Method for preparing modified conductive carbon black dispersion and modified conductive carbon black dispersion and applications thereof

Abstract

The application relates to the technical field of functional nanocomposites, and discloses a preparation method of modified conductive carbon black dispersion and the modified conductive carbon black dispersion and application thereof. The method comprises the following steps: (1) mixing conductive carbon black, coffee residue, grinding agent and water, adjusting the pH value of the mixed solution to alkalinity, and grinding at normal temperature to obtain a primary carbon black dispersion; (2) grinding nano silver iodide, nano palladium and the primary carbon black dispersion at normal temperature to obtain a carbon black composite dispersion in-situ modified by silver and palladium; and (3) grinding water-based polyurethane and the carbon black composite dispersion in-situ modified by silver and palladium at normal temperature to obtain the modified conductive carbon black dispersion. The core advantage of the method lies in that through multi-step synergistic action, efficient regulation and composite modification of the surface properties, dispersibility and functionality of the carbon black material are realized, and the modified conductive carbon black dispersion is attached to the surface of textiles to obtain a durable, antibacterial and conductive material.

Description

Technical Field

[0001] This invention relates to the field of functional nanocomposite materials technology, specifically to a method for preparing a modified conductive carbon black dispersion, the modified conductive carbon black dispersion, and its applications. Background Technology

[0002] With the advancement of nanotechnology, carbon black-based nanocomposites have shown broad application prospects in textiles, electronic devices, and biomedicine. Carbon black, as a traditional conductive filler and reinforcing agent, boasts advantages such as low cost, good conductivity, and high chemical stability. However, it still faces two major challenges in practical applications: First, the issue of dispersion stability. Strong van der Waals forces and π-π interactions exist between carbon black particles, making them prone to agglomeration and difficult to disperse uniformly in aqueous or organic media, affecting the uniformity and performance of composite materials. Second, the limitation of single function. Traditional carbon black materials mainly focus on single functions such as conductivity or coloring, lacking multifunctional integration such as antibacterial properties and high conductivity, making it difficult to meet the demands of modern smart textiles, wearable electronics, and other emerging fields for multifunctional material integration.

[0003] Currently, the main methods for modifying carbon black include: ① Chemical oxidation: Introducing oxygen-containing functional groups onto the carbon black surface through treatment with strong acids or oxidants, improving hydrophilicity and dispersibility. However, this often leads to structural damage and decreased conductivity of the carbon black, and the process generates environmental pollution. ② Surfactant modification: Utilizing ionic or nonionic surfactants adsorbed onto the carbon black surface, stabilizing the dispersion through electrostatic repulsion or steric hindrance. However, stability is greatly affected by pH and ionic strength, resulting in insufficient durability. ③ Polymer coating: Encapsulating carbon black with polymers to form a core-shell structure, improving dispersibility and compatibility. However, the process is complex and may reduce conductivity and other functionalities. ④ Noble metal nanoparticle composite: Imparting antibacterial and catalytic properties to carbon black by loading nanoparticles such as silver and palladium. However, noble metals are prone to agglomeration and uneven distribution. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of decreased conductivity, insufficient stability, and poor antibacterial properties caused by the easy agglomeration of precious metals in existing methods of modifying conductive carbon black. This invention provides a method for preparing a modified conductive carbon black dispersion, as well as the modified conductive carbon black dispersion and its application. The core advantage of this method is that through the synergistic effect of multiple steps, it achieves efficient control and composite modification of the surface properties, dispersibility, and functionality of carbon black materials. By coating the modified conductive carbon black dispersion onto the surface of textiles, a durable, antibacterial, and conductive material can be obtained.

[0005] To achieve the above objectives, the present invention provides a method for preparing a modified conductive carbon black dispersion, the method comprising the following steps: (1) The conductive carbon black, coffee grounds, abrasive and water are mixed, and the pH of the mixture is adjusted to alkaline. The mixture is then ground at room temperature to obtain a primary carbon black dispersion, wherein the abrasive contains a dispersant and a nonionic surfactant. (2) The nano-silver iodide, nano-palladium and the primary carbon black dispersion are subjected to a second grinding at room temperature to obtain a carbon black composite dispersion modified in situ with silver and palladium; (3) The aqueous polyurethane and the in-situ modified carbon black with silver and palladium are dispersed in a third grinding at room temperature to obtain a modified conductive carbon black dispersion. The first grinding speed is 1200-2500 rpm, and the time is 1-2 hours.

[0006] Preferably, based on a total mass percentage of conductive carbon black, coffee grounds, abrasive, nano silver iodide, nano palladium, waterborne polyurethane, and water, the amount of conductive carbon black is 1-5% by mass, the amount of coffee grounds is 3-5% by mass, the amount of abrasive is 1-3% by mass, the amount of nano silver iodide is 3-5% by mass, the amount of nano palladium is 0.5-3% by mass, the amount of waterborne polyurethane is 1-3% by mass, and water is the balance.

[0007] Preferably, the coffee grounds are dried, pulverized, and sieved through a 100-mesh sieve.

[0008] Preferably, in step (1), the mass ratio of the dispersant to the nonionic surfactant is 2:(0.5-2).

[0009] Preferably, the dispersant is sodium methylene dimethylnaphthalene sulfonate and / or sodium methylene dimethylnaphthalene sulfonate.

[0010] Preferably, the nonionic surfactant is styrene-based phenol polyoxyethylene ether.

[0011] Preferably, in step (1), the pH value of the mixture is adjusted to alkaline using an alkaline solution.

[0012] Preferably, in step (1), the alkaline pH value is 10-12.

[0013] Preferably, in step (1), the conditions for the first grinding include a temperature of 10-40°C.

[0014] Preferably, in step (2), the mass ratio of the nano-silver iodide to the nano-palladium is (15-35):1.

[0015] Preferably, the conditions for the second grinding include: a temperature of 10-40°C and a time of 1-2 hours.

[0016] Preferably, in step (3), the conditions for the third grinding include: a temperature of 10-40°C and a time of 0.5-2 hours.

