CN107383573B - Multifunctional transparent heat-insulating coating containing near-infrared absorption and reflection composite pigment, polyolefin co-extruded film and preparation - Google Patents
Multifunctional transparent heat-insulating coating containing near-infrared absorption and reflection composite pigment, polyolefin co-extruded film and preparation Download PDFInfo
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Abstract
A multifunctional transparent heat-insulating coating containing near-infrared absorption and reflection composite pigments, a polyolefin co-extruded film and a preparation method thereof belong to the technical field of heat-insulating materials. The transparent heat-insulating coating or the polyolefin co-extruded film comprises a coating and a co-extruded film which both contain surface-modified near-infrared absorbent bismuth oxychloride pigment and surface-modified reflective pigment M-CuxSyWherein M in the formula is doped metal ions, x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 1 and less than or equal to 2. The preparation process comprises the following steps: the method comprises the steps of firstly synthesizing a near-infrared absorption pigment by a solvothermal synthesis process, then synthesizing a near-infrared high-reflection pigment by a solvothermal method, mixing the near-infrared absorption pigment and the near-infrared high-reflection pigment according to a certain proportion, carrying out surface modification, uniformly mixing the mixture with a dispersion liquid prepared by dissolving transparent matrix resin in a solvent, coating a film or carrying out banburying with a transparent resin particle, and then carrying out melt extrusion on the film.
Description
Technical Field
The invention relates to a multifunctional transparent heat-insulating coating containing near-infrared absorption and reflection composite pigment, a polyolefin co-extruded film and a preparation method thereof.
Background
Heat transfer occurs in three ways in the heat exchange on the surface of an object: conductive heat, convective heat, radiant heat, wherein the thermal radiation accounts for more than 75%. Ultraviolet rays in the solar spectrum: the wave length is 100-400 nm, and the paint has the characteristics of strong penetrability, can deposit melanin on the skin of a human body, deepens the color, can cause skin cancer due to excessive ultraviolet exposure, and can cause fading of the carpet, the curtain, the fabric and the furniture paint. Visible light: the wavelength is 380-780 nm, and the ultraviolet light source is characterized in that the ultraviolet light source can see a unique spectrum by naked eyes, and the visible light wave band can be further divided into different colors (red, orange, yellow, green, blue and indigo violet) without direct damage to a human body. Infrared light: the wavelength is 700-2400 nm, and the solar energy heat-collecting device is characterized in that people can directly feel invisible heat of sunlight, and the contained energy is maximum, so that the heat is high. The infrared ray accounts for 53% of the highest proportion, and the visible light and the ultraviolet ray account for 44% and 3% respectively. Because the heat brought by ultraviolet rays is very limited and can be almost ignored, how to shield infrared rays is concentrated to achieve a good heat insulation effect. The near infrared reflection pigment is generally used and can be coated on the surface of an object, so that the temperature of the surface of the object is reduced, and the purpose of reducing the temperature is achieved. Near infrared absorbing pigments or films are used in places where visible light requirements are high, such as vehicle windows, building glass, and agricultural greenhouse films, and can block a part of infrared rays, thereby reducing the indoor temperature, but the heat insulation efficiency is not high.
Disclosure of Invention
In view of the above-mentioned deficiencies in the prior art, the present invention aims to provide a multifunctional transparent thermal insulation coating containing a composite pigment with near infrared absorption and reflection, a polyolefin co-extruded film and a preparation method thereof, wherein the film or the coating prepared by the method has the functions of absorbing and reflecting near infrared rays, and the thermal insulation efficiency is greatly improved without affecting the visible light transmittance.
In order to achieve the purposes, the invention adopts the following technical scheme to prepare the near-infrared high-reflection pigment:
the multifunctional transparent heat-insulating coating containing the near-infrared absorption and reflection composite pigment and the polyolefin co-extruded film are characterized in that the coating and the co-extruded film both contain a surface-modified near-infrared absorbent bismuth oxychloride pigment and a surface-modified reflection pigment M-CuxSyWherein M in the formula is doped metal ions, x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 1 and less than or equal to 2.
Preferably, the doping metal ion is selected from alkaline earth metals, transition metals, lanthanides, series, IIIA metals, VA metals and the like, such as Fe, Al, Mg, Cs, Ba, Zn, La, Ce, W, Sb and the like, and preferably one or two of them.
