A matting agent, its preparation method and application

Abstract

The application provides a matting agent, a preparation method and application thereof, and comprises: a core comprising a matting material; an antistatic layer coated on at least part of the surface of the core; a transition layer coated on the surface of the antistatic layer; and a silane-polyol-amine compatible layer coated on the surface of the transition layer. The matting agent has good matting performance and antistatic performance, and has the advantages of long-acting property, functional integration, dispersibility, color adaptability and the like.

Description

Technical Field

[0001] This invention relates to the field of polymer material additives technology, specifically to a matting agent, its preparation method, and its application. Background Technology

[0002] Traditional polymer materials lack electrical conductivity (volume resistivity is typically between 10¹⁰ and 10²⁰ Ω·cm), making them prone to static electricity generation during use due to friction and collisions. This static charge accumulation can attract dust, reducing the material's usability and appearance; in severe cases, it can interfere with the sensitivity and accuracy of instruments and meters, affecting their normal operation. Static discharge can also damage precision electronic components and instruments, rendering them unusable. In flammable and explosive environments, it can easily cause fires and explosions with potentially disastrous consequences.

[0003] In the existing technology, there are two main technical routes for the antistatic and matting requirements of polymer materials: (1) Physically mixed antistatic agents, which specifically refer to the direct physical mixing of traditional inorganic antistatic materials (such as carbon black, antimony tin oxide ATO) or organic antistatic agents (such as quaternary ammonium salt surfactants) into the polymer matrix. However, physically mixed antistatic agents have technical defects such as unstable antistatic performance; carbon black gives the material a black color, which limits its application in light-colored or transparent products; ATO material itself is dark blue, which can easily lead to color deviation after mixing with light-colored matrix. (2) Simple coating antistatic agents, which specifically refer to coating a layer of conductive material (such as ATO) on the surface of titanium dioxide, or embedding the antistatic agent into the polymer chain segment through in-situ polymerization. However, simple coating antistatic agents have technical defects such as fragile coating structure; the conductive layer is directly exposed to complex environment, and its performance is easily degraded under acid, alkali or high temperature and high humidity conditions; and poor dispersibility.

[0004] Therefore, developing an antistatic matting agent that combines advantages such as long-lasting effect, functional integration, dispersibility, and color compatibility is a key research focus in this field. Summary of the Invention

[0005] This invention provides a matting agent, its preparation method, and its application. The matting agent has good matting and antistatic properties, and also has advantages such as long-lasting effect, functional integration, dispersibility, and color compatibility.

[0006] The present invention provides a matting agent comprising: a core comprising a matting material; an antistatic layer covering at least a portion of the surface of the core; a transition layer covering the surface of the antistatic layer; and a silane-polyol-amine compatible layer covering the surface of the transition layer.

[0007] Optionally, the kernel's D 50 ≤0.4μm, D 90≤0.8μm; and / or, the matting material includes titanium dioxide.

[0008] Optionally, the antistatic layer comprises a conductive oxide; wherein the conductive oxide comprises antimony tin oxide; and / or, the transition layer comprises metal-doped zinc oxide; wherein the metal-doped zinc oxide comprises aluminum-doped zinc oxide.

[0009] Optionally, the D of the matting agent 50 ≤0.4μm, D 90 ≤0.8μm.

[0010] The present invention provides a method for preparing the matting agent as described above, comprising the following steps: sequentially forming the antistatic layer, the transition layer and the silane-polyol-amine compatibility layer on the surface of the core to obtain the matting agent.

[0011] Optionally, the process of sequentially forming the antistatic layer, the transition layer, and the silane-polyol-amine compatibility layer on the surface of the core to obtain the matting agent specifically includes: (1) providing a first dispersion comprising the core, a second dispersion comprising a conductive oxide precursor, a metal precursor solution, a zinc precursor solution, and a compounded organic modifier; wherein the compounded organic modifier comprises a modifier, a first stabilizer, and a regulator, the modifier comprising a silane coupling agent hydrolysate, the first stabilizer comprising a polyol, and the regulator comprising an amine; (2) adding the second dispersion dropwise to the first dispersion to obtain a first mixture; subjecting the first mixture to a first reaction to obtain a core dispersion coated with a conductive oxide; wherein the dropwise addition time is 1h~4h; and the dropwise addition process is controlled by... The pH of the system is less than 4 and the temperature is 70℃~95℃; the time of the first reaction is 4h~12h and the temperature is 70℃~95℃; (3) The metal precursor solution and the zinc precursor solution are added in parallel to the core dispersion coated with conductive oxide to obtain a second mixture; the second mixture is subjected to a second reaction, and then solid-liquid separation is performed to obtain a double-layer coated core; the time of parallel addition is 1h~3h, and the pH of the system is controlled to be 3~5 and the temperature is 70℃~95℃ during the parallel addition process; the time of the second reaction is 2h~4h and the temperature is 70℃~95℃; the mass ratio of the zinc precursor to the core is 0.2%-3% based on zinc oxide; (4) the double-layer coated core and the compounded organic modifier are mixed and spray-dried to obtain the matting agent.

[0012] Optionally, the first dispersion is prepared by a method comprising at least the following steps: mixing a first raw material system comprising the core, a dispersant, and a first solvent to obtain the first dispersion; wherein the dispersant comprises one or more of sodium silicate, pentaerythritol, sodium hexametaphosphate, sodium dihydrogen phosphate, sodium dodecylbenzenesulfonate, octylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, mono- and diglycerides of monolaurate, polyacrylate, polyphosphate, nonylphenol polyoxyethylene ether, sorbitan alkylphenol, polyoxyethylene ether phosphate, and phosphate salts, wherein the mass ratio of the dispersant to the core is 0.1% to 0.5%, and the first solvent comprises one or more of ethanol, water, dimethylacetamide, acetic acid, and caprolactam aqueous solution; and / or, the second dispersion is prepared by a method comprising at least the following steps: mixing a second stabilizer and a second solvent, and then adding a second raw material system comprising the conductive oxide precursor. The second dispersion is obtained; preferably, the conductive oxide precursor includes an antimony precursor and a tin precursor, the antimony precursor includes one or more of potassium antimony tartrate, antimony acetate, antimony glycolate, and antimony chloride, the tin precursor includes one or more of tin acetate and tin chloride, and the mass ratio of the tin precursor to the core is 0.5%-3% based on tin oxide; in the second dispersion, the molar ratio of antimony element to tin element is (0.01~0.3):1, and the molar amount of the second stabilizer to the total molar amount of tin element and antimony element is (2~5):1; the second stabilizer includes one or more of stearic acid, hydroxycellulose, polyacrylamide, disodium ethylenediaminetetraacetate, pentaerythritol oleate, pentaerythritol stearate, 1-vinyl-2-pyrrolidone homopolymer, polyethylene glycol laurate, polyvinyl alcohol, and sodium alginate phosphate; the second solvent includes one or more of water and ethanol.

[0013] Optionally, the zinc precursor solution contains 0.5% to 10% by mass of zinc precursor; the zinc precursor includes one or more of zinc sulfate, zinc chloride, and zinc acetate; and / or, the metal precursor solution contains 0.5% to 10% by mass of metal precursor; the metal precursor includes an aluminum precursor, which includes one or more of aluminum sulfate, sodium aluminate, and aluminum chloride; the molar ratio of the metal element in the metal precursor to the zinc element in the zinc precursor is (0.01 to 0.1):1; and / or, the silane coupling agent hydrolysate includes γ-glycidoxypropyltrimethoxysilane hydrolysate, γ-aminopropyltrimethoxysilane hydrolysate, etc. The compound contains one or more of triethoxysilane hydrolysate and γ-methacryloxypropyltrimethoxysilane hydrolysate, wherein the polyol comprises one or more of pentaerythritol, glycerol, ethylene glycol, trimethylolpropane, and trimethylolethane, and the amine comprises triethanolamine; and / or, the mass ratio of the compounded organic modifier to the core is 0.1% to 0.5%; and / or, in the compounded organic modifier, the mass ratio of the modifier, the first stabilizer, and the regulator is (8-10):(1-2):(0.1-0.5); and / or, the spray drying temperature is 160℃ to 260℃ and the flow rate is 1L / min to 10 L / min.

[0014] The present invention provides a fiber, wherein the raw material of the fiber comprises the matting agent as described above or the matting agent obtained according to the preparation method described above.

[0015] The present invention provides a method for preparing the fiber as described above, comprising the following steps: (1) mixing the matting agent with polyester monomer to obtain a spinning solution; (2) performing in-situ polymerization and spinning of the spinning solution to obtain the fiber.

