Water-soluble micro-nano volcanic ash environment-friendly formaldehyde-removing odor-removing decorative coating and application thereof

Abstract

The invention provides a water-soluble micro-nano volcanic ash environment-friendly formaldehyde-removing odor-removing decorative coating. The water-soluble micro-nano volcanic ash environment-friendly formaldehyde-removing odor-removing decorative coating is prepared from the following components in parts by weight: 45 to 55 parts of waterborne polyurethane, 3 to 8 parts of composite volcanic ash particles, 4 to 7 parts of porous cellulose fibers, 1 to 5 parts of pigment, 0.2 to 0.7 part of dispersing agent, 0.2 to 0.7 part of defoaming agent, 0.2 to 0.7 part of flatting agent and 20 to 30 parts of water, wherein the composite volcanic ash particles are compounded by coating large volcanic ash particles with small-particle-size volcanic ash particles; the porous cellulose fiber is a fiber with a skin-core structure, a skin layer is carboxymethyl cellulose, a core layer is PVA, and the length of the fiber is 2-10 mm. Through the environment-friendly substrate of the waterborne polyurethane, the efficient adsorption of the composite volcanic ash, the mechanical enhancement of the porous cellulose and the collaborative optimization of the functional additive, the multiple improvements of the environmental protection property and the odor removal capability are realized.

Description

Technical Field

[0001] The present invention relates to the field of functional coatings, and in particular to a water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating and its application. Background Art

[0002] As people increasingly demand higher levels of indoor air quality and living environments, the development of environmentally friendly decorative coatings has become an industry focus. Volcanic ash odorless decorative coatings, as an emerging category, are gaining prominence thanks to the unique physical and chemical properties of volcanic ash. Volcanic ash, often formed in volcanic eruptions, possesses a well-developed multi-level pore structure and a large specific surface area, endowing it with powerful physical adsorption properties, capable of actively absorbing formaldehyde, benzene, and various odors from the air. At present, the research on volcanic ash decorative coatings mainly focuses on the following aspects: (1) Optimization of adsorption performance: Through physical and chemical modifications, the adsorption capacity of volcanic ash is further improved, so that it can more effectively adsorb and decompose odors and harmful gases in the air; (2) Improvement of photocatalytic performance: Studies have found that the combination of photocatalytic materials such as nano-titanium dioxide and volcanic ash can efficiently decompose organic pollutants under visible light, solving the limitation of traditional photocatalytic materials requiring ultraviolet light excitation; (3) Multifunctional integration: In addition to the functions of deodorization and formaldehyde removal, volcanic ash coatings are also endowed with multiple functions such as fire prevention, heat insulation, humidity control and mildew prevention, which gives it a wider application prospect in interior decoration. However, the development of volcanic ash decorative coatings still faces numerous technical challenges. While volcanic ash possesses adsorption capacity, further research is needed to improve its efficiency in the adsorption and decomposition of harmful gases, particularly in high-humidity environments. Some volcanic ash, once saturated with adsorption, may pose a risk of secondary release of pollutants. Effectively addressing this issue and ensuring the coating's long-term, stable purification performance is a key challenge that needs to be overcome. In summary, volcanic ash odorless decorative paint, as a new type of environmentally friendly material, has broad application prospects, but it still needs further optimization and improvement in practical applications to overcome existing technical difficulties and improve its market competitiveness and application effect. Summary of the Invention

[0003] Technical problem to be solved: The purpose of the present invention is to provide a water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating, which achieves the effect of odor-free adsorption and decomposition through the synergistic effect of volcanic ash and porous cellulose fibers.

