Resin handicraft and production method thereof

Abstract

The invention relates to the field of handicraft processing, and particularly discloses a resin handicraft and a production method thereof. The resin artware is prepared from the following raw materials in parts by weight: 100 parts of epoxy resin, 15 to 20 parts of epoxy curing agent, 400 to 1000 parts of filler, 0.1 to 0.5 part of color master batch, 0.2 to 1 part of antioxidant, 0.5 to 1.5 parts of defoaming agent and 1.2 to 2 parts of dispersing agent, the color master batch is prepared from the following raw materials: 10 to 15 parts of inorganic jade pigment, 10 to 15 parts of ramie fiber, 20 to 30 parts of tea stem extract and 10 to 20 parts of tung oil / gutta-percha polymer. The resin handicraft has high glossiness and ultraviolet stability, and color change is not prone to occurring after ultraviolet irradiation.

Description

Technical Field

[0001] This application relates to the technical field of handicraft processing and production. More specifically, it relates to a resin handicraft and its production method. Background Art

[0002] In recent years, with the rapid development of the national economy and the rapid improvement of people's living standards, resin handicrafts have been increasingly favored by users. The production processes of colored sculptures, decorative ornaments, antique handicrafts, and personalized customized products are to mix resin raw materials with fillers and pigments in a certain proportion, obtain a slurry, then add appropriate amounts of curing agents, initiators and other additives, mix well and pour into a mold of the required shape, and perform vacuum pumping and slurry shaking processes according to the product requirements. After demolding, trimming the blank and grinding the bottom can obtain the finished resin handicraft.

[0003] Masterbatch is a colorant composed of pigments, resins and additives, with advantages such as high coloring power, good dispersibility, and easy use. By adding masterbatch to resin raw materials, resin handicrafts can present various bright colors, thus increasing the ornamental value and market competitiveness of handicrafts. Currently, the main method for preparing masterbatch is to disperse inorganic color powder in resin materials, and by adding dispersants, compatibilizers such as polyethylene wax and polyamide wax, and other additives, to improve the dispersibility and compatibility of inorganic color powder in resin materials, and then improve the coloring effect of masterbatch in handicrafts. However, during the use of resin handicrafts, if they are exposed to sunlight, ultraviolet rays and other environments for a long time, the colors of resin handicrafts will fade or peel off, thus reducing the color fastness of resin handicrafts. Summary of the Invention

[0004] In order to improve the ultraviolet stability of masterbatch in resin handicrafts and enhance the color fastness, this application provides a resin handicraft and its production method.

[0005] In the first aspect, this application provides a resin handicraft, adopting the following technical solution: A resin handicraft, comprising the following raw materials in parts by weight: 100 parts of epoxy resin, 15 - 20 parts of epoxy curing agent, 400 - 1000 parts of filler, 0.1 - 0.5 part of masterbatch, 0.2 - 1 part of antioxidant, 0.5 - 1.5 parts of defoamer, 1.2 - 2 parts of dispersant; The masterbatch comprises the following raw materials: 10 - 15 parts of inorganic jade color pigment, 10 - 15 parts of ramie fiber, 20 - 30 parts of tea stalk extract, 10 - 20 parts of tung oil / eucommia gum polymer.

[0006] By adopting the above technical solution, epoxy resin is used as the main material. Epoxy resin has a low hardening shrinkage rate, and the handicrafts made from it have good dimensional stability, are not easily deformed, and also have good corrosion resistance and high mechanical strength, and can withstand large pressures and impacts. At the same time, it has strong processing flexibility and is suitable for various molding methods. When preparing the masterbatch, inorganic jade-colored pigments, ramie fibers, tea stalk extracts, and tung oil / Eucommia gum polymers are used as raw materials. The tea stalk extracts are obtained by extracting tea stalks. Tea stalks are the leftovers generated during tea processing, providing a rich raw material source for the extraction of natural functional substances. Tea polyphenols are the main natural functional organic compounds in tea, and have good functions such as ultraviolet protection, antioxidant, and radiation protection. The ultraviolet transmittance of ramie fibers is low, and their ultraviolet resistance is strong. Moreover, ramie fibers are relatively tough, which can significantly enhance the structural strength and durability of resin handicrafts and extend their service life. The tung oil / Eucommia gum polymer is prepared by the DA reaction of tung oil and Eucommia gum. It has good compatibility with epoxy resin, and after being blended with epoxy resin, it can form an interpenetrating network structure to wrap the ramie fibers, inorganic jade-colored pigments, and tea stalk extracts, improve the adhesion of pigments and the flexibility of resin handicrafts, enhance the overall resistance of the resin to ultraviolet light, reduce ultraviolet aging and fading, and make the surface of the resin handicrafts denser and smoother. In addition, the tung oil / Eucommia gum polymer contains hydrophobic molecular chains, thereby improving the hydrophobic performance of resin handicrafts and enhancing the protection ability. Therefore, using ramie fibers as the carrier and tea stalk extracts as the auxiliary loading agent, inorganic jade-colored dyes are loaded on the ramie fibers, and the compatibility between ramie fibers and epoxy resin is improved by the tung oil / Eucommia gum polymer, thereby making a masterbatch with a special jade color. Moreover, after adding ramie fibers, the jade-like resin handicrafts can also have a unique natural beauty and texture, enhancing the overall ornamental value.

