Sun-resistant environment-friendly resin slurry as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of resin, and particularly relates to sun-resistant environment-friendly resin slurry as well as a preparation method and application thereof. The invention provides sun-resistant environment-friendly resin slurry. The sun-resistant environment-friendly resin slurry comprises unsaturated polyester resin, recycled powder formed by grinding waste or defective products generated in the production process of resin buttons, an organic ultraviolet light absorber, a vinyl monomer diluent, a metal organic salt accelerant and an organic peroxide curing agent. According to the resin slurry, through the synergistic effect of the organic ultraviolet light absorber and the recycled powder, the problem of color change of the recycled material resin button under the solarization condition is effectively solved. The organic ultraviolet light absorber can absorb and convert ultraviolet light energy and prevent the damage of ultraviolet light to a resin molecular chain, so that the solarization resistance of the button is remarkably improved. Meanwhile, due to the reasonable addition of the recycled powder, not only is the reutilization of wastes realized, but also the stability and the processing performance of the slurry are ensured through a specific ratio and a specific process.

Description

Technical Field

[0001] This application belongs to the field of resin technology, specifically relating to sun-resistant and environmentally friendly resin slurries, their preparation methods, and applications. Background Technology

[0002] Buttons, as an indispensable component of clothing, not only serve the practical function of connecting garment pieces but also play an important decorative and artistic role. With the development of the fashion industry and materials technology, the materials used for buttons have become increasingly diverse, mainly falling into two categories: natural materials and synthetic materials. Among them, resin buttons, as a representative of synthetic materials, are widely used in clothing, bags, and other fields due to their excellent mechanical properties, rich design options, and diverse color effects.

[0003] In recent years, with the increasing global awareness of environmental protection, the concepts of green manufacturing and circular economy have gradually gained popularity, and using recycled materials to make buttons has become an important development direction for the industry. These eco-friendly buttons not only reduce reliance on virgin resources but also meet consumers' expectations for sustainable products. However, the promotion of recycled resin buttons still faces significant technical bottlenecks—color stability issues, especially under sunlight. Because recycled materials have been previously processed and used, their physical and chemical properties are significantly lower than those of virgin materials, their structural aging is higher, and they are more sensitive to light, especially ultraviolet light.

[0004] When clothing is worn outdoors, buttons are inevitably exposed to natural sunlight. The ultraviolet rays in strong sunlight trigger photodegradation of the button material, causing fading, yellowing, or discoloration. This discoloration not only shortens the button's lifespan but also severely affects the overall aesthetics of the garment, becoming a major obstacle to the wider application of recycled materials in button manufacturing.

[0005] Therefore, how to reduce the risk of discoloration under sunlight and maintain the button's long-lasting and stable appearance is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] Based on this, one embodiment of this application provides a sun-resistant environmentally friendly resin slurry, its preparation method, and its application.

[0007] This application provides a sun-resistant and environmentally friendly resin slurry, comprising the following components:

[0008] Unsaturated polyester resin, recycled powder, organic ultraviolet absorber, vinyl monomer diluent, organometallic salt accelerator and organic peroxide curing agent;

[0009] The recycled powder is obtained by grinding waste and / or defective products generated during the production of resin buttons.

[0010] In some embodiments, the unsaturated polyester resin includes one or both of orthophthalic unsaturated polyester resin and isophthalic unsaturated polyester resin.

[0011] In some embodiments, the organic ultraviolet absorber includes cyanoacrylate ultraviolet absorbers;

[0012] In some embodiments, the cyanoacrylate ultraviolet absorber includes one or both of ethyl 2-cyano-3,3-diphenylacrylate and isooctyl 2-cyano-3,3-diphenylacrylate.

[0013] In some embodiments, the vinyl monomer diluent includes one or both of styrene and methylstyrene.

[0014] In some embodiments, the organometallic salt promoter includes one or both of cobalt isooctanoate and cobalt naphthenate.

[0015] In some embodiments, the organic peroxide curing agent includes one or both of methyl ethyl ketone peroxide and butanone peroxide.

[0016] In some embodiments, the resin slurry comprises: 54wt%-82wt% of the unsaturated polyester resin, 5wt%-10wt% of the vinyl monomer diluent, 0.8wt%-1.2wt% of the organometallic salt accelerator, 0.8wt%-1.2wt% of the organic peroxide curing agent, 0.2wt%-0.8wt% of the organic ultraviolet absorber, and 10wt%-33wt% of the recycled powder.

[0017] In some embodiments, 0.8wt%-2.5wt% of color paste is also included.

[0018] This application also provides the application of the aforementioned sun-dried environmentally friendly resin slurry in the preparation of buttons.

[0019] In some embodiments, the preparation method of the sun-resistant and environmentally friendly resin slurry includes the following steps:

[0020] The sun-resistant and environmentally friendly resin slurry is prepared by mixing the unsaturated polyester resin, the recycled powder, the organic ultraviolet absorber, the vinyl monomer diluent, the organometallic salt accelerator, and the organic peroxide curing agent.

[0021] In some embodiments, mixing includes the following steps:

[0022] The unsaturated polyester resin, the vinyl monomer diluent, and the organometallic salt accelerator are mixed and stirred. The recycled powder is added and stirring continues. Finally, the organic ultraviolet absorber dissolved in the vinyl monomer diluent is added and stirring continues. Before production, the organic peroxide curing agent is added for curing treatment.