Further preferably, the surfactant or dispersant used for surface modification is any one or a combination of two selected from a silane coupling agent KH550, a silane coupling agent KH560, castor oil, white oil, stearamide, higher alcohols, vinyl bis stearamide, Glycerol Monostearate (GMS), glycerol tristearate (HTG), liquid paraffin, zinc stearate (ZnSt), polyethylene wax, polyethylene glycol 200 or 400.
The coating or film is made of transparent matrix resin which is polyolefin resin, including any one or more of polyethylene resin, low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polyester resin, polyvinyl chloride, ethylene-ethyl acetate, ethylene-vinyl alcohol copolymer, polypropylene, poly-4-methyl-1-pentene resin, polyester PET and the like.
The surfactant or dispersant accounts for 1-20% of the total mass of the system.
The mass ratio of the near infrared absorption pigment to the reflection pigment is 10:1-10, and the near infrared absorption pigment and the reflection pigment in the coating or the film account for 0.01-5% of the total mass of the system.
The preparation method of the multifunctional transparent heat-insulating coating containing the near-infrared absorption and reflection composite pigment and the polyolefin co-extruded film is characterized by comprising the following steps of:
mixing the near-infrared absorption and reflection pigments according to a certain proportion, carrying out surface modification, then uniformly mixing with a dispersion liquid prepared by dissolving transparent matrix resin in a solvent to coat a film or compounding with transparent resin particles, carrying out banburying in a banbury mixer, and then carrying out melt extrusion on the film to obtain the multifunctional transparent heat-insulation coating or polyolefin co-extrusion film containing the near-infrared absorption and reflection composite pigments,
preferably, wherein the solvent is an aromatic hydrocarbon: benzene, toluene, xylene, etc.; aliphatic hydrocarbons: pentane, hexane, octane, and the like; alicyclic hydrocarbons: cyclohexane, cyclohexanone, tolucyclohexanone, etc.; halogenated hydrocarbons: chlorobenzene, dichlorobenzene, dichloromethane, and the like; alcohols: methanol, ethanol, isopropanol, etc.; ethers: ethyl ether, propylene oxide, and the like; esters: methyl acetate, ethyl acetate, propyl acetate, and the like; ketones: acetone, methyl butanone, methyl isobutyl ketone, N-methylpyrrolidone, and the like; diol derivatives: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and the like; and others: acetonitrile, pyridine, phenol, dimethylacetamide, tetrahydrofuran, and the like, water. Wherein the resin accounts for 5 to 90 percent of the solvent.
Among them, the preparation of the preferred bismuth oxychloride pigment comprises the following steps: dissolving a mixture prepared from a bismuth source, a chlorine source and a protective agent in a solvent, adjusting the pH value of the system, and ultrasonically dispersing for a period of time; transferring the mixture into a reactor, sealing, putting into an oven, and keeping the temperature; then, cooling to room temperature, alternately cleaning the product in the reaction kettle for a plurality of times by using distilled water and absolute ethyl alcohol, and then drying the powder in a vacuum oven; and then calcining the powder at high temperature for a period of time, and then grinding the powder in a mortar to obtain the bismuth oxychloride near-infrared high-reflection heat-insulation pigment particles.
The solvent is one of glycol, ethanol and water; the chlorine source is one of HCl, KCl, NaCl and CTAC; the protective agent is C6H8O7·H2O; the pH is 1-9. The ultrasonic treatment time is 20-60 min. Putting the mixture into an oven, keeping the temperature at 80-180 ℃ for 3-9 h; the calcining temperature is 200-800 ℃ and the time is1h-4 h. The molar ratio of the bismuth source to the chlorine source is 1 (0.5-1.5); the molar ratio of the bismuth source to the protective agent is 1 (0-2.0);
near infrared reflective pigment M-CuxSyThe preparation method comprises the following steps:
(1) dissolving a mixture prepared from a copper source, a sulfur source, a protective agent and a metal ion-doped metal salt in a solvent, adjusting the pH of the system to 1-9, and then performing ultrasonic dispersion for a period of time to obtain a dispersion mixture;
(2) transferring the dispersion mixture into a lining pressure reaction kettle, sealing, putting into a drying oven, and keeping the temperature for a period of time; cooling to room temperature, alternately cleaning the product in the reaction kettle with distilled water and anhydrous ethanol for several times, and drying in an oven (such as drying at 90 deg.C for 12 hr); the obtained powder was put into a mortar and ground to obtain near-infrared absorbing heat-shielding pigment particles.