[0016] This invention provides a matting agent, its preparation method, and its application. This technical solution achieves a significant synergistic effect through a multi-layered structural design: the core provides basic matting functionality, while the introduction of the antistatic layer solves the problem of static charge accumulation in polymer materials. However, a standalone antistatic layer often suffers from poor durability. By setting a transition layer and a silane-polyol-amine compatibility layer, not only is effective protection formed for the antistatic layer, significantly improving its stability under water washing, acid and alkali resistance, and high temperature and humidity conditions, ensuring long-term antistatic performance, but this compatibility layer also acts as a "bridge" between the inorganic core and the organic polymer matrix, greatly improving the dispersibility and chemical compatibility of the matting agent in the matrix. This synergy between structure and function allows the matting agent particles to be uniformly distributed and stably function in the matrix, ultimately achieving long-term, stable coexistence of both matting and antistatic functions in the polymer material. Its overall technical effect far exceeds the simple superposition of the functions of each layer. Detailed Implementation

[0017] To enable those skilled in the art to better understand the present invention, the present invention will be further described in detail below. The specific embodiments listed below are merely descriptions of the principles and features of the present invention, and the examples are only for explaining the present invention and are not intended to limit the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Current research on antistatic matting agents (such as antistatic titanium dioxide) mostly focuses on achieving a single function or simple physical mixing. For example, a patent for antistatic titanium dioxide ceramic (CN113135751A) involves simply mixing and sintering titanium dioxide with materials such as silicon dioxide and calcium oxide to create a ceramic material for antistatic purposes in spinning. This technical approach only utilizes titanium dioxide as one of the basic raw materials and does not involve functional structural design of the titanium dioxide particles themselves. While the method for preparing PET materials using antistatic agents (CN201310029494.1) involves titanium dioxide / layered bimetallic hydroxide, it employs a physical doping method, mixing the antistatic agent into the polymer matrix and achieving the antistatic effect through in-situ polymerization. Titanium dioxide is merely one of the fillers; it does not form a functional particle structure with titanium dioxide as the core. Therefore, the stability and durability of the antistatic function are difficult to compare with chemically bonded multilayer coatings. A patent for an anti-adhesion, antistatic heat-sealing coating (CN202011379611.3) mentions "titanium dioxide conductive microparticles (surface coated with antimony tin oxide)," but these microparticles are only physically dispersed as one component of the coating solution and do not form a complete functional particle structure with titanium dioxide as the core. The conductive layer is directly exposed to complex environments and is prone to performance degradation under acidic, alkaline, or high-temperature and high-humidity conditions. Fuzhou University's patent for anti-pollution flashover insulators (CN200510018529.7), although using titanium dioxide sol coating to form a thin film, only utilizes its photocatalytic and antistatic adsorption properties, without designing a multi-layer structure for the titanium dioxide particles themselves, resulting in limited strength and durability of the functional layer.

[0019] Overall, the above-mentioned antistatic matting agents have the following problems: (1) It is difficult to obtain a long-lasting antistatic effect, and the antistatic agent becomes ineffective after several washes; (2) Existing domestic antistatic titanium dioxide related patents either remain at the physical mixing level or lack multi-layer protective structure design, and have single functions and narrow application range; (3) Inorganic antistatic agents have poor compatibility and dispersion stability in polymer melts; (4) Although some antistatic agents can meet the usage requirements in all aspects, their color is dark, and the application fields of the prepared fibers are greatly limited, making it difficult to meet the visual requirements of clothing fibers.

[0020] To overcome the deficiencies in the prior art, embodiments of the present invention provide a matting agent, comprising: a core, including a matting material; an antistatic layer, covering at least a portion of the surface of the core; a transition layer, covering the surface of the antistatic layer; and a silane-polyol-amine compatible layer, covering the surface of the transition layer.

[0021] This technical solution achieves a significant synergistic effect through a multi-layered structural design: the core provides basic matting function, while the introduction of the antistatic layer solves the problem of easy accumulation of static charge in polymer materials. However, the antistatic layer alone often suffers from poor durability. By setting a transition layer and a silane-polyol-amine compatibility layer, not only is the antistatic layer effectively protected, but its stability under water washing, acid and alkali resistance, and high temperature and humidity environments is significantly improved, ensuring the long-term effectiveness of antistatic performance. At the same time, the compatibility layer also acts as a "bridge" between the inorganic core and the organic polymer matrix, greatly improving the dispersion and chemical compatibility of the matting agent in the matrix. This synergy between structure and function allows the matting agent particles to be uniformly distributed and stably function in the matrix, ultimately achieving the long-term and stable coexistence of matting and antistatic functions in the polymer material. Its overall technical effect far exceeds the simple superposition of the functions of each layer.

[0022] Furthermore, the aforementioned matting agents can be directly used in the synthesis of chemical fibers. Highly compatible matting agents can be uniformly dispersed in polymer monomers, effectively reducing the formation of matting material agglomerates and thus significantly improving the continuity and stability of the polymerization process. Based on this, antistatic polymers prepared via in-situ polymerization exhibit more stable filtration pressure and significantly reduced fiber breakage during spinning, greatly improving fiber production efficiency and batch consistency. Ultimately, a complete set of technologies covering polymerization and modification has been formed, providing key technical support for the stable industrial production of light-colored antistatic polymers.

[0023] In some embodiments, the kernel's D 50 ≤0.4μm, D 90 ≤0.8μm.

[0024] For example, the kernel's D 50 The value can be in the range of 0.1μm, 0.2μm, 0.3μm, 0.4μm, or any combination thereof, and the kernel's D... 90 It can be a range of 0.2μm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.7μm, 0.8μm or any combination thereof.

[0025] By controlling the kernel's D 50 and D 90Meeting the above-mentioned range results in a smaller core particle size. With the increased specific surface area of ​​the core, combined with the protection and bridging effect of the transition layer and the silane-polyol-amine compatibility layer, the unit mass efficiency of the matting agent can be significantly improved, resulting in a more delicate and uniform matting effect. At the same time, the small particle size core helps to form a thinner, denser, and continuous functional layer coating on the particle surface, shortening the electronic conduction path of the antistatic layer and further enhancing the stability of the antistatic performance. Thus, the dual optimization of matting efficiency and functional durability is achieved at the microstructure level.

[0026] In some embodiments, the matting material includes titanium dioxide, such as titanium white.

[0027] Introducing titanium dioxide (TiO2) into matting materials allows for efficient light scattering primarily through the refractive index difference between its high refractive index and that of the polymer matrix. This results in rapid reduction of gloss, increased opacity, and a matting effect on the product.

[0028] In some embodiments, the antistatic layer comprises a conductive oxide. The stable semiconductor bandgap structure of the conductive oxide enables rapid conduction and dissipation of electrostatic charges through a conductive network formed between particles, thereby significantly reducing the surface resistivity of the material. Simultaneously, because conductive oxides are typically light-colored or transparent, compared to traditional antistatic agents such as carbon black, they can minimize interference with the color and matting effect of the substrate material while imparting efficient and durable antistatic properties to polymer materials, achieving the dual functions of antistatic properties and maintaining aesthetic quality.

[0029] Furthermore, the conductive oxide can include antimony tin oxide (ATO, also known as antimony-doped tin oxide). As a functional material for the antistatic layer, antimony tin oxide can effectively dissipate static charge through its excellent conductivity, achieving long-lasting antistatic protection, while maintaining the light color and transparency of the polymer material or without affecting the matting effect.

[0030] In some embodiments, the transition layer comprises metal-doped zinc oxide. The metal-doped zinc oxide provides dense coating protection to the antistatic layer within the matting agent structure, preventing the antistatic layer from failing in complex environments. Simultaneously, its doping properties optimize surface chemistry, providing an ideal interface for the subsequent organic coating of the silane-polyol-amine compatibility layer. This synergistically improves overall conductivity, dispersibility, and weather resistance while ensuring the integrity of the conductive network.

[0031] Furthermore, metal-doped zinc oxide includes aluminum-doped zinc oxide. Aluminum-doped zinc oxide provides dense coating protection for the antistatic layer, preventing its failure in complex environments. Simultaneously, its doping properties optimize surface chemistry, providing an ideal interface for subsequent organic coating of the silane-polyol-amine compatibility layer. This synergistically improves overall conductivity, dispersibility, and weather resistance while ensuring the integrity of the conductive network. In addition, the aluminum-doped zinc oxide (AZO) layer effectively neutralizes the inherent blue hue of antistatic layers (such as ATO), significantly reducing the optical interference of matting agents on the color of the polymer material itself, thereby greatly expanding the application range of this matting agent in light-colored, transparent, or high-appearance-requirement products.

[0032] In some specific embodiments, the matting agent includes a core comprising a matting material including titanium dioxide (such as titanium dioxide); an antistatic layer covering at least a portion of the surface of the core, the antistatic layer comprising antimony tin oxide (ATO); a transition layer covering the surface of the antistatic layer, the transition layer comprising aluminum-doped zinc oxide (AZO); and a silane-polyol-amine compatibility layer covering the surface of the transition layer.

