A sculpture production process with a metal surface and natural texture

Abstract

The present invention discloses a sculpture production process having a surface with a metallic texture and natural texture, comprising the following steps: (1) laying a glass slag layer; (2) spraying a water-based metallic paint on the surface of the glass slag layer to obtain a metallic paint layer; (3) coating a first layer of resin slurry on the surface of the metallic paint layer, laying a glass fiber cloth on the surface of the resin slurry after the resin slurry solidifies, and then coating a second layer of resin slurry on the glass fiber cloth to obtain a resin layer after solidification; (4) placing a supporting steel piece on the back of the resin layer and then trimming the edges; (5) splicing the female molds together and then filling the edges; (6) connecting the supporting steel pieces into a whole, removing the outer molds, and then polishing the surface to obtain a sculpture having a surface with a metallic texture and natural texture. The present invention can obtain a sculpture having a bright metallic texture and a granular natural texture on the surface and having a long service life by combining the glass slag layer, the metallic paint layer, and the resin layer provided with the glass fiber cloth.

Description

Technical Field

[0001] The invention relates to the field of sculpture surface treatment technology, in particular to a sculpture production process with a surface having a metallic texture and natural texture. Background Art

[0002] At present, the commonly used methods for making sculptures with metallic surfaces are:

[0003] 1. Copper casting: For example, patent application number CN201711224445.8 discloses "A Copper Cast Sculpture Material and a Process for Preparing Copper Cast Sculptures." Copper casting, due to its high-temperature dissolution and infusion process, can be used to create complex forms. It is widely used in figurative sculptures featuring figures, especially those with complex forms. However, the high cost of raw materials and the demanding casting conditions hinder its widespread development.

[0004] 2. Sculpture surface gilding: For example, patent application number CN200610012592.4 discloses a "Metallization Process for Sculptures, Furniture, and Crafts." This involves applying metal sheets to the surface of a sculpture to create a unique artistic effect. However, gilding is difficult for sculptures with complex surface morphologies, and the natural texture effect cannot be achieved.

[0005] 3. Surface spraying: Spraying metallic paint on sculptures made of materials like fiberglass can also give the sculpture a metallic finish. While the process is relatively simple, metallic paint is susceptible to oxidation. Prolonged exposure to sunlight can cause the paint layer to thin, dull, and lose its metallic luster. It can also easily crack, shortening the lifespan of the finished sculpture. Summary of the Invention

[0006] The present invention aims to overcome the above-mentioned problems existing in the prior art of sculpture production processes with a metallic texture, and provides a sculpture production process with a surface having a metallic texture and natural texture. By combining a glass slag layer, a metallic paint layer and a resin layer provided with glass fiber cloth, a sculpture with a bright metallic texture and a granular natural texture on the surface and a long service life can be obtained.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A sculpture production process having a surface with a natural metallic texture comprises the following steps:

[0009] (1) Add glass slag to a transparent adhesive, stir evenly, and spread it on the inner surface of the female mold of the sculpture mold to obtain a glass slag layer;

[0010] (2) After the adhesive solidifies, spray water-based metallic paint on the surface of the glass slag layer to obtain a metallic paint layer;

[0011] (3) After the metallic paint layer is dried, a first layer of resin slurry is applied on the surface of the metallic paint layer. After the resin slurry solidifies, a glass fiber cloth is laid on the surface. Then, a second layer of resin slurry is applied on the glass fiber cloth. After solidification, a resin layer is obtained.

[0012] (4) Place a supporting steel piece on the back of the resin layer, and then trim it so that the turned decorative surface does not exceed the edge of the female mold;

[0013] (5) After all the female molds are made according to the above method, they are spliced ​​together and then the edges are filled;

[0014] (6) Connect all the supporting steel parts into a whole, remove the outer mold, and then polish the surface to obtain a sculpture with a natural metallic texture.

[0015] When making a sculpture, the present invention first adheres a layer of glass slag to the inner surface of the female mold using a transparent adhesive, then sprays a metallic paint layer on the surface of the glass slag layer, and finally coats the metallic paint layer with a resin layer provided with glass fiber cloth. After the outer mold is removed, the glass slag layer on the surface of the sculpture formed can form a granular natural texture, and the metallic paint layer can give the sculpture surface a metallic texture. The glass slag layer can also protect the metallic paint layer, preventing the metallic paint layer from contacting the external environment and causing oxidation, thereby extending the service life of the sculpture. The inner resin layer plays a shaping role, and the arrangement of glass fiber cloth within the resin layer can make the decorative surface support more firm and less prone to cracking, thereby increasing the service life of the finished sculpture. Therefore, by adopting the process of the present invention, the glass slag layer, the metallic paint layer, and the resin layer provided with glass fiber cloth are arranged in sequence, and a sculpture having a bright metallic texture and a granular natural texture on the surface and having a long service life can be obtained.