[0023] In some embodiments, the stirring conditions include a rotation speed of 150 rpm to 350 rpm.

[0024] In some embodiments, the stirring time for a single cycle is 30-40 minutes.

[0025] This application provides a sun-resistant, environmentally friendly resin slurry, comprising unsaturated polyester resin, recycled powder derived from waste or defective products generated during the production of resin buttons, an organic ultraviolet absorber, a vinyl monomer diluent, an organometallic salt accelerator, and an organic peroxide curing agent. Through the synergistic effect of the organic ultraviolet absorber and the recycled powder, this resin slurry effectively solves the discoloration problem of recycled resin buttons under sunlight, ensuring a long-lasting and stable appearance. Furthermore, the appropriate addition of the recycled powder not only achieves the reuse of waste materials but also ensures the stability and processing performance of the slurry through the combination of other specific components. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of this application and to more completely understand this application and its beneficial effects, the drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This is a comparison image of a button before testing and after sun exposure, provided in Embodiment 1 of this application.

[0028] Figure 2 A comparison image of the button before testing and after sun exposure, provided as Comparative Example 1 of this application;

[0029] Figure 3 This is a comparison image of a button before testing and after sun exposure, provided in Embodiment 2 of this application.

[0030] Figure 4 This is a comparison image of the button before testing and after sun exposure, provided as Comparative Example 2 of this application;

[0031] Figure 5 This is a comparison image of a button before testing and after sun exposure, provided in Embodiment 3 of this application.

[0032] Figure 6Comparative Example 3 of this application shows the button before testing and after sun exposure.

[0033] Figure 7 This is a comparison image of the button before testing and after sun exposure, provided in Embodiment 4 of this application;

[0034] Figure 8 The button provided in Comparative Example 4 of this application is shown before and after sun exposure. Detailed Implementation

[0035] The present application will be further described in detail below with reference to the embodiments and examples. It should be understood that these embodiments and examples are for illustrative purposes only and are not intended to limit the scope of the present application. The purpose of providing these embodiments and examples is to enable a more thorough and comprehensive understanding of the disclosure of the present application. It should also be understood that the present application can be implemented in many different forms and is not limited to the embodiments and examples described herein. Those skilled in the art can make various modifications or alterations without departing from the spirit of the present application, and the equivalent forms obtained also fall within the protection scope of the present application. Furthermore, numerous specific details are set forth in the following description to provide a fuller understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0036] Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0037] Unless otherwise stated or in case of contradiction, the terms or phrases used herein shall have the following meanings:

[0038] The terms "and / or," "or / and," and "and / or" as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical AND," and also undoubtedly includes technical solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, a technical solution that is connected by "logical OR"), as well as any and all combinations of A, B, C, and D, that is, combinations of any two or three of A, B, C, and D, and also combinations of all four of A, B, C, and D (that is, a technical solution that is connected by "logical AND").

[0039] In this application, the terms "multiple", "various", "multiple times", "multi-dimensional", etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more than or equal to two.

[0040] The terms “combinations of,” “any combination of,” and “any combination of” used in this article include all suitable combinations of any two or more of the listed items.

[0041] In this document, the term "suitable" as used in phrases such as "suitable combination," "suitable method," and "any suitable method" refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0042] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0043] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0044] In this application, the technical features described in an open-ended manner include both closed technical solutions composed of the listed features and open technical solutions composed of the listed features.

[0045] In this application, numerical intervals (i.e., numerical ranges) are involved. Unless otherwise specified, the selected numerical distributions within the aforementioned numerical intervals are considered continuous and include the two endpoints (i.e., the minimum and maximum values) of the numerical range, as well as every value between these two endpoints. Unless otherwise specified, when a numerical interval refers only to integers within that interval, it includes the two endpoint integers of the numerical range, as well as every integer between the two endpoints. In this document, this is equivalent to directly listing every integer. For example, if t is an integer selected from 1 to 10, it means that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Furthermore, when multiple ranges are provided to describe features or characteristics, these ranges can be merged. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0046] Unless otherwise specified, the temperature parameters in this application are permitted to be either constant-temperature treatment or variations within a certain temperature range. It should be understood that the constant-temperature treatment allows temperature fluctuations within the precision range of the instrument control, such as ±5℃, ±4℃, ±3℃, ±2℃, or ±1℃.

[0047] In this application, % (w / w) and wt% both represent weight percentage, % (v / v) refers to volume percentage, and % (w / v) refers to mass-volume percentage.

[0048] All references to documents mentioned in this application are incorporated herein by reference as if each document were individually incorporated herein by reference. Unless they conflict with the inventive purpose and / or technical solution of this application, all cited documents are incorporated herein by reference in their entirety and for all purposes. When citing documents in this application, the definitions of relevant technical features, terms, nouns, phrases, etc., are also incorporated herein by reference. When citing documents in this application, examples and preferred embodiments of the cited technical features may also be incorporated herein by reference, but only to the extent that they enable the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, this application shall prevail or modifications shall be made adaptably to the description in this application.