[0033] This invention constructs a composite structure of "titanium dioxide-ATO-AZO-silane-polyol-amine compatibility layer." While retaining the excellent conductivity of ATO, the white properties of titanium dioxide successfully neutralize the blue undertone of ATO, achieving a breakthrough in conductive filler color from dark to light. AZO also effectively neutralizes the inherent blue hue of ATO. This design allows the matting agent to impart highly efficient antistatic properties to polymer products while significantly reducing interference with the intrinsic color of the material. It is widely applicable to color-sensitive fields such as electronic product casings, medical devices, white goods, and food packaging. This "light-colored antistatic" characteristic not only meets functional requirements but also greatly enhances the visual appeal of the product, providing downstream users with greater freedom in color matching and design flexibility. The silane-polyol-amine compatibility layer, an organic film layer formed by silane, polyol, and amine, helps improve the compatibility and dispersibility of the matting agent in the polymer matrix. Furthermore, the aforementioned matting agents exhibit good dispersibility and chemical compatibility in the polymer matrix, synergistically improving overall conductivity, dispersibility, and weather resistance while ensuring the integrity of the conductive network. In addition, the well-compatible matting agents can be uniformly dispersed in the polymer monomers, effectively reducing the formation of titanium dioxide agglomerates, thereby significantly improving the continuity and stability of the polymerization process. Based on this, the antistatic polymer prepared by in-situ polymerization exhibits more stable filtration pressure and a significantly reduced fiber breakage rate during spinning, greatly improving fiber production efficiency and batch consistency. Ultimately, a complete set of technologies covering polymerization and modification has been formed, providing key technical support for the stable industrial production of light-colored antistatic polymers.

[0034] Through a core-multi-shell structure design consisting of an "ultrafine titanium dioxide core – antimony-doped tin oxide conductive layer – aluminum-doped zinc oxide transition layer – organically modified outer layer," matting performance, antistatic properties, and excellent coating applicability are integrated into a single particle, breaking the limitations of traditional matting agents with only one function. The ultrafine titanium dioxide core ensures basic matting efficiency; the first layer, antimony-doped tin oxide, provides permanent and highly efficient intrinsic antistatic properties; the second layer (aluminum-doped) zinc oxide improves surface chemistry, providing an ideal substrate for subsequent organic processing and further enhancing weather resistance or dispersibility; the third layer, an organic coating, greatly improves compatibility, dispersibility, and anti-settling properties with organic coating systems. This structure solves the industry problem of uneven performance and easy failure of traditional physically mixed additives. Through chemically bonded multi-layer coating, the antistatic function is "anchored" inside each matting agent particle, achieving uniform, stable, and durable performance.

[0035] This invention significantly simplifies the production process of downstream coatings. Users no longer need to add matting agents and antistatic agents separately, avoiding the complexity of formulation adjustments, while improving product dispersibility and storage stability. This enables downstream users to more efficiently develop high-end products that combine a delicate texture with antistatic properties; it also brings comprehensive cost advantages to the industry chain: helping to reduce raw material management costs, improve production efficiency, and by endowing end products with high-value-added characteristics such as "dust resistance and high-quality feel," it opens up the high-end industrial and consumer coatings market, forming a differentiated competitive advantage.

[0036] In practical applications, the thicknesses of the antistatic layer, transition layer, and silane-polyol-amine compatibility layer can all be in the nanometer range.

[0037] In some embodiments, the D of the matting agent 50 ≤0.4μm, D 90 ≤0.8μm.

[0038] For example, the D of the matting agent 50 The value can be in the range of 0.1μm, 0.2μm, 0.3μm, 0.4μm, or any combination thereof, and the kernel's D... 90 It can be a range of 0.2μm, 0.3μm, 0.4μm, 0.5μm, 0.6μm, 0.7μm, 0.8μm or any combination thereof.

[0039] The small particle size of the aforementioned matting agent means a significantly increased specific surface area, which provides more scattering units per unit mass in the matrix. This results in efficient matting with lower addition amounts, contributing to a smoother and more delicate surface feel and appearance. At the same time, the small particle size makes it easier for the silane-polyol-amine compatibility layer, i.e., the organic coating layer, to be uniformly dispersed and stably exist in the polymer system, avoiding performance degradation caused by gravity settling or agglomeration, thereby improving the transparency and mechanical integrity of the coating.

[0040] The present invention also provides a method for preparing the above-mentioned matting agent, comprising the following steps: forming an antistatic layer, a transition layer and a silane-polyol-amine compatibility layer sequentially on the surface of the core to obtain the matting agent.

[0041] The above preparation method can produce a long-lasting and stable matting agent with dual functions of matting and antistatic properties.

[0042] In specific implementation, an antistatic layer, a transition layer, and a silane-polyol-amine compatibility layer are sequentially formed on the surface of the core to obtain a matting agent. The process includes: (1) providing a first dispersion containing the core, a second dispersion containing a conductive oxide precursor, a metal precursor solution, an aluminum precursor solution, and a compounded organic modifier; wherein the compounded organic modifier includes a modifier, a first stabilizer, and a regulator, the modifier includes a silane coupling agent hydrolysate, the first stabilizer includes a polyol, and the regulator includes amines; (2) adding the second dispersion dropwise to the first dispersion to obtain a first mixture; subjecting the first mixture to a first reaction to obtain a core dispersion coated with conductive oxide; wherein the dropwise addition time is 1 hour. 4h; During the dropwise addition, the pH of the system is controlled to be less than 4 and the temperature is 70℃~95℃; The time of the first reaction is 4h~12h and the temperature is 70℃~95℃; (3) The metal precursor solution and the zinc precursor solution are added in parallel to the core dispersion coated with conductive oxide to obtain the second mixture; The second mixture is subjected to the second reaction, and then solid-liquid separation is performed to obtain the double-layer coated core; The time of parallel addition is 1h~3h, and the pH of the system is controlled to be 3~5 and the temperature is 70℃~95℃ during the parallel addition; The time of the second reaction is 2h~4h and the temperature is 70℃~95℃; (4) The double-layer coated core and the compounded organic modifier are mixed and spray-dried to obtain the matting agent.

[0043] The process involves first coating with an antistatic layer, then with a transition layer, and finally performing organic modification. This sequence ensures that: the antistatic layer adheres firmly to the core surface; the transition layer effectively covers and protects the antistatic layer, preventing its failure in complex systems and further improving conductivity; and the silane-polyol-amine compatibility layer, i.e., the organic coating, maximizes its bonding with the polymer without detaching due to the instability of the underlying structure. This multi-layer coating process, especially the continuous and uniform coating technology for the antistatic and transition layers, has a high technological barrier, is not easily imitated, and is conducive to building high technological barriers, maintaining a long-term competitive advantage and pricing power in the market.

[0044] In some embodiments, the first dispersion is prepared by a method comprising at least the following steps: mixing a first raw material system comprising a core, a dispersant, and a first solvent to obtain the first dispersion. For example, the above process may include: mixing the core with the first solvent to form a core suspension; mixing the dispersant with water to form a dispersant solution; and mixing the core suspension with the dispersant solution to obtain the first dispersion.

[0045] In specific implementation, the core and dispersant can be added to the first solvent to mix the first raw material system, and then shear dispersion is performed to obtain the first dispersion. The present invention does not impose a particular limitation on the solid content of the first dispersion. For example, its solid content can be 7% or around. The rotation speed of the shear dispersion (such as high-speed shear dispersion) can be 3000 rpm ± 500 rpm and the time can be 30 minutes ± 5 minutes.

[0046] kernel D 50 It can be ≤0.4μm, D 90 With a particle size of ≤0.8μm, the smaller core can form a denser and more uniform micro-rough surface in the paint film, thus enabling the matting agent to achieve a better matting effect and a more delicate feel at the same addition amount.

[0047] The dispersant may include one or more of sodium silicate, pentaerythritol, sodium hexametaphosphate, sodium dihydrogen phosphate, sodium dodecylbenzene sulfonate, octylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, mono- and diglycerides of monolaurate, polyacrylate, polyphosphate, nonylphenol polyoxyethylene ether, sorbitan alkylphenol, polyoxyethylene ether phosphate, and phosphate salts. Preferably, the dispersant includes at least one of octylphenol polyoxyethylene ether, polyphosphate, nonylphenol polyoxyethylene ether, sorbitan alkylphenol, polyoxyethylene ether phosphate, and phosphate salts.

[0048] The mass ratio of dispersant to core can be 0.1% to 0.5%, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, or any combination thereof, which helps to improve the dispersion effect of the core, thereby improving the coating effect of the antistatic layer and enhancing the matting and antistatic properties of the matting agent.

[0049] The first solvent may include one or more of ethanol, water (such as deionized water), dimethylacetamide, acetic acid, and caprolactam aqueous solution.

[0050] In some embodiments, the second dispersion is prepared by a method comprising at least the following steps: mixing a second stabilizer and a second solvent, then adding a second raw material system comprising a conductive oxide precursor, stirring and mixing uniformly to obtain the second dispersion.

[0051] By pre-preparing the conductive oxide precursor and the second stabilizer into a uniform, stable, and clear second dispersion, the problems of poor uniformity, loose coating layer, and poor repeatability in the preparation of doped coating materials by the traditional co-precipitation method are fundamentally solved. In the end, a conductive matting agent with excellent conductivity, high stability, and uniform performance is produced.

[0052] Specifically, conductive oxide precursors may include antimony precursors and tin precursors.