[0004] Technical solution: A water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint, comprising the following components by weight: 45-55 parts of waterborne polyurethane 3 to 8 parts of composite volcanic ash particles 4-7 parts porous cellulose fiber 1 to 5 parts pigment 0.2-0.7 parts of dispersant 0.2-0.7 parts of defoaming agent 0.2-0.7 parts of leveling agent 20-30 parts water; The composite volcanic ash particles are formed by coating large volcanic ash particles with small-sized volcanic ash particles; the porous cellulose fibers are sheath-core fibers, with the sheath being carboxymethyl cellulose and the core being PVA, and are 2 to 10 mm in length. The method for preparing the water-soluble micro-nano volcanic ash, environmentally friendly, formaldehyde-free, and odor-free decorative coating comprises the following steps: S1. The composite volcanic ash particles are added to an ethanol aqueous solution containing γ-aminopropyl-triethoxysilane, and the reaction is stirred to obtain amino-modified composite volcanic ash particles; S2. The porous cellulose fibers were added to a DMF solution containing pyromellitic dianhydride and stirred to react to obtain carboxyl-modified porous cellulose fibers; S3. The carboxyl-modified porous cellulose fibers were added to water and ultrasonically dispersed, and then amino-modified composite volcanic ash particles were added and ultrasonically dispersed to obtain a cellulose / volcanic ash dispersion; S4. Add water-based polyurethane, dispersant, defoamer, leveling agent and pigment to the cellulose / volcanic ash dispersion in sequence, disperse uniformly by ultrasonication, and obtain a coating. Preferably, the method for preparing the porous cellulose fiber comprises the following steps: S11 polyvinyl alcohol and an inorganic salt were added to water and stirred to dissolve to obtain a core spinning solution; S12. Carboxymethyl cellulose, inorganic salts and nano-titanium dioxide were added to water and stirred to dissolve to obtain a cortex spinning solution; S13. CMC / PVA fibers with a skin-core structure were prepared by coaxial double-nozzle wet spinning technology using ice water as a coagulation bath. The CMC / PVA fibers were first desalted in water and then freeze-dried to obtain porous cellulose fibers. Preferably, the method for preparing the composite volcanic ash particles comprises the following steps: S21. The volcanic ash is treated with alkali and then sieved to separate volcanic ash A with a particle size greater than 0.5 mm and volcanic ash B with a particle size less than 0.2 mm; S22. The volcanic ash B was added to a polyvinyl pyrrolidone aqueous solution and ultrasonically dispersed to obtain a dispersion; S23. Add volcanic ash A to the dispersion, disperse evenly, and then centrifuge and dry to obtain composite volcanic ash particles. Preferably, the waterborne polyurethane is one of Witcobond W240 and Witcobond W260; and / or, the dispersant is one of BYK-190 and TEGO Dispers 755W; and / or, The defoamer is one of BYK-024 and TEGO Foamex 805N; and / or, The leveling agent is one of BYK-333, LGH-7499, and TEGO Glide 450. Preferably, in step S1, the concentration of γ-aminopropyl-triethoxysilane in the ethanol aqueous solution is 0.5-1.5 wt %, the mass volume ratio of the composite volcanic ash particles to the ethanol aqueous solution containing γ-aminopropyl-triethoxysilane is 5-12 g:100 mL, the stirring reaction temperature is 40-60° C., and the time is 1-2 h; and / or, In step S2, the mass ratio of the porous cellulose fibers to the pyromellitic dianhydride is 1:0.8-1.5, the stirring reaction temperature is 60-80° C., and the time is 3-4 hours; and / or, The ultrasonic dispersion time in step S3 is 1 to 3 hours. Preferably, the inorganic salt is one of sodium chloride, potassium chloride or calcium chloride; and / or, In step S11, the degree of polymerization of polyvinyl alcohol is 1800-2300, the mass ratio of polyvinyl alcohol to inorganic salt is 15-20:1, and the concentration of the core layer spinning solution is 10-13 wt%; and / or, In step S12, the mass ratio of carboxymethyl cellulose, inorganic salt and nano-titanium dioxide is 15-20:1.2-1.5:1-1.5, and the concentration of the skin spinning solution is 10-15wt%. Preferably, the alkali treatment in step S21 is carried out using sodium hydroxide at a concentration of 0.5 to 2 mol / L for 1 to 2 hours; and / or the concentration of the polyvinyl pyrrolidone aqueous solution in step S22 is 2 to 3.5 wt %; the concentration of volcanic ash B in the dispersion is 4 to 8 wt %; In the step S23, the mass ratio of volcanic ash B to volcanic ash A in the dispersion is 2 to 3:1. The beneficial effects of the application of the above-mentioned water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint in interior decoration: The water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint prepared by the present invention has the following advantages: 1. The present invention does not directly add volcanic ash to the coating. Instead, small-sized volcanic ash particles cover large particles to form a composite structure, significantly increasing the specific surface area and improving the adsorption capacity of harmful gases such as formaldehyde. 2. The sheath-core fiber (CMC / PVA) of the present invention is freeze-dried to form a porous network, which efficiently captures harmful gases such as formaldehyde through a dual mechanism of physical adsorption and chemical bonding, capturing and adsorbing the gas in the fiber. The addition of nano-titanium dioxide in the sheath layer imparts photocatalytic degradation function, effectively decomposing harmful gases such as formaldehyde. 3. In the coating preparation process, amino-modified volcanic ash particles and carboxyl-modified cellulose fibers are first electrostatically interacted in water to form a three-dimensional cross-linked network. Waterborne polyurethane and other ingredients are then added. During use, the three-dimensional cross-linked network is distributed throughout the coating. The composite volcanic ash particles act as an adsorbent, while the porous cellulose fibers act to adsorb and decompose harmful gases. The two synergistically adsorb and decompose harmful gases. 