[0049] The term "cyanoacrylate UV absorber" in this field refers to a class of highly efficient UV absorbers containing a cyano (-CN) group and an acrylate structure. These compounds absorb UV energy through an intramolecular conjugated system and release the absorbed energy as heat through an intramolecular energy transfer mechanism, thereby preventing UV damage to resin materials. Cyanoacrylate UV absorbers are characterized by a wide absorption range, good photostability, and excellent compatibility with resins. In this invention, ethyl 2-cyano-3,3-diphenylacrylate and isooctyl 2-cyano-3,3-diphenylacrylate are primarily selected as specific compounds.

[0050] The term "dispersion performance of recycled powder" in this field refers to the degree of uniformity and stability of the recycled powder in resin slurry. Good dispersion performance means that the recycled powder can be uniformly distributed in the resin matrix and is not prone to sedimentation, agglomeration, or other phenomena. In this invention, through specific stirring processes (such as staged stirring, controlling stirring speed and time) and formulation design (such as controlling the particle size and addition amount of recycled powder), the dispersion performance of the recycled powder is significantly improved, ensuring the processing stability of the resin slurry and the consistency of the final product quality.

[0051] The term "sunlight resistance" in this field refers to the ability of a material to maintain its original properties and appearance under sunlight exposure. For resin buttons, sunlight resistance mainly manifests as resistance to discoloration, aging, and performance degradation caused by ultraviolet radiation. In this invention, by adding cyanoacrylate ultraviolet absorbers, the sunlight resistance of resin buttons is effectively improved. In some embodiments, the sunlight test rating reaches 4.0, significantly better than the comparative examples (2.0-3.0) without added ultraviolet absorbers.

[0052] This application provides a sun-resistant and environmentally friendly resin slurry, comprising the following components:

[0053] Unsaturated polyester resin, recycled powder made from waste or defective products generated during the production of resin buttons, organic ultraviolet absorbers, vinyl monomer diluents, organometallic salt accelerators, and organic peroxide curing agents.

[0054] The recycled powder, derived from the grinding of waste or defective products generated during the production of resin buttons, refers to the fine particles obtained by crushing and grinding scraps and substandard products generated during button production. In this field, the particle size of this recycled powder is typically 150-300 mesh, and it can be reused in the preparation of resin slurries, achieving resource recycling. The main components of the recycled powder are similar to the virgin resin, but due to processing and use, its molecular chains may undergo partial degradation, resulting in a decrease in performance compared to the original material.

[0055] This application provides a sun-resistant, environmentally friendly resin slurry, comprising unsaturated polyester resin, recycled powder obtained by grinding waste or defective products generated during the production of resin buttons, an organic ultraviolet absorber, a vinyl monomer diluent, an organometallic salt accelerator, and an organic peroxide curing agent. This resin slurry effectively solves the discoloration problem of recycled resin buttons under sunlight conditions through the synergistic effect of the organic ultraviolet absorber and the recycled powder. The organic ultraviolet absorber can absorb and convert ultraviolet energy, preventing ultraviolet rays from damaging the resin molecular chains, thereby significantly improving the sun resistance of the buttons. Simultaneously, the rational addition of recycled powder not only achieves the reuse of waste materials but also ensures the stability and processing performance of the slurry through specific proportions and processes.

[0056] In some embodiments, the unsaturated polyester resin includes one or both of phthalic and isophthalic unsaturated polyester resins. Phthalic and isophthalic unsaturated polyester resins possess good mechanical and chemical resistance properties, good compatibility with recycled powder, and can form stable resin systems.

[0057] In some embodiments, the organic ultraviolet absorber includes cyanoacrylate ultraviolet absorbers. Cyanoacrylate ultraviolet absorbers possess excellent ultraviolet absorption performance and good compatibility, effectively absorbing ultraviolet light in the 290-400 nm wavelength band, preventing photo-oxidative degradation of the resin molecular chains, thereby significantly improving the button's resistance to sunlight. Specifically, the cyanoacrylate ultraviolet absorber is selected from at least one of ethyl 2-cyano-3,3-diphenylacrylate and isooctyl 2-cyano-3,3-diphenylacrylate.

[0058] In some embodiments, the cyanoacrylate ultraviolet absorber includes one or both of ethyl 2-cyano-3,3-diphenylacrylate and isooctyl 2-cyano-3,3-diphenylacrylate.

[0059] In some embodiments, the vinyl monomer diluent includes one or both of styrene and methylstyrene. The vinyl monomer diluent can adjust the viscosity of the resin slurry, improve processing performance, and participate in the curing reaction to enhance the mechanical properties of the cured product.

[0060] In some embodiments, the organometallic salt accelerator includes one or both of cobalt isooctanoate and cobalt naphthenate. Organometallic salt accelerators can accelerate the curing reaction, improve curing efficiency, and ensure that the resin slurry completes curing within a suitable time.

[0061] In some embodiments, the organic peroxide curing agent includes one or both of methyl ethyl ketone peroxide and butanone peroxide. Under the action of an accelerator, the organic peroxide curing agent decomposes to generate free radicals, initiating a cross-linking curing reaction of the unsaturated polyester resin to form a three-dimensional network structure.