[0053] The antimony precursor may include one or more of potassium antimony tartrate, antimony acetate, antimony glycolate, and antimony chloride (such as antimony trichloride).

[0054] In specific implementation, the antimony precursor is mixed with the second stabilizer and the second solvent in the form of an antimony precursor solution. The mass percentage of antimony precursor in the antimony precursor solution can be 0.5% to 10%, for example, 0.5%, 1%, 3%, 5%, 8%, 10%, or any combination thereof.

[0055] Tin precursors may include one or more of tin acetate and tin chloride (such as tin tetrachloride).

[0056] In specific implementation, the tin precursor is mixed with the second stabilizer and the second solvent in the form of a tin precursor solution. The mass percentage of the tin precursor in the tin precursor solution can be 0.5% to 10%, for example, 0.5%, 1%, 3%, 5%, 8%, 10%, or any combination thereof.

[0057] The mass ratio of tin precursor to core, based on tin oxide, can be 0.5% to 3%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, or any combination thereof.

[0058] In the second dispersion, the molar ratio of antimony to tin can be (0.01~0.3):1, for example, 0.01:1, 0.05:1, 0.1:1, 0.15:1, 0.2:1, 0.25:1, 0.3:1, or any combination thereof. The molar ratio of antimony to tin, i.e., the antimony doping ratio, exhibits a "volcano-like" influence on the conductivity of antistatic layers such as antimony tin oxide (ATO). When the molar ratio of antimony to tin meets the above range, the conductivity of the matting agent or antistatic layer is better. Specifically, when the doping ratio is within the above range, Sb... 3+ Ion-substituted Sn 4+ It releases free electrons, increasing carrier concentration, decreasing resistivity, and improving conductivity. When the optimal doping ratio is reached, the effective carrier concentration is highest, the resistivity is lowest, and the conductivity is best. However, if the above range is exceeded, such as with excessive antimony, it can lead to lattice distortion and the generation of Sb that does not contribute electrons. 3+ Furthermore, enhanced impurity scattering actually reduces carrier mobility, increases resistivity, and degrades conductivity. Therefore, precisely controlling the antimony doping level is crucial for optimizing the conductivity of ATO.

[0059] The second stabilizer may include one or more of the following: stearic acid, hydroxycellulose, polyacrylamide, disodium ethylenediaminetetraacetate, pentaerythritol oleate, pentaerythritol stearate, 1-vinyl-2-pyrrolidone homopolymer, polyethylene glycol laurate, polyvinyl alcohol, and sodium alginate phosphate.

[0060] The ratio of the molar amount of the second stabilizer to the total molar amount of tin and antimony can be (2~5):1, for example, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1 or any combination thereof.

[0061] The second solvent may include one or more of water and ethanol, for example, it may include a mixed solvent of water and ethanol in a volume ratio of 1:(1±0.1).

[0062] Preferably, the second stabilizer includes at least one of disodium ethylenediaminetetraacetate, pentaerythritol oleate, pentaerythritol stearate, 1-vinyl-2-pyrrolidone homopolymer, and polyethylene glycol laurate; the antimony precursor includes at least one of antimony acetate, antimony glycolate, and antimony chloride; in the second dispersion, the molar ratio of antimony to tin is (0.05-0.2):1; based on tin oxide, the mass ratio of tin precursor to core is 1%-3%; the molar amount of the second stabilizer to the total molar amount of tin and antimony is (2-4):1.

[0063] Under the aforementioned preferred ratio and method, firstly, molecular-level uniform mixing can be achieved: in the solution state, tin and antimony ions are highly dispersed and stably bound, ensuring atomic-level uniform doping of the two elements in the subsequent coating layer from the source; secondly, the stabilizer effectively "binds" the metal ions, allowing them to be slowly and controllably released and hydrolyzed when subsequently added to the core suspension, avoiding instantaneous large-scale precipitation. Controlled hydrolysis deposition is beneficial for forming a dense, uniform, and thin layer of antimony-doped tin oxide coating on the surface of the core particles, which is crucial for improving the conductivity, weather resistance, and other properties of the core.

[0064] In step (2), the second dispersion is added dropwise to the first dispersion to obtain the first mixture; the first mixture is subjected to a first reaction to obtain a core dispersion coated with conductive oxide. The dropwise addition time is 1h to 4h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or any combination thereof; the pH of the system is controlled to be less than 4 during the dropwise addition, for example, 2.0, 2.5, 3.0, 3.5, 3.8, 3.9 or any combination thereof; the temperature of the system is controlled to be 70℃ to 95℃ during the dropwise addition, for example, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or any combination thereof; the time of the first reaction is 4h to 12h, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h or any combination thereof; the temperature of the first reaction is 70℃ to 95℃, for example, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃ or any combination thereof. Preferably, the dropping time is 2h to 4h, and the temperature of the system is controlled at 70℃ to 90℃ during the dropping process; the first reaction time is 6h to 12h, and the temperature of the first reaction is 70℃ to 90℃.

[0065] In specific implementation, the first dispersion can be heated to 70℃~95℃, preferably 70℃~90℃, and then the second dispersion can be slowly added to the first dispersion through a constant pressure dropping funnel to obtain the first mixture; the first mixture is subjected to a first reaction (or aging) to obtain a core dispersion coated with conductive oxide.

[0066] Under the aforementioned process parameters, the performance of the matting agent is ensured. Coating under acidic conditions strongly inhibits the rapid hydrolysis and precipitation of tin and antimony ions, ensuring sufficient time for precursor ions to migrate and adsorb onto the surface of the core particles before undergoing in-situ surface reactions. This results in predominantly heterogeneous nucleation, avoiding the formation of impurity particles through homogeneous nucleation in solution. Slow dropwise addition further ensures that the addition rate matches the surface reaction rate, achieving uniform growth of the coating layer. A suitable reaction temperature provides sufficient activation energy to promote the formation and crystallization of a dense oxide layer, while avoiding excessively high temperatures that could lead to runaway reactions or severe solvent evaporation. Sufficient reaction time ensures complete coating reaction, resulting in a fully densified and stabilized coating layer. This invention provides a selection list of various stabilizers, solvents, and precursors, demonstrating the universality and adjustability of the method.

[0067] In addition, a 3wt%-5wt% dilute sulfuric acid solution can be used to control the pH of the system to be less than 4 to prevent excessive local acidity in the system.

[0068] The process of preparing the kernel dispersion described above can be carried out under stirring conditions of 300±100 rpm (such as strong stirring), which helps to improve the reaction effect.

[0069] In step (3), the pH of the core dispersion coated with conductive oxide can be adjusted to 3-5, for example, by using dilute ammonia. Then, the metal precursor solution and the aluminum precursor solution are added co-currently to the core dispersion coated with conductive oxide to obtain a second mixture. The second mixture is subjected to a second reaction, followed by solid-liquid separation to obtain a double-layer coated core. The co-current addition time is 1h~3h, for example, 1h, 1.5h, 2h, 2.5h, 3h or any combination thereof. The pH of the system is controlled during the co-current addition process. The temperature of the system during the co-current feeding process is controlled at 70℃ to 95℃, for example, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, or any two of these values. The time of the second reaction is 2h to 4h, for example, 2h, 2.5h, 3h, 3.5h, 4h, or any two of these values. The temperature of the second reaction is 70℃ to 95℃, for example, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, or any two of these values.

[0070] Aluminum-doped zinc oxide (ZnO / Al2O3) coatings are commonly used to enhance the weather resistance, dispersibility, and chemical stability of the core. The innovation of this step lies in its non-isolated nature; rather, it involves constructing a synergistic protective / modifying layer on top of an existing antistatic or conductive layer (such as an ATO coating). The simultaneous and co-current addition of zinc and aluminum precursor solutions to the reaction system is a key technological innovation for achieving uniform co-precipitation and atomic-level doping. This ensures that zinc and aluminum ions hydrolyze and co-precipitate simultaneously in the solution, forming a uniformly doped alumina-based mixed oxide layer on the particle surface, rather than a simple physical mixture or layered structure.

[0071] In practice, the above-mentioned parallel feeding process can be carried out using a dual-channel peristaltic pump.

[0072] More preferably, the temperature of the system is controlled at 70℃~90℃ during the parallel feeding process.

[0073] In practice, the pH of the core dispersion coated with conductive oxide can be slowly adjusted to 3-5. Then, the metal precursor solution and the aluminum precursor solution are added to it in parallel, and the addition time is controlled to be 1-3 hours. During this period, the pH of the system is controlled to be 3-5 by adding dilute sulfuric acid. Then, the system is heated and stirred for 2-4 hours. After centrifugation and washing, a double-layer coated core is obtained.

[0074] For example, a 3wt%-5wt% dilute sulfuric acid solution can be used to control the pH of the system to 3-5 to prevent excessively high local acidity in the system.

[0075] In addition, after the second reaction, the reaction system can be cooled to room temperature and then centrifuged to remove the supernatant and obtain the precipitate. The precipitate is then resuspended and washed multiple times with sufficient deionized water until the conductivity of the centrifuged effluent is less than 100 μS / cm. The filter cake is then collected to obtain the double-layer coated core.