[0016] Preferably, the adhesive used in step (1) is selected from a polyurethane adhesive, a polyacrylic resin adhesive, a silicone adhesive, and an epoxy resin adhesive. The adhesive in the glass slag layer serves to shape the glass slag and, after curing, protects the metal paint layer from contact with the external environment.

[0017] Preferably, the components of the water-based metallic paint in step (2) include, by weight, 8 to 12 parts of water-based copper-gold paste, 40 to 60 parts of water-based acrylic emulsion, 3 to 5 parts of film-forming aid, 5 to 8 parts of thickening thixotropic agent, and 40 to 50 parts of water; the solid content of the water-based acrylic emulsion is 40 to 50 wt%.

[0018] The present invention uses water-based metallic paint to spray the surface of the glass slag layer. Water-based metallic paint uses water as a diluent, does not contain harmful solvents, has low VOC emissions, causes little environmental pollution, and does not harm human health. Copper-gold powder (copper-zinc alloy powder) is the most commonly used metallic pigment in metallic paint and is generally a flaky powder. The present invention adds a water-based copper-gold slurry containing copper-gold powder to the water-based metallic paint. After the paint film is formed, the copper-gold powder is arranged in multiple layers in the paint film in a direction parallel to the substrate or the paint film surface, resulting in a "angle-dependent color" effect: when the observation angle is equal to the incident angle, a shining metallic bright spot is visible. When observed from other angles, the shimmering light is found to weaken and darken, and the color of the coating changes, giving the sculpture surface a "shimmering" metallic effect.

[0019] Preferably, the preparation method of the aqueous copper-gold slurry comprises the following steps:

[0020] A) adding cardanol to dichloromethane, stirring and dissolving in an ice-water bath, adding fuming sulfuric acid, and performing an aging reaction at room temperature; after the reaction, separating the solvent, dissolving the product with ethanol, and then neutralizing it with sodium hydroxide solution, filtering and drying to obtain cardanol sulfonate;

[0021] B) mixing cardanol sulfonate and epichlorohydrin, stirring evenly, adding benzyltriethylammonium chloride, adding sodium hydroxide solution after etherification reaction to carry out ring-closure reaction, and separating the solvent to obtain epoxidized cardanol sulfonate; mixing the epoxidized cardanol sulfonate with γ-aminopropyltriethoxysilane to obtain silane-modified cardanol sulfonate;

[0022] C) dispersing copper-gold powder in anhydrous ethanol, passing nitrogen through the mixture to remove oxygen, adding ethyl orthosilicate and vinyltriethoxysilane, stirring the mixture evenly, and then dropwise adding ethanol aqueous solution and ammonia water to obtain a silica-coated modified copper-gold paste after hydrolysis reaction;

[0023] D) adding azobisisobutyronitrile to the obtained silica-coated modified copper-gold paste, then dropwise adding a polymerization monomer, and after the polymerization reaction, filtering the product to obtain the aqueous copper-gold paste; the polymerization monomer includes silane-modified cardanol sulfonate, methacrylic acid, and hydroxyethyl methacrylate in a mass ratio of 1:6 to 9:8 to 10.

[0024] Copper-gold powder is easily corroded and oxidized in water-based paint, causing its metallic gloss to be greatly reduced. Therefore, the existing metallic paints on the market are mostly solvent-based, and are difficult to obtain water-based metallic paints with good stability. And water-based paint generally presents low viscosity and weak thixotropy (rheological controllability), and rheological controllability is the basis for realizing the directional arrangement of metallic pigments, and the weak thixotropy of water-based paint can cause the metallic gloss of paint film to be poor. Therefore, in order to avoid the corrosion of metallic pigments in water-based metallic paints, and to improve the directional arrangement performance of metallic pigments, thus to improve the glossiness of the sculpture surface metal paint layer, the present invention has modified the metallic pigment copper-gold powder.