4. The coating of the present invention can also effectively decompose formaldehyde under high humidity conditions. This is because the porous structure of cellulose fibers can absorb more water vapor. Formaldehyde is soluble in water and can be adsorbed in the fibers along with the water. Under the action of ultraviolet light, the titanium dioxide on the fiber surface will decompose the formaldehyde adsorbed in the fibers. DETAILED DESCRIPTION The present invention will be further described below in conjunction with examples, which are provided to explain the present invention and are not limited to the following examples: Example 1 The method for preparing porous cellulose fibers comprises the following steps: S11. Polyvinyl alcohol 1800 and calcium chloride in a mass ratio of 15:1 were added to water and stirred to dissolve to obtain a core spinning solution, wherein the concentration of polyvinyl alcohol in the core spinning solution was 10 wt %; S12. Carboxymethyl cellulose, inorganic salts and nano-titanium dioxide in a mass ratio of 15:1.2:1 were added to water and stirred to dissolve to obtain a cortex spinning solution, wherein the concentration of carboxymethyl cellulose in the cortex spinning solution was 10wt%; S13. CMC / PVA fibers with a sheath-core structure were prepared by coaxial double-nozzle wet spinning technology using ice water as a coagulation bath. The flow rate ratio of the core layer solution to the sheath solution was 1.2:1, and the draw ratio was 1.1. The CMC / PVA fibers were first desalted in water for 24 hours and then freeze-dried at -40°C for 20 hours to obtain porous cellulose fibers. The porous cellulose fibers were then sheared to a length of 2 to 10 mm. Example 2 The method for preparing porous cellulose fibers comprises the following steps: S11. Polyvinyl alcohol 1800 and calcium chloride in a mass ratio of 16:1 were added to water and stirred to dissolve to obtain a core spinning solution, wherein the concentration of polyvinyl alcohol in the core spinning solution was 11 wt%; S12. Carboxymethyl cellulose, inorganic salts and nano-titanium dioxide in a mass ratio of 16:1.3:1.2 were added to water and stirred to dissolve to obtain a cortex spinning solution, wherein the concentration of carboxymethyl cellulose in the cortex spinning solution was 11.5wt%; S13. CMC / PVA fibers with a sheath-core structure were prepared by coaxial double-nozzle wet spinning technology using ice water as a coagulation bath. The flow rate ratio of the core layer solution to the sheath solution was 1.2:1, and the draw ratio was 1.1. The CMC / PVA fibers were first desalted in water for 24 hours and then freeze-dried at -40°C for 20 hours to obtain porous cellulose fibers. The porous cellulose fibers were then sheared to a length of 2 to 10 mm. Example 3 The method for preparing porous cellulose fibers comprises the following steps: S11. Polyvinyl alcohol 1800 and calcium chloride in a mass ratio of 18:1 were added to water and stirred to dissolve to obtain a core spinning solution, wherein the concentration of polyvinyl alcohol in the core spinning solution was 12 wt %; S12. Carboxymethyl cellulose, inorganic salts and nano-titanium dioxide in a mass ratio of 18:1.4:1.4 were added to water and stirred to dissolve to obtain a cortex spinning solution, wherein the concentration of carboxymethyl cellulose in the cortex spinning solution was 13wt%; S13. CMC / PVA fibers with a sheath-core structure were prepared by coaxial double-nozzle wet spinning technology using ice water as a coagulation bath. The flow rate ratio of the core layer solution to the sheath solution was 1.2:1, and the draw ratio was 1.1. The CMC / PVA fibers were first desalted in water for 24 hours and then freeze-dried at -40°C for 20 hours to obtain porous cellulose fibers. The porous cellulose fibers were then sheared to a length of 2 to 10 mm. Example 4 The method for preparing porous cellulose fibers comprises the following steps: S11. Polyvinyl alcohol 1800 and calcium chloride in a mass ratio of 20:1 were added to water and stirred to dissolve to obtain a core spinning solution, wherein the concentration of polyvinyl alcohol in the core spinning solution was 13 wt %; S12. Carboxymethyl cellulose, inorganic salts and nano-titanium dioxide in a mass ratio of 20:1.5:1.5 were added to water and stirred to dissolve to obtain a cortex spinning solution, wherein the concentration of carboxymethyl cellulose in the cortex spinning solution was 15wt%; S13. CMC / PVA fibers with a sheath-core structure were prepared by coaxial double-nozzle wet spinning technology using ice water as a coagulation bath. The flow rate ratio of the core layer solution to the sheath solution was 1.2:1, and the draw ratio was 1.1. The CMC / PVA fibers were first desalted in water for 24 hours and then freeze-dried at -40°C for 20 hours to obtain porous cellulose fibers. The porous cellulose fibers were then sheared to a length of 2 to 10 mm. Example 5 A water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint, comprising the following components in parts by weight: 48 parts of waterborne polyurethane Witcobond W260, 5 parts of composite volcanic ash particles, 5 parts of porous cellulose fibers prepared in Example 1, 2 parts of pigment, 0.4 parts of dispersant BYK-190, 0.6 parts of defoamer BYK-024, 0.2 parts of leveling agent BYK-333, and 26 parts of water; The preparation method of the above-mentioned water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating comprises the following steps: S1. The composite volcanic ash particles were added to an ethanol aqueous solution containing γ-aminopropyl-triethoxysilane, the concentration of γ-aminopropyl-triethoxysilane in the ethanol aqueous solution was 0.8 wt %, and the mass volume ratio of the composite volcanic ash particles to the ethanol aqueous solution containing γ-aminopropyl-triethoxysilane was 8 g:100 mL. The reaction was stirred at a temperature of 45 ° C for 1.5 h to obtain amino-modified composite volcanic ash particles; S2. The porous cellulose fibers were added to a DMF solution containing pyromellitic dianhydride, with the mass ratio of the porous cellulose