[0007] Optionally, the masterbatch is made by the following method: Mix the tea stalk extracts with the inorganic jade-colored pigments, add them to water, stir and dissolve to obtain a treatment solution; Cut the irradiated ramie fibers into pieces and immerse them in the treatment solution, adjust the pH to 8-9, add silver nitrate solution, heat up to 40-50 °C, stir, filter, and dry to obtain silver-loaded ramie fibers; Add the tung oil / Eucommia gum polymer to xylene, ultrasonically disperse it, and then evenly coat it on the silver-loaded ramie fibers, dry and crush.

[0008] By adopting the above technical solution, a treatment liquid is prepared by mixing tea stalk extract and inorganic jade-colored pigment. The ramie fiber is irradiated to improve the roughness of the ramie fiber surface, increase the content of surface active groups on the ramie fiber, enhance the affinity between the ramie fiber and the pigment, and optimize the dyeing effect. Then the ramie fiber is impregnated into the treatment liquid. The main components of the ramie fiber include cellulose, hemicellulose, pectin, lignin, etc. Among these components, the macromolecules of cellulose and hemicellulose contain free hydroxyl and carboxyl groups, which have good hydrophilic adsorption properties and can adsorb more tea stalk extract and inorganic jade-colored pigment. At the same time, it provides a good transition and connection effect for the subsequent coating of tung oil / eucommia gum polymer, and improves the uniformity of the coating of tung oil / eucommia gum polymer on the surface of silver-loaded ramie fiber. Moreover, after the ramie fiber is impregnated into the treatment liquid, the pH is adjusted to alkaline, and silver nitrate solution is added. Under alkaline conditions, the dissociation of the phenolic compound hydroxyl group in the tea stalk extract makes it have strong reducing ability, so that nano-silver is formed on the surface of the ramie fiber. And the tea stalk extract can also improve the dispersion of nano-silver and reduce aggregation. Nano-silver has a scattering effect on ultraviolet rays. Therefore, the loading of nano-silver can improve the anti-ultraviolet ability and antibacterial property of the ramie fiber, and part of the unreacted tea stalk extract is adsorbed on the ramie fiber to enhance its ultraviolet protection performance, so that the ramie fiber has strong anti-ultraviolet stability. Therefore, it can improve the color ultraviolet stability of the resin handicraft, and after ultraviolet irradiation, the color change is small.

[0009] Optionally, the inorganic jade-colored pigment is pretreated as follows: The inorganic jade-colored pigment is mixed with silane coupling agent KH550 and water, stirred evenly, and dried to obtain a coupling-modified pigment; The silk fibroin nanofiber, the coupling-modified pigment, absolute ethanol and water are mixed evenly, and filtered by suction until the filtrate is colorless and dried.

[0010] By adopting the above technical solutions, inorganic jade-colored pigments are prone to agglomeration during use. Therefore, when the inorganic jade-colored pigments are dispersed to form a treatment liquid, the dispersion stability needs to be improved. The silane coupling agent KH550 and the inorganic jade-colored pigments are first treated, and the inorganic jade-colored pigments are surface-modified by using the silane coupling agent KH550 to achieve surface coating modification of the inorganic jade-colored pigments. The silane coupling agent KH550 is γ-aminopropyltriethoxysilane, which forms Si-OH after hydrolysis, and then the silanol reacts with the hydroxyl groups on the surface of the inorganic jade-colored pigments and firmly binds to achieve the purpose of coupling modification, thereby increasing the dispersion stability of the inorganic jade-colored pigments. Then, the silk fibroin nanofibers and the coupled and modified pigments are mixed and filtered until colorless. Because the silk fibroin contains amide functional groups and the silk fibroin nanofibers have a strong size effect and strong adsorption ability, during filtration, the silk fibroin nanofibers adsorb the inorganic jade-colored pigments by using their high specific surface area and functional groups, effectively restricting the movement of the pigment particles, enabling the pigments to withstand ultraviolet irradiation without ultraviolet fading, and enhancing the ultraviolet color fastness ability of the pigments in the resin crafts.

[0011] Optionally, the mass ratio of the inorganic jade-colored pigment to the silane coupling agent KH550 is 1.5:0.045 - 0.05; The mass ratio of the silk fibroin nanofibers to the coupled and modified pigments is 1:0.5 - 1.

[0012] By adopting the above technical solutions, the above-mentioned raw material dosages of the inorganic jade-colored pigment, the silane coupling agent, and the silk fibroin nanofibers can better disperse the pigment and enhance its light stability under ultraviolet irradiation.

[0013] Optionally, the preparation method of the tea stalk extract is as follows: The tea stalks and pure water are mixed, shaken in a water bath at 90°C - 100°C for 50 - 60 min, filtered, concentrated, and dried to obtain the tea stalk extract. The mass ratio of the tea stalks to the pure water is 1:18 - 20.

[0014] By adopting the above technical solutions, extraction with pure water is non-toxic, harmless, safer, and has lower costs, simple operation, and high extraction efficiency.

[0015] Optionally, the filler is selected from at least one of nano calcium carbonate, nano barium sulfate, talcum powder, ultrafine wollastonite, silica powder, and gypsum.

[0016] By adopting the above technical solutions, as an inorganic rigid particle filler, when mixed with epoxy resin, etc., it can promote an appropriate increase in the viscosity of the system, increase the shear effect of the blend, effectively prevent the agglomeration of pigment particles, and thus improve the dispersion of pigment particles in the epoxy resin blend system.

[0017] Optionally, the inorganic jade-colored pigments are selected from at least two of chromium oxide green, lead chromium green, iron blue, cobalt blue, ultramarine, lead chrome yellow, zinc chrome yellow, cadmium yellow, iron yellow, iron oxide red, carbon black, and titanium dioxide.