[0017] A second aspect of the present invention provides a modified conductive carbon black dispersion prepared by the method described above.

[0018] A third aspect of the present invention provides the application of the modified conductive carbon black dispersion described above in the preparation of multifunctional textiles.

[0019] A fourth aspect of the present invention provides a functional textile fabric, the preparation process of which includes: The textile fabric is immersed in the modified conductive carbon black dispersion described above, and then dried and baked.

[0020] Preferably, the impregnation conditions include: a liquid yield of 75-85% and an impregnation temperature of 10-40°C. Preferably, the baking conditions include: a temperature of 130-160℃ and a time of 1-5 minutes.

[0021] In this invention, the carbon black is conductive carbon black, and the coffee grounds are biomass waste (dry product). Coffee grounds are a complex plant-based biomass, mainly containing cellulose, hemicellulose, lignin, and organic pigments (such as chlorogenic acid and melanoidins). Using an alkaline medium (hydroxyl ions) and a grinding method, the organic pigments can be rapidly dissociated from the coffee grounds. Simultaneously, under strong alkalinity (preferably pH 10-12) and high-speed grinding energy, the ester bonds in the chlorogenic acid and melanoidin organic pigment molecules undergo significant saponification and hydrolysis reactions, generating caffeic acid, quinic acid, and glycoside structures. Caffeic acid is a phenolic acid with a catechol structure, quinic acid is a polyol acid, and glycoside structures have more polar / ionization sites. These coffee organic pigment molecules are more easily loaded onto the surface of carbon black nanoparticles and also facilitate the reduction of silver ions to elemental silver, which is then firmly adsorbed onto the surface of the carbon black nanoparticles.

[0022] In this invention, under strong alkaline conditions (preferably pH 10-12) and high-speed grinding, coffee grounds are separated into cellulose, hemicellulose, lignin, etc. These "natural dispersants" can be adsorbed onto the carbon black surface, forming a thick hydrophilic layer that provides strong steric hindrance and significantly improves the dispersion stability of the carbon black. These natural products can synergistically interact with added synthetic dispersants (such as anionic dispersants MF and NNO) and hydrophilic nonionic surfactants (such as styrene-based phenolic polyoxyethylene ether, agricultural emulsion 600#) to form a denser and more stable composite adsorption layer at the carbon black / water interface. This reduces the amount of synthetic dispersants and nonionic surfactants used, providing a new application for biomass coffee grounds and reducing the adverse environmental impact of synthetic additives.

[0023] In this invention, nano-palladium (Pd) itself has certain antibacterial properties. It can catalyze the generation of reactive oxygen species and produce a synergistic antibacterial effect with silver, thereby reducing the amount of silver used while maintaining high efficiency.

[0024] In this invention, coffee grounds-derived phenolic acids are known natural antibacterial agents that can disrupt the integrity of microbial cell membranes.

[0025] In this invention, nano silver (Ag / Ag) + The primary source of antibacterial activity is the nano-silver (Ag) generated in situ during step (2) and the slowly released silver ions (Ag). + It is a broad-spectrum, highly effective, and classic antibacterial agent that can disrupt bacterial cell membranes, interfere with enzyme function, and damage DNA.

[0026] Coffee grounds, as an abundant biomass waste, have been explored in recent years as a low-cost, sustainable carbon source and functional filler. Their natural porous structure and high specific surface area are beneficial for adsorbing and loading nanoparticles, while their surface contains abundant oxygen-containing functional groups, which can enhance interfacial interactions with the matrix. However, direct use of coffee grounds suffers from unstable performance and limited functionality. How to efficiently composite them with other nanomaterials to achieve a synergistic enhancement effect remains a technical challenge. This invention uses coffee grounds to modify conductive carbon black. Utilizing the polyphenolic structures in coffee, the hydrophobic properties of the carbon black are balanced, resulting in superior hydrophilicity. Based on the porous structure of the carbon black, it can effectively load nanoparticles such as silver and palladium. The pigments in coffee grounds, mainly chlorogenic acid and Maillard reaction products (melanoidins), are not inert colorants under the described process conditions but rather perform multiple key chemical functions. Chlorogenic acid rapidly saponifies and hydrolyzes in a strongly alkaline environment at pH 10-12 to generate caffeic acid (catechol structure). Caffeic acid anion is a strong polydentate ligand, and its ortho-phenolic group is associated with Ag. + Caffeic acid exhibits extremely high affinity for the surface of Pd nanoparticles. Through π-π stacking and coordination, it is pre-adsorbed firmly onto the carbon black surface. This facilitates subsequent Ag... + Pd nanoparticles provide specific "binding sites," guiding metal species to nucleate and grow in situ on the carbon black surface, rather than homogeneously in solution, ensuring uniform modification and strong binding. Furthermore, the coffee grounds saponified hydrolyzed pigment contains catechins, whose structure itself has mild reducing properties, which can assist in the binding of Ag loaded on the carbon black. + The ions are partially reduced to Ag, thus enabling more controllable generation of silver nanoparticles.

[0027] Nano-palladium (Pd) is an excellent hydrogenation / reduction catalyst that can greatly accelerate Ag... +It is reduced to Ag, and the resulting Ag nanoparticles are finer and more uniformly dispersed. In addition, nano-palladium (Pd) can act as a strong "anchor point" to firmly bind with carbon black and inhibit the migration of in-situ generated Ag nanoparticles.

[0028] Due to the application of the above-described technical solution, the present invention has at least the following advantages compared with the prior art: This invention utilizes the organic pigment components of coffee grounds to promote the loading of nano-AgI and nano-Pd onto carbon black and the in-situ generation of Ag, solving the technical difficulty of insufficient loading of nano-AgI and nano-palladium (Pd) due to the lack of polar sites in single carbon black. The non-organic pigment components of coffee grounds, containing polar groups, can partially replace the function of synthetic chemical surfactants, reducing their use. This aligns with the sustainable and environmentally friendly development direction of high-value utilization of waste biomass.

