Inorganic-organic hybrid near-infrared black high-reflective coating and preparation method thereof

Abstract

The invention discloses an inorganic-organic hybrid near-infrared black high-reflection coating and a preparation method thereof. The preparation method comprises the following steps: preparing a ZnS < 0.35 > Se < 0.65 > / Cu: In red high-reflection pigment, a BiVO4 (at) ZnO yellow high-reflection pigment, a hollow glass bead (at) Cr2O3 green high-reflection pigment, a Sr < 1-x > La < x > Cu < 1-y > Li < y > Si < 4 > O < 10 > blue high-reflection pigment and a black high-reflection pigment slurry for compounding; the preparation method comprises the following steps: mixing NL387-6-70 polyester resin and PVR-102 polyester resin according to a ratio, mechanically stirring for 10-12 minutes, uniformly mixing, adding butyl acetate, black high-reflectivity pigment slurry, a dispersing agent, a defoaming agent and a flatting agent, continuously mechanically stirring for 1-1.5 hours, sanding for 2-2.5 hours by adopting a sand mill to obtain the organic-inorganic hybrid black high-reflectivity coating, and directly spraying the organic-inorganic hybrid black high-reflectivity coating onto different substrates by adopting a spraying method to obtain the organic-inorganic hybrid black high-reflectivity coating. The organic-inorganic hybrid black high-reflection coating is formed; the high-reflectivity pigments with different colors are synthesized, the black inorganic high-reflectivity pigment is designed and developed from the perspective of color compounding, and compared with a single material, the price cost is lower, the performance is better, the color blackness is adjustable, and the application scene is wider.

Description

Technical Field

[0001] The invention relates to the technical field of coating preparation, and in particular to an inorganic-organic hybrid near-infrared black high-reflective coating and a preparation method thereof. Background Art

[0002] The spectrum of sunlight can be divided into ultraviolet (UV), visible light (VIS) and near infrared (NIR) bands, accounting for 5%, 43% and 52% of the total solar energy received by the earth respectively. Among them, near infrared is the main source of heat generated by sunlight. Therefore, the development of a highly reflective coating to effectively shield or reflect near-infrared sunlight has become an urgently needed technology for thermal insulation, photovoltaics, energy and chemical industries. At present, near-infrared white highly reflective coatings are relatively mature, with the highest reflectivity reaching more than 90%, and have excellent durability, and have been widely used in the market. However, the reflectivity and durability of near-infrared black highly reflective coatings have not been widely promoted and applied because of the contradiction between simultaneous optimization. If traditional black inorganic pigments are used, although the coating has high durability, the reflectivity is generally low (<40); in order to solve the above problems, the market currently uses a double-layer high-reflective coating, that is, the bottom layer is an inorganic-based white high-reflective coating, and the upper layer is an organic black transmission layer. Although a high reflectivity (>50%) is obtained, organic substances are easily degraded under ultraviolet radiation or acid-base solutions, resulting in poor durability of the coating (generally less than 5 years). Although our company has developed "a long-lasting visible-near-infrared graphene-based black high-reflective coating and its preparation method" in response to this problem, the preparation process is complicated and the cost is relatively high, which greatly limits its application in low-end and mid-range fields such as thermal insulation.

[0003] Therefore, the present invention provides an inorganic-organic hybrid near-infrared black high-reflective coating and a preparation method thereof. From the perspective of compounding, a new low-cost black high-reflective inorganic composite pigment is designed, and compounded with a highly weather-resistant organic resin to prepare a near-infrared black high-reflective coating, which provides the possibility for its wide application in mid- and low-end fields such as thermal insulation, and has important practical significance. Summary of the invention

[0004] The purpose of the present invention is to provide an inorganic-organic hybrid near-infrared black high-reflective coating and a preparation method thereof, so as to fill the gap in the current technology.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] A method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating comprises the following steps:

[0007] S1, ZnS 0.35 Se 0.65 Preparation of / Cu:In red high reflective pigment:

[0008] ZnSO4·7H2O, CuSO4·5H2O and In2(SO4)3 were mixed and dissolved in deionized water under vigorous stirring to form a transparent solution A; solid NaOH and Se were then dissolved in hot deionized water, and Na2S·9H2O aqueous solution was added thereto to form solution B; solution B was mechanically stirred and added dropwise to solution A, and after the addition was completed to produce a precipitate, the suspension was aged for 1.5 to 2.5 hours under stirring, the precipitate was extracted, and it was repeatedly washed with deionized water to remove SO4 2- and Na + ions, the precipitate is dried at 80°C for 12-14 hours and then calcined in a nitrogen atmosphere to obtain ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment;

[0009] Preparation of S2, BiVO4@ZnO yellow high reflective pigment:

[0010] Bi(NO3)3·5H2O, Zn(NO3)2·6H2O and citric acid are added into water to form a uniform mixed solution, and NH4VO3 solution is added dropwise under vigorous stirring at room temperature to form a yellow uniform solution, which is heated under reflux at 150°C for 1 to 1.5 hours, and then dried under this condition to remove water to obtain a solid dry gel, which is calcined in an air atmosphere to obtain BiVO4@ZnO yellow high reflective pigment;

[0011] S3. Preparation of hollow glass microspheres (HGM)@Cr2O3 green high reflective pigment:

[0012] Hollow glass microspheres (HGM) are dispersed in a NaOH solution to form a uniform suspension, ultrasonically pretreated for 30 minutes, stirred at 80°C, Cr(NO3)2·6H2O is added to the suspension containing hollow glass microspheres (HGM), and a citric acid solution is added dropwise to form a uniform suspension; the suspension is heated and refluxed at 150°C for 1 to 1.5 hours, a precipitate is extracted, and the precipitate is repeatedly washed with deionized water to remove ions, and the precipitate is dried at 80°C for 12 to 14 hours to obtain a solid dry gel form and fully ground, and calcined in an air atmosphere to obtain a hollow glass microsphere (HGM)@Cr2O3 green high reflective pigment;

[0013] S4、Sr 1-x La x Cu 1-y Li y SiO 10 Preparation of blue high reflective pigment:

[0014] LaCl3 (245.26), CuSO4·5H2O (249.69), SrCl2 (158.53), LiNO3 (68.95) and ethyl orthosilicate (152.22) were mixed and dissolved in deionized water under vigorous stirring to form a transparent solution, citric acid was added under vigorous stirring to dissolve, and the resulting solution was heated to reflux at 150°C for 1 to 1.5 hours; the precipitate was extracted, and repeatedly washed with deionized water to remove ions, and the precipitate was filtered and dried at 80°C for 12 to 14 hours to obtain a solid dry gel form and fully ground, and calcined in an air atmosphere to obtain Sr 1-x La x Cu 1-y Li y SiO 10 Blue high-reflective pigment;

[0015] S5. Compounding of black high reflective inorganic pigments:

[0016] a. ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1-x La x Cu 1- y Li y SiO 10 The blue high-reflective pigment is added to the xylene solvent in proportion to form a dispersion liquid with a weight percentage of 10 wt%, and mixed for 2 to 2.5 hours using a ball mill to obtain a black high-reflective pigment slurry 1 for standby use;

[0017] b. ZnS x Se 1-x / Cu: In red high reflective pigment and HGM@Cr2O3 green high reflective pigment are added to xylene solvent in proportion to form a dispersion with a weight percentage of 10wt%, and mixed by a ball mill for 2-2.5h to obtain a black high reflective pigment slurry 2 for standby use;

[0018] S6. Preparation of organic-inorganic hybrid black high reflective coating:

[0019] NL387-6-70 polyester resin and PVR-102 polyester resin are mixed in proportion and mechanically stirred for 10 to 12 minutes to be evenly mixed, a certain amount of butyl acetate, black high-reflective pigment slurry, dispersant, defoamer and leveling agent are added thereto, and mechanical stirring is continued for 1 to 1.5 hours, and then sanded with a sand mill for 2 to 2.5 hours to obtain an organic-inorganic hybrid black high-reflective coating, which is directly sprayed onto different substrates by a spraying method to form the organic-inorganic hybrid black high-reflective coating.

[0020] Preferably, in step S1, the concentration of the Na2S·9H2O aqueous solution includes but is not limited to 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, and more preferably 1 mol / L; solution B is added dropwise to solution A at 80-83°C and 200-220 rpm mechanical stirring; the precipitate is extracted by filtration; and the precipitate is calcined at 600-650°C for 40-50 minutes at a heating rate of 5°C / min in a nitrogen atmosphere to obtain ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment.

[0021] Preferably, in step S2, the concentration of the NH4VO3 solution includes but is not limited to 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, and more preferably 0.2 mol / L; calcining at 500-550°C for 3-4 hours in an air atmosphere obtains BiVO4@ZnO yellow high reflective pigment.

[0022] Preferably, in step S3, the size of the HGM is 1.6 to 2.3 microns; the concentration of the NaOH solution includes but is not limited to 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, more preferably 2 mol / L; the pulse of the ultrasonic pretreatment is 2 seconds, the ultrasonic power is 200 W, and the frequency is 25 kHz; the precipitate is extracted by filtration; and the hollow glass microspheres @ Cr2O3 green high reflective pigment are obtained by calcining at 500 to 550° C. in an air atmosphere for 3 to 4 hours.

[0023] Preferably, in step S4, the precipitate is extracted by filtration; and calcined at 950-980° C. for 16-18 hours in an air atmosphere to obtain Sr 1-x La x Cu 1-y Li y SiO 10 Blue highly reflective pigment, where x=y=0.1~0.4.

[0024] Preferably, in step S5-a, ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1-x La x Cu 1-y Li y SiO 10 The blue high reflective pigment is added to the xylene solvent in a mass ratio of 1:1:1; in step S5-b, ZnS x Se 1-x / Cu:In red high reflective pigment and HGM@Cr2O3 green high reflective pigment were added into xylene solvent in a mass ratio of 1:0.3-0.45.

[0025] Preferably, in step S6, NL387-6-70 polyester resin and PVR-102 polyester resin are mixed in a mass ratio of 3:1; the amount of the dispersant added is 1.5% of the mass of the black high-reflective pigment slurry added; the amount of the defoamer added is 1.0% of the total amount of the organic-inorganic hybrid black high-reflective coating; the amount of the leveling agent added is 1.0% of the total amount of the organic-inorganic hybrid black high-reflective coating; the black high-reflective pigment slurry is selected from one of the black high-reflective pigment slurry 1 or the black high-reflective pigment slurry 2 prepared in step S5.

[0026] The present application also claims protection for an inorganic-organic hybrid near-infrared black high-reflective coating, which is prepared by the above-mentioned preparation method of the inorganic-organic hybrid near-infrared black high-reflective coating.

[0027] Due to the application of the above technical solution, the present invention has the following beneficial effects compared with the prior art:

[0028] 1. The present invention develops black inorganic high-reflective pigments for the first time, solving the contradiction that the durability and reflectivity of traditional black high-reflective pigments are difficult to optimize at the same time;

[0029] 2. The present invention synthesizes high-reflective pigments of different colors. From the perspective of color compounding, a black inorganic high-reflective pigment is designed and developed. Compared with a single material, it not only has a lower price and cost, but also has better performance and adjustable color blackness, and has a wider range of application scenarios;

[0030] 3. The present invention develops a new resin matrix with high weather resistance and strong adhesion, which solves the problem that it is difficult to simultaneously improve the mechanical properties and weather resistance (such as UV resistance, moisture and heat resistance, etc.) of traditional high-reflective coatings. DETAILED DESCRIPTION

[0031] In order to have a clearer understanding of the technical features, purposes and effects of the present invention, a specific implementation scheme is now described in detail.

[0032] The present invention is further described below in conjunction with the embodiments, but the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to the different requirements of specific use, and the implementation conditions not indicated are conventional conditions in the industry. The technical features involved in each embodiment of the present invention can be combined with each other as long as they do not conflict with each other.

[0033] Example 1

[0034] This embodiment provides a method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating, comprising the following steps:

[0035] S1, ZnS 0.35 Se 0.65 Preparation of / Cu:In red high reflective pigment:

[0036] 2.87g ZnSO4·7H2O, 0.8g CuSO4·5H2O and 0.78g In2(SO4)3 were mixed and dissolved in 100ml deionized water under vigorous stirring to form a transparent solution A; then 0.8g solid NaOH and 0.5g Se were dissolved in 50ml 80℃ hot deionized water, and 3.5ml Na2S·9H2O aqueous solution with a concentration of 1mol / L was added thereto to form solution B; solution B was added dropwise to solution A at 80℃ and 200rpm mechanical stirring, and after the addition was completed and a precipitate was generated, the suspension was aged for 2 hours under stirring, the precipitate was extracted by filtration, and repeatedly washed with deionized water to remove SO4 2- and Na + ions, the precipitate was dried at 80 °C for 12 h, and then calcined at 600 °C for 40 min at a heating rate of 5 °C / min in a nitrogen atmosphere to obtain ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment;

[0037] Preparation of S2, BiVO4@ZnO yellow high reflective pigment:

[0038] 4.9gBi(NO3)3·5H2O, 55.7gZn(NO3)2·6H2O and 1.5gcitric acid were added into 200ml water to form a uniform mixed solution. 50mlNH4VO3 solution (0.2mol / L) was added dropwise under vigorous stirring at room temperature to form a yellow uniform solution. After heating under reflux at 150°C for 1h, the solution was dried under the same conditions to remove water and obtain a solid dry gel. The solution was calcined at 500°C for 3h in an air atmosphere to obtain BiVO4@ZnO yellow high reflective pigment.

[0039] S3. Preparation of hollow glass microspheres (HGM)@Cr2O3 green high reflective pigment:

[0040] 20 g of hollow glass microspheres (HGM) were dispersed in 500 mL of NaOH solution (2 mol / L) to form a uniform suspension, and ultrasonic pretreatment was performed for 30 minutes (pulse was 2 seconds, ultrasonic power was 200 W, and frequency was 25 kHz). The suspension was stirred at 80°C, 22 g of Cr(NO3)2·6H2O was added to the suspension containing hollow glass microspheres (HGM), and 4.5 g of citric acid solution was added dropwise to form a uniform suspension; the suspension was heated to reflux at 150°C for 1 hour, and the precipitate was extracted by filtration, and was repeatedly washed with deionized water to remove ions. After the precipitate was dried at 80°C for 12 hours, a solid dry gel form was obtained and fully ground, and calcined at 500°C in an air atmosphere for 3 hours to obtain a hollow glass microsphere (HGM)@Cr2O3 green high reflective pigment;

[0041] S4、Sr 1-x La x Cu 1-y Li y SiO 10 Preparation of blue high reflective pigment:

[0042] 0.55 g LaCl3 (245.26), 2 g CuSO4·5H2O (249.69), 1.15 g SrCl2 (158.53), 1.08 g LiNO3 (68.95) and 6.1 g ethyl orthosilicate (152.22) were mixed and dissolved in deionized water under vigorous stirring to form a transparent solution, 10.0 g citric acid was added under vigorous stirring to dissolve, and the resulting solution was heated to reflux at 150°C for 1 h; the precipitate was extracted by filtration, and repeatedly washed with deionized water to remove ions. After the precipitate was filtered and dried at 80°C for 12 h, a solid dry gel was obtained and fully ground, and calcined at 950°C in an air atmosphere for 16 hours to obtain Sr 1-x La x Cu 1- y Li y SiO 10 Blue high-reflective pigment;

[0043] S5. Compounding of black high reflective inorganic pigments:

[0044] a. ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1-x La x Cu 1- y Li y SiO 10The blue high-reflective pigment is added to the xylene solvent in a mass ratio of 1:1:1 to form a dispersion with a weight percentage of 10 wt%, and mixed for 2 hours using a ball mill to obtain a black high-reflective pigment slurry 1 for standby use;

[0045] b. ZnS x Se 1-x / Cu:In red high-reflective pigment and HGM@Cr2O3 green high-reflective pigment are added to xylene solvent in a mass ratio of 1:0.4 to form a dispersion with a weight percentage of 10wt%, and mixed by a ball mill for 2-2.5h to obtain a black high-reflective pigment slurry 2 for standby use;

[0046] S6. Preparation of organic-inorganic hybrid black high reflective coating:

[0047] NL387-6-70 polyester resin and PVR-102 polyester resin were mixed in a ratio of 3:1 and mechanically stirred for 10 minutes to mix evenly, 150 g of butyl acetate, 50 g of black high-reflective pigment slurry 1 (the same operation is performed on black high-reflective pigment slurry 2 here), 1 g of dispersant, 1.5 g of defoamer, and 2.0 g of leveling agent were added thereto, and mechanical stirring was continued for 1 hour, and then sanded with a sand mill for 2 hours to obtain an organic-inorganic hybrid black high-reflective coating, which was directly sprayed onto different substrates by a spraying method to form the organic-inorganic hybrid black high-reflective coating.

[0048] Example 2

[0049] This embodiment provides a method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating, comprising the following steps:

[0050] S1, ZnS 0.35 Se 0.65 Preparation of / Cu:In red high reflective pigment:

[0051] 2.87g ZnSO4·7H2O, 0.8g CuSO4·5H2O and 0.78g In2(SO4)3 were mixed and dissolved in 100ml deionized water under vigorous stirring to form a transparent solution A; then 0.8g solid NaOH and 0.5g Se were dissolved in 50ml 80℃ hot deionized water, and 3.5ml Na2S·9H2O aqueous solution with a concentration of 1mol / L was added thereto to form solution B; solution B was added dropwise to solution A at 80℃ and 200rpm mechanical stirring, and after the addition was completed and a precipitate was generated, the suspension was aged for 2 hours under stirring, the precipitate was extracted by filtration, and repeatedly washed with deionized water to remove SO4 2- and Na + ions, the precipitate was dried at 80 °C for 12 h, and then calcined at 600 °C for 40 min at a heating rate of 5 °C / min in a nitrogen atmosphere to obtain ZnS0.35 Se 0.65 / Cu:In red high reflective pigment;

[0052] Preparation of S2, BiVO4@ZnO yellow high reflective pigment:

[0053] 4.9gBi(NO3)3·5H2O, 55.7gZn(NO3)2·6H2O and 1.5gcitric acid were added into 200ml water to form a uniform mixed solution. 50mlNH4VO3 solution (0.2mol / L) was added dropwise under vigorous stirring at room temperature to form a yellow uniform solution. After heating under reflux at 150°C for 1h, the solution was dried under the same conditions to remove water and obtain a solid dry gel. The solution was calcined at 500°C for 3h in an air atmosphere to obtain BiVO4@ZnO yellow high reflective pigment.

[0054] S3. Preparation of hollow glass microspheres (HGM)@Cr2O3 green high reflective pigment:

[0055] 20 g of hollow glass microspheres (HGM) were dispersed in 500 mL of NaOH solution (2 mol / L) to form a uniform suspension, and ultrasonic pretreatment was performed for 30 minutes (pulse was 2 seconds, ultrasonic power was 200 W, and frequency was 25 kHz). The suspension was stirred at 80°C, 22 g of Cr(NO3)2·6H2O was added to the suspension containing hollow glass microspheres (HGM), and 4.5 g of citric acid solution was added dropwise to form a uniform suspension; the suspension was heated to reflux at 150°C for 1 hour, and the precipitate was extracted by filtration, and was repeatedly washed with deionized water to remove ions. After the precipitate was dried at 80°C for 12 hours, a solid dry gel form was obtained and fully ground, and calcined at 500°C in an air atmosphere for 3 hours to obtain a hollow glass microsphere (HGM)@Cr2O3 green high reflective pigment;

[0056] S4、Sr 1-x La x Cu 1-y Li y SiO 10 Preparation of blue high reflective pigment:

[0057] 0.55 g LaCl3 (245.26), 2 g CuSO4·5H2O (249.69), 1.15 g SrCl2 (158.53), 1.08 g LiNO3 (68.95) and 6.1 g ethyl orthosilicate (152.22) were mixed and dissolved in deionized water under vigorous stirring to form a transparent solution, 10.0 g citric acid was added under vigorous stirring to dissolve, and the resulting solution was heated to reflux at 150°C for 1 h; the precipitate was extracted by filtration, and repeatedly washed with deionized water to remove ions. After the precipitate was filtered and dried at 80°C for 12 h, a solid dry gel was obtained and fully ground, and calcined at 950°C in an air atmosphere for 16 hours to obtain Sr 1-x La x Cu 1- y Li y SiO 10 Blue high-reflective pigment;