[0062] In some embodiments, the resin slurry comprises: 54wt%-82wt% unsaturated polyester resin, 5wt%-10wt% vinyl monomer diluent, 0.8wt%-2.5wt% color paste, 0.8wt%-1.2wt% organometallic salt accelerator, 0.8wt%-1.2wt% organic peroxide curing agent, 0.2wt%-0.8wt% organic ultraviolet absorber, and 10wt%-33wt% recycled powder, with the balance being other additives. This formulation range ensures that the resin slurry has good processing and curing properties, while achieving efficient utilization of recycled materials.

[0063] Specifically, the weight fraction of the unsaturated polyester resin can be selected from any value among 54 wt%, 58 wt%, 63 wt%, 68 wt%, 72 wt%, 77 wt%, and 82 wt%; the weight fraction of the vinyl monomer diluent can be selected from any value among 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, and 10 wt%; the weight fraction of the organic ultraviolet absorber can be selected from any value among 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, and 0.8 wt%; and the weight fraction of the recycled powder can be selected from any value among 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, and 33 wt%. The weight percentage of the organometallic salt accelerator can be selected from any value among 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, and 1.2 wt%; the weight percentage of the organic peroxide curing agent can be selected from any value among 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, and 1.2 wt%.

[0064] This application also provides the application of the aforementioned sun-dried environmentally friendly resin slurry in the preparation of buttons.

[0065] This application also provides a method for preparing the above-mentioned sun-resistant and environmentally friendly resin slurry, comprising the following steps:

[0066] The sun-resistant and environmentally friendly resin slurry is prepared by mixing the unsaturated polyester resin, the recycled powder, the organic ultraviolet absorber, the vinyl monomer diluent, the organometallic salt accelerator, and the organic peroxide curing agent.

[0067] In some embodiments, the following steps are included:

[0068] The mixing process includes the following steps: mixing and stirring the unsaturated polyester resin, the vinyl monomer diluent, and the organometallic salt accelerator; adding recycled powder and continuing stirring; finally adding an organic ultraviolet absorber dissolved in the vinyl monomer diluent and continuing stirring; and adding an organic peroxide curing agent for curing treatment before production. This preparation method ensures thorough mixing and dispersion of each component through stepwise addition and stirring, resulting in a uniform and stable resin slurry.

[0069] In some embodiments, the stirring speed in the step is 150 rpm to 350 rpm, the single stirring time is 30 to 40 minutes, and the final slurry viscosity is 800 mPa·s to 2150 mPa·s. Suitable stirring process parameters ensure uniform dispersion of the recovered powder and stability of the slurry. Specifically, the stirring speed can be selected from any value among 150 rpm, 180 rpm, 200 rpm, 250 rpm, 280 rpm, and 350 rpm; the stirring time can be selected from any value among 30 minutes, 35 minutes, and 40 minutes; and the slurry viscosity can be selected from any value among 800 mPa·s, 950 mPa·s, 1100 mPa·s, 1250 mPa·s, 1400 mPa·s, 1600 mPa·s, 1800 mPa·s, 2000 mPa·s, and 2150 mPa·s.

[0070] In some embodiments, the unsaturated polyester resin may be selected from either phthalic unsaturated polyester resin or isophthalic unsaturated polyester resin; the content of the unsaturated polyester resin may be selected from any one of 54wt%, 58wt%, 63wt%, 68wt%, 72wt%, 77wt%, and 82wt%.

[0071] In some embodiments, the organic ultraviolet absorber may be selected from cyanoacrylate ultraviolet absorbers, such as ethyl 2-cyano-3,3-diphenylacrylate, isooctyl 2-cyano-3,3-diphenylacrylate, etc.; the content of the organic ultraviolet absorber may be selected from any one of 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%.

[0072] In some embodiments, the recycled powder may be selected from either powder obtained by grinding waste generated during the production of resin buttons or powder obtained by grinding defective products generated during the production of resin buttons; the content of the recycled powder may be selected from any one of 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, and 33wt%.

[0073] In some embodiments, the vinyl monomer diluent may be selected from styrene and methylstyrene; the content of the vinyl monomer diluent may be selected from 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, and 10wt%.

[0074] In some embodiments, the weight percentage of the organometallic salt accelerator may be selected from any value among 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, and 1.2 wt%.

[0075] In some embodiments, the weight percentage of the organic peroxide curing agent may be selected from any value among 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.1 wt%, and 1.2 wt%.

[0076] In some embodiments, the stirring speed can be arbitrarily selected from 150 rpm, 180 rpm, 200 rpm, 250 rpm, 280 rpm, and 350 rpm; the stirring time can be arbitrarily selected from 30 minutes, 35 minutes, and 40 minutes.

[0077] The embodiments of this application will be described in detail below with reference to examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of this application. For experimental methods in the following embodiments where specific conditions are not specified, please refer to the guidelines given in this application, or follow experimental manuals or conventional conditions in the art, or follow the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0078] In the specific embodiments described below, the measurement parameters involving raw material components may have slight deviations within the weighing accuracy range unless otherwise specified. Temperature and time parameters are subject to acceptable deviations due to instrument testing accuracy or operational precision.

[0079] It should be understood that in the various embodiments of this application, the order of the above-mentioned processes does not imply the order of execution. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0080] Example 1

[0081] This embodiment provides a sun-resistant, environmentally friendly resin slurry and its preparation method.