fibers to the pyromellitic dianhydride being 1:1, and the reaction was stirred at 70°C for 4 h to obtain carboxyl-modified porous cellulose fibers; S3. The carboxyl-modified porous cellulose fibers were added to water and ultrasonically dispersed for 1.5 h. Then, amino-modified composite volcanic ash particles were added and ultrasonic dispersion was continued to obtain a cellulose / volcanic ash dispersion. S4. Sequentially add aqueous polyurethane, dispersant, defoamer, leveling agent and pigment to the cellulose / volcanic ash dispersion, and ultrasonically disperse uniformly to obtain a coating; The method for preparing the composite volcanic ash particles comprises the following steps: S21. The volcanic ash was treated with 1 mol / L sodium hydroxide for 2 h and then sieved to separate volcanic ash A with a particle size greater than 0.5 mm and volcanic ash B with a particle size less than 0.2 mm; S22. The volcanic ash B was added to a 2.5wt% aqueous solution of polyvinyl pyrrolidone, and ultrasonically dispersed to obtain a dispersion. The concentration of volcanic ash B in the dispersion was 5.5wt%; S23. Add volcanic ash A to the dispersion, wherein the mass ratio of volcanic ash B to volcanic ash A in the dispersion is 2.3:1. After uniform dispersion, centrifuge and dry the mixture to obtain composite volcanic ash particles. Example 6 A water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint, comprising the following components in parts by weight: 52 parts of waterborne polyurethane Witcobond W260, 7 parts of composite volcanic ash particles, 6 parts of porous cellulose fibers prepared in Example 2, 3 parts of pigment, 0.6 parts of dispersant BYK-190, 0.4 parts of defoamer BYK-024, 0.5 parts of leveling agent BYK-333, and 24 parts of water; The preparation method of the above-mentioned water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating comprises the following steps: S1. The composite volcanic ash particles were added to an ethanol aqueous solution containing γ-aminopropyl-triethoxysilane, the concentration of γ-aminopropyl-triethoxysilane in the ethanol aqueous solution was 1.2 wt %, the mass volume ratio of the composite volcanic ash particles to the ethanol aqueous solution containing γ-aminopropyl-triethoxysilane was 10 g: 100 mL, and the reaction was stirred at a temperature of 50 ° C for 1.5 h to obtain amino-modified composite volcanic ash particles; S2. The porous cellulose fibers were added to a DMF solution containing pyromellitic dianhydride, with the mass ratio of the porous cellulose fibers to the pyromellitic dianhydride being 1:1.2, and the reaction was stirred at 65 ° C for 3.5 h to obtain carboxyl-modified porous cellulose fibers; S3. The carboxyl-modified porous cellulose fibers were added to water and ultrasonically dispersed for 2.5 h. Then, the amino-modified composite volcanic ash particles were added and ultrasonic dispersion was continued to obtain a cellulose / volcanic ash dispersion. S4. Sequentially add aqueous polyurethane, dispersant, defoamer, leveling agent and pigment to the cellulose / volcanic ash dispersion, and ultrasonically disperse uniformly to obtain a coating; The method for preparing the composite volcanic ash particles comprises the following steps: S21. The volcanic ash was treated with 1.2 mol / L sodium hydroxide for 1.5 h and then sieved to separate volcanic ash A with a particle size greater than 0.5 mm and volcanic ash B with a particle size less than 0.2 mm; S22. The volcanic ash B was added to a 3 wt % aqueous solution of polyvinyl pyrrolidone, and ultrasonically dispersed to obtain a dispersion. The concentration of the volcanic ash B in the dispersion was 6 wt %; S23. Add volcanic ash A to the dispersion, wherein the mass ratio of volcanic ash B to volcanic ash A in the dispersion is 2.8:1. After uniform dispersion, centrifuge and dry to obtain composite volcanic ash particles. Example 7 A water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint, comprising the following components in parts by weight: 45 parts of waterborne polyurethane Witcobond W260, 3 parts of composite volcanic ash particles, 4 parts of porous cellulose fibers prepared in Example 3, 1 part of pigment, 0.2 parts of dispersant BYK-190, 0.2 parts of defoamer BYK-024, 0.2 parts of leveling agent BYK-333, and 20 parts of water; The preparation method of the above-mentioned water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating comprises the following steps: S1. The composite volcanic ash particles were added to an ethanol aqueous solution containing γ-aminopropyl-triethoxysilane, the concentration of γ-aminopropyl-triethoxysilane in the ethanol aqueous solution was 0.5 wt %, and the mass volume ratio of the composite volcanic ash particles to the ethanol aqueous solution containing γ-aminopropyl-triethoxysilane was 5 g:100 mL. The reaction was stirred at a temperature of 60 ° C for 1 h to obtain amino-modified composite volcanic ash particles; S2. The porous cellulose fibers were added to a DMF solution containing pyromellitic dianhydride, with the mass ratio of the porous cellulose fibers to the pyromellitic dianhydride being 1:0.8, and the reaction was stirred at 60 ° C for 4 h to obtain carboxyl-modified porous cellulose fibers; S3. The carboxyl-modified porous cellulose fibers were added to water and ultrasonically dispersed for 1 h. Then, the amino-modified composite volcanic ash particles were added and ultrasonic dispersion was continued to obtain a cellulose / volcanic ash dispersion. S4. Sequentially add aqueous polyurethane, dispersant, defoamer, leveling agent and pigment to the cellulose / volcanic ash dispersion, and ultrasonically disperse uniformly to obtain a coating; The method for preparing the composite volcanic ash particles comprises the following steps: S21. The volcanic ash was treated with 0.5 mol / L sodium hydroxide for 2 h and then sieved to separate volcanic ash A with a particle size greater than 0.5 mm and volcanic ash B with a particle size less than 0.2 mm; S22. The volcanic ash B was added to a 2 wt% aqueous solution of polyvinyl pyrrolidone and ultrasonically dispersed to obtain a dispersion. The concentration of the volcanic ash B in the