[0029] This invention innovatively introduces a two-step method: "coffee grounds synergy" and "in-situ composite with nano-precious metals." Coffee grounds not only serve as a dispersing agent, but their structure also provides abundant sites for subsequent loading of nanoparticles. In a stabilized carbon black / coffee grounds composite system, nano-silver iodide and nano-palladium are introduced and immobilized in situ, achieving a dual mechanism of antibacterial action through silver ions and silver-released slow-release antibacterial action, as well as catalytic / synergistic antibacterial action through nano-palladium, overcoming the problems of narrow antibacterial spectrum and easy inactivation of single components.

[0030] Many functional coatings (especially nanoparticle coatings) have weak adhesion to textile substrates and are prone to peeling off during daily use such as friction and washing, leading to rapid functional degradation and poor coating material durability. This invention utilizes the multiple effects of coffee grounds and the film-forming and cross-linking effects of polyurethane to improve the density and firmness of the coating formed by the modified conductive carbon black dispersion on textile fabrics, thereby achieving functional durability. Attached Figure Description

[0031] Figure 1 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 1 (after 1 day of storage). Figure 2 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 1 (stored for 60 days). Figure 3 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 2 (after 1 day of storage). Figure 4 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 2 (stored for 60 days). Figure 5 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 3 (after 1 day of storage). Figure 6The particle size test results are for the modified conductive carbon black dispersion prepared in Example 3 (stored for 60 days). Figure 7 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 4 (after 1 day of storage). Figure 8 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 4 (stored for 60 days). Figure 9 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 5 (after 1 day of storage). Figure 10 The particle size test results are for the modified conductive carbon black dispersion prepared in Example 5 (stored for 60 days). Figure 11 The particle size test results are for the modified conductive carbon black dispersion prepared in Comparative Example 1 (after 1 day of storage). Figure 12 The particle size test results are for the modified conductive carbon black dispersion prepared in Comparative Example 2 (after 1 day of storage). Figure 13 The particle size test results are for the modified conductive carbon black dispersion prepared in Comparative Example 3 (after 1 day of storage). Figure 14 The particle size test results are for the modified conductive carbon black dispersion prepared in Comparative Example 4 (after 1 day of storage). Figure 15 The particle size test results are for the modified conductive carbon black dispersion prepared in Comparative Example 5 (after 1 day of storage). Figure 16 The particle size test results are for the modified conductive carbon black dispersion prepared in Comparative Example 6 (with a standing time of 1 day). Figure 17 The particle size test results are for the modified conductive carbon black dispersion prepared in Comparative Example 7 (after 1 day of storage). Figure 18 The particle size test results are for the modified conductive carbon black dispersion prepared in Comparative Example 8 (within 1 day). Detailed Implementation

[0032] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0033] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0034] The method for preparing the modified conductive carbon black dispersion provided by the present invention includes the following steps: (1) The conductive carbon black, coffee grounds, abrasive and water are mixed, and the pH of the mixture is adjusted to alkaline. The mixture is then ground at room temperature to obtain a primary carbon black dispersion, wherein the abrasive contains a dispersant and a nonionic surfactant. (2) The nano-silver iodide, nano-palladium and the primary carbon black dispersion are subjected to a second grinding at room temperature to obtain a carbon black composite dispersion modified in situ with silver and palladium; (3) The aqueous polyurethane and the in-situ modified carbon black with silver and palladium are dispersed in a third grinding at room temperature to obtain a modified conductive carbon black dispersion. The first grinding speed is 1200-2500 rpm, and the time is 1-2 hours.

[0035] In the method described in this invention, the first grinding, the second grinding, and the third grinding can all be performed in a conventional vertical grinding machine.

[0036] In this invention, the source of the coffee grounds is not particularly limited. Exemplarily, the coffee grounds originate from coffee shops or from the production of instant coffee. Before application, the coffee grounds can be pre-treated, specifically including drying, pulverizing, and passing them through a 100-mesh sieve.

[0037] In some preferred embodiments, based on a total mass percentage (100% by weight) of conductive carbon black, coffee grounds, abrasive, nano-silver iodide, nano-palladium, waterborne polyurethane, and water, the amounts of conductive carbon black, coffee grounds, abrasive, nano-silver iodide, nano-palladium, and water are as follows: 1-5% by mass; 3-5% by mass; 1-3% by mass; 1-3% by mass; and water as the balance. Limiting the content of each component within this range simultaneously improves the dispersion stability and antibacterial properties of the prepared modified conductive carbon black dispersion. Preferably, the amount of waterborne polyurethane is 1-2% by mass.

[0038] In some preferred embodiments, in step (1), the mass ratio of the dispersant to the nonionic surfactant can be 2:(0.5-2).

[0039] Preferably, the dispersant is an anionic dispersant. In some embodiments, the dispersant is sodium methylene dimethylnaphthalene sulfonate (MF) and / or sodium methylene dinaphthalene sulfonate (NNO). When the dispersant is a combination of sodium methylene dimethylnaphthalene sulfonate (MF) and sodium methylene dinaphthalene sulfonate (NNO), the mass ratio of sodium methylene dimethylnaphthalene sulfonate to sodium methylene dinaphthalene sulfonate is 1:1. In another more preferred embodiment, the nonionic surfactant is styrene-based phenolic polyoxyethylene ether, such as agricultural emulsion 600#.

[0040] In step (1), the pH value of the mixture can be adjusted to alkaline using an alkaline solution; specifically, the alkaline solution can be a sodium hydroxide solution, etc.

[0041] In this invention, the alkalinity is strong alkalinity. Preferably, in step (1), the pH value of the alkalinity can be 10-12. Limiting the pH value to this range facilitates the rapid dissociation and hydrolysis of organic pigments from coffee grounds, and facilitates the adsorption of carbon black and reduction of silver ions, thereby improving the dispersion stability and antibacterial properties of carbon black.