[0082] Raw materials for resin slurry preparation:

[0083] Phthalic unsaturated polyester resin (Xin Shuangli (Huizhou) Resin Co., Ltd., trade name: H51EVT): 72 parts

[0084] Pigment paste: 0.8 parts

[0085] Accelerator cobalt naphthenate (Guangzhou Yongyi Chemical Co., Ltd., cobalt solution A-40 and CA-10): 0.8 parts

[0086] Styrene (Guangdong Chenbao Composite Materials Co., Ltd.): 2 parts

[0087] Recycled powder (made from waste generated during the production of resin buttons, 150-300 mesh, factory-produced, mainly composed of thermosetting cross-linked polymer + styrene copolymer network + residual additives + additive filler / fiber composite): 20 parts

[0088] 0.2 parts of ethyl 2-cyano-3,3-diphenylacrylate, a UV absorber (purchased from Shanghai Juyuansu E-commerce Co., Ltd., product name: UV absorber FT8900).

[0089] Curing agent: Methyl ethyl ketone peroxide (Wenzhou Shuochuan Chemical Co., Ltd., trade name: H5 Environmentally Friendly): 0.8 parts

[0090] Preparation method of resin slurry:

[0091] In a mixing tank, add 72 parts of phthalic unsaturated polyester resin, 0.8 parts of color paste, 0.8 parts of cobalt naphthenate accelerator, and 2 parts of styrene in sequence. Mix and stir for 30 minutes at 250 rpm until the viscosity reaches 920 mPa·s. Then, slowly add 20 parts of recycled powder and increase the stirring speed to 350 rpm until the viscosity reaches 1150 mPa·s. At this point, add 3.4 parts of styrene and 0.2 parts of UV absorber (fully dissolved in styrene) to reduce the viscosity to 950 mPa·s and stir for at least 30 minutes. Take a small sample of about 100 grams of the mixture in a transparent cup, add the appropriate proportion of curing agent, stir evenly, and let it stand. Test the curing time: 6.5 minutes. The viscosity of the mixture is 940 mPa·s. Observe the settling time of the recycled powder: approximately 9.5 minutes, which meets the requirements for film preparation.

[0092] Button making (flat button):

[0093] Clean the centrifuge thoroughly. Add 0.8 parts of curing agent to the mixed slurry and stir for 1 minute. Set the centrifuge speed to 250 rpm. Pour the mixed slurry onto the centrifuge and disperse for 15-20 seconds. After even dispersion, reduce the speed to 160 rpm for 30 minutes, until the slurry has solidified and is no longer flowing. Increase the speed to 250 rpm for 10 minutes. Remove the sheet from the machine to obtain a Shore hardness of 68. Punch-cut the sheet to obtain button blanks of the corresponding size. Immerse the button blanks in hot water at 80℃±2℃ for 30 minutes, then in hot water at 60℃±2℃ for 8 minutes, and finally in cold water at room temperature for 2 minutes to fully cure. Finally, after processing such as button making, water grinding, and polishing, the finished buttons are made. The button hardness and tensile strength meet the corresponding quality standards.

[0094] Example 2

[0095] This embodiment provides a sun-resistant, environmentally friendly resin slurry and its preparation method.

[0096] Raw materials for resin slurry preparation:

[0097] Phthalate-type unsaturated polyester resin: 53 parts; color paste: 2.8 parts; accelerator cobalt naphthenate: 1.2 parts; styrene: 2 parts; recycled powder: 33 parts; UV absorber ethyl 2-cyano-3,3-diphenylacrylate: 0.8 parts; curing agent methyl ethyl ketone peroxide: 1.2 parts.

[0098] Preparation method of resin slurry:

[0099] Add 53 parts of phthalic unsaturated polyester resin, 2.8 parts of color paste, 1.2 parts of cobalt naphthenate accelerator, and 2 parts of styrene to a mixing tank in sequence. Mix and stir for 30 minutes at a speed of 250 rpm until the viscosity reaches 880 mPa·s. Then, slowly add 33 parts of recycled powder and increase the speed to 350 rpm until the viscosity reaches 1250 mPa·s. At this point, add 6 parts of styrene and 0.8 parts of UV absorber (fully dissolved in styrene) to reduce the viscosity to 980 mPa·s and stir for at least 30 minutes. Take a small sample of about 100 grams of the mixed slurry in a transparent cup, add the appropriate proportion of curing agent, stir evenly, and let stand. Test the curing time: 7.9 minutes; slurry viscosity: 980 mPa·s; and observe the settling time of the recycled powder: approximately 8.5 minutes. This meets the requirements for film preparation.

[0100] Button making (flat button):

[0101] Clean the centrifuge thoroughly. Add 1.2 parts of curing agent to the mixed slurry and stir for 1 minute. Set the centrifuge speed to 200 rpm. Pour the slurry mixture onto the machine and allow it to disperse evenly for 20-25 seconds. Reduce the speed to 160 rpm and stir for 30 minutes until the slurry solidifies and stops flowing. Increase the speed to 250 rpm and stir for 10 minutes. Remove the sheet from the machine to obtain a Shore hardness of 75. Punch-cut the sheet to obtain button blanks of the corresponding size. Immerse the button blanks in hot water at 80℃±2℃ for 30 minutes, then in hot water at 60℃±2℃ for 8 minutes, and finally in cold water at room temperature for 2 minutes to fully cure. Finally, process the button through machining, water grinding, and polishing to create finished buttons. The button hardness and tensile strength meet the corresponding quality standards.