[0076] In some embodiments, the mass percentage of zinc precursor in the zinc precursor solution can be 0.5% to 10%, for example, 0.5%, 1%, 3%, 5%, 8%, 10%, or any combination thereof.

[0077] Zinc precursors include one or more of zinc sulfate and zinc chloride; aluminum precursors may include one or more of aluminum sulfate, sodium aluminate, and aluminum chloride.

[0078] The mass ratio of zinc precursor to core, based on zinc oxide, can be 0.2%-3%, for example, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3% or any combination thereof, preferably 0.5%-2%.

[0079] In some embodiments, the mass percentage of the metal precursor in the aluminum metal precursor solution is 0.5% to 10%, for example, 0.5%, 1%, 3%, 5%, 8%, 10%, or any combination thereof.

[0080] Aluminum precursors may include one or more of aluminum sulfate, sodium aluminate, and aluminum chloride.

[0081] The molar ratio of the metal element in the metal precursor to the aluminum element in the zinc precursor can be (0.01~0.1):1, 0.01:1, 0.02:1, 0.03:1, 0.05:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1 or any combination thereof, preferably (0.02~0.1):1.

[0082] Taking aluminum-doped zinc oxide (AZO) as an example, the conductivity of aluminum-doped zinc oxide exhibits a "first increases, then decreases" pattern with the change in aluminum doping ratio, indicating an optimal doping range as described above. Within this range, when the aluminum doping amount is low, Al... 3+ Ion effective substitute for Zn 2+ Lattice sites provide free electrons, increasing carrier concentration and decreasing resistivity. However, when the aluminum doping amount exceeds the above range, excess aluminum will segregate at grain boundaries due to thermodynamic solid solubility limitations, forming inactive Al2O3 phases or defect complexes. This, in turn, reduces the effective carrier concentration and mobility, leading to a rebound in resistivity and degradation of conductivity. Therefore, precisely controlling the aluminum doping ratio within the above range is crucial for obtaining highly conductive AZO materials.

[0083] In step (4), the double-layer coated core can be dispersed in water (such as deionized water) and the solid content can be adjusted to 30%±3%. Then, it is mixed with a compounded organic modifier and reacted in a warm water bath. Then, it is spray-dried to obtain a matting agent. The temperature of the warm water bath reaction can be 60℃±5℃ and the time can be 2h±0.2h.

[0084] As can be seen from the above, the compound organic modifier includes a modifier, a first stabilizer, and a regulator. The modifier includes a silane coupling agent hydrolysate, the first stabilizer includes a polyol, and the regulator includes amines.

[0085] The modifier grafts titanium dioxide by forming hydrogen bonds between silanol groups and hydroxyl groups on the surface of titanium dioxide, and controls the product environment to prevent particle agglomeration by using a regulator. In some embodiments, the silane coupling agent hydrolysate includes one or more of γ-glycidoxypropyltrimethoxysilane hydrolysate, γ-aminopropyltriethoxysilane hydrolysate, and γ-methacryloyloxypropyltrimethoxysilane hydrolysate; the polyol includes one or more of pentaerythritol, glycerol, ethylene glycol, trimethylolpropane, and trimethylolethane; and the amine includes triethanolamine.

[0086] The hydrolysate of silane coupling agent can be obtained by a method including at least the following steps: Mix water and ethanol in a ratio (e.g., 1:1 to 1:9), then take 50 to 90 parts and adjust the pH to the target level of 3 to 6 with acetic acid. Then, slowly add 5 to 20 parts of the silane coupling agent while stirring, avoiding excessively high local concentrations. Stir at room temperature for 10 to 30 minutes, and let stand for 0.5 to 2 hours before use.

[0087] In some embodiments, the mass ratio of the compounded organic modifier to the core is 0.1% to 0.5%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, or any combination thereof, preferably 0.2% to 0.5%.

[0088] In some embodiments, the mass ratio of the modifier, the first stabilizer, and the regulator in the compounded organic modifier is (8-10):(1-2):(0.1-0.5), preferably (9-10):(1-2):(0.1-0.4).

[0089] The spray drying temperature (or inlet temperature) can be 160℃~260℃, and the flow rate can be 1L / min~10 L / min. For example, the spray drying temperature can be a range of 160℃, 180℃, 200℃, 220℃, 240℃, 260℃ or any combination thereof, preferably 200℃~260℃; the flow rate, i.e., the feed pump velocity, can be a range of 1L / min, 2L / min, 3L / min, 4L / min, 5L / min, 6L / min, 7L / min, 8L / min, 9L / min, 10 L / min or any combination thereof, preferably 3L / min~10 L / min.

[0090] This invention employs spray drying for organic modification to form a silane-polyol-amine compatible layer. The technical advantages are as follows: by rapidly evaporating moisture, the compounded organic modifier is uniformly loaded onto the surface of the core particles, avoiding thermal damage to the modifier. At the same time, it provides precursor powder for the high-energy collision of the modifier and particles in subsequent air jet milling, thereby synergistically achieving efficient, uniform, and firm adhesion of the modifier to the core surface, which helps to improve the dispersibility and chemical compatibility of the matting agent in the polymer matrix.

[0091] After spray drying, the resulting powder can be pulverized and deagglomerated, for example, using an air jet mill, to obtain a matting agent with a suitable particle size. For instance, this can help the matting agent achieve a particle size distribution of D. 50 ≤ 0.4 μm, D 90 Technical requirement: ≤ 0.8 μm.

[0092] The embodiments of the present invention do not impose special limitations on the conditions for the above-mentioned pulverization and deagglomeration treatment, such as the nozzle pressure of the air jet mill, the speed of the classifier wheel, etc., as long as the above-mentioned particle size distribution can be achieved.

[0093] This invention also provides a fiber, the raw material of which includes the above-mentioned matting agent or a matting agent obtained according to the above preparation method.

[0094] Based on this matting agent, the above-mentioned fibers have long-lasting and stable matting properties and antistatic properties.

[0095] The present invention also provides a method for preparing the above-mentioned fiber, comprising the following steps: (1) mixing a matting agent with a polyester monomer (or fiber precursor) to obtain a spinning solution; (2) performing in-situ polymerization and spinning of the spinning solution to obtain the fiber.

[0096] The aforementioned fibers possess long-lasting and stable antistatic and matting properties.

[0097] In practice, after the above-mentioned fibers are washed with water, they still retain long-term and stable antistatic properties.

[0098] The above preparation method is particularly suitable for preparing conventional polyesters, antimony-free environmentally friendly polyesters, cationic dyeable polyesters, polyamides, and polyurethanes with good antistatic and matting properties.

[0099] In some embodiments, the preparation method of polyester using the above-mentioned matting agent includes the following steps: adding polyester raw materials into a polymerization reactor for pulping, closing the polymerization reactor for nitrogen purging, carrying out esterification reaction under certain temperature and pressure conditions, removing esterification water after separation in a process tower and cooling in a condenser, adding matting agent to the esterified product, vacuuming and depressurizing, controlling a certain polycondensation temperature, and carrying out low-vacuum pre-polymerization and high-vacuum polycondensation reactions. After reaching the expected stirring power, the melt is cast into a strip, cooled underwater, and pelletized to obtain antistatic polyester chips.

[0100] Polyester raw materials may include monomers and catalysts. Monomers may include terephthalic acid and ethylene glycol, and catalysts may include antimony glycolate catalysts.

[0101] The embodiments of the present invention do not impose special limitations on the amount and operating conditions of the above-mentioned raw materials; selection can be made in accordance with conventional techniques in the field.

[0102] The present invention will be further described below through specific embodiments and comparative examples. Unless otherwise specified, the reagents, materials and instruments used below are all conventional reagents, materials and instruments, all of which are commercially available, and the reagents and materials involved can also be synthesized by conventional synthetic methods.

[0103] Example 1

[0104] This embodiment provides a method for preparing a matting agent, including:

[0105] (1) Providing a first dispersion comprising a core, comprising mixing a first raw material system comprising a core, a dispersant and a first solvent, and dispersing it at a high speed of 3000 rpm for 30 minutes to obtain the first dispersion; wherein the core comprises 100 parts by mass of titanium dioxide, the dispersant comprises 0.3 parts by mass of sodium hexametaphosphate, the mass ratio of the dispersant to the core is 0.3%, and the first solvent comprises 500 parts by mass of deionized water; the core's D 50 0.35μm, D 90 It is 0.6μm;

[0106] A second dispersion comprising a conductive oxide precursor is provided, comprising mixing a second stabilizer and a second solvent, then adding the mixture to a second raw material system comprising the conductive oxide precursor solution, and stirring to mix evenly to obtain the second dispersion; wherein the conductive oxide precursor solution comprises 6 parts by mass of an antimony precursor solution and 70 parts by mass of a tin precursor solution, the antimony precursor in the antimony precursor solution comprising antimony trichloride and the antimony trichloride mass percentage being 5%, and the tin precursor in the tin precursor solution comprising tin tetrachloride and the tin tetrachloride mass percentage being 5%; in the second dispersion, the molar ratio of antimony to tin is 0.1:1, the second stabilizer comprises 17 parts by mass of disodium ethylenediaminetetraacetate, and the molar ratio of the second stabilizer to the total molar amount of tin and antimony is 3.5:1; the second solvent comprises a mixed solvent of water and ethanol in a volume ratio of 1:1.