dispersion was 4 wt%; S23. Add volcanic ash A to the dispersion, wherein the mass ratio of volcanic ash B to volcanic ash A in the dispersion is 3:1. After uniform dispersion, centrifuge and dry the mixture to obtain composite volcanic ash particles. Example 8 A water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint, comprising the following components in parts by weight: 55 parts of waterborne polyurethane Witcobond W260, 8 parts of composite volcanic ash particles, 7 parts of porous cellulose fibers prepared in Example 4, 3 parts of pigment, 0.7 parts of dispersant BYK-190, 0.7 parts of defoamer BYK-024, 0.7 parts of leveling agent BYK-333, and 30 parts of water; The preparation method of the above-mentioned water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating comprises the following steps: S1. The composite volcanic ash particles were added to an ethanol-water solution containing γ-aminopropyl-triethoxysilane, the concentration of γ-aminopropyl-triethoxysilane in the ethanol-water solution was 1.5 wt %, and the mass volume ratio of the composite volcanic ash particles to the ethanol-water solution containing γ-aminopropyl-triethoxysilane was 12 g:100 mL. The reaction was stirred at a temperature of 40 ° C for 2 h to obtain amino-modified composite volcanic ash particles; S2. The porous cellulose fibers were added to a DMF solution containing pyromellitic dianhydride, with the mass ratio of the porous cellulose fibers to the pyromellitic dianhydride being 1:1.5, and the reaction was stirred at 80°C for 3 h to obtain carboxyl-modified porous cellulose fibers; S3. The carboxyl-modified porous cellulose fibers were added to water and ultrasonically dispersed for 3 h. Then, amino-modified composite volcanic ash particles were added and ultrasonic dispersion was continued to obtain a cellulose / volcanic ash dispersion. S4. Sequentially add aqueous polyurethane, dispersant, defoamer, leveling agent and pigment to the cellulose / volcanic ash dispersion, and ultrasonically disperse uniformly to obtain a coating; The method for preparing the composite volcanic ash particles comprises the following steps: S21. The volcanic ash was treated with 2 mol / L sodium hydroxide for 1 hour and then sieved to separate volcanic ash A with a particle size greater than 0.5 mm and volcanic ash B with a particle size less than 0.2 mm; S22. The volcanic ash B was added to a 3.5wt% aqueous solution of polyvinyl pyrrolidone, and ultrasonically dispersed to obtain a dispersion. The concentration of the volcanic ash B in the dispersion was 8wt%; S23. Add volcanic ash A to the dispersion, wherein the mass ratio of volcanic ash B to volcanic ash A in the dispersion is 2:1. After uniform dispersion, centrifuge and dry the mixture to obtain composite volcanic ash particles. Comparative Example 1 The difference between Comparative Example 1 and Example 8 is that no composite volcanic ash particles are added. Comparative Example 2 The difference between Comparative Example 2 and Example 8 is that volcanic ash particles are directly added without using composite volcanic ash particles. Comparative Example 3 The difference between Comparative Example 3 and Example 8 is that chopped wood fibers are directly added without using porous cellulose fibers. Comparative Example 4 The difference between Comparative Example 4 and Example 8 is that no porous cellulose fibers are added. Comparative Example 5 The difference between Comparative Example 5 and Example 8 is that the preparation method of the porous cellulose fibers is different; A water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint, comprising the following components in parts by weight: The water-based polyurethane Witcobond W260 is 55 parts, the composite volcanic ash particles are 8 parts, the porous cellulose fiber is 7 parts, the pigment is 3 parts, the dispersant BYK-190 is 0.7 parts, the defoamer BYK-024 is 0.7 parts, the leveling agent BYK-333 is 0.7 parts, and the water is 30 parts; The preparation method of the above-mentioned water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating comprises the following steps: S1. The composite volcanic ash particles were added to an ethanol-water solution containing γ-aminopropyl-triethoxysilane, the concentration of γ-aminopropyl-triethoxysilane in the ethanol-water solution was 1.5 wt %, and the mass volume ratio of the composite volcanic ash particles to the ethanol-water solution containing γ-aminopropyl-triethoxysilane was 12 g:100 mL. The reaction was stirred at a temperature of 40 ° C for 2 h to obtain amino-modified composite volcanic ash particles; S2. The porous cellulose fibers were added to a DMF solution containing pyromellitic dianhydride, with the mass ratio of the porous cellulose fibers to the pyromellitic dianhydride being 1:1.5, and the reaction was stirred at 80°C for 3 h to obtain carboxyl-modified porous cellulose fibers; S3. The carboxyl-modified porous cellulose fibers were added to water and ultrasonically dispersed for 3 h. Then, amino-modified composite volcanic ash particles were added and ultrasonic dispersion was continued to obtain a cellulose / volcanic ash dispersion. S4. Sequentially add aqueous polyurethane, dispersant, defoamer, leveling agent and pigment to the cellulose / volcanic ash dispersion, and ultrasonically disperse uniformly to obtain a coating; The method for preparing the composite volcanic ash particles comprises the following steps: S21. The volcanic ash was treated with 2 mol / L sodium hydroxide for 1 hour and then sieved to separate volcanic ash A with a particle size greater than 0.5 mm and volcanic ash B with a particle size less than 0.2 mm; S22. The volcanic ash B was added to a 3.5wt% aqueous solution of polyvinyl pyrrolidone, and ultrasonically dispersed to obtain a dispersion. The concentration of volcanic ash B in the dispersion was 8wt%; S23. Adding volcanic ash A to the dispersion, wherein the mass ratio of volcanic ash B to volcanic ash A in the dispersion is 2:1, and after uniform dispersion, centrifugation and drying are performed to obtain composite volcanic ash particles; The method for preparing porous cellulose fibers comprises the following steps: S11. The mass