Preferably: the molar ratio of the copper source to the protective agent is 1: 0-2.0. The molar ratio of the copper source to the sulfur source is 1: 0.5-4.0. The molar ratio of the doped metal ions to the copper source is 0-2:1, and 0 is excluded. The solvent is selected from: one of n-butanol, ethylene glycol, ethanol and water. The copper source is selected from: copper sulfate (CuSO)4·5H2O), copper nitrate (Cu (NO)3)2·3H2O), copper chloride (CuCl)2·2H2O), copper citrate (C)6H6CuO7) Copper oxalate (CuC)2O4) Phthalocyanine blue (C)32H16CuN8) Copper acetate (C)4H8CuO5) Preferably one or two of them. The concentration of the copper source is 0.00625-0.0625 mol/L. The sulfur source is selected from: sodium sulfide (Na)2S), thiourea (SC (NH)2)2) Sodium thiosulfate (Na)2S2O3) Carbon disulfide (CS)2) Preferably one or two of them. The protective agent is selected from: EDTA (ethylenediaminetetraacetic acid) citric acid monohydrate (C)6H8O7·H2O), polyvinylpyrrolidone (PVP), preferably one of them; doping metal ion metal salt, such as nitrate, sulfate, hydrochloride, oxalate, etc. Preferably, the ultrasound time is 20min to 60 min. Step (ii) of(2) Preferably, the mixture is put into an oven, the heat preservation temperature is 60-190 ℃, and the time is 1-9 h.
The invention has the advantages that:
the film has the performance of near-infrared absorption and near-infrared reflection, the function of the film is diversified, and the heat insulation efficiency of the film is greatly improved. The preparation method is simple and low in cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principles of the invention:
FIG. 1 is a UV-visible near IR transmission spectrum of example 1.
Detailed Description
The present invention will be described in detail with reference to the drawings and specific embodiments, which are illustrative of the present invention and are not to be construed as limiting the present invention. In order to facilitate a further understanding of the invention by those skilled in the art, the following examples are prepared in accordance with the same preparative procedures.
Example 1
Preparation of multifunctional transparent heat-insulating coating containing near-infrared absorption and reflection composite pigment and polyolefin co-extruded film (preparation of multifunctional transparent heat-insulating coating containing near-infrared absorption and reflection composite pigment and polyolefin co-extruded film 1)
The first step is as follows: according to Bi (NO)3)35H2O，HCl，C6H8O7·H2The mixture prepared with an O molar ratio of 1:1:0.5 was dissolved in 100mL of water, pH 1 was adjusted with concentrated hydrochloric acid, followed by ultrasonic dispersion for 30 minutes, and then the mixture was transferred into a polytetrafluoroethylene-lined autoclave having a capacity of 300mL, sealed, placed in an oven, and reacted at 100 ℃ for 4 hours. Then, the reaction kettle is cooled to room temperature along with the furnace, products in the reaction kettle are alternately cleaned for 3 times by using distilled water and absolute ethyl alcohol, and then the powder is dried for 12 hours in a vacuum oven at 70 ℃. The obtained powder was then put into a mortar and ground for 10 minutes to obtain a near-infrared reflective white powder.
The second step is that: according to CuSO4·5H2O，SC(NH2)2EDTA, doping with metal ions Bi+The mixture prepared in a molar ratio of 2:1:1:0.5 was dissolved in 100mL of ethylene glycol, the pH was adjusted to 1 with concentrated hydrochloric acid, followed by ultrasonic dispersion for 20min, and then the mixture was transferred into a polytetrafluoroethylene-lined autoclave having a capacity of 300mL, sealed, placed in an oven, and reacted for 4h while maintaining the temperature at 100 ℃. Then, the reaction kettle is cooled to room temperature along with the furnace, products in the reaction kettle are alternately cleaned for 3 times by using distilled water and absolute ethyl alcohol, and then the powder is dried for 12 hours in a vacuum oven at the temperature of 90 ℃. Then the obtained powder is put into a mortar for grinding for 10 minutes to obtain near infrared absorption black powder Bi-Cu1.78S。
The third step: 0.5g of near-infrared reflection pigment and 0.5g of near-infrared absorption pigment are weighed and mixed, 4g of ethylene glycol dispersion liquid is weighed and stirred uniformly for 6 hours.