[0025] The present invention first coats the surface of the copper-gold powder with a silicon dioxide layer through the hydrolysis reaction of ethyl orthosilicate and silane. The silicon dioxide coating can isolate the copper-gold powder from contact with the corrosive medium, thereby protecting the copper-gold powder from corrosion in water-based metallic paint and maintaining the metallic luster for a long time. In addition, the present invention introduces double bonds into the coating layer by vinyltriethoxysilane, and then, through step D), a polymer layer is coated on the outside of the silica layer through a polymerization reaction between the added polymerization monomer and the double bonds on the surface of the coating layer. The coating of the polymer layer can improve the compatibility of the metallic pigment with the film-forming substance acrylic resin in the water-based metallic paint, thereby preventing the metallic pigment from easily falling off from the paint film surface due to poor compatibility; on the other hand, the present invention adds a silane-modified cardanol sulfonate monomer to the polymer layer. The silane-modified cardanol sulfonate has the characteristics of a surfactant. Its introduction into the polymer layer is beneficial to improving the wettability of the water-based metallic paint on the surface of the glass slag layer, thereby promoting the leveling of the water-based metallic paint; at the same time, the long carbon chain in cardanol makes the polymer layer have greater shrinkage during the drying process. Under the tensile effect of this shrinkage force, the copper and gold powder can be oriented along the direction of the paint film, which is beneficial to improving the "sparkle" effect of the metallic paint layer; the introduction of silane groups into the molecular chain of cardanol sulfonate is also beneficial to further improving the metallic flash index of the metallic paint layer.

[0026] Preferably, in step A), the volume ratio of cardanol to fuming sulfuric acid is 10:5-6, the aging reaction time is 3-5 h, and the solution is neutralized with sodium hydroxide solution to a pH of 6-7.

[0027] Preferably, the molar ratio of cardanol sulfonate, epichlorohydrin and sodium hydroxide added in step B) is 1:3-5:1-1.5; the mass of benzyltriethylammonium chloride added is 2-3% of the total mass of cardanol sulfonate and epichlorohydrin; the etherification reaction temperature is 70-90°C, and the etherification reaction time is 2-4h; the ring-closing reaction temperature is 50-70°C, and the ring-closing reaction time is 2-4h; the molar ratio of epoxidized cardanol sulfonate to γ-aminopropyltriethoxysilane is 1:1-2, the mixed reaction temperature of epoxidized cardanol sulfonate and γ-aminopropyltriethoxysilane is 50-70°C, and the reaction time is 3-5h.

[0028] Preferably, in step C), the volume ratio of ethanol to water in the added ethanol aqueous solution is 7:3-9:1, and the mass fraction of ammonia water is 25-28%; the volume ratio of the copper gold powder to the added ethyl orthosilicate, vinyl triethoxysilane, ethanol aqueous solution and ammonia water is: 2 g: 2-3 mL: 3-4.5 mL: 35-45 mL: 3-6 mL; the hydrolysis reaction temperature is 40-60 ° C, and the hydrolysis reaction time is 5-7 h.

[0029] Preferably, the mass ratio of the polymerization monomer added in step D) to the copper-gold powder added in step C) is 4-6:2; the mass of azobisisobutyronitrile is 1-3% of the mass of the polymerization monomer; the polymerization reaction temperature is 75-85° C., and the polymerization reaction time is 20-30 h.

[0030] Preferably, the film-forming aid is selected from one or more of ethylene glycol butyl ether, ethylene glycol ethyl ether, propylene glycol butyl ether, and propylene glycol ethyl ether; and the thickening thixotropic agent is BYK Laponite-RD.

[0031] Preferably, in parts by weight, the components of the first layer of resin slurry in step (3) include: 50 parts of epoxy resin, 10 to 15 parts of talc, 1.5 to 2 parts of curing agent, and 2 to 3 parts of epoxy resin curing accelerator; the components of the second layer of resin slurry include: 50 parts of epoxy resin, 25 to 35 parts of talc, 1.5 to 2 parts of curing agent, and 2 to 2.5 parts of epoxy resin curing accelerator.

[0032] Preferably, the epoxy resin is selected from one or both of epoxy resin E-51 and epoxy resin E-44; and the curing agent is an aliphatic amine curing agent.

[0033] Therefore, the present invention has the following beneficial effects:

[0034] (1) The glass slag layer, the metal paint layer and the resin layer with glass fiber cloth are arranged in sequence. The glass slag layer can form a natural texture with a granular feel, the metal paint layer can make the sculpture surface have a metallic texture, and the glass slag layer can protect the metal paint layer to prevent the metal paint layer from contacting with the external environment and being oxidized; the inner resin layer plays a shaping role. Under the joint action of the three layers, a sculpture with a bright metallic texture and a natural texture with a granular feel and a long service life can be obtained;

[0035] (2) Use water-based metallic paint to spray the surface of the glass slag layer. Water-based metallic paint uses water as a diluent, does not contain harmful solvents, has low VOC emissions, has little pollution to the environment, and does not harm human health;

[0036] (3) The metallic pigments in the water-based metallic paint are coated with a silica layer and a polymer layer to avoid the corrosion of the copper-gold powder in the water-based metallic paint. The directional arrangement performance of the copper-gold powder is improved by introducing the silane-modified cashew phenol sulfonate monomer in the polymer layer, thereby improving the glossiness of the metallic paint layer on the sculpture surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is a physical picture of the sculpture obtained in Example 1 of the present invention. DETAILED DESCRIPTION

[0038] The present invention will be further described below with reference to the accompanying drawings and specific embodiments.