ratio of 20:1.5:1.5 carboxymethyl cellulose, inorganic salts and nano-titanium dioxide was added to water and stirred to dissolve to obtain a spinning solution, the concentration of carboxymethyl cellulose in the cortex spinning solution was 15wt%; S13. CMC fibers were prepared by wet spinning technology using ice water as a coagulation bath. The flow rate ratio of the core layer solution to the sheath layer solution was 1.2:1, and the draw ratio was 1.1. The CMC fibers were first desalted in water for 24 hours and then freeze-dried at -40°C for 20 hours to obtain porous cellulose fibers. The porous cellulose fibers were then cut to a length of 2 to 10 mm. Comparative Example 6 The difference between Comparative Example 6 and Example 8 is that the composite volcanic ash particles and porous cellulose fibers are not modified but are directly added to the coating. Comparative Example 7 The difference between Comparative Example 7 and Example 8 is that the cellulose fibers do not contain pores; A water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint, comprising the following components in parts by weight: 55 parts of waterborne polyurethane Witcobond W260, 8 parts of composite volcanic ash particles, 7 parts of porous cellulose fibers prepared in Example 4, 3 parts of pigment, 0.7 parts of dispersant BYK-190, 0.7 parts of defoamer BYK-024, 0.7 parts of leveling agent BYK-333, and 30 parts of water; The preparation method of the above-mentioned water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating comprises the following steps: S1. The composite volcanic ash particles were added to an ethanol-water solution containing γ-aminopropyl-triethoxysilane, the concentration of γ-aminopropyl-triethoxysilane in the ethanol-water solution was 1.5 wt %, and the mass volume ratio of the composite volcanic ash particles to the ethanol-water solution containing γ-aminopropyl-triethoxysilane was 12 g:100 mL. The reaction was stirred at a temperature of 40 ° C for 2 h to obtain amino-modified composite volcanic ash particles; S2. The porous cellulose fibers were added to a DMF solution containing pyromellitic dianhydride, with the mass ratio of the porous cellulose fibers to the pyromellitic dianhydride being 1:1.5, and the reaction was stirred at 80°C for 3 h to obtain carboxyl-modified porous cellulose fibers; S3. The carboxyl-modified porous cellulose fibers were added to water and ultrasonically dispersed for 3 h. Then, amino-modified composite volcanic ash particles were added and ultrasonic dispersion was continued to obtain a cellulose / volcanic ash dispersion. S4. Sequentially add aqueous polyurethane, dispersant, defoamer, leveling agent and pigment to the cellulose / volcanic ash dispersion, and ultrasonically disperse uniformly to obtain a coating; The method for preparing the composite volcanic ash particles comprises the following steps: S21. The volcanic ash was treated with 2 mol / L sodium hydroxide for 1 hour and then sieved to separate volcanic ash A with a particle size greater than 0.5 mm and volcanic ash B with a particle size less than 0.2 mm; S22. The volcanic ash B was added to a 3.5wt% aqueous solution of polyvinyl pyrrolidone, and ultrasonically dispersed to obtain a dispersion. The concentration of volcanic ash B in the dispersion was 8wt%; S23. Adding volcanic ash A to the dispersion, wherein the mass ratio of volcanic ash B to volcanic ash A in the dispersion is 2:1, and after uniform dispersion, centrifugation and drying are performed to obtain composite volcanic ash particles; The method for preparing porous cellulose fibers comprises the following steps: S11. Polyvinyl alcohol 1800 was added to water and stirred to dissolve to obtain a core spinning solution having a concentration of 13 wt%; S12. Carboxymethyl cellulose and nano-titanium dioxide in a mass ratio of 20:1.5 were added to water and stirred to dissolve to obtain a cortex spinning solution, wherein the concentration of carboxymethyl cellulose in the cortex spinning solution was 15wt%; S13. CMC / PVA fibers with a sheath-core structure were prepared by coaxial double-nozzle wet spinning technology using ice water as a coagulation bath. The flow rate ratio of the core layer solution to the sheath solution was 1.2:1, and the draw ratio was 1.1. The CMC / PVA fibers were first desalted in water for 24 hours and then freeze-dried at -40°C for 20 hours to obtain porous cellulose fibers. The porous cellulose fibers were then sheared to a length of 2 to 10 mm. Odor removal effect test: The formaldehyde purification rate is tested in accordance with JC / T 1074-2021 "Purification Performance of Indoor Air Purification Functional Coating Materials". Table 1 shows the formaldehyde purification rate under no light conditions Purification rate / % Purification rate / % Example 5 82.6 Comparative Example 1 65.8 Example 6 83.2 Comparative Example 2 74.9 Example 7 82.4 Comparative Example 3 78.5 Example 8 83.5 Comparative Example 4 71.2 Comparative Example 5 82.8 Comparative Example 6 79.5 Table 2 shows the purification rate of formaldehyde under ultraviolet light conditions Table 3 shows the formaldehyde purification rate under the condition of relative humidity of 95% and ultraviolet light. Purification rate / % Purification rate / % Example 5 91.6 Comparative Example 1 72.4 Example 6 91.5 Comparative Example 2 82.2 Example 7 92.1 Comparative Example 3 77.6 Example 8 91.9 Comparative Example 4 70.5 Comparative Example 5 88.3 Comparative Example 6 82.7 Comparative Example 7 84.6 Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint, characterized in that: Contains the following components by weight: 45-55 parts of waterborne polyurethane 3 to 8 parts of composite volcanic ash particles 4-7 parts porous cellulose fiber 1 to 5 parts pigment 0.2-0.7 parts of dispersant 0.2-0.7 parts of defoaming agent 0.2-0.7 parts of leveling agent 20-30 parts water; The composite volcanic ash particles are formed by coating large-particle volcanic ash particles with small-particle volcanic ash particles; the porous cellulose fibers are sheath-core structure fibers, with the sheath being carboxymethyl cellulose and the core being PVA, and the length is 2 to 10 mm.

