Benzene-free anti-silver-dropping mirror-like silver resin and preparation method thereof
A mirror-finish silver resin without anti-silver-dropping additives was prepared by using benzene-free environmentally friendly solvents and cellulose-modified polyurethane-acrylate composite resin with specific components. This solved the problems of toluene solvent hazards and silver powder detachment, achieving environmentally friendly construction and stable silver powder alignment.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-28
- Publication Date
- 2026-04-07
AI Technical Summary
Existing mirror silver resins pose significant health risks when using toluene solvents, and suffer from issues such as silver powder shedding, delamination, coarsening, and blackening. Furthermore, the high acid values of anti-silver-shedding additives on the market result in poor compatibility, affecting the stability of the paint film performance.
A benzene-free, anti-slip silver mirror resin was prepared by using benzene-free environmentally friendly solvents and cellulose-modified polyurethane-acrylate composite resin with specific components, along with ester and ketone solvents. A specific process was used to ensure the encapsulation and interlayer adhesion of the silver powder.
It achieves environmentally friendly construction. The silver powder has excellent silver powder arrangement and metallic mirror effect on the surface of plastic substrate. It does not separate, coarse, or turn black during storage, and the paint film performance is stable.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the technical field of high polymers, and particularly relates to a benzene-free anti-silver-falling mirror silver resin and a preparation method thereof. BACKGROUND
[0002] ABS plastic is widely used in the fields of domestic and foreign household appliances, decoration, daily necessities, etc. Such plastic has the advantages of low cost, light weight, long service life, recyclability, etc. The appearance of silver powder paint made of ordinary thermoplastic acrylic resin is not beautiful and delicate, and has no metal effect. The wrapping property of the silver powder is not good, and the paint film is easy to cause the silver powder to fall off due to friction. Moreover, most of the ordinary thermoplastic acrylic resin used in the market adopts toluene solvent, which is extremely harmful to the human body. In order to overcome these defects and achieve these performance requirements, the formula design personnel in the paint industry usually choose to add cellulose acetate butyrate to promote the arrangement of the silver powder. However, with the addition of cellulose acetate butyrate, the coating film of the prepared paint becomes soft, and after PU and UV coating, it is easy to bite the bottom, which makes the appearance of the paint film worse and affects the interlayer adhesion of the paint film. The solid content of the electroplated silver resin on the market is not high, and the wrapping property of the aluminum powder is poor, so there is basically no interlayer adhesion after PU and UV coating. In order to solve the problem of the wrapping property of the silver powder, the paint technicians usually add LTW produced by Degussa Company and domestic anti-silver-falling adhesion enhancer. However, although the addition of LTW and domestic anti-silver-falling adhesion enhancer can solve the problem of silver falling, the acid value of LTW and domestic anti-silver-falling adhesion enhancer is relatively high (AV: 20-30 mgKOH / g). The polarity of the resin is quite different from that of the mirror silver resin, which not only affects the compatibility, but also causes the silver powder paint to have the problems of serious delamination, coarsening and blackening during production and storage, and even the phenomenon of gelation, and the performance of the paint film is not stable. Therefore, it is urgent to develop a mirror silver resin that can solve the above technical problems. SUMMARY
[0003] The technical problem to be solved by the present application is to provide a benzene-free anti-silver-falling mirror silver resin and a preparation method thereof. The resin of the present application uses a benzene-free environmentally friendly solvent, which greatly reduces the harm to the human body and the environment during construction. The resin does not contain an anti-silver-falling additive. The silver powder paint made of the resin and aluminum silver powder has excellent silver powder arrangement, metal mirror effect and anti-silver-falling property on the surface of a plastic substrate. Moreover, the silver powder paint prepared therefrom will not delaminate, coarsen or blacken during storage.