[0039] In the present invention, unless otherwise specified, all raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments, unless otherwise specified, are all conventional methods in the art.

[0040] Example 1:

[0041] A sculpture production process with a metallic and natural texture, the steps are as follows:

[0042] (1) Polish the inner surface of the female mold of the sculpture mold until smooth, clean it, and dry it; add crushed glass slag into a transparent two-component epoxy resin adhesive (3M DP100), stir it evenly, and then spread it on the inner surface of the female mold of the sculpture mold and compact it to obtain a glass slag layer;

[0043] (2) After the adhesive solidifies, spray water-based metallic paint on the surface of the glass slag layer. Do not spray directly when spraying, pay more attention to side spraying, keep the spray gun 22 cm away from the spraying surface, and spray in a windless, dry environment at room temperature of 25°C; spray three times to obtain a metallic paint layer;

[0044] (3) After the metallic paint layer is completely dry, a first layer of resin slurry is applied on the surface of the metallic paint layer with a coating thickness of 50 mm; the components of the first layer of resin slurry include, by weight, 50 parts of epoxy resin E-51, 10 parts of talc powder, 1.8 parts of ethylenediamine curing agent, and 2.4 parts of epoxy resin curing accelerator DMP-30; after the resin slurry solidifies, a layer of glass fiber cloth is laid on the surface thereof, with each small piece of glass fiber cloth overlapping by 2 cm; then a second layer of resin slurry is applied on the glass fiber cloth with a coating thickness of 50 mm; the components of the second layer of resin slurry include, by weight, 50 parts of epoxy resin, 30 parts of talc powder, 1.6 parts of ethylenediamine curing agent, and 2.4 parts of epoxy resin curing accelerator DMP-30; after solidification, a resin layer is obtained;

[0045] (4) Place a supporting steel piece on the back of the resin layer, and then trim it so that the turned decorative surface does not exceed the edge of the female mold;

[0046] (5) After all the female molds are made according to the above method, they are spliced ​​together, and then the edge lines are filled in the order of glass slag layer, metal paint layer, and resin layer;

[0047] (6) Connect the supporting steel parts into a whole, remove the outer mold, and then polish the surface to obtain the following Figure 1 The sculpture shown has a metallic, natural-looking surface.

[0048] The components of the water-based metallic paint used in step (2) include, by weight, 10 parts of water-based copper-gold paste, 50 parts of water-based acrylic emulsion (Dow Maincote HG-100, solid content 47.5%), 4 parts of ethylene glycol butyl ether, 6 parts of Byk Laponite-RD, and 45 parts of water. The preparation method of the water-based copper-gold paste is as follows:

[0049] A) adding cardanol to dichloromethane, stirring and dissolving in an ice-water bath, and then adding fuming sulfuric acid, the volume ratio of cardanol to fuming sulfuric acid being 10:5.5, and performing an aging reaction at room temperature for 4 hours; after completion of the reaction, separating the solvent, dissolving the product with ethanol, and then neutralizing it with sodium hydroxide solution to pH=6.6, filtering and drying to obtain cardanol sulfonate;

[0050] B) mixing cardanol sulfonate and epichlorohydrin, stirring evenly, adding benzyltriethylammonium chloride, etherification reaction at 80° C. for 3 h, adding sodium hydroxide solution, ring-closing reaction at 60° C. for 3 h, separating the solvent to obtain epoxidized cardanol sulfonate; wherein the molar ratio of the added cardanol sulfonate, epichlorohydrin and sodium hydroxide is 1:4:1.3; the mass of the added benzyltriethylammonium chloride is 2.5% of the total mass of the cardanol sulfonate and epichlorohydrin; mixing the epoxidized cardanol sulfonate with γ-aminopropyltriethoxysilane in a molar ratio of 1:1.5, stirring and reacting at 60° C. for 4 h to obtain silane-modified cardanol sulfonate;

[0051] C) Copper-gold powder (Zhongke Aimi (Shenzhen) New Materials Co., Ltd., particle size 8-12 μm) was dispersed in anhydrous ethanol, deoxygenated with nitrogen, and then tetraethyl orthosilicate and vinyl triethoxysilane were added. After stirring, an ethanol aqueous solution (ethanol:water = 7:3 v / v) and 25 wt% ammonia water were added dropwise. The volume ratio of the copper-gold powder to the tetraethyl orthosilicate, vinyl triethoxysilane, ethanol aqueous solution, and ammonia water was 2 g:2.5 mL:4 mL:40 mL:5 mL. The mixture was hydrolyzed at 50° C. for 6 h to obtain a silica-coated modified copper-gold paste.