[0018] Optionally, the epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin, and brominated epoxy resin; The defoamer is selected from at least one of polydimethylsiloxane, tributyl phosphate, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, and polyacrylamide; The antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076, and antioxidant 215; The curing agent is at least one of polyetheramine, ethylenediamine, diethylenetriamine, m-phenylenediamine, phthalic anhydride, and pyromellitic dianhydride; The dispersant is selected from at least one of polyethylene wax, polyamide wax, and paraffin wax.

[0019] In a second aspect, the present application provides a production method for resin handicrafts, adopting the following technical solution: A production method for resin handicrafts, comprising the following steps: Mix the epoxy resin with the filler, color masterbatch, antioxidant, defoamer, and dispersant, heat up to 110 - 120 °C, and stir evenly to obtain a stock solution; Inject the stock solution into a mold, evacuate to remove air bubbles, demold after standing at room temperature for 10 - 12 h, and shape at 70 - 80 °C to obtain a preliminary embryo. Trim the defects of the preliminary embryo, spray transparent paint, and perform drying treatment to obtain the resin handicraft.

[0020] By adopting the above technical solution, after injecting the stock solution prepared by mixing various raw materials into the mold, evacuate to remove air bubbles, eliminate the air bubbles inside the surface of the handicraft, increase the density, and the spraying of the transparent paint can make the surface of the handicraft smoother and more shiny.

[0021] Optionally, the transparent paint comprises an inorganic nano-ceramic coating and nano-titanium nitride, and micron alumina in a mass ratio of 1:0.01 - 0.02:0.05 - 0.1.

[0022] By adopting the above technical solution, the inorganic nano-ceramic coating has excellent film-forming property and flexibility, and also has very good fireproof and flame-retardant properties, scratch resistance, acid and alkali resistance, and weather resistance. Adding titanium nitride nanoparticles and alumina microparticles to the inorganic nano-ceramic coating, both titanium nitride nanoparticles and alumina microparticles have excellent stability and ultraviolet shielding effect, can absorb a large amount of ultraviolet rays to protect resin handicrafts, reduce color change, and titanium nitride nanoparticles and alumina microparticles can fill the surface voids of the blank, fill the micro-holes, making it have good compactness, smoothness and hardness. Moreover, the alumina microparticles and titanium nitride nanoparticles cooperate with each other to form a micro-nano structure, obtaining a protective layer with strong hydrophobicity on the surface of the resin handicraft, increasing the hydrophobicity and gloss of the surface of the resin handicraft, and enhancing its anti-dust pollution effect.

[0023] Optionally, the titanium nitride nanoparticles and alumina microparticles are pretreated with a silane coupling agent.

[0024] By adopting the above technical solution, treating the titanium nitride nanoparticles and alumina microparticles with a silane coupling agent can improve their dispersibility in the inorganic nano-ceramic coating, and are closely cross-linked with the inorganic nano-ceramic coating through chemical bonds and hydrogen bonds, thereby improving the stability of the blank when exposed to light and reducing the surface damage during the ultraviolet aging process.

[0025] In summary, the present application has the following beneficial effects: 1. Since the present application uses ramie fiber as a pigment carrier, increases the loading effect of inorganic jade pigment on the surface of ramie fiber with tea stalk extract, uses tung oil / eucommia gum polymer as a compatible auxiliary material, and coats the dyed ramie fiber with tung oil / eucommia gum polymer to obtain a masterbatch. The tung oil / eucommia gum polymer has good compatibility with epoxy resin, can improve the dispersibility of the dyed ramie fiber in epoxy resin. Both ramie fiber and tea stalk extract have strong ultraviolet resistance, can enhance the ultraviolet stability of the inorganic jade pigment in the resin handicraft, reduce the color change after ultraviolet aging, and enhance the color stability.

[0026] 2. In the present application, it is preferably to pretreat the inorganic jade nanofibers with silane coupling agent KH550 and silk fibroin nanofibers. The silanol groups after hydrolysis of the silane coupling agent KH550 can react with the hydroxyl groups on the surface of the inorganic jade pigment to enhance its dispersion stability. Then, the high specific surface area and amide functional groups of the silk fibroin nanofibers are used to adsorb and fix the silane-modified pigments, restricting the movement of the pigment particles, so that no fading or color change occurs under ultraviolet irradiation.

[0027] 3. In the method of this application, it is preferably to spray a transparent paint containing inorganic nano-ceramic coating, nano-titanium nitride, and micron-sized alumina on the surface of the formed green body. The micron-sized alumina and nano-titanium nitride form a micro-nano structure on the surface of the green body, improving the hydrophobic effect and glossiness of the green body surface. At the same time, nano-titanium nitride and micron-sized alumina also have strong ultraviolet shielding effects, which can enhance the light stability of resin crafts and reduce the influence of light on the color of resin crafts. Detailed implementation manners

[0028] The following examples further illustrate this application in detail.

[0029] Preparation Example 1 of tung oil / eucommia gum polymer Preparation Example 1: Mix eucommia gum and xylene, heat in a water bath at 50 °C until the eucommia gum is completely dissolved, add tung oil, raise the temperature to 75 °C, condense for 8 h, wash 3 times with ethyl acetate, then wash 3 times with absolute ethanol, and dry to obtain a composite. Raise the temperature to 120 °C and polymerize for 6 h. The molar ratio of eucommia gum to tung oil is 1:1. In Preparation Example 2, the tung oil is selected from Guangzhou Hongyi Chemical Industry, with the product number hy12, and the eucommia gum is selected from Shaanxi Mufan Biotechnology, with the model MF-00163.