[0102] Example 3: Roller Button

[0103] This embodiment provides a sun-resistant, environmentally friendly resin slurry and its preparation method.

[0104] Raw materials for preparing color paste one:

[0105] Phthalic unsaturated polyester resin: 79.2 parts, thickener silica: 1.5 parts, color paste: 1.5 parts, accelerator cobalt naphthenate: 0.8 parts, styrene: 3 parts, recycled powder: 10 parts, ultraviolet absorber ethyl 2-cyano-3,3-diphenyl acrylate: 0.2 parts, curing agent methyl ethyl ketone peroxide: 0.8 parts.

[0106] Preparation method of color paste one:

[0107] Add 79.2 parts of phthalic unsaturated polyester resin to a mixing tank, slowly add 1.5 parts of thickener silica, stirring at 150 rpm. After adding all the thickener, stir for another 40 minutes to ensure thorough dispersion. Then add 1.5 parts of color paste, 0.8 parts of accelerator cobalt naphthenate, and 3 parts of styrene, and mix for 20 minutes at 200 rpm to prepare a mixture with a viscosity of 1850 mPa·s. Next, slowly add 10 parts of recycled powder, stirring at 250 rpm for 30 minutes to ensure thorough dispersion and mixing, preparing a mixture with a viscosity of 2050 mPa·s. Finally, add the remaining 3 parts of monomer diluent and 0.2 parts of UV absorber dissolved in the monomer diluent to the above mixture to prepare a mixture with a viscosity of 1980 mPa·s. Finally, vacuum the mixture for 3 minutes (relative pressure approximately -0.09 to -0.1 MPa) to remove air bubbles.

[0108] Preparation of Color Paste II:

[0109] It is made using the same method as the color paste, except that the color paste is white, while the proportions of other materials remain the same.

[0110] Preparation of clear slurry:

[0111] It is made using the same method as the color paste, except that no pigment is added and 0.8 parts of hardener are added instead, while the proportions of the other materials are the same.

[0112] Button making (stick button):

[0113] Take approximately 100 grams of each of the above-mentioned rod color pastes in a transparent plastic cup, add them to the curing agent, stir evenly, and let stand. Test the curing time and settling time as follows: Color paste one: curing time 10.2 minutes, settling time 11.2 minutes; Color paste two: curing time 10.5 minutes, settling time 11.6 minutes; Clear slurry: curing time 9.8 minutes, settling time 10.8 minutes, which meets the process requirements. Then, insert the double rubber hoses of the rod flower machine's pump into the color paste and clear slurry respectively (one hose into the color paste and the other into the clear slurry). Adjust the pumping speed ratio according to the different color paste ratios: color paste one: color paste two: clear slurry = 8:3:25. The slurry flows out through the designed and installed tools and finally collects in an aluminum cylinder. Stir the slurry every 3-5 minutes. After 40 minutes, the soft rod is removed from the aluminum cylinder and immersed in room temperature water to reduce the impact of the exothermic reaction during resin curing. The mixture is kept in this state until the Shore hardness reaches 72. It is then sliced ​​to a predetermined thickness of 4.5 mm to obtain a cylindrical button blank. The button blank is immersed in hot water at 80℃±2℃ for 20 minutes, then in hot water at 60℃±2℃ for another 20 minutes, and finally in cold water at room temperature for 10 minutes to ensure complete curing. Finally, the button is processed through machining, water grinding, and polishing to create the finished button. The button's hardness and tensile strength meet the corresponding quality standards.

[0114] Example 4:

[0115] This embodiment provides a sun-resistant, environmentally friendly resin slurry and its preparation method.

[0116] Raw materials for preparing color paste one:

[0117] Phthalic unsaturated polyester resin: 66 parts, thickener silica: 1.5 parts, color paste: 2 parts, accelerator cobalt naphthenate: 1 part, styrene: 4 parts, recycled powder: 20 parts, ultraviolet absorber ethyl 2-cyano-3,3-diphenyl acrylate: 0.5 parts, curing agent methyl ethyl ketone peroxide: 1 part.

[0118] Preparation method of color paste one:

[0119] Add 66 parts of phthalic unsaturated polyester resin to a mixing tank, slowly add 1.5 parts of thickener silica, and stir at 150 rpm. After adding the thickener, stir for another 40 minutes to ensure thorough dispersion. Then add 2 parts of color paste, 1 part of accelerator cobalt naphthenate, and 4 parts of styrene, and mix for 20 minutes at 200 rpm to prepare a mixture with a viscosity of 1850 mPa·s. Next, slowly add 20 parts of recycled powder, and stir at 250 rpm for 30 minutes to ensure thorough dispersion and mixing, preparing a mixture with a viscosity of 2150 mPa·s. Finally, add the remaining 4 parts of monomer diluent and 0.5 parts of UV absorber dissolved in the monomer diluent to the above mixture to prepare a mixture with a viscosity of 2010 mPa·s. Finally, vacuum the mixture for 3 minutes (relative pressure approximately -0.09 to -0.1 MPa) to remove air bubbles.