[0052] D) adding azobisisobutyronitrile to the obtained silica-coated modified copper-gold paste, and then dropwise adding a polymerization monomer, wherein the polymerization monomer consists of silane-modified cardanol sulfonate, methacrylic acid, and hydroxyethyl methacrylate in a mass ratio of 1:7:9, the mass ratio of the total mass of the polymerization monomer to the copper-gold powder added in step C) is 5:2, and the mass of the added azobisisobutyronitrile is 2% of the mass of the polymerization monomer; after the polymerization reaction is carried out at 80° C. for 24 hours, the product is filter-pressed to obtain the aqueous copper-gold paste.

[0053] Example 2:

[0054] The production process of the sculpture in Example 2 is the same as that in Example 1. The components of the water-based metallic paint used in step (2) include, by weight: 8 parts of water-based copper-gold paste, 40 parts of water-based acrylic emulsion (Dow Maincote HG-100, solid content 47.5%), 3 parts of ethylene glycol butyl ether, 5 parts of Byk Laponite-RD, and 40 parts of water;

[0055] The preparation method of water-based copper-gold slurry is as follows:

[0056] A) adding cardanol to dichloromethane, stirring and dissolving in an ice-water bath, and then adding fuming sulfuric acid, the volume ratio of cardanol to fuming sulfuric acid being 10:5, and performing an aging reaction at room temperature for 3 hours; after completion of the reaction, separating the solvent, dissolving the product with ethanol, and then neutralizing it with sodium hydroxide solution to pH=6.2, filtering and drying to obtain cardanol sulfonate;

[0057] B) mixing cardanol sulfonate and epichlorohydrin, stirring evenly, adding benzyltriethylammonium chloride, etherification reaction at 70° C. for 4 hours, adding sodium hydroxide solution, ring-closing reaction at 50° C. for 4 hours, separating the solvent to obtain epoxidized cardanol sulfonate; wherein the molar ratio of the added cardanol sulfonate, epichlorohydrin and sodium hydroxide is 1:3:1; the mass of the added benzyltriethylammonium chloride is 2% of the total mass of the cardanol sulfonate and epichlorohydrin; mixing the epoxidized cardanol sulfonate with γ-aminopropyltriethoxysilane in a molar ratio of 1:1, stirring and reacting at 70° C. for 3 hours, to obtain silane-modified cardanol sulfonate;

[0058] C) Copper-gold powder (Zhongke Aimi (Shenzhen) New Materials Co., Ltd., particle size 8-12 μm) was dispersed in anhydrous ethanol, deoxygenated with nitrogen, and then tetraethyl orthosilicate and vinyl triethoxysilane were added. After stirring, an ethanol aqueous solution (ethanol:water = 9:1 v / v) and 25 wt% ammonia water were added dropwise. The volume ratio of the copper-gold powder to the tetraethyl orthosilicate, vinyl triethoxysilane, ethanol aqueous solution, and ammonia water was 2 g:2 mL:4.5 mL:45 mL:3 mL. The mixture was hydrolyzed at 40°C for 7 h to obtain a silica-coated modified copper-gold paste.

[0059] D) adding azobisisobutyronitrile to the obtained silica-coated modified copper-gold paste, and then dropwise adding a polymerization monomer, wherein the polymerization monomer consists of silane-modified cardanol sulfonate, methacrylic acid, and hydroxyethyl methacrylate in a mass ratio of 1:6:10, the mass ratio of the total mass of the polymerization monomer to the copper-gold powder added in step C) is 4:2, and the mass of the added azobisisobutyronitrile is 1% of the mass of the polymerization monomer; after the polymerization reaction is carried out at 85° C. for 24 hours, the product is filter-pressed to obtain the aqueous copper-gold paste.