2. The method for preparing the water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative coating according to claim 1, characterized in that: The following steps are involved: S1. The composite volcanic ash particles are added to an ethanol aqueous solution containing γ-aminopropyl-triethoxysilane, and the reaction is stirred to obtain amino-modified composite volcanic ash particles; S2. The porous cellulose fibers were added to a DMF solution containing pyromellitic dianhydride and stirred to react to obtain carboxyl-modified porous cellulose fibers; S3. The carboxyl-modified porous cellulose fibers were added to water and ultrasonically dispersed, and then amino-modified composite volcanic ash particles were added and ultrasonically dispersed to obtain a cellulose / volcanic ash dispersion; S4. Add water-based polyurethane, dispersant, defoamer, leveling agent and pigment to the cellulose / volcanic ash dispersion in sequence, disperse uniformly by ultrasonication, and obtain a coating.

3. The water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint according to claim 1, characterized in that: The method for preparing the porous cellulose fiber comprises the following steps: S11 polyvinyl alcohol and an inorganic salt were added to water and stirred to dissolve to obtain a core spinning solution; S12. Carboxymethyl cellulose, inorganic salts and nano-titanium dioxide were added to water and stirred to dissolve to obtain a cortex spinning solution; S13. CMC / PVA fibers with a skin-core structure were prepared by coaxial double-nozzle wet spinning technology using ice water as a coagulation bath. The CMC / PVA fibers were first desalted in water and then freeze-dried to obtain porous cellulose fibers.