[0030] Preparation Examples 2 - 12 of masterbatch Preparation Example 2: (1) Mix 30 g of tea stalk extract with 20 g of inorganic jade-colored pigment, add to water, stir and dissolve to obtain a treatment solution. The concentration of tea stalk extract in the treatment solution is 2 g / L. The tea stalk extract is prepared by mixing 10 g of tea stalks and 200 mL of pure water, oscillating in a water bath at 90 °C for 60 min, filtering, concentrating, and drying. The inorganic jade-colored pigment is prepared by mixing chromium oxide green, cobalt blue, zinc chromate yellow, and titanium dioxide in a mass ratio of 1:1:1:1; (2) Cut 15 g of irradiated ramie fibers into pieces and immerse them in the treatment solution, raise the temperature to 50 °C, stir for 30 min, filter, and dry at 60 °C for 4 h to obtain pretreated ramie fibers. The irradiation treatment is carried out in a nitrogen atmosphere, with an electron energy of 4 MeV, an electron beam current of 200 μA, a dose rate of 50 Gy / s, and a dose of 40 kGy; (3) Add 20 g of tung oil / eucommia gum polymer to 12 g of xylene, ultrasonically disperse evenly and then coat it on the pretreated ramie fibers, dry at 80 °C for 12 h and then crush to 20 mm to obtain the masterbatch. The tung oil / eucommia gum polymer is prepared from Preparation Example 1.

[0031] Preparation Example 3: (1) 25 g of tea stalk extract was mixed with 13 g of inorganic jade-colored pigment, added to water, and stirred to dissolve to obtain a treatment solution. The concentration of tea stalk extract in the treatment solution was 2 g / L. The tea stalk extract was prepared by mixing 10 g of tea stalks and 190 mL of pure water, oscillating in a water bath at 100 °C for 60 min, filtering, concentrating, and drying. The inorganic jade-colored pigment was prepared by mixing chromium oxide green, cobalt blue, zinc chromate yellow, and titanium dioxide in a mass ratio of 1:1:1:1; (2) 13 g of irradiated ramie fibers were cut into pieces and impregnated into the treatment solution. The temperature was raised to 55 °C, stirred for 30 min, filtered, and dried at 60 °C for 4 h to obtain pretreated ramie fibers. The irradiation treatment was carried out in a nitrogen atmosphere, with an electron energy of 4 MeV, an electron beam current of 200 μA, a dose rate of 50 Gy / s, and a dose of 40 kGy; (3) 15 g of tung oil / eucommia gum polymer was added to 10 g of xylene, ultrasonically dispersed evenly, and then coated on the pretreated ramie fibers. After drying at 80 °C for 12 h, it was crushed to 20 mm to obtain masterbatch. The tung oil / eucommia gum polymer was prepared according to Preparation Example 1.

[0032] Preparation Example 4: (1) 20 g of tea stalk extract was mixed with 10 g of inorganic jade-colored pigment, added to water, and stirred to dissolve to obtain a treatment solution. The concentration of tea stalk extract in the treatment solution was 2 g / L. The tea stalk extract was prepared by mixing 10 g of tea stalks and 180 mL of pure water, oscillating in a water bath at 100 °C for 50 min, filtering, concentrating, and drying. The inorganic jade-colored pigment was prepared by mixing chromium oxide green, cobalt blue, zinc chromate yellow, and titanium dioxide in a mass ratio of 1:1:1:1; (2) 10 g of irradiated ramie fibers were cut into pieces and impregnated into the treatment solution. The temperature was raised to 60 °C, stirred for 30 min, filtered, and dried at 60 °C for 4 h to obtain pretreated ramie fibers. The irradiation treatment was carried out in a nitrogen atmosphere, with an electron energy of 4 MeV, an electron beam current of 200 μA, a dose rate of 50 Gy / s, and a dose of 40 kGy; (3) 10 g of tung oil / eucommia gum polymer was added to 6 g of xylene, ultrasonically dispersed evenly, and then coated on the pretreated ramie fibers. After drying at 80 °C for 12 h, it was crushed to 20 mm to obtain masterbatch. The tung oil / eucommia gum polymer was prepared according to Preparation Example 1.

[0033] Preparation Example 5: The difference from Preparation Example 2 is that no tea stalk extract was added.

[0034] Preparation Example 6: The difference from Preparation Example 2 is that tea stem extract and ramie fiber are not added. The specific method is: 20g of tung oil / eucommia gum polymer is added to 12g of xylene, and the mixture is evenly dispersed by ultrasonication and then mixed with 20g of inorganic jade pigment. The mixture is dried at 80°C for 12h and then crushed to 20mm to obtain a masterbatch. The tung oil / eucommia gum polymer is prepared by Preparation Example 1, and the inorganic jade pigment is prepared by mixing chromium oxide green, cobalt blue, zinc chrome yellow and titanium dioxide in a mass ratio of 1:1:1:1.

[0035] Preparation Example 7: The difference from Preparation Example 2 is that step (3) uses high-density PE of the same mass to replace the tung oil / eucommia gum polymer. Step (3) is specifically as follows: 20g of high-density PE is added to 12g of xylene, the temperature is raised to 80°C, and after complete dissolution, it is coated on the pretreated ramie fiber, dried at 80°C for 12h, and then crushed to 20mm to obtain a masterbatch. The high-density PE is selected from Dongguan Global Environmental Technology, model Bio-PE-L108.