And fourthly, mixing 5g of dispersion liquid with 45g of EVA resin particles, and banburying in an internal mixer at 140 ℃ for 15 min. The frequency is 15 HZ.
And fifthly, extruding the film by a single-screw extruder, wherein the temperature of the first zone is 130 ℃, the temperature of the second zone is 130 ℃, the temperature of the third zone is 145 ℃, and the temperature of a machine head is 145 ℃. The screw rotation frequency is 5-30 HZ. Obtaining the multifunctional transparent heat-insulating polyolefin co-extruded film containing the near-infrared absorption and reflection composite pigment. The thickness was 0.2mm, and the optical spectrum of the obtained film is shown in FIG. 1.
Example 2
Preparation of multifunctional transparent heat-insulating coating containing near-infrared absorption and reflection composite pigment and polyolefin co-extruded film (preparation of multifunctional transparent heat-insulating coating containing near-infrared absorption and reflection composite pigment and polyolefin co-extruded film 2)
According to Bi (NO)3)35H2O，NaCl，C6H8O7·H2Dissolving the mixture prepared with the molar ratio of O of 1:1:1 in 100mL of ethylene glycol, adjusting the pH value to 3 by using concentrated hydrochloric acid, then ultrasonically dispersing for 30 minutes, transferring the mixture into a polytetrafluoroethylene-lined pressure kettle with the volume of 300mL, sealing,the mixture is put into an oven and kept at 100 ℃ for reaction for 4 h. Then, the reaction kettle is cooled to room temperature along with the furnace, products in the reaction kettle are alternately cleaned for 3 times by using distilled water and absolute ethyl alcohol, and then the powder is dried for 12 hours in a vacuum oven at 70 ℃. Then the mixture is placed into a muffle furnace to be calcined for 2 hours at 200 ℃. The obtained powder was then put into a mortar and ground for 10 minutes to obtain a near-infrared reflective brown powder.
The second step is that: according to CuSO4·5H2O，SC(NH2)2Dissolving EG (ethylene glycol) and a mixture prepared by doping metal tungsten salt (such as sodium tungstate) in a molar ratio of 1:1:1:1 in 100mL of water, adjusting the pH value to 3 by using concentrated hydrochloric acid, then ultrasonically dispersing for 20min, transferring the mixture into a polytetrafluoroethylene-lined pressure kettle with the volume of 300mL, sealing, putting the pressure kettle into an oven, and reacting for 4h at 100 ℃. Then, the reaction kettle is cooled to room temperature along with the furnace, products in the reaction kettle are alternately cleaned for 3 times by using distilled water and absolute ethyl alcohol, and then the powder is dried for 12 hours in a vacuum oven at the temperature of 90 ℃. Then, the obtained powder was put into a mortar and ground for 10 minutes to obtain near-infrared absorbing black powder W-CuS.
The third step: weighing 45g of TPU, dissolving the TPU by using 20g of tetrahydrofuran solvent, uniformly stirring, and stirring for 6 h.
The fourth step: 0.5g of near-infrared reflection pigment and 0.5g of near-infrared absorption pigment are weighed and mixed, then 4g of coupling agent KH560 is added, and the mixture is added into the dissolved TPU solution and stirred for 4 hours.
The fifth step: coating 1ml of the mixed solution on a polytetrafluoroethylene plate or glass, making into 50mm × 500mm × 0.02mm, and drying at 45-70 deg.C. The multifunctional transparent heat-insulating coating containing the near-infrared absorption and reflection composite pigment is obtained.
