the transverse direction of the film.
Tensile strength was measured according to GB/T1040.3-2006.
The visible light transmittance and the infrared absorption rate are measured according to GB/T2410-2008, and the performances of the film after being stored for 0 day and 30 days are respectively tested. The visible light transmittance detection wave band is 380-780nm, and the infrared absorption rate detection wave band is 780-2500nm.
TABLE 2 data on infrared absorbing film Performance test as described in examples 1-3 and comparative examples 1-4
As shown in Table 2, the films of examples 1-3 of the present invention have high visible light transmittance and infrared absorption, and after being left for 30 days, the films still have high visible light transmittance and infrared absorption, which means that the infrared absorption films of the present invention have good stability, and at the same time, the films have high tensile strength and low heat shrinkage, which means that the films have good mechanical properties and heat resistance. As is clear from example 1 and comparative example 1, the infrared absorbing master batch in comparative example 1 does not contain K xWO3, and the visible light transmittance of the obtained film is significantly reduced. As is clear from examples 1 and 2, the infrared light absorbing masterbatch content in comparative example 2 was low, and the visible light transmittance and infrared absorption of the obtained film were both greatly reduced. As is clear from examples 1 and 3, the infrared light absorbing masterbatch content in comparative example 3 is higher, and the visible light transmittance and infrared absorption rate of the obtained film are both greatly reduced after the film is placed for 30 days, which means that K xWO3 and Cs yWO3 in the film are separated out, thereby affecting the optical stability of the film. As is clear from examples 1 and 4, the film of comparative example 4 does not contain polyethylene naphthalate, and the film has significantly reduced stretching properties and significantly increased heat shrinkage.
In summary, according to the invention, an infrared absorption master batch with excellent performance is prepared by firstly mixing K xWO3 and modified Cs yWO3 and further finding the optimal adding proportion of the two substances, and then the master batch is added into polyester resin and a certain amount of modified resin, so that an infrared absorption film is obtained. The film has excellent heat resistance and mechanical properties, and can achieve maximum infrared absorption performance without sacrificing visible light transmittance, while having excellent long-term stability.
It should be understood that the foregoing examples of the present invention are provided for the purpose of illustration only and are not intended to limit the embodiments of the present invention, and that various other changes and modifications can be made by one skilled in the art based on the foregoing description, and it is not intended to be exhaustive of all the embodiments, and all obvious changes and modifications that come within the spirit of the invention are desired to be protected.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411091718.6A CN118956112B (en) | 2024-08-09 | 2024-08-09 | Infrared absorbing film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411091718.6A CN118956112B (en) | 2024-08-09 | 2024-08-09 | Infrared absorbing film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118956112A CN118956112A (en) | 2024-11-15 |
| CN118956112B true CN118956112B (en) | 2025-03-18 |
Family
ID=93388130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411091718.6A Active CN118956112B (en) | 2024-08-09 | 2024-08-09 | Infrared absorbing film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118956112B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643563A (en) * | 2012-03-30 | 2012-08-22 | 南亚塑胶工业股份有限公司 | Transparent thermal insulation material and preparation method thereof |
| CN110157162A (en) * | 2019-06-08 | 2019-08-23 | 纳琳威纳米科技南通有限公司 | Stiffened anti-flaming thermal-insulation master batch and its manufacturing method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021132450A1 (en) * | 2019-12-25 | 2021-07-01 | 住友金属鉱山株式会社 | Near-infrared absorbing material particles, near-infrared absorbing material particle dispersing solution, and near-infrared absorbing material particle dispersion |
| CN117043299A (en) * | 2021-03-31 | 2023-11-10 | 住友金属矿山株式会社 | Infrared absorbing particles, infrared absorbing particle dispersion, infrared absorbing interlayer transparent substrate, and infrared absorbing transparent substrate |
| CN113185871A (en) * | 2021-04-14 | 2021-07-30 | 华南理工大学 | Tungsten bronze-based super-hydrophobic transparent heat-insulating coating and preparation method thereof |
| CN116284883A (en) * | 2023-04-06 | 2023-06-23 | 奈蓝(上海)新材料科技有限公司 | Preparation method of high-transparency infrared barrier color master batch |
| CN117209938A (en) * | 2023-10-10 | 2023-12-12 | 杭州两山环境科技有限公司 | Composite material with infrared ray efficient shielding performance and preparation method and application thereof |
-
2024
- 2024-08-09 CN CN202411091718.6A patent/CN118956112B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643563A (en) * | 2012-03-30 | 2012-08-22 | 南亚塑胶工业股份有限公司 | Transparent thermal insulation material and preparation method thereof |
| CN110157162A (en) * | 2019-06-08 | 2019-08-23 | 纳琳威纳米科技南通有限公司 | Stiffened anti-flaming thermal-insulation master batch and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118956112A (en) | 2024-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106220996A (en) | The preparation method of silicon white carbon black/composite polyolefine material | |
| CN112920509A (en) | Antibacterial polypropylene composite material and preparation method thereof | |
| CN111234416B (en) | PVC-O pipe for coal mine and preparation method thereof | |
| CN114539593A (en) | High-wave-transmittance composite material and preparation method and application thereof | |
| CN118956112B (en) | Infrared absorbing film and preparation method thereof | |
| CN111423723A (en) | Reinforced polyphenylene sulfide composition for 5G and preparation method thereof | |
| CN112662077A (en) | Antistatic graphene-coated aluminum microsphere modified PP composite material and preparation method thereof | |
| CN115850885B (en) | Overhead cable with corrosion-resistant shell and preparation method thereof | |
| CN116199938B (en) | Phosphorus-silicon flame-retardant synergist, ultrathin halogen-free flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN114773837B (en) | A kind of high wear-resistant low-temperature impact nylon caster material and its preparation method | |
| CN118931010B (en) | Multi-band infrared absorption masterbatch and preparation method thereof | |
| CN113698670B (en) | Calcium zinc stabilizer and application thereof in SPC floor base material production | |
| CN113321446B (en) | Ceramic polymer composite material and preparation method thereof, shell and preparation method thereof, and electronic equipment | |
| CN110982234B (en) | Preparation method of high-end photodiffusion polycarbonate | |
| CN113150327B (en) | Nylon functional master batch and preparation method and application thereof | |
| CN112455043A (en) | Super-barrier TPU film and preparation method thereof | |
| CN118931010A (en) | Multi-band infrared absorption masterbatch and preparation method thereof | |
| CN112280298A (en) | Preparation method of high-impact polyvinyl alcohol/polyetherimide composite material | |
| CN110903623A (en) | 30% mineral-reinforced electroplated PC/ABS alloy material and preparation method thereof | |
| CN112126230A (en) | A kind of wear-resistant polyethersulfone composite material and preparation method thereof | |
| CN119039691B (en) | High-flexibility X-ETFE insulating material and preparation method thereof | |
| CN110591336A (en) | Special flame-retardant synergistic functional master batch for thermoplastic polyurethane modification and preparation method thereof | |
| CN119081292B (en) | Antibacterial masterbatch and preparation method thereof | |
| CN110437533B (en) | Fiber modified board and application thereof | |
| CN119798995A (en) | Polyphenylene sulfide composition and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20250220 Address after: Building 1, No. 25 Gangchang Road, Qingxi Town, Dongguan City, Guangdong Province 523000 Applicant after: Guangdong Dicai New Materials Co.,Ltd. Country or region after: China Address before: Room 101, Building 1, No. 133 Songgang Road, Qingxi Town, Dongguan City, Guangdong Province 523645 Applicant before: DONGGUAN DICOLORS PLASTIC & METAL Co.,Ltd. Country or region before: China |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |