Manufacturing method of organic-inorganic composite functional pigment

Abstract

The manufacturing method of the present invention is as follows: Step 1: Dissolve 10 parts by weight of raw material A in 300 parts by weight of water, and add 2 parts by weight of raw material B and 0.2 parts by weight of polyethylene glycol. Step 2: Add 5 parts by weight of butyl titanate and 1 part by weight of organic acid, and heat at 75°C for 2 hours to react. Step 3: Add 4 parts by weight of ethylene glycol and 0.2 parts by weight of hydrochloric acid, and stir for 1 hour. Step 4: Sealed and aged at 50°C for 24 hours, washed with water, centrifuged, isolated from oxygen, and calcined for 4 hours to obtain a preliminary product. Step 5: Disperse 10 parts by weight of the product in 400 parts by weight of N,N'-dimethylacetamide, add 0.2 parts by weight of 4-dimethylaminopyridine and 5 parts by weight of styrene-maleic anhydride copolymer, and heat to 45°C to react for 12 hours. Step 6: Wash with ethanol, separate, and dry, then mix with dispersant, pigment, coupling agent, and solvent, and grind to form a composite functional pigment.

Description

[Technical Field]

[0001] The present invention relates to the technical field of functional pigments, and more particularly to a method for producing organic-inorganic composite functional pigments. [Background technology]

[0002] Pigments enrich the world with color and are widely used in all fields. Traditional pigments are inorganic-based and have stable colors, but often lack vividness. Organic pigments offer a wide range of colors, but in actual use, they often suffer from poor weather resistance, discoloration, and fading. Organic-inorganic composite pigments can complement each other to a certain extent, providing pigments with heat insulation and UV protection functions. This not only enriches the visual experience, but also enhances the comprehensive value of materials, thereby meeting the social development needs of energy conservation and environmental protection.

[0003] Currently, pigments offer more functionality than just color. Chinese Patent CN106398321A discloses a method for producing green organic / inorganic composite infrared-reflective pigments. The pigments are produced by hydrolyzing tetrabutyl titanate as a precursor and coating it with phthalocyanine green pigment particles, resulting in a series of dark and light-colored infrared-reflective pigments. The total solar reflectance of these pigments reaches approximately 60%. Chinese Patent CN110028811A discloses a blue pigment with high near-infrared reflectance, which uses rutile titanium dioxide as a core and a combustion reaction to form a cobalt blue shell on the surface, and a method for producing the same. The resulting blue pigments can control color depth and achieve infrared reflectances of approximately 70%. These research efforts have enriched the functionality of organic / inorganic composite pigments, further expanding their composite functionality and enhancing their energy-saving and emission-reduction effects. Furthermore, technological improvements can further expand the richness of colors to meet the needs of practical applications. Summary of the Invention [Problem to be solved by the invention]

[0004] The object of the present invention is to provide a method for producing an organic-inorganic composite functional pigment that solves the problem of functional pigments produced for the above-mentioned applications, which have a single color and insufficient stability of the composite structure. [Means for solving the problem]

[0005] To achieve the above objectives, the present invention provides the following technical solutions: A method for producing an organic-inorganic composite functional pigment, The method for producing a multifunctional pigment that can achieve heat insulation and ultraviolet blocking functions is as follows: Step 1: dissolving 10 parts by mass of raw material A in 300 parts by mass of water, and adding 1 to 3 parts by mass of raw material B and 0.2 parts by mass of polyethylene glycol; Step 2: Add 5 parts by mass of butyl titanate and 1 part by mass of an organic acid, and heat at 70 to 80°C for 2 hours to cause a reaction; Step 3: adding 3 to 5 parts by mass of ethylene glycol and stirring for 1 hour, and adding 0.2 parts by mass of hydrochloric acid and stirring for 1 hour; Step 4: Sealing the mixture at 50°C for 24 hours, aging it, washing it with water, centrifuging it, isolating it from oxygen, and calcining it at a calcination temperature of 150-220°C for 3-5 hours to obtain a preliminary product. Step 5: dispersing 10 parts by mass of the product in 300 to 500 parts by mass of N,N'-dimethylacetamide, adding 0.1 to 0.3 parts by mass of 4-dimethylaminopyridine and 5 parts by mass of styrene-maleic anhydride copolymer, and heating to 40 to 50°C to react for 12 hours; and step 6, washing with ethanol to separate the pigment, drying, and then mixing with 0.2 parts by weight of dispersant, 0.5 to 2 parts by weight of pigment, 0.1 parts by weight of coupling agent, and 50 parts by weight of solvent, heating at 50 to 70°C for 2 to 5 hours, stirring, and pulverizing to form a composite functional pigment.

[0006] In a preferred embodiment of the present invention, in Step 1, raw material A is a mixture of sodium tungstate and sodium metavanadate in a mass ratio of 2:8.

[0007] In a preferred embodiment of the present invention, in step 1, raw material B is two or three selected from aluminum nitrate, zinc nitrate, cobalt nitrate, barium nitrate, manganese nitrate, and indium nitrate.

[0008] In a preferred embodiment of the present invention, in step 4, the organic acid is a mixture of citric acid and glacial acetic acid in a mass ratio of 4:1.

[0009] In a preferred embodiment of the present invention, the dispersant in step 6 is selected from polyvinylpyrrolidone and polymeric polyether, the coupling agent is a silane coupling agent, and the solvent is selected from acetone, ethylene glycol methyl ether acetate, and butyl acetate.

[0010] In a preferred embodiment of the present invention, in step 1, the number average molecular weight of the polyethylene glycol is 800 to 2000 g / mol.

[0011] In a preferred embodiment of the present invention, in step 5, the number average molecular weight of the styrene-maleic anhydride copolymer is 2000 to 5000 g / mol.

[0012] In a preferred embodiment of the present invention, in step 6, the red pigment is selected from Pigment Red 254, the yellow pigment is selected from Pigment Yellow 138, the green pigment is selected from Pigment Green 7, the blue pigment is selected from Pigment Blue 15:4, and the violet pigment is selected from Pigment Violet 23.

[0013] In a preferred embodiment of the present invention, the composite functional pigment is produced by the production method described in any one of claims 1 to 8. [Effects of the Invention]

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0015] In the present invention, primary functional particles are obtained by doping with a hydrolysis catalyst and multiple metal ions, followed by aging and calcination. Then, a styrene-maleic anhydride copolymer is coated on the surface of the primary functional particles. The styrene-maleic anhydride copolymer and pigment are physically and chemically composited through the π-π conjugated particles and coupling action to obtain the final product. The organic-inorganic composite functional pigment achieves rich colors by highly complexing inorganic particles and organic pigments, while also possessing excellent functionality and weather resistance. This manufacturing method provides a composite pigment with excellent performance that can be widely used in various applications requiring color, such as plastic films, plastic products, and coatings, in a relatively simple manner. This composite pigment exhibits excellent composite properties between the organic pigment and inorganic particles, excellent weather resistance, and rich colors. The resulting composite functional pigment has excellent dual properties of UV and IR blocking. The resulting composite functional pigment achieves rich colors, high transparency, and high visibility. The manufacturing method is simple, consumes little energy, meets the requirements of industrial production, has a wide range of applications, and is economical and efficient for mass production. DETAILED DESCRIPTION OF THE INVENTION

[0016] The following provides a clear and complete description of the technical solutions in the embodiments of the present invention with reference to the embodiments of the present invention, but it is clear that the described embodiments are only a part of the embodiments of the present invention, and do not include all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without any creative work fall within the scope of protection of the present invention.

[0017] Example 1 The present invention provides a method for producing an organic-inorganic composite functional pigment, which includes the following steps: Step 1: 2 g of sodium tungstate and 8 g of sodium metavanadate were dissolved in 300 ml of water, and 0.5 g of barium nitrate, 1 g of aluminum nitrate, and 0.8 g of zinc nitrate were added. Then, 0.2 g of polyethylene glycol (Mn=1000 g / mol) was added with stirring. Step 2: 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid were added and heated at 70°C for 2 hours to react. Step 3: 3 g of ethylene glycol was added and stirred for 1 hour, and 0.2 g of hydrochloric acid was added and stirred for 1 hour. Step 4: The mixture was sealed and aged at 50°C for 24 hours, washed with water three times, centrifuged, isolated from oxygen, and calcined at 220°C for 5 hours to obtain a preliminary product. Step 5: 10 g of the pre-product was dispersed in 400 ml of N,N'-dimethylacetamide, and 0.1 g of 4-dimethylaminopyridine and 5 g of styrene-maleic anhydride copolymer (Mn=2000 g / mol) were added. The mixture was heated to 40°C and reacted for 12 hours. Step 6: After washing with ethanol three times, centrifuging and vacuum drying, the product, 0.2 g of polyoxyethylene ether oleate 105, 0.7 g of Pigment Red 254, and 0.1 g of silane coupling agent KH550 were mixed with a solvent of 20 g of acetone and 30 g of ethylene glycol methyl ether acetate, heated and stirred at 50°C for 3 hours, and then pulverized to form a red composite functional pigment.

[0018] Example 2 The method for producing the organic-inorganic composite functional pigment includes the following steps: Step 1: 2 g of sodium tungstate and 8 g of sodium metavanadate were dissolved in 300 ml of water, and 0.8 g of aluminum nitrate, 0.3 g of cobalt nitrate, and 0.5 g of zinc nitrate were added. Then, 0.2 g of polyethylene glycol (Mn=800 g / mol) was added with stirring. Step 2: 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid were added and heated at 70°C for 2 hours to react. Step 3: 3 g of ethylene glycol was added and stirred for 1 hour, and 0.2 g of hydrochloric acid was added and stirred for 1 hour. Step 4: The mixture was sealed and aged at 50°C for 24 hours, washed with water three times, centrifuged, isolated from oxygen, and calcined at 200°C for 5 hours to obtain a preliminary product. Step 5: 10 g of the pre-product was dispersed in 400 ml of N,N'-dimethylacetamide, and 0.1 g of 4-dimethylaminopyridine and 5 g of styrene-maleic anhydride copolymer (Mn=3000 g / mol) were added. The mixture was heated to 40°C and reacted for 12 hours. Step 6: After washing with ethanol three times, centrifuging and vacuum drying, the product, 0.2 g of polyvinylpyrrolidone, 0.7 g of Pigment Blue 15:4, and 0.1 g of silane coupling agent KH550 were dissolved in a solvent of 20 g of acetone and 30 g of ethylene glycol methyl ether acetate, heated and stirred at 50°C for 5 hours, and then pulverized to form a blue composite functional pigment.

[0019] Example 3 The method for producing the organic-inorganic composite functional pigment includes the following steps: Step 1: 2 g of sodium tungstate and 8 g of sodium metavanadate were dissolved in 300 ml of water, and 0.8 g of aluminum nitrate, 0.2 g of indium nitrate, and 0.7 g of zinc nitrate were added. Then, 0.2 g of polyethylene glycol (Mn=800 g / mol) was added with stirring. Step 2: 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid were added and heated at 70°C for 2 hours to react. Step 3: 3 g of ethylene glycol was added and stirred for 1 hour, and 0.2 g of hydrochloric acid was added and stirred for 1 hour. Step 4: The mixture was sealed and aged at 50°C for 24 hours, washed with water three times, centrifuged, isolated from oxygen, and calcined at 180°C for 5 hours to obtain a preliminary product. Step 5: 10 g of the pre-product was dispersed in 400 ml of N,N'-dimethylacetamide, and 0.1 g of 4-dimethylaminopyridine and 5 g of styrene-maleic anhydride copolymer (Mn=3000 g / mol) were added. The mixture was heated to 40°C and reacted for 12 hours. Step 6: After washing with ethanol three times, centrifuging, and vacuum drying, the product, 0.2 g of polyvinylpyrrolidone, 0.8 g of Pigment Yellow 138, and 0.1 g of silane coupling agent KH560 were mixed with a solvent of 20 g of acetone, 20 g of ethylene glycol methyl ether acetate, and 10 g of butyl acetate, heated and stirred at 70°C for 3 hours, and then pulverized to form a yellow composite functional pigment.

[0020] Example 4 The method for producing the organic-inorganic composite functional pigment includes the following steps: Step 1: 2 g of sodium tungstate and 8 g of sodium metavanadate were dissolved in 300 ml of water, and 0.8 g of aluminum nitrate, 0.3 g of manganese nitrate, and 0.5 g of zinc nitrate were added. Then, 0.2 g of polyethylene glycol (Mn=1000 g / mol) was added with stirring. Step 2: 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid were added and heated at 70°C for 2 hours to react. Step 3: 4 g of ethylene glycol was added and stirred for 1 hour, and 0.2 g of hydrochloric acid was added and stirred for 1 hour. Step 4: The mixture was sealed and aged at 50°C for 24 hours, washed with water three times, centrifuged, isolated from oxygen, and calcined at 220°C for 5 hours to obtain a preliminary product. Step 5: 10 g of the pre-product was dispersed in 400 ml of N,N'-dimethylacetamide, and 0.1 g of 4-dimethylaminopyridine and 5 g of styrene-maleic anhydride copolymer (Mn=3000 g / mol) were added. The mixture was heated to 45°C and reacted for 12 hours. Step 6: After washing with ethanol three times, centrifuging and vacuum drying, the product, 0.2 g of TEGO 655, 0.7 g of Pigment Violet 23, and 0.1 g of silane coupling agent KH560 were mixed with a solvent of 20 g of acetone, 25 g of ethylene glycol methyl ether acetate, and 5 g of butyl acetate, heated and stirred at 60°C for 5 hours, and then pulverized to form a purple composite functional pigment.

[0021] Example 5 The method for producing the organic-inorganic composite functional pigment includes the following steps: Step 1: 2 g of sodium tungstate and 8 g of sodium metavanadate were dissolved in 300 ml of water, and 0.8 g of aluminum nitrate, 0.3 g of barium nitrate, and 0.5 g of zinc nitrate were added. Then, 0.2 g of polyethylene glycol (Mn=800 g / mol) was added with stirring. Step 2: 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid were added and heated at 70°C for 2 hours to react. Step 3: 5 g of ethylene glycol was added and stirred for 1 hour, and 0.2 g of hydrochloric acid was added and stirred for 1 hour. Step 4: The mixture was sealed and aged at 50°C for 24 hours, washed with water three times, centrifuged, isolated from oxygen, and calcined at 200°C for 4 hours to obtain a preliminary product. Step 5: 10 g of the pre-product was dispersed in 400 ml of N,N'-dimethylacetamide, and 0.1 g of 4-dimethylaminopyridine and 5 g of styrene-maleic anhydride copolymer (Mn=2000 g / mol) were added. The mixture was heated to 45°C and reacted for 12 hours. Step 6: After washing with ethanol three times, centrifuging and vacuum drying, the product, 0.2 g of TEGO 655, 0.9 g of Pigment Green 7, and 0.1 g of silane coupling agent KH550 were mixed with a solvent of 20 g of acetone, 25 g of ethylene glycol methyl ether acetate, and 5 g of butyl acetate, heated and stirred at 60°C for 3 hours, and then pulverized to form a green composite functional pigment.

[0022] Test Example A mixture of the composite functional pigment obtained in each example and acrylic resin (40% solids) in a 4:1 ratio was applied to a PET film to form a coating thickness of approximately 10 μm. This coating was then covered with another PET film to form a three-layer composite film. After drying in an oven at 100°C for 2 minutes, the film was allowed to cool naturally and then tested for visible light transmittance, infrared blocking rate, and ultraviolet blocking rate using a spectrophotometer and a Hayashijosha LS101 solar film transmittance measuring device. The haze value of the sample was tested using a WGT-S haze meter. Weather resistance was tested for 5,000 hours using the ASTM-D4329-13 artificial accelerated weathering test method. The test results are shown in Table 1.

[0023] [Table 1]

[0024] As can be seen from Table 1, the film samples produced in each example possessed excellent UV and IR blocking properties, while still maintaining good transparency and visibility (haze). Furthermore, they exhibited excellent weather resistance, with no fading occurring even after a 5,000-hour QUV test. This indicates that the organic-inorganic composite functional pigment obtained by the production method of the present invention possesses UV and IR blocking properties, high transparency, high visibility, and high weather resistance, making it applicable to a variety of related fields, including functional window films, textile printing, coatings, fibers, and plastic products, demonstrating significant application value in these markets.

[0025] It should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art may modify the technical solutions described in the above embodiments or replace some of the technical features with equivalents. Any modifications, equivalent substitutions, improvements, etc. made without departing from the spirit and principles of the present invention shall be included in the protection scope of the present invention.

[0026] (Addendum) (Appendix 1) A method for producing an organic-inorganic composite functional pigment, The method for producing a multifunctional pigment that can achieve heat insulation and ultraviolet blocking functions is as follows: Step 1: dissolving 10 parts by mass of raw material A in 300 parts by mass of water, and adding 1 to 3 parts by mass of raw material B and 0.2 parts by mass of polyethylene glycol; Step 2: Add 5 parts by mass of butyl titanate and 1 part by mass of an organic acid, and heat at 70 to 80°C for 2 hours to cause a reaction; Step 3: adding 3 to 5 parts by mass of ethylene glycol and stirring for 1 hour, and adding 0.2 parts by mass of hydrochloric acid and stirring for 1 hour; Step 4: Sealing the mixture at 50°C for 24 hours, aging it, washing it with water, centrifuging it, isolating it from oxygen, and calcining it at a calcination temperature of 150-220°C for 3-5 hours to obtain a preliminary product. Step 5: dispersing 10 parts by mass of the product in 300 to 500 parts by mass of N,N'-dimethylacetamide, adding 0.1 to 0.3 parts by mass of 4-dimethylaminopyridine and 5 parts by mass of styrene-maleic anhydride copolymer, and heating to 40 to 50°C to react for 12 hours; and step 6 of washing the resulting mixture with ethanol to separate the pigment, drying the resulting mixture, and then mixing the resulting mixture with 0.2 parts by mass of a dispersant, 0.5 to 2 parts by mass of a pigment, 0.1 parts by mass of a coupling agent, and 50 parts by mass of a solvent, and heating the resulting mixture at 50 to 70°C for 2 to 5 hours, stirring, and pulverizing the mixture to form a composite functional pigment.

[0027] (Appendix 2) The method for producing an organic-inorganic composite functional pigment according to Appendix 1, wherein in step 1, raw material A is a mixture of sodium tungstate and sodium metavanadate in a mass ratio of 2:8.

[0028] (Appendix 3) The method for producing an organic-inorganic composite functional pigment according to Appendix 1, characterized in that in Step 1, raw material B is two or three selected from aluminum nitrate, zinc nitrate, cobalt nitrate, barium nitrate, manganese nitrate, and indium nitrate.

[0029] (Appendix 4) The method for producing an organic-inorganic composite functional pigment according to Appendix 1, wherein in step 4, the organic acid is a mixture of citric acid and glacial acetic acid in a mass ratio of 4:1.

[0030] (Appendix 5) The method for producing an organic-inorganic composite functional pigment described in Appendix 1, characterized in that the dispersant in Step 6 is selected from polyvinylpyrrolidone and polymeric polyether, the coupling agent is a silane coupling agent, and the solvent is selected from acetone, ethylene glycol methyl ether acetate, and butyl acetate.