[0107] (2) Under stirring, the second dispersion is added dropwise to the first dispersion to obtain the first mixture; the first mixture is subjected to the first reaction to obtain the core dispersion coated with conductive oxide; wherein, the dropwise addition time is 2.5h; during the dropwise addition, the pH of the system is controlled to be 3.5±0.2 and the temperature is 85℃ by simultaneously adding 5wt% dilute sulfuric acid solution; the first reaction time is 8h and the temperature is 85℃.

[0108] (3) The pH of the core dispersion coated with conductive oxide was slowly adjusted to 4.5 with dilute ammonia water. Then, 4 parts by mass of the metal precursor solution and 135 parts by mass of the aluminum precursor solution were added to the core dispersion coated with conductive oxide in a parallel flow to obtain a second mixture. The second mixture was subjected to a second reaction under stirring. After the second reaction was completed, the reaction system was cooled to room temperature and then centrifuged. The supernatant was discarded to obtain the precipitate. The precipitate was then resuspended and washed multiple times with sufficient deionized water until the conductivity of the centrifuged effluent was less than 100%. μS / cm, collecting the filter cake yields a double-layered coated core; the zinc precursor solution contains zinc sulfate with a mass percentage of 5%; the metal precursor solution contains aluminum sulfate with a mass percentage of 2%; the metal precursor includes a zinc precursor, which includes one or more of zinc sulfate, zinc chloride, and zinc acetate; the molar ratio of aluminum in the metal precursor to aluminum in the zinc precursor is 0.05:1; the co-current feeding time is 2h, and the pH of the system is controlled at 4.5±0.2 and the temperature at 85℃ by continuously adding 4wt% dilute sulfuric acid during the co-current feeding process; the second reaction time is 3h;

[0109] (4) The double-layer coated core is dispersed in deionized water and the solid content is adjusted to 30%±3%. Then it is mixed with the compounded organic modifier and reacted in a warm water bath. Then it is spray dried and the spray-dried product is crushed and depolymerized to obtain a matting agent. The compounded organic modifier includes a modifier, a first stabilizer and a regulator. Water and ethanol are mixed in a ratio of 1:5. 90 parts are taken and acetic acid is added to adjust the pH to the target pH 5. 100 parts of γ-glycidyl etheroxypropyltrimethoxysilane are slowly added under stirring. The mixture is stirred at room temperature for 30 minutes and allowed to stand for 2 hours. 0.36 parts are then taken out as the modifier. The first stabilizer includes 0.06 parts by mass of trimethylolpropane, and the modifier includes 0.018 parts by mass of triethanolamine; that is, the mass ratio of the modifier, the first stabilizer and the modifier is 9:1.5:0.45, the mass ratio of the compounded organic modifier to the core is 0.438%, the spray drying temperature is 200℃ and the flow rate is 5L / min, and the warm water bath reaction temperature can be 60℃ and the time can be 2h.

[0110] Example 2

[0111] This embodiment is basically the same as Embodiment 1, except that:

[0112] The conductive oxide precursor solution includes 2 parts by mass of antimony precursor solution and 35 parts by mass of tin precursor solution; in the second dispersion, the molar ratio of antimony to tin is 0.067:1, and other conditions remain unchanged.

[0113] Example 3

[0114] This embodiment is basically the same as Embodiment 1, except that:

[0115] The amount of the metal precursor solution, namely aluminum sulfate solution, was adjusted to 2 parts by mass, and the amount of the zinc precursor solution was adjusted to 67.5 parts by mass; other conditions remained unchanged.

[0116] Example 4

[0117] This embodiment is basically the same as Embodiment 1, except that:

[0118] The amount of antimony precursor solution was adjusted to 3 parts by mass, and the molar ratio of antimony to tin in the second dispersion was 0.05:1; other conditions remained unchanged.

[0119] Example 5

[0120] This embodiment is basically the same as Embodiment 1, except that:

[0121] The amount of the second stabilizer, disodium ethylenediaminetetraacetate, is adjusted to 9.7 parts by mass, and the molar ratio of the second stabilizer to the total molar amount of tin and antimony is 2:1; other conditions remain unchanged.

[0122] Example 6

[0123] This embodiment is basically the same as Embodiment 1, except that:

[0124] The amount of the metal precursor solution, i.e., aluminum sulfate solution, was adjusted to 2 parts by mass, and the molar ratio of aluminum in the metal precursor to zinc in the zinc precursor was 0.025:1; other conditions remained unchanged.

[0125] Example 7

[0126] This embodiment is basically the same as Embodiment 1, except that:

[0127] In step (2), the pH of the system is controlled at 3 ± 0.2; other conditions remain unchanged.

[0128] Example 8

[0129] This embodiment is basically the same as Embodiment 1, except that:

[0130] The dripping time was 1 hour; other conditions remained unchanged.

[0131] Example 9

[0132] This embodiment is basically the same as Embodiment 1, except that:

[0133] kernel D 50 0.4μm, D 90 It is 0.8μm;

[0134] In the first dispersion, the dispersant is replaced with octylphenol polyoxyethylene ether; the amount of dispersant is adjusted so that the mass ratio of dispersant to core is 0.1%; in the second dispersion, the antimony precursor is replaced with potassium antimony tartrate and the tin precursor is replaced with tin acetate; the amount of antimony precursor is adjusted so that the molar ratio of antimony to tin is 0.01:1; at the same time, the amount of the second stabilizer is adjusted so that the molar ratio of the second stabilizer to the total molar ratio of tin and antimony is 2:1; the second stabilizer is replaced with stearic acid.

[0135] In step (2), the dropping time is 4 hours, and the temperature of the system is controlled at 70°C during the dropping process; the first reaction time is 12 hours and the temperature is 70°C.

[0136] In step (3), the co-current feeding time is 1 hour, and the pH of the system is controlled at 3 and the temperature at 95°C during the co-current feeding process; the second reaction time is 2 hours and the temperature is 95°C; the mass percentage of zinc precursor in the zinc precursor solution is 0.5%; the zinc precursor is replaced with zinc chloride; the mass percentage of metal precursor in the metal precursor solution is 0.5%; the metal precursor includes aluminum precursor, which is replaced with sodium aluminate; the amount of sodium aluminate is adjusted so that the molar ratio of aluminum in the metal precursor to zinc in the zinc precursor is 0.01~0.1:1;

[0137] In step (4), the modifier includes γ-aminopropyltriethoxysilane hydrolysate, the polyol includes pentaerythritol, and the mass ratio of the modifier, the first stabilizer, and the regulator is 8:2:0.1; the mass ratio of the compounded organic modifier to the core is 0.1%; the spray drying temperature is 160℃ and the flow rate is 1L / min;

[0138] All other conditions remain unchanged.

[0139] Example 10

[0140] This embodiment is basically the same as Embodiment 1, except that:

[0141] In the first dispersion, the dispersant is replaced with glyceryl mono- and di-caprylate monolaurate; the amount of dispersant is adjusted so that the mass ratio of dispersant to core is 0.5%; in the second dispersion, the antimony precursor is replaced with antimony acetate, and the amount of antimony precursor is adjusted so that the molar ratio of antimony to tin is 0.3:1, while the amount of the second stabilizer is adjusted so that the molar ratio of the second stabilizer to the total molar ratio of tin and antimony is 5:1; the second stabilizer is replaced with pentaerythritol stearate.

[0142] kernel D 50 0.3μm, D 90 It is 0.7μm;

[0143] In step (2), the dropping time is 4 hours, and the temperature of the system is controlled at 95°C during the dropping process; the first reaction time is 4 hours and the temperature is 95°C.

[0144] In step (3), the co-current feeding time is 3 hours, and the pH of the system is controlled at 5 and the temperature at 70°C during the co-current feeding process; the second reaction time is 4 hours and the temperature is 70°C; the mass percentage of zinc precursor in the zinc precursor solution is 10%; the zinc precursor is replaced with zinc chloride; the mass percentage of metal precursor in the metal precursor solution is 10%; the metal precursor includes aluminum precursor, and the aluminum precursor is replaced with aluminum chloride; the amount of aluminum chloride is adjusted so that the molar ratio of aluminum in the metal precursor to zinc in the zinc precursor is 0.1:1;

[0145] In step (4), the modifier includes γ-aminopropyltriethoxysilane hydrolysate, the polyol includes pentaerythritol, and the mass ratio of the modifier, the first stabilizer, and the regulator is 10:1:0.5; the mass ratio of the compounded organic modifier to the core is 0.5%; the spray drying temperature is 260℃ and the flow rate is 10L / min;

[0146] All other conditions remain unchanged.