[0004] The technical scheme adopted by the present application to solve the above problems is as follows: On the one hand, the present application provides a benzene-free anti-silver-falling mirror silver resin, which is prepared from A component, B component and C component. The components and the mass percentage of each component in the benzene-free anti-silver-falling mirror silver resin are as follows: A component: butyl acetate 35-45%, diisobutyl ketone 7-15%, diethylene glycol ethyl ether acetate 5-10%, cellulose modified polyurethane-acrylate composite resin 20-30%; B component: methyl methacrylate 5-10%, hydroxy acrylate 3-5%, functional monomer 1-3%; C component: first initiator 0.5-1.5%.
[0005] The benzene-free anti-silver-dropping mirror silver resin of the present application uses ester and specific ketone solvents in combination with cellulose modified polyurethane-acrylate composite resin, and can realize sufficient wrapping of aluminum silver powder without adding anti-silver-dropping aids, so as to achieve the effect of not dropping silver. At the same time, the resin has good arrangement of aluminum silver powder, and the formed paint film has excellent comprehensive performance such as mirror effect, adhesion to substrate, interlayer adhesion of PU and UV, etc.
[0006] Preferably, the benzene-free anti-silver-dropping mirror silver resin is prepared from A component, B component and C component, and the components and the mass percentage of each component in the benzene-free anti-silver-dropping mirror silver resin are as follows: A component: butyl acetate 35-45%, diisobutyl ketone 7-15%, diethylene glycol ethyl ether acetate 5-10%, cellulose modified polyurethane-acrylate composite resin 20-30%; B component: methyl methacrylate 5-10%, hydroxy acrylate 3-5%, functional monomer 1-3%; C component: first initiator 0.5-1.5%.
[0007] Further, the cellulose modified polyurethane-acrylate composite resin is prepared from raw materials with the following mass percentages: butyl acetate 40-50%, MIBK 15-25%, cellulose acetate butyrate 5-10%, cellulose acetate propionate 3-5%, methyl methacrylate 5-10%, hydroxyethyl methacrylate 4-8%, second initiator 0.3-0.5%, IPDI 3-5%, catalyst 0.01-0.05%, chain extender 1-3%.
[0008] Wherein, MIBK refers to methyl isobutyl ketone, and IPDI refers to isophorone diisocyanate.
[0009] Further, the second initiator is azobis isobutyronitrile, the catalyst is dibutyl tin dilaurate, and the chain extender is diethylene triamine.
[0010] Further, the preparation method of the cellulose modified polyurethane-acrylate composite resin comprises the following steps: Methyl methacrylate, hydroxyethyl methacrylate, and the second initiator are mixed uniformly to obtain a monomer mixture; butyl acetate, MIBK, cellulose acetate butyrate, and cellulose acetate propionate are put into a reaction kettle and heated to dissolve; when the temperature of the reaction kettle is warmed to the reflux starting point, the monomer mixture is added dropwise, and the addition is completed in 1-1.5 h, then refluxed for 2 h, cooled to 60±2℃, and then the IPDI and the catalyst are added in 0.5 h, and the mixture is kept at 60±2℃ for 3 h, then the chain extender is added and the temperature is increased to 80℃ for 3 h, to obtain the cellulose modified polyurethane-acrylate composite resin.
[0011] In the technical solution, the propionyl and butyryl in the cellulose modified polyurethane-acrylate composite resin are reacted with the hydroxyl in the hydroxyethyl methacrylate, the IPDI containing the -NCO group is grafted and chain-extended, and an ultrahigh molecular weight product is prepared, which can make the silver powder in the subsequently prepared mirror silver resin arrange better, has good wrapping performance for the silver powder, and increases the interlayer adhesion between the paint films.
[0012] Further, the functional monomer is 2-acrylamide modified polyester phosphate.
[0013] Further, the first initiator is dimethyl azobisisobutyrate.