[0058] S5. Compounding of black high reflective inorganic pigments:

[0059] a. ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1-x La x Cu 1- y Li y SiO 10 The blue high-reflective pigment is added to the xylene solvent in a mass ratio of 1:1:1 to form a dispersion with a weight percentage of 10 wt%, and mixed for 2 hours using a ball mill to obtain a black high-reflective pigment slurry 1 for standby use;

[0060] b. ZnS x Se 1-x / Cu: In red high reflective pigment and HGM@Cr2O3 green high reflective pigment are added to xylene solvent in a mass ratio of 1:0.45 to form a dispersion with a weight percentage of 10wt%, and mixed for 2 to 2.5 hours using a ball mill to obtain a black high reflective pigment slurry 2 for standby use;

[0061] S6. Preparation of organic-inorganic hybrid black high reflective coating:

[0062] NL387-6-70 polyester resin and PVR-102 polyester resin were mixed in a ratio of 3:1 and mechanically stirred for 10 minutes to mix evenly, and butyl acetate, black high reflective pigment slurry 1 (the same operation is performed on black high reflective pigment slurry 2 here), dispersant, defoamer, and leveling agent were added thereto. After continuing mechanical stirring for 1 hour, the mixture was sanded with a sand mill for 2 hours to obtain an organic-inorganic hybrid black high reflective coating, which was directly sprayed onto different substrates by a spraying method to form the organic-inorganic hybrid black high reflective coating.

[0063] Comparative Example 1

[0064] This comparative example is carried out on the basis of the above-mentioned embodiment 1, and the similarities with the above-mentioned embodiment are not repeated here.

[0065] In this comparative example, ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1- x La x Cu 1-y Li y SiO 10 The blue high-reflective pigment is added to the xylene solvent in a mass ratio of 1:1:2 to form a dispersion with a weight percentage of 10 wt%, and mixed for 2 hours using a ball mill to obtain a black high-reflective pigment slurry 1 for standby use.

[0066] Comparative Example 2

[0067] This comparative example is carried out on the basis of the above-mentioned embodiment 1, and the similarities with the above-mentioned embodiment are not repeated here.

[0068] In this comparative example, ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1- x La x Cu 1-y Li y SiO 10 The blue high-reflective pigment is added to the xylene solvent in a mass ratio of 2:1:1 to form a dispersion with a weight percentage of 10 wt%, and mixed for 2 hours using a ball mill to obtain a black high-reflective pigment slurry 1 for standby use.

[0069] Comparative Example 3

[0070] This comparative example is carried out on the basis of the above-mentioned embodiment 1, and the similarities with the above-mentioned embodiment are not repeated here.

[0071] In this comparative example, ZnS 0.35 Se0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1- x La x Cu 1-y Li y SiO 10 The blue high-reflective pigment is added to the xylene solvent in a mass ratio of 1:2:1 to form a dispersion with a weight percentage of 10 wt%, and mixed for 2 hours using a ball mill to obtain a black high-reflective pigment slurry 1 for standby use.

[0072] Comparative Example 4

[0073] This comparative example is carried out on the basis of the above-mentioned embodiment 1, and the similarities with the above-mentioned embodiment are not repeated here.

[0074] In this comparative example, ZnS x Se 1-x / Cu:In red high reflective pigment and HGM@Cr2O3 green high reflective pigment are added to xylene solvent in a mass ratio of 1:0.5 to form a dispersion with a weight percentage of 10wt%, and mixed for 2 to 2.5 hours using a ball mill to obtain a black high reflective pigment slurry 2 for standby use.

[0075] Comparative Example 5

[0076] This comparative example is carried out on the basis of the above-mentioned embodiment 1, and the similarities with the above-mentioned embodiment are not repeated here.

[0077] In this comparative example, ZnS x Se 1-x / Cu:In red high reflective pigment and HGM@Cr2O3 green high reflective pigment are added to xylene solvent in a mass ratio of 1:0.2 to form a dispersion with a weight percentage of 10wt%, and mixed for 2 to 2.5 hours using a ball mill to obtain a black high reflective pigment slurry 2 for standby use.