Claims (9)
1. The multifunctional transparent heat-insulating coating or polyolefin co-extruded film containing the near-infrared absorption and reflection composite pigment is characterized in that the coating or the co-extruded film contains a surface-modified near-infrared reflection agent bismuth oxychloride pigment and a surface-modified pigment M-CuxSyWherein M in the formula is doped metal ions, x is more than or equal to 1 and less than or equal to 2, and y is more than or equal to 1 and less than or equal to 2;
the preparation of the bismuth oxychloride pigment comprises the following steps: dissolving a mixture prepared from a bismuth source, a chlorine source and a protective agent in a solvent, adjusting the pH value of the system, and ultrasonically dispersing for a period of time; transferring the mixture into a reactor, sealing, putting into an oven, and keeping the temperature; then, cooling to room temperature, alternately cleaning the product in the reaction kettle for a plurality of times by using distilled water and absolute ethyl alcohol, and then drying the powder in a vacuum oven; calcining the powder at high temperature for a period of time, and grinding the powder in a mortar to obtain bismuth oxychloride near-infrared high-reflection heat-insulation pigment particles;
the solvent is one of glycol, ethanol and water; the chlorine source is one of HCl, KCl, NaCl and CTAC; the protective agent is C6H8O7·H2O; the pH is 1-9;
the ultrasonic treatment time is 20min-60 min; putting the mixture into an oven, keeping the temperature at 80-180 ℃ for 3-9 h; the calcining temperature is 200-800 ℃, and the time is 1-4 h; the molar ratio of the bismuth source to the chlorine source is 1 (0.5-1.5); the molar ratio of the bismuth source to the protective agent is 1 (0-2.0);
pigment M-CuxSyThe preparation method comprises the following steps:
(1) dissolving a mixture prepared from a copper source, a sulfur source, a protective agent and a metal ion-doped metal salt in a solvent, adjusting the pH of the system to 1-9, and then performing ultrasonic dispersion for a period of time to obtain a dispersion mixture;
(2) transferring the dispersion mixture into a lining pressure reaction kettle, sealing, putting into a drying oven, and keeping the temperature for a period of time; cooling to room temperature, alternately cleaning the product in the reaction kettle with distilled water and absolute ethyl alcohol for several times, and drying in an oven; grinding the obtained powder in a mortar to obtain near-infrared absorption heat-shielding pigment particles;
the molar ratio of the copper source to the protective agent is 1: 0-2.0; the molar ratio of the copper source to the sulfur source is 1: 0.5-4.0; the molar ratio of the doped metal ions to the copper source is 0-2:1, and 0 is not included; the solvent is selected from: one of n-butanol, ethylene glycol, ethanol and water; the copper source is selected from: copper sulfate, copper nitrate, copper chloride, lemonCopper citrate, copper oxalate, phthalocyanine blue (C)32H16CuN8) Copper acetate (C)4H8CuO5) One or two of them; the concentration of the copper source is 0.00625-0.0625 mol/L; the sulfur source is selected from: sodium sulfide (Na)2S), thiourea (SC (NH)2)2) Sodium thiosulfate (Na)2S2O3) Carbon disulfide (CS)2) One or two of them; the protective agent is selected from: EDTA (ethylenediaminetetraacetic acid) citric acid monohydrate (C)6H8O7·H2O), one of polyvinylpyrrolidone (PVP); the metal salt doped with metal ions is nitrate, sulfate, hydrochloride or oxalate; the ultrasonic time is 20min to 60 min; putting the mixture into an oven, keeping the temperature at 60-190 ℃ for 1-9 h;
the surfactant or dispersant used for surface modification is any one or a combination of two selected from silane coupling agent KH550, silane coupling agent KH560, castor oil, stearamide, higher alcohol, vinyl bis stearamide, stearic acid monoglyceride (GMS), tristearin (HTG), liquid paraffin, zinc stearate (ZnSt), polyethylene wax, polyethylene glycol 200 or 400.
2. The multifunctional transparent heat-insulating coating or polyolefin coextruded film containing a composite near-infrared absorbing and reflecting pigment according to claim 1, wherein the coating or film is made of a transparent matrix resin which is any one or more of polyolefin resins including polyethylene resin, ethylene-vinyl alcohol copolymer, polypropylene, poly-4-methyl-1-pentene resin.
3. The multifunctional transparent heat-insulating coating or the polyolefin co-extruded film containing the near-infrared absorption and reflection composite pigment according to claim 1, wherein the polyolefin is one or more selected from low-density polyethylene and high-density polyethylene.