[0042] In this invention, the first grinding process employs a conventional grinding method. The first grinding is performed at a high speed; this high grinding rate shortens the grinding time and accelerates the separation of pigments and non-pigment components in the coffee grounds, facilitating the rapid dissociation of organic pigments from the coffee grounds and their role in subsequent steps. Specifically, the first grinding rate can be 1200 rpm, 1400 rpm, 1600 rpm, 1800 rpm, 2000 rpm, 2200 rpm, 2300 rpm, or 2500 rpm. Specifically, the first grinding time can be 60 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, or 120 minutes.

[0043] In step (1) of the present invention, the first grinding is performed at room temperature. For example, the temperature of the first grinding can be 10-40°C.

[0044] In some preferred embodiments, in step (2), the mass ratio of the nano-silver iodide to the nano-palladium can be (15-35):1, for example, it can be 30:1, 25:1, 20:1, 16:1 or 15:1.

[0045] In this invention, the second grinding is performed using a conventional grinding reaction method. In some embodiments, the grinding rate in step (2) can be 1000-2500 r / min. Excessively high grinding rates (e.g., exceeding 2800 rpm) will exacerbate the generation of surfactant foam, which is detrimental to the adsorption of carbon black and coffee pigments by nano-silver iodide and nano-palladium.

[0046] In step (2) of this invention, the second grinding can be carried out at room temperature. For example, the temperature of the second grinding can be 10-40°C. Appropriately increasing the temperature can shorten the reaction time and enhance the rate of reduction of nano-silver iodide to silver. However, the maximum temperature of the grinding system should not exceed 70°C, otherwise flocculent precipitation will occur.

[0047] In some embodiments, the second grinding time can be 1-2 hours.

[0048] In this invention, the aqueous polyurethane added in step (3) can be a commercially available product; specifically, the aqueous polyurethane is a high-concentration polyurethane stock solution with a mass fraction of 80-90%.

[0049] In some embodiments, the third grinding can be performed using a conventional grinding method. In step (3), the conditions for the third grinding include: a speed of 1000-2500 r / min, a temperature of 10-40℃, and a time of 0.5-2 hours.

[0050] This invention proposes a novel design concept of "co-modification of biomass waste," which organically combines dispersion, modification, and functionalization, and is innovative in principle.

[0051] This invention also provides a modified conductive carbon black dispersion prepared by the method described above. The modified conductive carbon black dispersion prepared by this invention exhibits excellent dispersion stability and antibacterial properties.

[0052] The present invention also provides an application of the modified conductive carbon black dispersion described above in the preparation of multifunctional textiles.

[0053] The modified conductive carbon black dispersion prepared by this invention can be applied to textiles using conventional methods such as padding, coating, and printing to form a functional coating material.

[0054] The present invention also provides a functional textile fabric, the preparation process of which includes: impregnating the textile fabric in the modified conductive carbon black dispersion described above, and then drying and baking.

[0055] In a preferred embodiment, before immersing the textile fabric in the modified conductive carbon black dispersion described above, the modified conductive carbon black dispersion can be diluted before use, preferably by a dilution of 8-12 times.

[0056] In this invention, after the dispersion forms a film, the textile surface simultaneously possesses: a) physical contact killing: the sharp nano-carbon black / metal composite structure may pierce bacterial cells. b) ion release killing: Ag is continuously released from the material. + And phenolic acid molecules.

[0057] In this invention, when the dispersion forms a film, the modified conductive carbon black dispersion not only achieves the construction of conductive function, but also derives a strong and long-lasting antibacterial function.

[0058] Specifically, the sizing can be a two-dip, two-roll process. In some embodiments, the sizing conditions include: a modified conductive carbon black concentration of 0.5-20 wt%, a roll-up ratio of 75-85%, and an impregnation temperature of 10-40°C (room temperature).

[0059] In some embodiments, the baking conditions include a temperature of 130-160°C and a time of 1-5 minutes. Specifically, baking can be performed using high-temperature hot air.

[0060] To further improve its colorfastness, conventional methods such as adding adhesives and crosslinking agents can be used to enhance the bonding strength with the fiber-based material. In this way, functional textiles that combine colorfastness and functionality can be prepared on textile substrates.

[0061] This invention develops a novel functional nanocomposite material: based on carbon black, a composite dispersion integrating conductivity and antibacterial properties is prepared through synergistic modification technology. A simple, efficient, and controllable preparation method is designed to achieve stable dispersion of carbon black and in-situ, uniform compounding of multiple functional components (coffee grounds, nano-silver iodide, and nano-palladium). Using coffee grounds, a common biomass waste, as a key modifying component enables its high-value-added application, aligning with the concept of green and sustainable development. The prepared dispersion is applied to the surface treatment of textiles to develop durable, antibacterial, and conductive smart textiles.

[0062] In the technical solution described in this invention, firstly, through a dual synergistic stabilization mechanism, coffee grounds (physical adsorption and steric hindrance) and nonionic surfactants (steric hindrance) work synergistically under alkaline conditions to form a dual physical and chemical stabilizing layer, resulting in a more uniform dispersion and more stable storage. Secondly, conductive carbon black, coffee grounds (structural support), and nano-silver / palladium iodide (antibacterial) are in-situ composited during the preparation process, producing a "1+1+1>3" effect (e.g., coffee grounds promote uniform loading of precious metals, thus enhancing antibacterial properties). Simultaneously, the abundant hydrophilic and lipophilic polyphenols in the coffee grounds are used to modify the conductive carbon black to achieve water-oil balance, resulting in a stable conductive carbon black liquid with a stable aqueous phase. This achieves multifunctional in-situ integration and synergistic enhancement. Thirdly, coffee grounds, as a "biomass bridging agent," with its porous structure interwoven with fibers, firmly "anchors" the functional components to the fabric, making the antibacterial and conductive properties durable and long-lasting. Utilizing coffee grounds waste transforms waste into treasure; the process is mild (alkaline aqueous phase), reducing pollution; and the amount of precious metals used can be reduced due to the synergistic effect, significantly lowering the overall cost.

[0063] The following examples further illustrate the preparation method of the modified conductive carbon black dispersion, the modified conductive carbon black dispersion, and its applications according to the present invention. The examples are implemented based on the technical solution of the present invention, and detailed implementation methods and specific operating procedures are provided. However, the scope of protection of the present invention is not limited to the following examples.