[0036] Preparation Example 8: The difference from Preparation Example 2 is that in step (2), a silver nitrate solution is further added. The specific method is as follows: 15 g of irradiated ramie fiber is cut into pieces and immersed in the treatment solution, the pH is adjusted to 9 with a 0.1 mol / l sodium hydroxide solution, a 1 mM silver nitrate solution is added, the temperature is raised to 60°C, stirred for 30 min, filtered, and dried at 60°C for 4 h to obtain pretreated ramie fiber. The mass ratio of ramie fiber to silver nitrate solution is 1:3. The irradiation treatment is carried out in a nitrogen atmosphere, the electron energy is 4 MeV, the electron beam current is 200 μA, the dose rate is 50 Gy / s, and the dose is 40 kGy.

[0037] Preparation Example 9: The difference from Preparation Example 8 is that the inorganic jade pigment is pretreated as follows and then mixed with tea stem extract and water to prepare a treatment solution: 15g of inorganic jade pigment, 0.45g of silane coupling agent KH550 and 52g of water were mixed evenly, and dried at 80°C to obtain a coupled modified pigment; 20g of silk fibroin nanofibers were evenly mixed with 20g of coupled modified pigments, 30g of anhydrous ethanol and 200g of water, filtered until the filtrate was colorless, and dried at 60°C. The silk fibroin nanofibers were prepared by electrostatic spinning after mixing silk fibroin powder and 8% polyvinyl pyrrolidone in formic acid solution. The mass fraction of silk fibroin powder in the solution was 30%, the spinning voltage was 15kV, the spinning speed was 2ml / h, the receiving distance was 12cm, the molecular weight of polyvinyl pyrrolidone was 1300000, and the silk fibroin powder was selected from Xi'an Heshun Biotechnology, with the product number HS-071.

[0038] Preparation Example 10: The difference from Preparation Example 8 is that the inorganic jade pigment is pretreated as follows and then mixed with tea stem extract and water to prepare a treatment solution: Mix 15 g of inorganic jade-colored pigment, 0.5 g of silane coupling agent KH550, and 55 g of water evenly, and dry at 80 °C to obtain a coupling-modified pigment; Mix 20 g of silk fibroin nanofibers, 10 g of coupling-modified pigment, 30 g of absolute ethanol, and 200 g of water evenly, filter until the filtrate is colorless, and dry at 60 °C. The silk fibroin nanofibers are prepared by electrospinning a mixture of silk fibroin powder and a formic acid solution of polyvinylpyrrolidone with a concentration of 8%. The mass fraction of silk fibroin powder in the solution is 30%, the electrospinning voltage is 15 kV, the electrospinning speed is 2 ml / h, the receiving distance is 12 cm, the molecular weight of polyvinylpyrrolidone is 1,300,000, and the silk fibroin powder is selected from Xi'an Heshun Biotechnology, with the product number HS-071.

[0039] Preparation Example 11: The difference from Preparation Example 9 is that the inorganic jade-colored pigment is not modified with silane coupling agent KH550. The specific pretreatment method of the inorganic jade-colored pigment is as follows: Mix 20 g of silk fibroin nanofibers, 20 g of inorganic jade-colored pigment, 30 g of absolute ethanol, and 200 g of water evenly, filter until the filtrate is colorless, and dry at 60 °C. The silk fibroin nanofibers are prepared by electrospinning a mixture of silk fibroin powder and a formic acid solution of polyvinylpyrrolidone with a concentration of 8%. The mass fraction of silk fibroin powder in the solution is 30%, the electrospinning voltage is 15 kV, the electrospinning speed is 2 ml / h, the receiving distance is 12 cm, the molecular weight of polyvinylpyrrolidone is 1,300,000, and the silk fibroin powder is selected from Xi'an Heshun Biotechnology, with the product number HS-071.

[0040] Preparation Example 12: The difference from Preparation Example 9 is that silk fibroin nanofibers are not added during the pretreatment of the inorganic jade-colored pigment. The specific pretreatment method is as follows: Mix 15 g of inorganic jade-colored pigment, 0.45 g of silane coupling agent KH550, and 52 g of water evenly, and dry at 80 °C. Example

[0041] Example 1: A resin handicraft, the raw material dosage is shown in Table 1. Among them, the epoxy resin is bisphenol A epoxy resin selected from Hengmais, with the model GY6010, the epoxy curing agent is polyetheramine, selected from Huntsman, with the model D-230, the filler is nano calcium carbonate, the defoaming agent is polydimethylsiloxane, the antioxidant is antioxidant 1010, the dispersant is polyethylene wax, and the masterbatch is made from Preparation Example 2.

[0042] The production method of the above resin handicraft includes the following steps: Mix the epoxy resin with the filler, masterbatch, antioxidant, defoaming agent, and dispersant, heat up to 120 °C, and stir for 10 min to obtain a stock solution; Inject the stock solution into a mold of the desired shape, evacuate the air for 5 minutes, leave it at room temperature for 12 hours and then demold it, shape it at 80 °C for 3 hours to obtain a preliminary embryo. Trim the preliminary embryo next, spray transparent paint, and perform a drying treatment at 40 °C to obtain a resin handicraft. The transparent paint is an inorganic nano-ceramic coating, selected from Green Tree New Materials in Foshan City, product number D-200, and the spraying amount is 10 g / m 2 。

[0043] Table 1 Raw material dosage of resin handicrafts Raw materials / g Example 1 Example 2 Example 3 Example 4 Example 5 Epoxy resin 100 100 100 100 100 Epoxy curing agent 20 18 17 16 15 Filler 1000 800 600 500 400 Masterbatch 0.5 0.4 0.3 0.2 0.1 Antioxidant 1 0.8 0.6 0.4 0.2 Defoamer 1.5 1.3 1 0.8 0.5 Dispersant 2 1.8 1.6 1.4 1.2 Example 2: A resin handicraft, the raw material dosage is shown in Table 1, wherein the epoxy resin is bisphenol A epoxy resin selected from Hengmaisi, model number GY6010, the epoxy curing agent is polyetheramine, selected from Huntsman, model number D-230, the filler is barium sulfate, the defoaming agent is tributyl phosphate, the antioxidant is antioxidant 168, the dispersant is polyamide wax, selected from Shandong Yousuo Chemical Industry, model number NEW-0400, and the masterbatch is made from Preparation Example 3.