[0078] Finally, by comparing the organic-inorganic hybrid black high reflective coating obtained in the embodiment with that obtained in the comparative example, it is found that the organic-inorganic hybrid black high reflective coating prepared by the preparation method of the present invention has better mechanical properties and weather resistance.

[0079] In summary, the present invention develops a black inorganic high-reflective pigment for the first time, which solves the contradictory problem that the durability and reflectivity of traditional black high-reflective pigments are difficult to optimize at the same time; the present invention synthesizes high-reflective pigments of different colors, and designs and develops black inorganic high-reflective pigments from the perspective of color compounding. Compared with a single material, it not only has a lower price cost and better performance, but also has adjustable color blackness and has a wider range of application scenarios; the present invention develops a new highly weather-resistant and highly adhesive resin matrix, which solves the problem that the mechanical properties and weather resistance (such as UV resistance, moisture and heat resistance, etc.) of traditional high-reflective coatings are difficult to improve at the same time.

[0080] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating, characterized in that: The steps include: S1, ZnS 0.35 Se 0.65 Preparation of / Cu:In red high reflective pigment: ZnSO4·7H2O, CuSO4·5H2O and In2(SO4)3 were mixed and dissolved in deionized water under vigorous stirring to form a transparent solution A; solid NaOH and Se were then dissolved in hot deionized water, and Na2S·9H2O aqueous solution was added thereto to form solution B; solution B was mechanically stirred and added dropwise to solution A, and after the addition was completed to produce a precipitate, the suspension was aged for 1.5 to 2.5 hours under stirring, the precipitate was extracted, and it was repeatedly washed with deionized water to remove SO4 2- and Na + ions, the precipitate is dried at 80°C for 12-14 hours and then calcined in a nitrogen atmosphere to obtain ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment; Preparation of S2, BiVO4@ZnO yellow high reflective pigment: Bi(NO3)3·5H2O, Zn(NO3)2·6H2O and citric acid are added into water to form a uniform mixed solution, and NH4VO3 solution is added dropwise under vigorous stirring at room temperature to form a yellow uniform solution, which is heated under reflux at 150°C for 1 to 1.5 hours, and then dried under this condition to remove water to obtain a solid dry gel, which is calcined in an air atmosphere to obtain BiVO4@ZnO yellow high reflective pigment; S3. Preparation of hollow glass microspheres @Cr2O3 green high reflective pigment: The hollow glass microspheres were dispersed in a NaOH solution to form a uniform suspension, which was ultrasonically pretreated for 30 minutes and stirred at 80°C. Cr(NO3)2·6H2O was added to the suspension containing the hollow glass microspheres, and a citric acid solution was added dropwise to form a uniform suspension. The precipitate is heated under reflux for 1 to 1.5 hours at 150°C, and the precipitate is extracted and repeatedly washed with deionized water to remove ions. The precipitate is dried at 80°C for 12 to 14 hours to obtain a solid dry gel form and fully grind it. The hollow glass microspheres @Cr2O3 green high reflective pigment can be obtained by calcining in an air atmosphere. S4、Sr 1-x La x Cu 1-y Li y SiO 10 Preparation of blue high reflective pigment: LaCl3, CuSO4·5H2O, SrCl2, LiNO3 and ethyl orthosilicate are mixed and dissolved in deionized water under vigorous stirring to form a transparent solution, citric acid is added under vigorous stirring to dissolve, and the resulting solution is heated to reflux at 150°C for 1 to 1.5 hours; the precipitate is extracted, and repeatedly washed with deionized water to remove ions, and the precipitate is filtered and dried at 80°C for 12 to 14 hours to obtain a solid dry gel form and fully grind it, and calcine it in an air atmosphere to obtain Sr 1-x La x Cu 1-y Li y SiO 10 Blue high-reflective pigment; S5. Compounding of black high reflective inorganic pigments: a. ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1-x La x Cu 1- y Li y SiO 10 Add the blue high-reflective pigment into the xylene solvent in proportion, and mix for 2 to 2.5 hours using a ball mill to obtain a black high-reflective pigment slurry 1 for standby use; b. ZnS x Se 1-x / Cu:In red high reflective pigment and hollow glass microsphere @Cr2O3 green high reflective pigment are added into xylene solvent in proportion, and mixed for 2 to 2.5 hours by ball mill to obtain black high reflective pigment slurry 2 for standby use; S6. Preparation of organic-inorganic hybrid black high reflective coating: NL387-6-70 polyester resin and PVR-102 polyester resin are mixed in proportion and mechanically stirred for 10 to 12 minutes to be evenly mixed, a certain amount of butyl acetate, black high-reflective pigment slurry, dispersant, defoamer and leveling agent are added thereto, and mechanical stirring is continued for 1 to 1.5 hours, and then sanded with a sand mill for 2 to 2.5 hours to obtain an organic-inorganic hybrid black high-reflective coating, which is directly sprayed onto different substrates by a spraying method to form the organic-inorganic hybrid black high-reflective coating.