[0064] The following examples illustrate the preparation process of the modified conductive carbon black dispersion. Because the grinding process in the vertical mill is an exothermic reaction due to mechanical friction, the system temperature does not exceed 70°C. This will not be specifically explained in the examples and comparative examples.

[0065] Unless otherwise specified, the experimental methods used in the following examples are conventional methods in the art. The raw materials used in the following examples are all commercially available products.

[0066] The conductive carbon black is commercially available conductive carbon black N472; the coffee grounds are dried, pulverized, and sieved through a 100-mesh sieve; the average molecular weight of styrene-phenol polyoxyethylene ether emulsifier 600# is 1100; the waterborne polyurethane (PU, with a molecular weight of approximately 20,000-40,000) is a high-concentration polyurethane stock solution with a mass fraction of 80-90%; the particle size of nano silver iodide is 75-90 nm; and the particle size of nano palladium is 40-55 nm.

[0067] The following examples illustrate the preparation process of modified conductive carbon black dispersions.

[0068] The raw material formulations for each embodiment are shown in Table 1: The pH values ​​in Tables 1 and 2 are the alkaline pH values ​​in step (1).

[0069] Table 1

[0070] The proportions of raw materials for each comparative example are shown in Table 2: Table 2

[0071] Example 1 (1) Mix 4g of conductive carbon black (dry), 3g of coffee grounds (dry), 3g of grinding agent (1g of dispersant MF, 1g of dispersant NNO, 1g of agricultural emulsion 600#) and 70g of water, and adjust the pH to 10.5 with NaOH aqueous solution. Grind at 1600rpm for 90 minutes at room temperature (25℃) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0072] (2) Add 3 g of nano silver iodide and 0.1 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 100 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0073] (3) Add 1.9 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 85 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion A-1.

[0074] Example 2 (1) Mix 1 gram of conductive carbon black (dry), 4 grams of coffee grounds (dry), 1 gram of grinding agent (0.3 grams of dispersant MF, 0.3 grams of dispersant NNO, 0.4 grams of agricultural emulsion 600#) and 70 grams of water, and adjust the pH to 10.5 with NaOH aqueous solution. Grind at 1600 rpm for 75 minutes at room temperature (25°C) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0075] (2) Add 4 g of nano silver iodide and 0.2 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 120 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0076] (3) Add 1.8 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 88 g. Grind at 1600 rpm at room temperature (25°C) for 35 minutes to obtain modified conductive carbon black dispersion A-2.

[0077] Example 3 (1) Mix 3g of conductive carbon black (dry), 5g of coffee grounds (dry), 1.3g of grinding agent (0.8g of dispersant MF, 0.5g of agricultural emulsion 600#) and 70g of water, and adjust the pH to 11 with NaOH aqueous solution. Grind at 1600rpm for 70 minutes at room temperature (25℃) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0078] (2) Add 5 g of nano silver iodide and 0.3 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 120 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0079] (3) Add 1.4 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 84 g. Grind at 1600 rpm at room temperature (25°C) for 50 minutes to obtain modified conductive carbon black dispersion A-3.

[0080] Example 4 (1) Mix 5 g of conductive carbon black (dry), 5 g of coffee grounds (dry), 2.4 g of grinding agent (0.6 g of dispersant MF, 0.6 g of dispersant NNO, 1.2 g of agricultural emulsion 600#) and 70 g of water, and adjust the pH to 11.5 with NaOH aqueous solution. Grind at 1600 rpm for 60 minutes at room temperature (25°C) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0081] (2) Add 4.5 g of nano silver iodide and 0.18 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 110 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0082] (3) Add 2.92 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 80 g. Grind at 1600 rpm at room temperature (25°C) for 60 minutes to obtain modified conductive carbon black dispersion A-4.

[0083] Example 5 (1) Mix 2.5 g of conductive carbon black (dry), 4.5 g of coffee grounds (dry), 2.5 g of grinding agent (1 g of dispersant NNO, 1 g of agricultural emulsion 600#) and 70 g of water, and adjust the pH to 12.0 with NaOH aqueous solution. Grind at 1600 rpm for 80 minutes at room temperature (25°C) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0084] (2) 3.3 g of nano silver iodide and 0.2 g of nano palladium were added to the above primary carbon black dispersion and ground at room temperature (25°C) for 110 minutes at a rate of 1600 rpm to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0085] (3) Add 1.5 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 86 g. Grind at 1600 rpm at room temperature (25°C) for 60 minutes to obtain modified conductive carbon black dispersion A-5.

[0086] Comparative Example 1 The method of Example 1 was implemented, except that coffee grounds were not added in step (1), and the grinding agent was increased from 3 grams to 6 grams.

[0087] The specific operations include: (1) Mix 4 g of conductive carbon black (dry product), 6 g of grinding agent (2 g of dispersant MF, 2 g of dispersant NNO, 2 g of agricultural emulsion 600#) and 70 g of water, and adjust the pH value to 10.5 with NaOH aqueous solution. Grind at 1600 rpm for 90 minutes at room temperature (25℃) on a conventional vertical mill to obtain a primary carbon black dispersion.

[0088] (2) Add 3 g of nano silver iodide and 0.1 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 100 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0089] (3) Add 1.9 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 85 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion B-1.

[0090] Comparative Example 2 The method of Example 1 was implemented, except that silver iodide was not added in step (2), and the total amount of water was increased by 3 grams.

[0091] The specific operations include: (1) Mix 4 g of conductive carbon black (dry product), 6 g of grinding agent (2 g of dispersant MF, 2 g of dispersant NNO, 2 g of agricultural emulsion 600#) and 70 g of water, and adjust the pH value to 10.5 with NaOH aqueous solution. Grind at 1600 rpm for 90 minutes at room temperature (25℃) on a conventional vertical mill to obtain a primary carbon black dispersion.

[0092] (2) Add 0.1 g of nano-palladium to the above primary carbon black dispersion and grind it at 1600 rpm at room temperature (25°C) for 100 minutes to obtain a palladium-modified carbon black composite dispersion.

[0093] (3) Add 1.9 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 88 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion B-2.

[0094] Comparative Example 3 The method of Example 1 was implemented, except that no nano-palladium was added in step (2).

[0095] The specific operations include: (1) Mix 4g of conductive carbon black (dry), 3g of coffee grounds (dry), 3g of grinding agent (1g of dispersant MF, 1g of dispersant NNO, 1g of agricultural emulsion 600#) and 70g of water, and adjust the pH to 10.5 with NaOH aqueous solution. Grind at 1600rpm for 90 minutes at room temperature (25℃) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0096] (2) Add 3 g of nano silver iodide to the above primary carbon black dispersion and grind it at room temperature (25°C) for 100 minutes at a rate of 1600 rpm to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0097] (3) Add 1.9 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 85.1 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion B-3.

[0098] Comparative Example 4 The method of Example 1 is implemented, except that water-based polyurethane is not added in step (3).

[0099] The specific operations include: (1) Mix 4g of conductive carbon black (dry), 3g of coffee grounds (dry), 3g of grinding agent (1g of dispersant MF, 1g of dispersant NNO, 1g of agricultural emulsion 600#) and 70g of water, and adjust the pH to 10.5 with NaOH aqueous solution. Grind at 1600rpm for 90 minutes at room temperature (25℃) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0100] (2) Add 3 g of nano silver iodide and 0.1 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 100 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0101] (3) Add the remaining water to the above carbon black composite dispersion. The total water content in the system is 86.9 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion B-4.

[0102] Comparative Example 5 The method of Example 1 is implemented, except that the pH is adjusted to neutral in step (1).

[0103] The specific operations include: (1) Mix 4 g of conductive carbon black (dry), 3 g of coffee grounds (dry), 3 g of grinding agent (1 g of dispersant MF, 1 g of dispersant NNO, 1 g of agricultural emulsion 600#) and 70 g of water, and adjust the pH to 7.5 with NaOH aqueous solution. Grind at 1600 rpm for 90 minutes at room temperature (25°C) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0104] (2) Add 3 g of nano silver iodide and 0.1 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 100 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0105] (3) Add 1.9 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 85 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion B-5.

[0106] Comparative Example 6 The method is implemented according to Example 1, except that in step (1), the control speed is reduced from 1600 rpm to 800 rpm.

[0107] The specific operations include: (1) Mix 4g of conductive carbon black (dry), 3g of coffee grounds (dry), 3g of grinding agent (1g of dispersant MF, 1g of dispersant NNO, 1g of agricultural emulsion 600#) and 70g of water, and adjust the pH to 10.5 with NaOH aqueous solution. Grind at 800rpm for 90 minutes at room temperature (25℃) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0108] (2) Add 3 g of nano silver iodide and 0.1 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 100 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0109] (3) Add 1.9 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 85 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion B-6.

[0110] Comparative Example 7 The method of Example 1 is implemented, except that in step (1), the control speed is reduced from 1600 rpm to 800 rpm and the time is increased from 90 minutes to 300 minutes.

[0111] The specific operations include: (1) Mix 4g of conductive carbon black (dry), 3g of coffee grounds (dry), 3g of grinding agent (1g of dispersant MF, 1g of dispersant NNO, 1g of agricultural emulsion 600#) and 70g of water, and adjust the pH to 10.5 with NaOH aqueous solution. Grind at 800rpm for 300 minutes at room temperature (25℃) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0112] (2) Add 3 g of nano silver iodide and 0.1 g of nano palladium to the above primary carbon black dispersion, and grind and react at room temperature (25°C) at a rate of 1600 rpm for 100 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0113] (3) Add 1.9 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 85 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion B-7.

[0114] Comparative Example 8 The method of Example 1 was implemented, except that in step (2), the temperature of the grinding system was increased from room temperature to 75°C.

[0115] The specific operations include: (1) Mix 4g of conductive carbon black (dry), 3g of coffee grounds (dry), 3g of grinding agent (1g of dispersant MF, 1g of dispersant NNO, 1g of agricultural emulsion 600#) and 70g of water, and adjust the pH to 10.5 with NaOH aqueous solution. Grind at 1600rpm for 90 minutes at room temperature (25℃) on a conventional vertical grinder to obtain a primary carbon black dispersion.

[0116] (2) Add 3 g of nano silver iodide and 0.1 g of nano palladium to the above primary carbon black dispersion, and grind and react at 75°C at a rate of 1600 rpm for 100 minutes to obtain a carbon black composite dispersion modified in situ with silver and palladium.

[0117] (3) Add 1.9 g of waterborne polyurethane and the remainder of water to the above carbon black composite dispersion. The total water content in the system is 85 g. Grind at 1600 rpm at room temperature (25°C) for 45 minutes to obtain modified conductive carbon black dispersion B-8.

[0118] The following application examples illustrate the preparation process of conductive textiles.

[0119] Application Example 1 10 grams of the modified conductive carbon black dispersion A-1 prepared in Example 1 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. A polyester / spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip rate of 80%. After impregnation, the fabric was conventionally dried and treated with high-temperature hot air (145°C) for 2 minutes to obtain conductive polyester / spandex fabric C-1.

[0120] Application Example 2 10 grams of the modified conductive carbon black dispersion A-2 prepared in Example 2 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. A polyester / spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip rate of 80%. After impregnation, the fabric was conventionally dried and treated with high-temperature hot air (145°C) for 2 minutes to obtain conductive polyester / spandex fabric C-2.

[0121] Application Example 3 10 grams of the modified conductive carbon black dispersion A-3 prepared in Example 3 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. A polyester / spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip rate of 80%. After impregnation, the fabric was conventionally dried and treated with high-temperature hot air (145°C) for 2 minutes to obtain conductive polyester / spandex fabric C-3.