[0060] Example 3:

[0061] The production process of the sculpture in Example 3 is the same as that in Example 1. The components of the water-based metallic paint used in step (2) include, by weight: 12 parts of water-based copper-gold paste, 60 parts of water-based acrylic emulsion (Dow Maincote HG-100, solid content 47.5%), 5 parts of ethylene glycol butyl ether, 8 parts of Byk Laponite-RD, and 50 parts of water;

[0062] The preparation method of water-based copper-gold slurry is as follows:

[0063] A) adding cardanol to dichloromethane, stirring and dissolving in an ice-water bath, and then adding fuming sulfuric acid, the volume ratio of cardanol to fuming sulfuric acid being 10:6, and performing an aging reaction at room temperature for 5 hours; after completion of the reaction, separating the solvent, dissolving the product with ethanol, and then neutralizing it with sodium hydroxide solution to pH=6.8, filtering and drying to obtain cardanol sulfonate;

[0064] B) mixing cardanol sulfonate and epichlorohydrin, stirring evenly, adding benzyltriethylammonium chloride, etherification reaction at 90° C. for 2 h, adding sodium hydroxide solution, ring-closing reaction at 70° C. for 2 h, separating the solvent to obtain epoxidized cardanol sulfonate; wherein the molar ratio of the added cardanol sulfonate, epichlorohydrin and sodium hydroxide is 1:5:1.5; the mass of the added benzyltriethylammonium chloride is 3% of the total mass of the cardanol sulfonate and epichlorohydrin; mixing the epoxidized cardanol sulfonate with γ-aminopropyltriethoxysilane in a molar ratio of 1:2, stirring and reacting at 50° C. for 5 h to obtain silane-modified cardanol sulfonate;

[0065] C) Copper-gold powder (Zhongke Aimi (Shenzhen) New Materials Co., Ltd., particle size 8-12 μm) was dispersed in anhydrous ethanol, deoxygenated with nitrogen, and then tetraethyl orthosilicate and vinyl triethoxysilane were added. After stirring, an ethanol aqueous solution (ethanol:water = 7:3 v / v) and 25 wt% ammonia water were added dropwise. The volume ratio of the copper-gold powder to the tetraethyl orthosilicate, vinyl triethoxysilane, ethanol aqueous solution, and ammonia water was 2 g:3 mL:3 mL:35 mL:6 mL. The mixture was hydrolyzed at 60° C. for 5 h to obtain a silica-coated modified copper-gold paste.

[0066] D) adding azobisisobutyronitrile to the obtained silica-coated modified copper-gold paste, and then dropwise adding a polymerization monomer, wherein the polymerization monomer consists of silane-modified cardanol sulfonate, methacrylic acid, and hydroxyethyl methacrylate in a mass ratio of 1:9:8, the mass ratio of the total mass of the polymerization monomer to the copper-gold powder added in step C) is 6:2, and the mass of the added azobisisobutyronitrile is 3% of the mass of the polymerization monomer; after the polymerization reaction is carried out at 75° C. for 24 hours, the product is filter-pressed to obtain the aqueous copper-gold paste.

[0067] Comparative Example 1 (Silane-modified cardanol sulfonate monomer is not added to the polymer layer):

[0068] In the water-based metallic paint used in Comparative Example 1, the preparation method of the water-based copper-gold paste is as follows:

[0069] A) Copper-gold powder (Zhongke Aimi (Shenzhen) New Materials Co., Ltd., particle size 8-12 μm) was dispersed in anhydrous ethanol. After nitrogen deoxygenation, tetraethyl orthosilicate and vinyl triethoxysilane were added. After stirring, an ethanol aqueous solution (ethanol:water = 7:3 v / v) and 25 wt% ammonia water were added dropwise. The volume ratio of copper-gold powder mass to tetraethyl orthosilicate, vinyl triethoxysilane, ethanol aqueous solution, and ammonia water was 2 g:2.5 mL:4 mL:40 mL:5 mL. The mixture was hydrolyzed at 50°C for 6 h to obtain a silica-coated modified copper-gold paste.

[0070] B) adding azobisisobutyronitrile to the obtained silica-coated modified copper-gold paste, and then dropwise adding a polymerization monomer, wherein the polymerization monomer consists of methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 7:9, the mass ratio of the total mass of the polymerization monomer to the copper-gold powder added in step A) is 5:2, and the mass of the added azobisisobutyronitrile is 2% of the mass of the polymerization monomer; after a polymerization reaction at 80° C. for 24 hours, the product is filter-pressed to obtain the aqueous copper-gold paste;

[0071] The rest are the same as in Example 1.