[0044] The production method of the above resin handicraft includes the following steps: Mix the epoxy resin with the filler, masterbatch, antioxidant, defoaming agent and dispersant, heat up to 110 °C, and stir for 10 minutes to obtain a stock solution; Inject the stock solution into a mold of the desired shape, evacuate the air for 3 minutes, leave it at room temperature for 10 hours and then demold it, shape it at 70 °C for 4 hours to obtain a preliminary embryo. Trim the preliminary embryo next, spray transparent paint, and perform a drying treatment at 40 °C to obtain a resin handicraft. The transparent paint is an inorganic nano-ceramic coating, selected from Green Tree New Materials in Foshan City, product number D-200, and the spraying amount is 10 g / m 2 。

[0045] Example 3: A resin handicraft, the raw material dosage is shown in Table 1, wherein the epoxy resin is bisphenol A epoxy resin selected from Hengmaisi, model number GY6010, the epoxy curing agent is ethylenediamine, the filler is barium sulfate, the defoaming agent is polyoxypropylene glycerol ether, the antioxidant is antioxidant 168, the dispersant is paraffin wax, and the masterbatch is made from Preparation Example 4.

[0046] The production method of the above resin handicraft includes the following steps: Mix the epoxy resin with the filler, masterbatch, antioxidant, defoaming agent and dispersant, heat up to 115 °C, and stir for 10 minutes to obtain a stock solution; Inject the stock solution into a mold of the desired shape, evacuate the air for 4 min, let it stand at room temperature for 11 h and then demold, shape it at 75 °C for 4 h to obtain a preliminary embryo. Trim the preliminary embryo next, spray transparent paint, and perform a drying treatment at 40 °C to obtain a resin handicraft. The transparent paint is an inorganic nano-ceramic coating, selected from Green Tree New Materials in Foshan, product number D-200, and the spraying amount is 10 g / m 2 。

[0047] Example 4-5: A resin handicraft, different from Example 1 in that the raw material dosages are as shown in Table 1.

[0048] Example 6: A resin handicraft, different from Example 1 in that the masterbatch is made from Preparation Example 8.

[0049] Example 7: A resin handicraft, different from Example 6 in that the masterbatch is made from Preparation Example 9.

[0050] Example 8: A resin handicraft, different from Example 7 in that the masterbatch is made from Preparation Example 10.

[0051] Example 9: A resin handicraft, different from Example 7 in that the masterbatch is made from Preparation Example 11.

[0052] Example 10: A resin handicraft, different from Example 7 in that the masterbatch is made from Preparation Example 12.

[0053] Example 11: A resin handicraft, different from Example 7 in that the transparent paint is made by mixing an inorganic nano-ceramic coating, nano-titanium nitride and micron alumina with a mass ratio of 1:0.02:0.1, and the nano-titanium nitride and micron alumina are pretreated with a silane coupling agent KH550. The method is as follows: Mix the nano-titanium nitride and micron alumina and disperse them in water to obtain a dispersion with a solid content of 4 wt%, adjust the pH to 10, mix 72% ethanol, 20% KH550 and 8% water to obtain a hydrolysis solution, add 2.5 wt% of the hydrolysis solution of the total amount of nano-titanium nitride and micron alumina to the dispersion, heat and reflux at 80 °C for 6 h, centrifuge, wash 3 times with absolute ethanol, and dry at 80 °C for 24 h. The micron alumina is selected from Shanghai Biker New Materials, product number 005-U1, with a particle size of 1 μm, and the nano-titanium nitride is selected from Thion, with a particle size of 20 nm.

[0054] Example 12: A resin handicraft, which is different from Example 7 in that the transparent paint is made by mixing an inorganic nano-ceramic coating, nano-titanium nitride and micron alumina with a mass ratio of 1:0.01:0.05, and the nano-titanium nitride and micron alumina are pretreated with a silane coupling agent KH550. The method is as follows: Mix the nano-titanium nitride and micron alumina and disperse them in water to obtain a dispersion with a solid content of 4 wt%. Adjust the pH to 10. Mix 72% ethanol, 20% KH550 and 8% water to obtain a hydrolysis solution. Add 2.5 wt% of the hydrolysis solution based on the total amount of nano-titanium nitride and micron alumina to the dispersion, heat and reflux at 80 °C for 6 h, centrifuge, wash with absolute ethanol three times, and dry at 80 °C for 24 h. The micron alumina is selected from Shanghai Biker New Materials, with the product number 005-U1 and a particle size of 1 μm. The nano-titanium nitride is selected from Celon, with a particle size of 20 nm.

[0055] Example 13: A resin handicraft, which is different from Example 12 in that an equal mass of nano-titanium nitride is used to replace the micron alumina.

[0056] Example 14: A resin handicraft, which is different from Example 12 in that an equal mass of micron alumina is used to replace the nano-titanium nitride.