[0122] Application Example 4 10 grams of the modified conductive carbon black dispersion A-4 prepared in Example 4 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. A polyester / spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip rate of 80%. After impregnation, the fabric was conventionally dried and treated with high-temperature hot air (145°C) for 2 minutes to obtain conductive polyester / spandex fabric C-4.

[0123] Application Example 5 10 grams of the modified conductive carbon black dispersion A-5 prepared in Example 1 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. A polyester / spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip-out ratio of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester / spandex fabric C-5.

[0124] Application Comparative Example 1 10 grams of the modified conductive carbon black dispersion B-1 prepared in Comparative Example 1 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. Polyester-spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip-out ratio of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester-spandex fabric D-1.

[0125] Application Comparative Example 2 10 grams of the modified conductive carbon black dispersion B-2 prepared in Comparative Example 2 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. Polyester-spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip rate of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester-spandex fabric D-2.

[0126] Application Comparative Example 3 10 grams of the modified conductive carbon black dispersion B-3 prepared in Comparative Example 3 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. Polyester-spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip rate of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester-spandex fabric D-3.

[0127] Application Comparative Example 4 10 grams of the modified conductive carbon black dispersion B-4 prepared in Comparative Example 4 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. Polyester-spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip rate of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester-spandex fabric D-4.

[0128] Application Comparative Example 5 10 grams of the modified conductive carbon black dispersion B-5 prepared in Comparative Example 5 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. Polyester-spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip-out ratio of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester-spandex fabric D-5.

[0129] Application Comparative Example 6 10 grams of the modified conductive carbon black dispersion B-6 prepared in Comparative Example 6 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. Polyester-spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip-out ratio of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester-spandex fabric D-6.

[0130] Application Comparative Example 7 10 grams of the modified conductive carbon black dispersion B-7 prepared in Comparative Example 7 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. Polyester-spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip rate of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester-spandex fabric D-7.

[0131] Application Comparative Example 8 10 grams of the modified conductive carbon black dispersion B-8 prepared in Comparative Example 8 were mixed evenly with 90 grams of water to obtain a modified conductive carbon black dispersion. Polyester-spandex fabric was then impregnated with the above modified conductive carbon black dispersion at room temperature (25°C) using a two-dip, two-nip method, with a nip-out ratio of 80%. After impregnation, the fabric was subjected to conventional drying and high-temperature hot air treatment (145°C) for 2 minutes to obtain conductive polyester-spandex fabric D-8.

[0132] Test case Carbon black dispersion particle size: The particle size of the modified conductive carbon black dispersion (0 days of storage) was tested on a Top Sizer laser particle size analyzer and expressed as D25, D50 and D90 in micrometers.

[0133] Stability of carbon black dispersion: The particle size of the modified conductive carbon black dispersion was tested after 60 days of storage using a TopSizer laser particle size analyzer. The particle size was expressed as D25, D50, and D90 in micrometers.

[0134] Conductivity: The sheet resistance of the fabric was tested on a digital four-probe tester under the following conditions: temperature 20℃, humidity 65%, and sample equilibration for 24 hours.

[0135] Antibacterial properties: Place the standard blank sample and the fabric sample to be tested into sterile conical flasks, add 50 ml of 0.3 M PBS buffer and 5 ml of bacterial suspension (viable bacteria count of (1-5) × 10⁻⁶). 9 After incubating the sample (cfu / ml) at 23-25°C for 18 hours, 1 ml of the sample and 9 ml of 0.3 M PBS buffer were then mixed. The above steps were repeated, and the solution was diluted 10-fold to a final concentration of 3 × 10⁻⁶ CFU / ml. 3CFU / ml, then pipette 50 ml of the solution and spread it onto nutrient agar medium. Incubate at 37°C for 24 hours and record the number of colonies on the medium. The test strain is Escherichia coli.

[0136] Antibacterial rate (%) = [(KQ) / K] ×100% K represents the number of bacteria in the standard blank sample solution, and Q represents the number of bacteria in the sample solution containing fabric. The experiment was repeated 3 times, and the average antibacterial rate was calculated.

[0137] The particle size test results of the modified conductive carbon black dispersions prepared in each embodiment and comparative example are shown in the appendix. Figure 1 ~Appendix Figure 18 To clearly express the differences in particle size distribution, D25, D50, and D90 are used to represent particle size, and the summarized particle size results are shown in Table 3. Table 3 shows the particle size of the modified conductive carbon black dispersion prepared on the day of preparation (0 days) and the particle size of the modified conductive carbon black dispersion tested after 60 days of natural storage, reflecting the stability of the dispersion. Observing the shape and particle size changes in the particle size distribution diagram, when a single particle size peak splits into two or more peaks, it indicates poor storage stability, weak interaction between the additives and the conductive carbon black, and a tendency for secondary equilibrium to occur between the dispersions, potentially leading to sedimentation. Therefore, storing the modified conductive carbon black dispersion for a certain period allows for a direct reflection of the quality of the modification scheme.

[0138] Table 3

[0139] From the appendix Figure 1 , attached Figure 3 , attached Figure 5 , attached Figure 7 , attached Figure 9 As shown in Table 3, the modified conductive carbon black dispersions prepared using this invention all exhibit a single-peaked particle size distribution. Among them, the particle size of Example 4 (sample A-4) is relatively large, with D... 25 = 0.633 μm, D 50 =0.926 μm, D 90 = 1.934 μm. The Dm of the remaining four examples (sample A-1, sample A-2, sample A-3, sample A-5) 25 In the range of 0.080–0.088 μm, D 50 In the range of 0.107–0.119 μm, D 90The particle size ranges from 0.167 to 0.207 μm. This indicates that the added coffee grounds pigment has been completely dissociated into organic pigments and non-pigment components (such as cellulose, hemicellulose, lignin, etc.) in the nanoparticles. When the polyurethane concentration is high (as in Example 4), the high molecular weight of polyurethane (approximately 20,000-40,000) increases the viscosity, leading to an increase in the particle size of the carbon black dispersion.