[0072] Comparative Example 2 (cardanol sulfonate without silane modification):

[0073] In the water-based metallic paint used in Comparative Example 2, the preparation method of the water-based copper-gold paste is as follows:

[0074] A) adding cardanol to dichloromethane, stirring and dissolving in an ice-water bath, and then adding fuming sulfuric acid, the volume ratio of cardanol to fuming sulfuric acid being 10:5.5, and performing an aging reaction at room temperature for 4 hours; after completion of the reaction, separating the solvent, dissolving the product with ethanol, and then neutralizing it with sodium hydroxide solution to pH=6.6, filtering and drying to obtain cardanol sulfonate;

[0075] B) Copper-gold powder (Zhongke Aimi (Shenzhen) New Materials Co., Ltd., particle size 8-12 μm) was dispersed in anhydrous ethanol. After deoxygenation through nitrogen, tetraethyl orthosilicate and vinyl triethoxysilane were added. After stirring, an ethanol aqueous solution (ethanol:water = 7:3 v / v) and 25 wt% ammonia water were added dropwise. The volume ratio of the copper-gold powder to the tetraethyl orthosilicate, vinyl triethoxysilane, ethanol aqueous solution, and ammonia water was 2 g:2.5 mL:4 mL:40 mL:5 mL. The mixture was hydrolyzed at 50°C for 6 h to obtain a silica-coated modified copper-gold paste.

[0076] C) adding azobisisobutyronitrile to the obtained silica-coated modified copper-gold paste, and then dropwise adding a polymerization monomer, wherein the polymerization monomer consists of cardanol sulfonate, methacrylic acid, and hydroxyethyl methacrylate in a mass ratio of 1:7:9, the mass ratio of the total mass of the polymerization monomer to the copper-gold powder added in step C) is 5:2, and the mass of the added azobisisobutyronitrile is 2% of the mass of the polymerization monomer; after a polymerization reaction at 80° C. for 24 hours, the product is filter-pressed to obtain the aqueous copper-gold paste;

[0077] The rest are the same as in Example 1.

[0078] The performance of the water-based metallic paints in the above examples and comparative examples was tested, and the results are shown in Table 1. During testing, the resulting water-based metallic paint was evenly sprayed onto a tinplate, then placed in a vacuum drying oven and dried at 70°C for 72 hours to obtain a test sample. The water resistance of the paint film was tested according to GB / T 1733-1993; the corrosion resistance was tested according to GB / T 1771-2007; and the aging resistance was tested according to GB / T 1865-2009. Gloss was measured using a KGZ-1C gloss meter; and the dynamic color index (FI) was measured using an MA68II multi-angle spectrophotometer.

[0079] Table 1: Metallic paint film performance test results.

[0080]

[0081] As can be seen from Table 1, the metal paint films obtained by using the water-based metallic paint of the present invention in Examples 1 to 3 have good water resistance and corrosion resistance, which can ensure that the sculpture has a long service life; and the paint films have high gloss and dynamic color index, which can make the sculpture surface have good metallic gloss and metallic glitter effect (the larger the FI value, the more regular the arrangement of the copper and gold powder in the paint film, and the better the glitter effect of the paint film).

[0082] In Comparative Example 1, however, no silane-modified cardanol sulfonate monomer was added to the polymer coating on the surface of the copper-gold powder. The gloss and FI value of the paint film were significantly lower than those in Example 1. This may be due to the lack of the silane-modified cardanol sulfonate monomer, which was not conducive to the flow and directional arrangement of the copper-gold powder in the coating film. The metallic pigment in the paint film was distributed in a disordered manner, affecting its gloss and sparkle effect (i.e., the angular flop effect). In Comparative Example 2, cardanol sulfonate monomer was used for polymerization when the copper-gold powder was coated with the polymer layer, without silane modification. The gloss and FI value of the paint film were also reduced, indicating that the introduction of silicon-containing groups is beneficial to improving the gloss and angular flop effect of the metallic paint film.