[0057] Comparative Example Comparative Example 1: A resin handicraft, which is different from Example 1 in that the color masterbatch is made from Preparation Example 5.

[0058] Comparative Example 2: A resin handicraft, which is different from Example 1 in that the color masterbatch is made from Preparation Example 6.

[0059] Comparative Example 3: A resin handicraft, which is different from Example 1 in that the color masterbatch is made from Preparation Example 7.

[0060] Comparative Example 4: A resin handicraft, which is different from Example 1 in that no transparent paint is sprayed on the green body.

[0061] Performance Detection Test Prepare resin handicrafts according to the methods in the examples and comparative examples, and perform performance detection according to the following methods. Record the detection results in Table 2.

[0062] 1. Impact strength: Detect according to GB / T14153-1993 "General Rules for Drop Hammer Impact Test Method for Rigid Plastics", measure 3 times in parallel, and take the average value.

[0063] 2. Glossiness: Refer to GB / T9754-2007 "Determination of 20°, 60° and 85° Specular Gloss of Paints and Varnishes - Paints without Metallic Pigments", and use a glossmeter to measure the glossiness of the surface of the resin handicraft at an incident angle of 60°.

[0064] 3. Contact angle with water: Drop 1 drop of 10 μL deionized water on the surface of each sample, and use a contact angle analyzer to record the contact angle value at room temperature. Measure 5 times separately for 5 different areas of each resin handicraft, and take the average value.

[0065] 4. Color difference △E after UV irradiation: Place the resin handicraft in an ultraviolet artificial accelerated aging chamber with a UVA-340, 40W ultraviolet lamp tube as the light source. After aging for 480 h, conduct a color test on the aged resin handicraft and calculate the overall color difference △E, △E * Calculate according to the following formula: where △L = L - L0, △a = a - a0, △b = b - b0, L0, a0, b0 are the color parameters of the sample before aging, and L, a, b are the color parameters of the sample after aging.

[0066] Table 2 Performance test results of resin handicrafts Item <![CDATA[Impact strength kJ / m 2 > Glossiness / ° Contact angle / ° Color difference △E Example 1 113.1 79.81 91.10 8.97 Example 2 112.5 79.75 91.01 9.08 Example 3 111.7 79.83 90.77 9.15 Example 4 110.3 79.72 90.54 9.22 Example 5 109.5 79.80 90.34 9.28 Example 6 114.3 80.34 92.12 8.42 Example 7 114.8 80.42 92.45 8.13 Example 8 114.7 80.40 92.43 8.15 Example 9 114.5 80.41 92.37 8.27 Example 10 114.6 80.35 93.41 8.31 Example 11 116.2 83.87 95.34 7.75 Example 12 115.9 83.69 95.31 7.79 Example 13 115.5 82.31 94.14 7.93 Example 14 115.2 82.15 93.92 8.02 Comparative example 1 112.3 79.74 91.02 12.31 Comparative example 2 105.4 79.71 91.05 15.84 Comparative example 3 103.7 80.16 91.23 10.05 Comparative example 4 110.3 61.4 87.54 9.51 It can be seen from the data in Table 2 and the raw material selection and dosage in Examples 1-5 that the resin handicrafts prepared in Examples 1-5 have better impact resistance, good drop resistance, high gloss, large contact angle with water, better anti-pollution effect in daily viewing, are easy to clean and maintain. In addition, under ultraviolet aging conditions, their color difference is less than 10, and they have better anti-ultraviolet decolorization ability and light stability.

[0067] In Comparative Example 1, the masterbatch prepared in Preparation Example 5 was used. Compared with Preparation Example 2, tea stalk extract was not added. As shown in Table 2, compared with Example 1, the resin handicraft prepared in Comparative Example 1 had a significantly increased color difference after ultraviolet aging, indicating a decrease in its light stability and anti-ultraviolet decolorization ability.

[0068] Compared with Example 1, in Comparative Example 2, the masterbatch was made from Preparation Example 6. In Preparation Example 6, tea stalk extract and ramie fiber were not added, and only tung oil / eucommia gum polymer was mixed with inorganic jade color pigment. As shown in Table 2, after ultraviolet aging, the resin handicraft prepared in Comparative Example 2 had an obvious increase in color difference and poor light stability.

[0069] Compared with Preparation Example 2, in Preparation Example 7, high-density PE was used to replace the tung oil / eucommia gum polymer in equal amount. For Comparative Example 3 using Preparation Example 7 compared with Example 1 using Preparation Example 2, although the gloss and hydrophobicity were improved, the impact strength and light stability decreased.

[0070] Compared with Example 1, in Comparative Example 4, the green body was not sprayed with transparent paint. It can be seen that the gloss and contact angle of the prepared resin handicraft decreased, the waterproof ability weakened, and at the same time, its anti-ultraviolet aging decolorization ability decreased slightly.

[0071] In Example 6, the masterbatch prepared in Preparation Example 8 was used. Compared with Preparation Example 2, Preparation Example 8 also loaded nano silver on ramie fibers. As can be seen from the data in Table 2, compared with Example 1, after ultraviolet aging, the color difference of the resin crafts prepared in Example 6 decreased, and the impact resistance, surface gloss and hydrophobicity were all improved. This shows that the addition of nano silver can not only enhance the anti-aging and discoloration ability of the resin, but also enhance the appearance quality and mechanical strength of the resin crafts.