[0120] Preparation of Color Paste II:

[0121] It is made using the same method as the color paste, except that the color paste is white, while the proportions of other materials remain the same.

[0122] Preparation of clear slurry:

[0123] Prepare it using the same method as the color paste, except that instead of adding pigment, add 1 part of hardener, while keeping the other materials in the same proportions.

[0124] Button making (stick button):

[0125] Take approximately 100 grams of each of the above-mentioned rod color pastes in a transparent plastic cup, add them to the curing agent, stir evenly, and let stand. Test the curing time, viscosity, and settling time as follows: Color paste one: curing time 11.3 minutes, viscosity 2010 mPa·s, settling time 12.5 minutes; Color paste two: curing time 11.5 minutes, viscosity 1960 mPa·s, settling time 12.2 minutes; Clear slurry: curing time 9.6 minutes, viscosity 190 mPa·s, settling time 10.8 minutes, which meets the process requirements. Then, insert the double hoses of the rod flower machine's pump into the color paste and clear slurry respectively (one hose into the color paste and the other into the clear slurry). Adjust the pumping speed according to the ratio of different color pastes, with a speed ratio of color paste one: color paste two: clear slurry = 10:4:28. The slurry flows out through the designed and installed tools and finally collects in an aluminum cylinder to avoid recycling and settling. Stir the slurry every 3-5 minutes. After 40 minutes, the soft rod is removed from the aluminum cylinder and immersed in room temperature water to reduce the impact of the exothermic reaction during resin curing. The mixture is kept in this state until the Shore hardness reaches 75. It is then sliced ​​to a predetermined thickness of 4.5 mm to obtain a cylindrical button blank. The button blank is then immersed in hot water at 80℃±2℃ for 20 minutes, followed by immersion in hot water at 60℃±2℃ for another 20 minutes, and finally in cold water at room temperature for 10 minutes to ensure complete curing. Finally, the button is processed through machining, water grinding, and polishing to create the finished button. The button's hardness and tensile strength meet the corresponding quality standards.

[0126] Comparative Example 1:

[0127] No UV absorbers were added to this comparative example.

[0128] Raw materials for resin slurry preparation:

[0129] Phthalic unsaturated polyester resin: 72.2 parts, color paste: 0.8 parts, accelerator cobalt naphthenate: 0.8 parts, styrene: 2 parts, recycled powder: 20 parts, curing agent methyl ethyl ketone peroxide: 0.8 parts.

[0130] Preparation method (button):

[0131] The preparation method of Example 1 was followed, except that no ultraviolet absorber was added, and the amount of phthalic unsaturated polyester resin was adjusted to 72.2 parts, while other ingredients and operations remained unchanged.

[0132] Comparative Example 2

[0133] No UV absorbers were added to this comparative example.

[0134] Raw materials for preparing the resin slurry: Phthalic unsaturated polyester resin: 54.6 parts, color paste: 2.8 parts, cobalt naphthenate accelerator: 0.8 parts, styrene: 2 parts, recycled powder: 33 parts, methyl ethyl ketone peroxide curing agent: 0.8 parts

[0135] Preparation method (button):

[0136] The preparation method of Example 2 was followed, except that no ultraviolet absorber was added, the amount of phthalic unsaturated polyester resin was adjusted to 54.6 parts, the accelerator and curing agent were adjusted to 0.8 parts respectively, and other ingredients and operations remained unchanged.

[0137] Comparative Example 3

[0138] No UV absorbers were added to this comparative example.

[0139] Raw materials for resin slurry preparation:

[0140] Phthalic unsaturated polyester resin: 79.4 parts; Thickener: silica: 1.5 parts; Color paste: 1.5 parts; Accelerator: cobalt naphthenate: 0.8 parts; Styrene: 3 parts; Recycled powder: 10 parts; Curing agent: methyl ethyl ketone peroxide: 0.8 parts

[0141] Preparation method (stick):

[0142] The preparation method of Example 3 was followed, except that no ultraviolet absorber was added, and the amount of phthalic unsaturated polyester resin was adjusted to 79.4 parts, while other ingredients and operations remained unchanged.

[0143] Comparative Example 4

[0144] No UV absorbers were added to this comparative example.

[0145] Raw materials for preparing the resin slurry: 66.9 parts of phthalic unsaturated polyester resin, 1.5 parts of silica (thickener), 2 parts of color paste, 0.8 parts of cobalt naphthenate (accelerator), 4 parts of styrene, 20 parts of recycled powder, and 0.8 parts of methyl ethyl ketone peroxide (curing agent).

[0146] Preparation method (stick):

[0147] The preparation method of Example 4 was followed, except that no ultraviolet absorber was added, the amount of phthalic unsaturated polyester resin was adjusted to 66.9 parts, the accelerator and curing agent were adjusted to 0.8 parts respectively, and other ingredients and operations remained unchanged.

[0148] Performance testing methods:

[0149] Color fastness to rubbing test: The test is conducted according to AATCC 116 standard, testing the color fastness under dry and wet rubbing conditions respectively, and comparing it with the standard gray card to evaluate the color change level (0-5, with 5 being the highest level).