4. The multifunctional transparent heat-insulating coating or polyolefin co-extruded film containing the near-infrared absorption and reflection composite pigment according to claim 1, wherein the surfactant or the dispersant accounts for 1-20% of the total mass of the system.
5. The multifunctional transparent heat-insulating coating or the polyolefin coextruded film containing the near-infrared absorption and reflection composite pigment according to claim 1, characterized in that the doped metal ions are selected from one or more of alkaline earth metals, transition metals, lanthanides, series, IIIA metals and VA metals.
6. The multifunctional transparent heat-insulating coating or the polyolefin co-extruded film containing the near-infrared absorption and reflection composite pigment according to claim 1, wherein the doped metal ions are selected from one or two of Fe, Al, Mg, Cs, Ba, Zn, La, Ce, W and Sb.
7. The multifunctional transparent heat-insulating coating or polyolefin co-extrusion film containing the near-infrared absorption and reflection composite pigment according to claim 1, wherein the near-infrared absorption pigment and the reflection pigment in the coating or film account for 0.01-5% of the total mass; the mass ratio of the near infrared absorption pigment to the reflection pigment is 10: 1-10.
8. The method for preparing the multifunctional transparent heat-insulating coating or the polyolefin co-extruded film containing the near infrared absorption and reflection composite pigment according to any one of claims 1 to 7, is characterized by comprising the following steps:
mixing the near-infrared absorption and reflection pigments according to a certain proportion, carrying out surface modification, then uniformly mixing with a dispersion liquid prepared by dissolving transparent matrix resin in a solvent, coating a film or compounding with transparent resin particles, carrying out banburying in a banbury mixer, and then carrying out melt extrusion on the film to obtain the multifunctional transparent heat-insulation coating or polyolefin co-extrusion film containing the near-infrared absorption and reflection composite pigments.
9. The process of claim 8 wherein the solvent is an aromatic hydrocarbon; aliphatic hydrocarbons; alicyclic hydrocarbons; halogenated hydrocarbons; alcohols; ethers; esters; ketones; a diol derivative; and others: acetonitrile, pyridine, phenol, dimethylacetamide and water; wherein the resin accounts for 5 to 90 percent of the solvent by mass.
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| CA3039666C (en) | 2016-10-28 | 2022-08-23 | Ppg Industries Ohio, Inc. | Coatings for increasing near-infrared detection distances |
| KR20240144457A (en) | 2018-11-13 | 2024-10-02 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Method of detecting a concealed pattern |
| US11561329B2 (en) | 2019-01-07 | 2023-01-24 | Ppg Industries Ohio, Inc. | Near infrared control coating, articles formed therefrom, and methods of making the same |
| CN111391263B (en) * | 2020-02-21 | 2021-08-31 | 南京工业大学 | A kind of non-pigment method porous total reflection heat insulation and cooling polymer film and preparation method |
| CN111605276A (en) * | 2020-06-30 | 2020-09-01 | 江南大学 | A kind of melt co-extrusion multilayer transparent UV-near-infrared shielding polymer material, preparation method and application thereof |
| CN114678151B (en) * | 2022-03-24 | 2024-01-23 | 济南大学 | Preparation method and application of flexible transparent radiation protection film based on bismuth compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995107A (en) * | 2006-12-08 | 2007-07-11 | 江苏晨光涂料有限公司 | Transparent heat-insulated resin sheet |
| CN103131285A (en) * | 2013-04-03 | 2013-06-05 | 上海海事大学 | Photothermal conversion composition and preparation method thereof |
| CN105907202A (en) * | 2016-05-06 | 2016-08-31 | 陈昌 | Composite heat insulation paint and preparation method thereof |
-
2017
- 2017-07-13 CN CN201710571511.2A patent/CN107383573B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995107A (en) * | 2006-12-08 | 2007-07-11 | 江苏晨光涂料有限公司 | Transparent heat-insulated resin sheet |
| CN103131285A (en) * | 2013-04-03 | 2013-06-05 | 上海海事大学 | Photothermal conversion composition and preparation method thereof |
| CN105907202A (en) * | 2016-05-06 | 2016-08-31 | 陈昌 | Composite heat insulation paint and preparation method thereof |
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