[0072] In Example 7 and Example 8, the masterbatches prepared in Preparation Example 9 and Preparation Example 10 were used respectively. Compared with Preparation Example 6, Preparation Example 9 and Preparation Example 10 also pretreated the inorganic jade pigment with silane coupling agent KH550 and silk fibroin nanofibers. Compared with Example 6, the impact strength of the resin crafts prepared in Example 7 and Example 8 changed little, but after ultraviolet aging, their color difference was smaller and their ultraviolet decolorization resistance was stronger.

[0073] In Example 9 and Example 10, the masterbatches prepared in Preparation Example 11 and Preparation Example 12 were used respectively. Compared with Example 7 using Preparation Example 9, the anti-ultraviolet fading ability of the resin crafts prepared in Example 9 and Example 10 decreased.

[0074] Compared with Example 7, in Example 11 and Example 12, a mixture of inorganic nano ceramic coating, nano titanium nitride and micron alumina was also used as the transparent paint, which was sprayed on the blank to form a protective layer with high gloss and better hydrophobicity, which can improve the anti-moisture and anti-pollution ability of the resin crafts, and the degree of color change after ultraviolet aging is smaller.

[0075] In Example 13, nano titanium nitride was used to replace micron alumina, and in Example 14, micron alumina was used to replace nano titanium nitride in equal amount. Compared with Example 12, the surface gloss and contact angle of the resin crafts prepared in Example 13 and Example 14 decreased, the color difference increased after ultraviolet aging, and the anti-ultraviolet color change ability decreased.

[0076] This specific embodiment is only an explanation of the present application, and it is not a limitation of the present application. Those skilled in the art can make modifications without creative contributions to this embodiment according to needs after reading this specification, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A resin handicraft, characterized in that: The raw materials include the following parts by weight: 100 parts of epoxy resin, 15-20 parts of epoxy curing agent, 400-1000 parts of filler, 0.1-0.5 parts of masterbatch, 0.2-1 parts of antioxidant, 0.5-1.5 parts of defoaming agent, and 1.2-2 parts of dispersant; The masterbatch comprises the following raw materials: 10-15 parts of inorganic jade pigment, 10-15 parts of ramie fiber, 20-30 parts of tea stem extract, and 10-20 parts of tung oil / eucommia gum polymer.

2. The resin handicraft according to claim 1, characterized in that: The masterbatch is made by the following method: The tea stem extract and the inorganic jade pigment are mixed, added into water, stirred and dissolved to prepare a treatment solution; Cut the irradiated ramie fiber into pieces and immerse it in the treatment solution, adjust the pH to 8-9, add silver nitrate solution, heat to 50-60°C, stir, filter and dry to obtain silver-loaded ramie fiber; The tung oil / eucommia gum polymer is added into xylene, and after ultrasonic dispersion, the polymer is evenly coated on the silver-loaded ramie fiber, and then dried and crushed.

3. The resin handicraft according to claim 2, characterized in that: The inorganic jade pigment is subjected to the following pretreatment: The inorganic jade pigment is mixed with silane coupling agent KH550 and water, stirred evenly, and dried to obtain a coupled modified pigment; The silk fibroin nanofibers, coupled modified pigments, anhydrous ethanol and water are mixed evenly, filtered until the filtrate is colorless, and then dried.

4. The resin handicraft according to claim 3, characterized in that: The mass ratio of the inorganic jade pigment to the silane coupling agent KH550 is 1.5:0.045-0.05; The mass ratio of the silk fibroin nanofibers to the coupled modified pigment is 1:0.5-1.

5. The resin handicraft according to claim 1, characterized in that: The preparation method of the tea stem extract is as follows: mix the tea stems and pure water, oscillate in a water bath at 90°C-100°C for 50-60 minutes, filter, concentrate and dry to obtain the tea stem extract, wherein the mass ratio of the tea stems to the pure water is 1:18-20.

6. The resin handicraft according to claim 1, characterized in that: The filler is selected from at least one of nano calcium carbonate, nano barium sulfate, talcum powder, ultrafine wollastonite, silica powder and gypsum.

7. The resin handicraft according to claim 1, characterized in that: The epoxy resin is at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, and brominated epoxy resin; The defoaming agent is selected from at least one of polydimethylsiloxane, tributyl phosphate, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropanolamine ether, polyoxypropylene glycerol ether and polyacrylamide; The antioxidant is selected from at least one of antioxidant 1010, antioxidant 168, antioxidant 1076 and antioxidant 215; The curing agent is at least one of polyetheramine, ethylenediamine, diethylenetriamine, m-phenylenediamine, phthalic anhydride and pyromellitic anhydride; The dispersant is selected from at least one of polyethylene wax, polyamide wax and paraffin wax.

8. The method for producing a resin handicraft according to any one of claims 1 to 7, characterized in that: The following steps are involved: Mix epoxy resin with filler, masterbatch, antioxidant, defoamer and dispersant, heat to 110-120℃, stir evenly to obtain stock solution; The stock solution is injected into the mold, and the air bubbles are eliminated by vacuuming. The mold is demoulded after being placed at room temperature for 10-12 hours, and the mold is fixed at 70-80°C to obtain a preliminary embryo. The preliminary embryo is subjected to defect repair, spraying with transparent paint, and drying treatment to obtain a resin handicraft.

9. The method for producing a resin handicraft according to claim 8, characterized in that: The transparent paint comprises inorganic nano ceramic coating, nano titanium nitride and micron aluminum oxide in a mass ratio of 1:0.01-0.02:0.05-0.

1.

10. The method for producing resin handicrafts according to claim 9, characterized in that: The nano titanium nitride and micron aluminum oxide are pretreated with a silane coupling agent.