[0150] Color fastness to soap washing test: The test is conducted in accordance with the AATCC 61-2A standard to test the color change and staining. The color change grade is compared with the standard gray card and rated (0-5, with 5 being the highest grade).

[0151] Heat pressing color fastness test: The test is conducted according to AATCC 132 standard (150°C / 15S), and the color change and staining under dry pressing, damp pressing and wet pressing conditions are tested respectively. The color change level is rated by comparing with the standard gray card (0-5, with 5 being the highest level).

[0152] Storage color fastness test: The test is conducted according to AATCC 163 standard (24°C / 95% humidity / 48H) to test the staining and compare it with the standard gray card to evaluate the color change level (0-5, with 5 being the highest level).

[0153] Post-wash appearance test: Tested according to AATCC 135 standard (40°C water temperature, 3 washes, low temperature drying).

[0154] Impact test: The test was conducted according to ASTM D5171 (67mm) standard, testing the breakage of 10 buttons.

[0155] Tensile test: The test was conducted according to BS4162 standard, testing the button's detachment under 15LBS / 10S conditions.

[0156] Sun exposure test: The test is conducted according to AATCC 16.3 Option 3 @ 40 hrs. The button sample is placed under simulated sunlight for a certain period of time and then compared with the standard gray card to evaluate the discoloration level (0-5, with 5 being the highest level).

[0157] The test results are shown in Table 1:

[0158] Table 1

[0159]

[0160] The results of the sun exposure tests before and after Examples 1-4 and Comparative Examples 1-4 are shown in Tables 2-5:

[0161] Table 2

[0162]

[0163] Table 3

[0164]

[0165] Table 4

[0166]

[0167] Table 5

[0168]

[0169] Note: The rating is based on color matching using a standard grayscale card, with a standard range of 0-5, where 5 is the highest level and 0 is the lowest.

[0170] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. Furthermore, it should be understood that after reading the above teachings of this application, those skilled in the art can make various alterations or modifications to this application, and the equivalent forms obtained also fall within the scope of protection of this application. It should also be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A sun-resistant and environmentally friendly resin slurry, characterized in that, Includes the following components: Unsaturated polyester resin, recycled powder, organic ultraviolet absorber, vinyl monomer diluent, organometallic salt accelerator and organic peroxide curing agent; The recycled powder is obtained by grinding waste and / or defective products generated during the production of resin buttons.

2. The sun-resistant and environmentally friendly resin slurry according to claim 1, characterized in that, The unsaturated polyester resin includes one or both of orthophthalic unsaturated polyester resin and isophthalic unsaturated polyester resin.

3. The sun-resistant and environmentally friendly resin slurry according to claim 1, characterized in that, The organic ultraviolet absorber includes cyanoacrylate ultraviolet absorbers; Optionally, the cyanoacrylate ultraviolet absorber includes one or both of ethyl 2-cyano-3,3-diphenylacrylate and isooctyl 2-cyano-3,3-diphenylacrylate.

4. The sun-resistant and environmentally friendly resin slurry according to claim 1, characterized in that, The vinyl monomer diluent includes one or both of styrene and methylstyrene.

5. The sun-resistant and environmentally friendly resin slurry according to claim 1, characterized in that, The organometallic salt accelerator includes one or both of cobalt isooctanoate and cobalt naphthenate.

6. The sun-resistant and environmentally friendly resin slurry according to claim 1, characterized in that, The organic peroxide curing agent includes one or both of methyl ethyl ketone peroxide and butanone peroxide.

7. The sun-resistant and environmentally friendly resin slurry according to any one of claims 1 to 6, characterized in that, The resin slurry includes: 54wt%-82wt% of the unsaturated polyester resin, 5wt%-10wt% of the vinyl monomer diluent, 0.8wt%-1.2wt% of the organometallic salt accelerator, 0.8wt%-1.2wt% of the organic peroxide curing agent, 0.2wt%-0.8wt% of the organic ultraviolet absorber, and 10wt%-33wt% of the recycled powder; Optionally, it also includes 0.8wt%-2.5wt% of color paste.

8. The application of the sun-dried environmentally friendly resin slurry according to any one of claims 1 to 7 in the preparation of buttons.

9. The method for preparing the sun-resistant environmentally friendly resin slurry according to any one of claims 1 to 7, characterized in that, Includes the following steps: The sun-resistant and environmentally friendly resin slurry is prepared by mixing the unsaturated polyester resin, the recycled powder, the organic ultraviolet absorber, the vinyl monomer diluent, the organometallic salt accelerator, and the organic peroxide curing agent. Optionally, the mixing process includes the following steps: The unsaturated polyester resin, the vinyl monomer diluent, and the organometallic salt accelerator are mixed and stirred. Recycled powder is added and stirring continues. Finally, an organic ultraviolet absorber dissolved in the vinyl monomer diluent is added and stirring continues. The organic peroxide curing agent is added before production and then cured.

10. The preparation method according to claim 9, characterized in that, The stirring conditions include: a rotation speed of 150 rpm to 350 rpm; and / or; The stirring time for a single cycle is 30-40 minutes.

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