[0014] In another aspect, the present application provides a preparation method of the above-mentioned benzene-free anti-silver-falling mirror silver resin, which comprises the following steps: S1, the A component is put into a reaction kettle, and the temperature is increased to 110-120℃ while stirring; S2, the B component is mixed and stirred uniformly, and is added dropwise into the A component in 2-2.5 h, and is kept at 110-120℃ for 4 h; S3, the C component is added into the material obtained in S2, stirred uniformly, and the temperature is increased to 120-130℃ for 5-6 h; S4, after sampling and detecting, the material is cooled and filtered; In the preparation method, nitrogen is passed through the whole process.
[0015] It can be understood that, more preferably, nitrogen is passed for 5-10 min before feeding.
[0016] Further, the detection qualification is that the viscosity of the material is 6-10 Pa.s / 25℃.
[0017] Further, the cooling is to reduce the temperature to 80℃, and the mesh number of the filtration is less than or equal to 10 μm.
[0018] The present application has the following advantages: The benzene-free anti-silver-falling mirror silver resin of the present application uses a benzene-free environmentally friendly solvent, greatly reducing the harm to the human body and the environment during construction; the resin does not contain an anti-silver-falling additive, and the silver powder paint made of the resin and aluminum silver powder has excellent silver powder arrangement, metal mirror effect and anti-silver-falling performance on the surface of a plastic substrate, and the silver powder paint prepared therefrom will not delaminate, become coarse, or turn black during storage. The preparation method of the resin is simple and suitable for industrial production. DETAILED DESCRIPTION
[0019] To make the technical problems, technical solutions and technical advantages of the present application clearer, specific examples will be described in detail below, but the protection scope of the present application is not limited to the following specific examples, and the described examples are only a part of the examples of the present application, rather than all the examples, and are not a limitation on the present application. Based on the examples in the present application, all other examples obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.
[0020] Unless otherwise defined, all the professional terms used below have the same meaning as generally understood by those skilled in the art. The professional terms used in the present application are only for the purpose of describing specific examples, and are not intended to limit the protection scope of the present application.
[0021] Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by existing methods.
[0022] The present application designs examples 1-3 for the benzene-free anti-silver-falling mirror silver resin, and the formula is shown in Table 1. The content in Table 1 is mass percent.
[0023] Table 1 Formula of benzene-free anti-silver-falling mirror silver resin of examples and comparative examples (unit: %)
[0024] Among them, BFK-1001 is a 2-acrylamide modified polyester phosphate of BFK-1001 type produced by Huizhou Hua Lian Chemical Co., Ltd.
[0025] The cellulose modified polyurethane-acrylate composite resin is made of raw materials in the following mass percentages: butyl acetate 45%, MIBK 20%, cellulose acetate butyrate 8%, cellulose acetate propionate 4%, methyl methacrylate 8%, hydroxyethyl methacrylate 6%, azobisdimethylcyanide 0.4%, IPDI 4%, dibutyl tin dilaurate 0.03%, diethylenetriamine 2%; the preparation method of the cellulose modified polyurethane-acrylate composite resin comprises the following steps: uniformly mixing methyl methacrylate, hydroxyethyl methacrylate and a second initiator to obtain a monomer mixture; putting butyl acetate, MIBK, cellulose acetate butyrate and cellulose acetate propionate into a reaction kettle and heating to dissolve them; when the temperature of the reaction kettle is warmed up to the refluxing start, the monomer mixture is added dropwise into the reaction kettle, and the dropping is completed in 1 h; then the reaction kettle is refluxed and kept for 2 h; the temperature is lowered to 60±2℃, and IPDI and a catalyst are added into the reaction kettle in 0.5 h, and the reaction kettle is kept at 60±2℃ for 3 h; then a chain extender is added and the temperature is raised to 80℃ and kept for 3 h, to obtain the cellulose modified polyurethane-acrylate composite resin.