[0031] (Appendix 6) 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein in step 1, the number average molecular weight of the polyethylene glycol is 800 to 2000 g / mol.

[0032] (Appendix 7) 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein in step 5, the number average molecular weight of the styrene-maleic anhydride copolymer is 2000 to 5000 g / mol.

[0033] (Appendix 8) In step 6, the red pigment is selected from Pigment Red 254, the yellow pigment is selected from Pigment Yellow 138, the green pigment is selected from Pigment Green 7, the blue pigment is selected from Pigment Blue 15:4, and the violet pigment is selected from Pigment Violet 23.

[0034] (Appendix 9) The composite functional pigment is an organic-inorganic composite functional pigment, characterized by being produced by the production method described in any one of Appendices 1 to 8.

Claims

1. A method for producing an organic-inorganic composite functional pigment, The method for producing a multifunctional pigment that can achieve heat insulation and ultraviolet blocking functions is as follows: Step 1: dissolving 10 parts by mass of raw material A in 300 parts by mass of water, and adding 1 to 3 parts by mass of raw material B and 0.2 parts by mass of polyethylene glycol; Step 2: Add 5 parts by mass of butyl titanate and 1 part by mass of an organic acid, and heat at 70 to 80°C for 2 hours to react; Step 3: adding 3 to 5 parts by mass of ethylene glycol and stirring for 1 hour, and adding 0.2 parts by mass of hydrochloric acid and stirring for 1 hour; Step 4: Sealing the mixture at 50°C for 24 hours, aging it, washing it with water, centrifuging it, isolating it from oxygen, and baking it at a baking temperature of 150-220°C for 3-5 hours to obtain a preliminary product. Step 5: dispersing 10 parts by mass of the product in 300 to 500 parts by mass of N,N'-dimethylacetamide, adding 0.1 to 0.3 parts by mass of 4-dimethylaminopyridine and 5 parts by mass of styrene-maleic anhydride copolymer, and heating to 40 to 50°C to react for 12 hours; and step 6 of washing the resulting mixture with ethanol to separate it, drying it, and then mixing it with 0.2 parts by mass of a dispersant, 0.5 to 2 parts by mass of a pigment, 0.1 parts by mass of a coupling agent, and 50 parts by mass of a solvent, and heating and stirring the mixture at 50 to 70°C for 2 to 5 hours, and pulverizing the mixture to form a composite functional pigment.

2. 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein in step 1, raw material A is a mixture of sodium tungstate and sodium metavanadate in a mass ratio of 2:

8.

3. 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein in step 1, raw material B is two or three selected from aluminum nitrate, zinc nitrate, cobalt nitrate, barium nitrate, manganese nitrate, and indium nitrate.

4. 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein in step 4, the organic acid is a mixture of citric acid and glacial acetic acid in a mass ratio of 4:

1.

5. 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein the dispersant in step 6 is selected from polyvinylpyrrolidone and polymeric polyether, the coupling agent is a silane coupling agent, and the solvent is selected from acetone, ethylene glycol methyl ether acetate, and butyl acetate.

6. 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein in step 1, the number average molecular weight of polyethylene glycol is 800 to 2000 g / mol.

7. 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein in step 5, the number average molecular weight of the styrene-maleic anhydride copolymer is 2000 to 5000 g / mol.

8. 2. The method for producing an organic-inorganic composite functional pigment according to claim 1, wherein in step 6, the red pigment is selected from Pigment Red 254, the yellow pigment is selected from Pigment Yellow 138, the green pigment is selected from Pigment Green 7, the blue pigment is selected from Pigment Blue 15:4, and the purple pigment is selected from Pigment Violet 23.

9. The composite functional pigment is an organic-inorganic composite functional pigment, characterized in that it is produced by the production method according to any one of claims 1 to 8.

Images