[0147] Comparative Example 1

[0148] This comparative example is basically the same as Example 1, except that:

[0149] After cooling the core dispersion coated with conductive oxide obtained in step (2) to room temperature, centrifuge it, discard the supernatant, and obtain the precipitate. Then, resuspend and wash the precipitate with sufficient deionized water multiple times until the conductivity of the centrifuged effluent is less than 100 μS / cm, and collect the filter cake. Then, replace the double-layer coated core with the filter cake in step (4). That is, the coating in step (3) is not performed in this comparative example. Other conditions remain unchanged.

[0150] Comparative Example 2

[0151] This comparative example is basically the same as Example 1, except that:

[0152] Step (2) is skipped, and the first dispersion is used instead of the core dispersion coated with conductive oxide in step (3) for step (3) and subsequent steps; other conditions remain unchanged.

[0153] Comparative Example 3

[0154] This comparative example is basically the same as Example 1, except that:

[0155] Perform step (3) first, then step (2); keep other conditions unchanged.

[0156] The preparation method of Comparative Example 3 specifically includes:

[0157] (1) A first dispersion comprising a core is provided, comprising mixing a first raw material system comprising a core, a dispersant and a first solvent, and dispersing it at a high speed of 3000 rpm for 30 minutes to obtain the first dispersion; wherein the core comprises 100 parts by mass of titanium dioxide, the dispersant comprises 0.3 parts by mass of sodium hexametaphosphate, the mass ratio of the dispersant to the core is 0.3%, and the first solvent comprises 500 parts by mass of deionized water;

[0158] A second dispersion comprising a conductive oxide precursor is provided, comprising mixing a second stabilizer and a second solvent, then adding the mixture to a second raw material system comprising the conductive oxide precursor solution, and stirring to mix evenly to obtain the second dispersion; wherein the conductive oxide precursor solution comprises 6 parts by mass of an antimony precursor solution and 70 parts by mass of a tin precursor solution, the antimony precursor in the antimony precursor solution comprising antimony trichloride and the antimony trichloride mass percentage being 5%, and the tin precursor in the tin precursor solution comprising tin tetrachloride and the tin tetrachloride mass percentage being 5%; in the second dispersion, the molar ratio of antimony to tin is 0.1:1, the second stabilizer comprises 17 parts by mass of disodium ethylenediaminetetraacetate, and the molar ratio of the second stabilizer to the total molar amount of tin and antimony is 3.5:1; the second solvent comprises a mixed solvent of water and ethanol in a volume ratio of 1:1.

[0159] (2) The pH of the first dispersion was slowly adjusted to 4.5 with dilute ammonia water. Then, 4 parts by mass of the metal precursor solution and 135 parts by mass of the aluminum precursor solution were added to the first dispersion in a co-current manner to obtain the second mixture. The second mixture was subjected to a second reaction under stirring. After the second reaction was completed, the second reaction dispersion was obtained. The zinc precursor in the zinc precursor solution included zinc sulfate and the mass percentage of zinc sulfate was 5%. The metal precursor in the metal precursor solution included aluminum sulfate and the mass percentage of aluminum sulfate was 2%. The metal precursor included aluminum precursor, which included one or more of aluminum sulfate, sodium aluminate, and aluminum chloride. The molar ratio of aluminum in the metal precursor to zinc in the zinc precursor was 0.05:1. The co-current addition time was 2 hours. During the co-current addition process, the pH of the system was controlled to be 4.5±0.2 and the temperature was 85℃ by continuously adding 4wt% dilute sulfuric acid. The second reaction time was 3 hours.

[0160] (3) Under stirring, the second dispersion is added dropwise to the second reaction dispersion to obtain the first mixture; the first mixture is subjected to the first reaction, and after the first reaction is completed, the reaction system is cooled to room temperature and then centrifuged to separate the two layers. The supernatant is discarded to obtain the precipitate. The precipitate is then resuspended and washed multiple times with sufficient deionized water until the conductivity of the centrifuged discharge is less than 100 μS / cm. The filter cake is collected to obtain the double-layer coated core. The dropwise addition time is 2.5 h. During the dropwise addition, the pH of the system is controlled at 3.5 ± 0.2 and the temperature is 85 °C by simultaneously adding 5 wt% dilute sulfuric acid solution. The first reaction time is 8 h and the temperature is 85 °C.

[0161] (4) The double-layer coated core is dispersed in deionized water and the solid content is adjusted to 30%. Then it is mixed with the compounded organic modifier and reacted in a warm water bath. Then it is spray dried and the spray-dried product is crushed and depolymerized to obtain a matting agent. The compounded organic modifier includes a modifier, a first stabilizer and a regulator. The modifier includes 0.36 parts by mass of γ-glycidyl etheroxypropyltrimethoxysilane hydrolysate, the first stabilizer includes 0.06 parts by mass of trimethylolpropane, and the regulator includes 0.018 parts by mass of triethanolamine. The spray drying temperature is 200℃ and the flow rate is 5L / min. The warm water bath reaction temperature can be 60℃ and the time can be 2h.

[0162] Comparative Example 4

[0163] This comparative example is basically the same as Example 1, except that:

[0164] In step (2), the pH of the system was controlled at 7.5 ± 0.2; other conditions remained unchanged.

[0165] Comparative Example 5

[0166] This comparative example is basically the same as Example 1, except that:

[0167] In step (4), the double-layer coated core is dispersed in deionized water and the solid content is adjusted to 30%±3%. Then it is spray-dried. That is, the organic modification coating in step (4) is not performed in this comparative example; other conditions remain unchanged.

[0168] Application Example 1

[0169] The preparation steps for preparing antistatic polyester chips using the matting agents of each embodiment include:

[0170] 830 parts by mass of terephthalic acid, 387 parts by mass of ethylene glycol, and 200 ppm of ethylene glycol antimony catalyst were added to a polymerization reactor for pulping. The polymerization reactor was then closed and purged with nitrogen. Esterification was carried out at a temperature of 250°C and a pressure of 3.5 bar. After separation in a process tower and cooling in a condenser, the esterification water was removed. 21.6 parts of the matting agent from each of the above examples and comparative examples were added to the esterified product. The pressure was reduced by vacuum, and the polycondensation temperature was controlled at 280°C. After low-vacuum pre-polymerization and 50 Pa high-vacuum polycondensation, the expected stirring power was achieved. The melt was then cast, cooled underwater, and pelletized to obtain the polyester chips of each example and comparative example.

[0171] Upon testing, the particle size distribution of the matting agents in the above embodiments and comparative examples satisfies: D 50 ≤0.4μm, D 90 ≤0.8μm.

[0172] Detection example

[0173] The resistivity of the matting agent and polyester chips in each embodiment and comparative example was tested:

[0174] The resistivity of the matting agent, i.e., the powder resistivity test, is conducted according to the general rules of the national standard "Contact Measurement Method for Resistivity of Nanomaterials" GB / T 40007-2021. The prepared powder sample is carefully poured into the insulating mold of the testing instrument, and the surface is roughly smoothed. The instrument's pressurization system is activated, applying a preset pressure of 3.9 MPa to the powder in the mold and maintaining it stable. Under stable pressure, the four probes are brought into perpendicular contact with the surface of the compacted powder. The outer (two) probes: a known constant current I is applied. The inner (two) probes: the voltage difference V between these two points is measured. The resistivity of the powder is automatically calculated.

[0175] The resistivity of polyester chips is determined according to GB / T 1410-2006 / IEC 60093:1980 "Test methods for volume resistivity and surface resistivity of solid insulating materials". A three-electrode system is used to apply a constant DC voltage to the test sample, measure the leakage current flowing through the volume or surface of the sample, and calculate the volume resistivity using a formula.

[0176] First, polyester chips are pressed into round discs with a smooth surface and uniform thickness (typically 3 mm), and conductive silver paste is used to ensure good contact with the sample. A typical configuration is a three-electrode system (main electrode, guard electrode, and counter electrode) for measuring volume resistivity.

[0177] Test conditions: Tests are typically conducted in a standard laboratory environment (e.g., 23±2℃, 50±5% RH) and require sufficient time for equilibration. Using a high-resistivity meter or electrometer / source meter, apply the specified 100V DC voltage, read the stabilized resistance value, and calculate the resistivity based on the standard geometry of the sample.

[0178] The test results are shown in Tables 1 and 2.

[0179] Table 1 Resistivity of matting agents

[0180]

[0181] Table 2 Resistivity of Polyester Chips

[0182]

[0183] As can be seen from the above embodiments and comparative examples, the matting agent of the present invention has good conductivity and good antistatic properties. Moreover, the matting agent particles can be uniformly distributed in the polymer matrix and play a stable role. In the end, the dual functions of matting and antistatic are achieved in the polymer material in a long-term and stable manner. Its overall technical effect is far superior to the simple superposition of the functions of each layer.

[0184] Exploration Example

[0185] 1. The effect of tin content in the antistatic layer on the resistivity of the matting agent was investigated through Example 11.

[0186] Example 11

[0187] This embodiment is basically the same as Embodiment 1, except that:

[0188] The amount of antimony precursor solution was adjusted to 18 parts by mass, and the amount of tin precursor solution was adjusted to 210 parts by mass; other conditions remained unchanged.