[0026] The preparation method of the benzene-free anti-falling silver mirror silver resin of Example 1 comprises the following steps: S1, putting the A component into a reaction kettle, stirring and warming up to 120℃; S2, uniformly mixing and stirring the B component, and adding it dropwise into the A component in 2 h, and keeping at 115℃ for 4 h; S3, adding the C component into the material obtained in S2, uniformly stirring, and warming up to 125℃ and reacting for 5 h; S4, after sampling and detecting the viscosity of the material in the range of 6.0-10.0 Pa.s / 25℃, cooling to 80℃, and filtering through a silk cloth with a pore size of 10 μm.
[0027] The preparation method of the mirror silver resin of Examples 2-3 can be obtained in the same way, and if there are replaced / added components, they can be replaced / deleted in the corresponding preparation steps.
[0028] The benzene-free anti-falling silver mirror silver resins of Examples 1-3 are subjected to physical property tests, and are made into silver powder paint, which is sprayed on ABS substrates for comprehensive performance tests, and the test methods and results are shown in Table 2.
[0029] The formula and preparation method of the silver powder paint are as follows: taking 10 parts of aluminum silver powder, 80 parts of the benzene-free anti-falling silver mirror silver resin of the application, 5 parts of butyl acetate and 5 parts of ethyl acetate according to mass parts, mixing and uniformly stirring to obtain the silver powder paint.
[0030] Table 2 Performance test methods and results of the benzene-free anti-falling silver mirror silver resins of Examples
[0031] Note: The representation of the adhesion and interlayer adhesion of the silver mirror resin is as follows: 0 represents very good, and 5 represents very poor.
[0032] As shown in Table 2, the benzene-free anti-silver-falling silver mirror resin prepared in Examples 1-3 has good compatibility, and the silver powder paint prepared by using the resin has excellent mirror effect, excellent anti-silver-falling property, excellent adhesion to the substrate and excellent interlayer adhesion between the PU / UV layers. The formula of Example 2 is the optimal formula.
[0033] In addition, the storage stability of the silver powder paint prepared by using the benzene-free anti-silver-falling silver mirror resin of Example 2 is tested. The viscosity of the freshly prepared silver powder paint is 2500 cps / 25℃. After the silver powder paint is stored at 50±2℃ for 7 days, the silver powder paint does not show delamination, thickening or blackening, and the viscosity is 2550 cps / 25℃. After the silver powder paint is stored for 15 days, the silver powder paint does not show delamination, thickening or blackening, and the viscosity is 2700 cps / 25℃, and the viscosity growth is less than 10%. Therefore, the storage stability of the silver powder paint prepared by using the benzene-free anti-silver-falling silver mirror resin of the application meets the standard of GB / T 6753.3-1986.
[0034] In order to verify the influence of nitrogen protection on the product performance in the preparation process, Comparative Example 1 is designed. The resin formula of Comparative Example 1 is the same as that of Example 2, and the only difference is that nitrogen protection is not used in the preparation process.
[0035] The performance of the silver mirror resin of Example 2 and Comparative Example 1 is tested, and the test method and results are shown in Table 3.
[0036] Table 3: Performance test results of the resin of Example 2 and Comparative Example 1
[0037] As shown in Table 3, the appearance and color of the resin prepared by using nitrogen protection in the whole preparation process meet the market requirements, while the appearance and color of the resin prepared by not using nitrogen protection in the whole preparation process do not meet the market requirements.
[0038] The preferred embodiments of the application are described in detail above, but the application is not limited to the specific details in the above-described embodiments. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, and these simple modifications all belong to the protection scope of the application.
[0039] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not described again in the application.
[0040] Furthermore, the various embodiments of the present application can be combined with each other, as long as it does not violate the spirit of the present application, and it should be considered as disclosed in the present application.