4. The water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint according to claim 1, characterized in that: The method for preparing the composite volcanic ash particles comprises the following steps: S21. The volcanic ash is treated with alkali and then sieved to separate volcanic ash A with a particle size greater than 0.5 mm and volcanic ash B with a particle size less than 0.2 mm; S22. The volcanic ash B was added to a polyvinyl pyrrolidone aqueous solution and ultrasonically dispersed to obtain a dispersion; S23. Add volcanic ash A to the dispersion, disperse evenly, and then centrifuge and dry to obtain composite volcanic ash particles.

5. The water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint according to claim 1, characterized in that: The waterborne polyurethane is one of Witcobond W240 and Witcobond W260; and / or, The dispersant is one of BYK-190 and TEGO Dispers 755W; and / or, The defoamer is one of BYK-024 and TEGO Foamex 805N; and / or, The leveling agent is one of BYK-333, LGH-7499, and TEGO Glide 450.

6. The method for preparing the water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint according to claim 2, characterized in that: In step S1, the concentration of γ-aminopropyl-triethoxysilane in the ethanol aqueous solution is 0.5-1.5 wt %, the mass volume ratio of the composite volcanic ash particles to the ethanol aqueous solution containing γ-aminopropyl-triethoxysilane is 5-12 g:100 mL, the stirring reaction temperature is 40-60° C., and the time is 1-2 h; and / or, In step S2, the mass ratio of the porous cellulose fibers to the pyromellitic dianhydride is 1:0.8-1.5, the stirring reaction temperature is 60-80° C., and the time is 3-4 hours; and / or, The ultrasonic dispersion time in step S3 is 1 to 3 hours.

7. The water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint according to claim 3, characterized in that: The inorganic salt is one of sodium chloride, potassium chloride or calcium chloride; and / or, In step S11, the degree of polymerization of polyvinyl alcohol is 1800-2300, the mass ratio of polyvinyl alcohol to inorganic salt is 15-20:1, and the concentration of the core layer spinning solution is 10-13 wt%; and / or, In step S12, the mass ratio of carboxymethyl cellulose, inorganic salt and nano-titanium dioxide is 15-20:1.2-1.5:1-1.5, and the concentration of the skin spinning solution is 10-15wt%.

8. The water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint according to claim 4, characterized in that: In step S21, the alkali treatment is performed using sodium hydroxide at a concentration of 0.5 to 2 mol / L for 1 to 2 hours; and / or The concentration of the polyvinyl pyrrolidone aqueous solution in step S22 is 2 to 3.5 wt %; the concentration of the volcanic ash B in the dispersion is 4 to 8 wt %; In the step S23, the mass ratio of volcanic ash B to volcanic ash A in the dispersion is 2 to 3:

1.

9. Use of the water-soluble micro-nano volcanic ash environmentally friendly formaldehyde-free and odor-free decorative paint according to claim 1 in interior decoration.

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