[0189] Tests showed that the resistivity of the matting agent in Example 11 was 3435 Ω·mm, and the resistivity of the polyester chips was 8.2 × 10⁻⁶. 15 Ω·mm. In Example 11, due to the excessive amount of tin precursor compared to Example 1, some precursor failed to participate in the synthesis reaction of the antistatic layer and underwent self-nucleation. This microstructural defect resulted in a higher resistivity of the prepared matting agent compared to Example 1.

[0190] 2. Example 12 was used to investigate the effect of antimony content in the antistatic layer on the resistivity of the matting agent.

[0191] Example 12

[0192] This implementation is basically the same as Example 1, except that:

[0193] The amount of antimony precursor solution was adjusted to 30 parts by mass, and the molar ratio of antimony to tin in the second dispersion was 0.5:1; other conditions remained unchanged.

[0194] Tests showed that the resistivity of the matting agent in Example 12 was 3678 Ω·mm, and the resistivity of the polyester chips was 8.8 × 10⁻⁶. 15 Ω·mm. In Example 12, the excess antimony precursor diluted the relative content of tin, which plays a conductive role in the antistatic layer, resulting in a decrease in conductivity. Therefore, the resistivity of the prepared matting agent was higher than that in Example 1.

[0195] 3. Example 13 investigates the effect of the dropping time (or dropping rate) of the second dispersion on the resistivity of the matting agent.

[0196] Example 13

[0197] This embodiment is basically the same as Embodiment 1, except that:

[0198] The dripping time in step (2) is 10 min; other conditions remain unchanged.

[0199] Tests showed that the resistivity of the matting agent in Example 13 was 5561 Ω·mm, and the resistivity of the polyester chips was 8.5 × 10⁻⁶. 16 Ω·mm. In Example 13, the drop rate of the second dispersion (i.e., the raw material) during the formation of the antistatic layer was too fast compared to that in Example 1, resulting in incomplete deposition or failure to form an effective layer of the antistatic layer, which led to a higher resistivity of the final matting agent than in Example 1.

[0200] 4. The effect of the stabilizer on the resistivity of the matting agent in the second dispersion was investigated through Example 14.

[0201] Example 14

[0202] This embodiment is basically the same as Embodiment 1, except that:

[0203] The second dispersion does not contain the second stabilizer; other conditions remain unchanged.

[0204] Tests showed that the resistivity of the matting agent in Example 14 was 6132 Ω·mm, and the resistivity of the polyester chips was 7.7 × 10⁻⁶. 16 Ω·mm. In Example 14, because the raw material of the antistatic layer did not contain a stabilizer, the antistatic layer was not deposited completely or failed to form an effective layer. Therefore, the resistivity of the matting agent prepared was higher than that of Example 1.

[0205] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A matting agent, characterized in that, include: The core, including matting materials; An antistatic layer is applied to at least a portion of the surface of the core. A transition layer is formed by covering the surface of the antistatic layer. A silane-polyol-amine compatibility layer is coated on the surface of the transition layer.

2. The matting agent according to claim 1, characterized in that, The kernel's D 50 ≤0.4μm, D 90 ≤0.8μm; And / or, the matting material includes titanium dioxide.

3. The matting agent according to claim 1 or 2, characterized in that, The antistatic layer comprises a conductive oxide; wherein the conductive oxide comprises antimony tin oxide. And / or, the transition layer comprises metal-doped zinc oxide; wherein the metal-doped zinc oxide comprises aluminum-doped zinc oxide.

4. The matting agent according to any one of claims 1-3, characterized in that, The matting agent D 50 ≤0.4μm, D 90 ≤0.8μm.

5. A method for preparing the matting agent according to any one of claims 1-4, characterized in that, Includes the following steps: The antistatic layer, the transition layer, and the silane-polyol-amine compatibility layer are sequentially formed on the surface of the core to obtain the matting agent.

6. The preparation method according to claim 5, characterized in that, The process of sequentially forming the antistatic layer, the transition layer, and the silane-polyol-amine compatibility layer on the surface of the core to obtain the matting agent specifically includes: (1) Provide a first dispersion comprising the core, a second dispersion comprising a conductive oxide precursor, a metal precursor solution, a zinc precursor solution, and a compounded organic modifier; wherein the compounded organic modifier comprises a modifier, a first stabilizer, and a regulator, the modifier comprising a silane coupling agent hydrolysate, the first stabilizer comprising a polyol, and the regulator comprising an amine; (2) The second dispersion is added dropwise to the first dispersion to obtain a first mixture; the first mixture is subjected to a first reaction to obtain a core dispersion coated with conductive oxide; wherein the dropwise addition time is 1h~4h; the pH of the system is controlled to be less than 4 and the temperature is 70℃~95℃ during the dropwise addition process; the first reaction time is 4h~12h and the temperature is 70℃~95℃; (3) The metal precursor solution and the zinc precursor solution are added in parallel to the core dispersion coated with conductive oxide to obtain a second mixture; the second mixture is subjected to a second reaction, and then solid-liquid separation is performed to obtain a double-layer coated core; the parallel addition time is 1h~3h, and the pH of the system is controlled at 3~5 and the temperature at 70℃~95℃ during the parallel addition process; the second reaction time is 2h~4h and the temperature is 70℃~95℃; the mass ratio of the zinc precursor to the core is 0.2%-3% based on zinc oxide; (4) The double-layer coated core and the compounded organic modifier are mixed and then spray-dried to obtain the matting agent.

7. The preparation method according to claim 6, characterized in that, The first dispersion is prepared by a method comprising at least the following steps: mixing a first raw material system comprising the core, a dispersant, and a first solvent to obtain the first dispersion; wherein the dispersant comprises one or more of sodium silicate, pentaerythritol, sodium hexametaphosphate, sodium dihydrogen phosphate, sodium dodecylbenzenesulfonate, octylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, mono- and diglycerides of monolaurate, polyacrylate, polyphosphate, nonylphenol polyoxyethylene ether, sorbitan alkylphenol, polyoxyethylene ether phosphate, and phosphate salts, wherein the mass ratio of the dispersant to the core is 0.1% to 0.5%, and the first solvent comprises one or more of ethanol, water, dimethylacetamide, acetic acid, and caprolactam aqueous solution; And / or, the second dispersion is prepared by a method comprising at least the following steps: mixing a second stabilizer and a second solvent, and then adding the mixture to a second raw material system comprising the conductive oxide precursor to obtain the second dispersion; Preferably, the conductive oxide precursor includes an antimony precursor and a tin precursor. The antimony precursor includes one or more of potassium antimony tartrate, antimony acetate, antimony glycolate, and antimony chloride. The tin precursor includes one or more of tin acetate and tin chloride. The mass ratio of the tin precursor to the core is 0.5%-3% based on tin oxide. In the second dispersion, the molar ratio of antimony to tin is (0.01~0.3):1, and the molar ratio of the second stabilizer to the total molar amount of tin and antimony is (2~5):

1. The second stabilizer includes one or more of stearic acid, hydroxycellulose, polyacrylamide, disodium ethylenediaminetetraacetate, pentaerythritol oleate, pentaerythritol stearate, 1-vinyl-2-pyrrolidone homopolymer, polyethylene glycol laurate, polyvinyl alcohol, and sodium alginate phosphate. The second solvent includes one or more of water and ethanol.

8. The preparation method according to claim 6 or 7, characterized in that, The zinc precursor solution contains 0.5% to 10% by mass of zinc precursor; the zinc precursor includes one or more of zinc sulfate, zinc chloride, and zinc acetate. And / or, the mass percentage of the metal precursor in the metal precursor solution is 0.5%~10%; the metal precursor includes an aluminum precursor, which includes one or more of aluminum sulfate, sodium aluminate, and aluminum chloride; the molar ratio of the metal element in the metal precursor to the zinc element in the zinc precursor is (0.01~0.1):

1. And / or, the silane coupling agent hydrolysate includes one or more of γ-glycidoxypropyltrimethoxysilane hydrolysate, γ-aminopropyltriethoxysilane hydrolysate, and γ-methacryloyloxypropyltrimethoxysilane hydrolysate; the polyol includes one or more of pentaerythritol, glycerol, ethylene glycol, trimethylolpropane, and trimethylolethane; and the amine includes triethanolamine. And / or, the mass ratio of the compounded organic modifier to the core is 0.1%~0.5%; And / or, in the compounded organic modifier, the mass ratio of the modifier, the first stabilizer, and the regulator is (8-10):(1-2):(0.1-0.5). And / or, the spray drying temperature is 160℃~260℃ and the flow rate is 1L / min~10L / min.

9. A fiber, characterized in that, The raw material for the fiber includes the matting agent according to any one of claims 1-4 or the matting agent obtained according to the preparation method according to any one of claims 5-8.

10. A method for preparing the fiber according to claim 9, characterized in that, Includes the following steps: (1) The matting agent is mixed with polyester monomer to prepare a spinning solution; (2) The spinning solution is polymerized in situ and spun to obtain the fiber.

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