Claims
1. A benzene-free, anti-slip silver mirror resin, characterized in that, The benzene-free anti-silvering mirror silver resin is prepared from component A, component B and component C. The components and the mass percentages of the components in the benzene-free anti-silvering mirror silver resin are as follows: Component A: butyl acetate 35-45%, diisobutyl ketone 7-15%, diethylene glycol ethyl ether acetate 5-10%, cellulose-modified polyurethane-acrylate composite resin 20-30%; Component B: methyl methacrylate 5-10%, hydroxy acrylate 3-5%, functional monomer 1-3%; Component C: the first initiator 0.5-1.5%.
2. The benzene-free, anti-scratch silver mirror resin according to claim 1, characterized in that, The benzene-free anti-silvering mirror silver resin is prepared from component A, component B and component C. The components and the mass percentages of the components in the benzene-free anti-silvering mirror silver resin are as follows: Component A: butyl acetate 40%, diisobutyl ketone 7%, diethylene glycol ethyl ether acetate 10%, cellulose-modified polyurethane-acrylate composite resin 28%; Component B: methyl methacrylate 8%, hydroxy acrylate 4%, functional monomer 2%; Component C: the first initiator 1%.
3. The benzene-free, anti-slip silver mirror resin according to claim 1 or 2, characterized in that, The cellulose-modified polyurethane-acrylate composite resin is made from raw materials with the following mass percentages: butyl acetate 40-50%, MIBK 15-25%, cellulose acetate butyrate 5-10%, cellulose acetate propionate 3-5%, methyl methacrylate 5-10%, 2-hydroxyethyl methacrylate 4-8%, the second initiator 0.3-0.5%, IPDI 3-5%, catalyst 0.01-0.05%, chain extender 1-3%.
4. The benzene-free, anti-scratch silver mirror resin according to claim 3, characterized in that, The second initiator is azobisisobutyronitrile, the catalyst is dibutyltin dilaurate, and the chain extender is diethylenetriamine.
5. The benzene-free, anti-scratch silver mirror resin according to claim 4, characterized in that, The preparation method of the cellulose-modified polyurethane-acrylate composite resin comprises the following steps: Mix methyl methacrylate, 2-hydroxyethyl methacrylate and the second initiator evenly to obtain a monomer mixture; put butyl acetate, MIBK, cellulose acetate butyrate and cellulose acetate propionate into a reaction kettle and heat to dissolve them; when the temperature of the reaction kettle rises to the start of reflux, dropwise add the monomer mixture into it, finish dropping in 1 h, then keep the temperature under reflux for 2 h, cool down to (60±2) °C, add IPDI and the catalyst into it in 0.5 h, keep the temperature at (60±2) °C for 3 h, then add the chain extender and raise the temperature to 80 °C and keep the temperature for 3 h to obtain the cellulose-modified polyurethane-acrylate composite resin.
6. The benzene-free, anti-slip silver mirror resin according to claim 1 or 2, characterized in that, The functional monomer is 2-acrylamide modified polyester-based phosphate.
7. The benzene-free, anti-slip silver mirror resin according to claim 1 or 2, characterized in that, The first initiator is dimethyl azobisisobutyrate.
8. A method for preparing a benzene-free, anti-slip silver mirror resin as described in any one of claims 1-7, characterized in that, The preparation method comprises the following steps: S1. Put component A into a reaction kettle and heat it to 110-120 °C while stirring; S2. Mix component B evenly and dropwise add it into component A in 2-2.5 h, and keep the temperature at 110-120 °C for 4 h; S3. Add component C into the material obtained in S2, stir evenly, and raise the temperature to 120-130 °C and react for 5-6 h; S4. After sampling and passing the inspection, cool and filter; Nitrogen is introduced throughout the process for protection in this preparation method.
9. The benzene-free, anti-scratch silver mirror resin according to claim 8, characterized in that, The qualified inspection means that the viscosity of the material is 6-10 Pa·s / 25 °C.
10. The benzene-free, anti-scratch silver mirror resin according to claim 8, characterized in that, The cooling process involves reducing the temperature to 80°C, and the filter mesh size is less than or equal to 10 μm.