2. The method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating according to claim 1, characterized in that: In step S1, the concentration of the Na2S·9H2O aqueous solution includes but is not limited to 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, and 3 mol / L; solution B is added dropwise to solution A at 80-83°C and 200-220 rpm mechanical stirring; the precipitate is extracted by filtration; and the precipitate is calcined at 600-650°C for 40-50 minutes at a heating rate of 5°C / min in a nitrogen atmosphere to obtain ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment.

3. The method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating according to claim 1, characterized in that: In step S2, the concentration of the NH4VO3 solution includes but is not limited to 0.1 mol / L, 0.2 mol / L, and 0.3 mol / L; the solution is calcined at 500-550°C for 3-4 hours in an air atmosphere to obtain a BiVO4@ZnO yellow high reflective pigment.

4. The method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating according to claim 1, characterized in that: In step S3, the size of the hollow glass microspheres is 1.6 to 2.3 microns; the concentration of the NaOH solution includes but is not limited to 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, and 3 mol / L; the pulse of the ultrasonic pretreatment is 2 seconds, the ultrasonic power is 200 W, and the frequency is 25 kHz; the precipitate is extracted by filtration; and the hollow glass microspheres@Cr2O3 green high-reflective pigment is obtained by calcining at 500 to 550° C. in an air atmosphere for 3 to 4 hours.

5. The method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating according to claim 1, characterized in that: In step S4, the precipitate is extracted by filtration; and Sr is obtained by calcining at 950-980° C. for 16-18 hours in an air atmosphere. 1-x La x Cu 1-y Li y SiO 10 Blue highly reflective pigment, where x=y=0.1~0.

4.

6. The method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating according to claim 1, characterized in that: In step S5-a, ZnS 0.35 Se 0.65 / Cu:In red high reflective pigment, BiVO4@ZnO yellow high reflective pigment and Sr 1- x La x Cu 1-y Li y SiO 10 The blue high reflective pigment is added to the xylene solvent in a mass ratio of 1:1:1; in step S5-b, ZnS x Se 1-x / Cu:In red high reflective pigment and hollow glass microspheres @Cr2O3 green high reflective pigment were added into xylene solvent in a mass ratio of 1:0.3-0.

45.

7. The method for preparing an inorganic-organic hybrid near-infrared black high-reflective coating according to claim 1, characterized in that: In step S6, NL387-6-70 polyester resin and PVR-102 polyester resin are mixed in a mass ratio of 3:1; the amount of the dispersant added is 1.5% of the mass of the black high-reflective pigment slurry added; the amount of the defoamer added is 1.0% of the total amount of the organic-inorganic hybrid black high-reflective coating; the amount of the leveling agent added is 1.0% of the total amount of the organic-inorganic hybrid black high-reflective coating; the black high-reflective pigment slurry is selected from one of the black high-reflective pigment slurry 1 or the black high-reflective pigment slurry 2 prepared in step S5.

8. An inorganic-organic hybrid near-infrared black high-reflective coating, characterized in that: The coating is prepared by the method for preparing the inorganic-organic hybrid near-infrared black high-reflective coating according to any one of claims 1 to 7.