Claims

1. A sculpture production process with a metal surface and natural texture, characterized by the following steps: include: (1) Add glass slag to a transparent adhesive, stir evenly, and spread it on the inner surface of the female mold of the sculpture mold; (2) After the adhesive solidifies, spray water-based metallic paint on the surface of the glass slag to obtain a metallic paint layer; The components of the water-based metallic paint include, by weight: 8 to 12 parts of water-based copper-gold paste, 40 to 60 parts of water-based acrylic emulsion, 3 to 5 parts of film-forming aid, 5 to 8 parts of thickening thixotropic agent, and 40 to 50 parts of water; The preparation method of water-based copper-gold slurry is as follows: A) adding cardanol to dichloromethane, stirring in an ice-water bath to dissolve, then adding fuming sulfuric acid, and aging reaction at room temperature; after the reaction, separating the solvent, dissolving the product in ethanol, neutralizing with NaOH solution, filtering and drying; B) mixing the product of step A) and epichlorohydrin, stirring uniformly, adding benzyltriethylammonium chloride, and after etherification, adding NaOH solution to carry out ring closure reaction. After separating the solvent, mixing the product with APTES to react, thereby obtaining silane-modified cardanol sulfonate; C) Disperse the copper and gold powder in anhydrous ethanol, remove oxygen through nitrogen, add TEOS and vinyl triethoxysilane, stir evenly, and then dropwise add ethanol aqueous solution and ammonia water to carry out hydrolysis reaction; D) adding AIBN to the product obtained in step C), and then dropwise adding a polymerization monomer comprising silane-modified cardanol sulfonate, methacrylic acid, and HEMA in a mass ratio of 1:6-9:8-10. After the polymerization reaction, the product is filtered to obtain an aqueous copper-gold slurry; (3) After the metallic paint layer is dried, a first layer of resin slurry is applied on its surface. After the resin slurry solidifies, glass fiber cloth is laid on its surface. Then, a second layer of resin slurry is applied, and after solidification, a resin layer is obtained. (4) Place a supporting steel piece on the back of the resin layer, and then trim it so that the turned decorative surface does not exceed the edge of the female mold; (5) After all the female molds are made according to the above method, they are spliced ​​together and then the edges are filled; (6) Connect all supporting steel parts into a whole, remove the outer mold, and then polish the surface.

2. The sculpture production process according to claim 1, characterized in that: The adhesive used in step (1) is selected from one of polyurethane adhesive, polyacrylic resin adhesive, silicone adhesive and epoxy resin adhesive.

3. The sculpture production process according to claim 1, characterized in that: In parts by weight, the solid content of the water-based acrylic emulsion in the water-based metallic paint in step (2) is 40-50 wt %.

4. The sculpture production process according to claim 1, characterized in that: In step A), the volume ratio of cardanol to fuming sulfuric acid is 10:5-6, the aging reaction time is 3-5 hours, and the solution is neutralized with sodium hydroxide solution to a pH of 6-7.

5. The sculpture production process according to claim 1, characterized in that: The molar ratio of cardanol sulfonate, epichlorohydrin, and sodium hydroxide added in step B) is 1:3-5:1-1.5; the mass of benzyltriethylammonium chloride added is 2-3% of the total mass of cardanol sulfonate and epichlorohydrin; the etherification reaction temperature is 70-90°C, and the etherification reaction time is 2-4 hours; the ring-closing reaction temperature is 50-70°C, and the ring-closing reaction time is 2-4 hours; The molar ratio of epoxidized cardanol sulfonate to γ-aminopropyltriethoxysilane is 1:1-2, the mixed reaction temperature of epoxidized cardanol sulfonate and γ-aminopropyltriethoxysilane is 50-70° C., and the reaction time is 3-5 hours.

6. The sculpture production process according to claim 1, characterized in that: In step C), the volume ratio of ethanol to water in the added ethanol aqueous solution is 7:3-9:1, and the mass fraction of ammonia water is 25-28%. The volume ratio of the copper-gold powder to the added ethyl orthosilicate, vinyl triethoxysilane, ethanol aqueous solution, and ammonia water is 2 g: 2-3 mL: 3-4.5 mL: 35-45 mL: 3-6 mL. The hydrolysis reaction temperature is 40-60° C., and the hydrolysis reaction time is 5-7 h.

7. The sculpture production process according to claim 1 is characterized in that: The mass ratio of the polymerization monomer added in step D) to the copper-gold powder added in step C) is 4-6:2; the mass of azobisisobutyronitrile is 1-3% of the mass of the polymerization monomer; the polymerization reaction temperature is 75-85° C., and the polymerization reaction time is 20-30 hours.

8. The sculpture production process according to claim 1, characterized in that: The film-forming aid is selected from one or more of ethylene glycol butyl ether, ethylene glycol ethyl ether, propylene glycol butyl ether, and propylene glycol ethyl ether; and the thickening thixotropic agent is BYK Laponite-RD.

9. The sculpture production process according to claim 1, characterized in that: In parts by weight, the components of the first layer of resin slurry in step (3) include: 50 parts of epoxy resin, 10-15 parts of talc, 1.5-2 parts of curing agent, and 2-3 parts of epoxy resin curing accelerator; the components of the second layer of resin slurry include: 50 parts of epoxy resin, 25-35 parts of talc, 1.5-2 parts of curing agent, and 2-2.5 parts of epoxy resin curing accelerator.

Images