[0140] The particle size distribution of the modified conductive carbon black, compared with the samples of the above five examples, after being left to stand naturally for 60 days (see [reference]). Figure 2 , attached Figure 4 , attached Figure 6 , attached Figure 8 , attached Figure 10 After 60 days of natural storage, the modified conductive carbon black dispersion prepared using this invention exhibits a single-peaked particle size distribution, but the particle size shows an increasing trend.

[0141] Compared to Example 4 (sample A-4), sample A-4-60 has a larger particle size, D 25 = 0.890 μm, D 50 = 1.606 μm, D 90 = 4.153 μm. The D of the remaining four examples (sample A-1-60, sample A-2-60, sample A-3-60, sample A-5-60) 25 In the range of 0.437–0.531 μm, D 50 In the range of 0.699–0.869 μm, D 90 The particle size distribution is between 1.465 and 1.983 μm. This is because as the storage time increases, the mechanical shear force present during the grinding process gradually disappears. As the mechanical shear force disappears, the molecular motion slows down, and the molecules reach a new equilibrium. The unimodal particle size distribution in the embodiments of this invention indicates that the prepared modified conductive carbon black dispersion has excellent dispersion stability. During the storage process (60 days), no stratification occurs, maintaining the original colloidal equilibrium between molecules. Therefore, the modified conductive carbon black dispersion exhibits excellent performance in use.

[0142] The advantages of the present invention will be better illustrated by the following comparative examples.

[0143] From the appendix Figure 11 (Comparative Example 1, Sample B-1) It can be seen that its particle size distribution has three obvious peaks and a very wide particle size distribution. D 25 = 0.178 μm, D 50 = 1.400 μm, D 90 = 11.721 μm. Compared with Example 1 ( Figure 1Compared to sample B-1, which does not contain coffee grounds, the modified conductive carbon black dispersion prepared by sample B-1, despite having a higher amount of synthesis aids in the system, exhibits significantly better performance than the sample containing coffee grounds (A-1).

[0144] This is because: 1) Coffee grounds contain biomass-derived dispersants. Under strongly alkaline conditions, the hydroxyl groups in the molecules easily form sodium salts, increasing the electrostatic repulsion with carbon black molecules, resulting in better dispersing performance than synthetic auxiliaries. 2) Under strongly alkaline conditions and strong grinding forces (e.g., 1600 rpm), some colored pigments are easily hydrolyzed, and the components in the coffee grounds easily dissociate, forming strong interactions with carbon black molecules, providing polar sites for the subsequent loading of nano-silver iodide and nano-palladium. The presence of biomass coffee grounds provides excellent dispersing performance and polar groups, outperforming conventional synthetic auxiliaries. This is one of the innovative aspects of this invention.

[0145] From the appendix Figure 12 (Comparative Example 2, Sample B-2) shows that its particle size distribution has two obvious peaks and a relatively wide particle size distribution. 25 = 0.135 μm, D 50 = 0.232 μm, D 90 = 1.621 μm. Compared with Example 1 ( Figure 1 In contrast, sample B-1 does not contain nano-silver iodide. Because nano-silver iodide ionizes into silver ions, it forms a strong electrostatic interaction with the positive charges of the carbon black and coffee grounds components, and also forms a strong interaction with nano-palladium, thus improving its stability. When sample B-1 does not contain nano-silver iodide, it will also affect the stability of the carbon black dispersion system and reduce its conductivity and antibacterial properties.

[0146] When the carbon black dispersion system does not contain palladium nanoparticles, it affects the loading of silver iodide nanoparticles and the in-situ reduction of silver ions. See Comparative Example 3 (attached). Figure 13 The particle size distribution of sample B-3 also showed a bimodal pattern. 25 = 0.112 μm, D 50 = 0.179 μm, D 90 = 1.376 μm.

[0147] When the carbon black dispersion system does not contain high molecular weight polyurethane, it will also affect the modified properties of the carbon black dispersion system, resulting in bimodal phenomena, as shown in Comparative Example 4 (see Appendix). Figure 14 (Sample B-4) This is because polyurethane not only has polar groups, but its viscosity can also effectively prevent intermolecular collisions, which is beneficial to improving the stability of the carbon black dispersion system.

[0148] When the pH of the carbon black dispersion system deviates from the alkaline range, such as neutral or slightly alkaline (pH = 7.5), the saponification and hydrolysis of chlorogenic acid in coffee grounds are weak, making it difficult to separate the various components. This results in poor dispersibility, almost no AgI conversion reaction, and extremely poor stability of the carbon black dispersion system. The particle size distribution exhibits a broad multi-peak pattern, making sedimentation very likely. See Comparative Example 5 (attached). Figure 15 D of sample B-5 50 = 8.423 μm, D 90 = 80.328 μm.

[0149] In the process of preparing the modified conductive carbon black dispersion system, the effective separation of each component in the coffee grounds is related to the grinding rate. When the grinding rate is low (e.g., 800 rpm in step (1)), the components of the coffee grounds cannot be effectively separated within the same grinding time, resulting in an unstable carbon black dispersion system with multiple peaks in its particle size distribution and larger particle sizes, such as those from the attached... Figure 16 (Comparative Example 6). However, by maintaining the low grinding rate (e.g., 800 rpm) in step (1) and extending the grinding time (to 300 minutes), a well-dispersed carbon black dispersion system can also be prepared, as shown in the appendix. Figure 17 (Comparative Example 7).

[0150] Furthermore, when the temperature of the grinding system is too high (e.g., 75°C), severe foaming will occur, which will seriously affect the stability of the carbon black dispersion system. (See attached diagram) Figure 18 (Comparative Example 8).

[0151] Table 4 shows the application performance of fabrics (polyester spandex) in Examples 1 to 5 and Comparative Examples 1 to 5.

[0152] Table 4

[0153] Table 4 shows that the modified conductive carbon black dispersion prepared using this invention, when applied to polyester / spandex fabrics using a conventional roll-to-bake process, exhibits excellent antibacterial rates against *E. coli*, ranging from 98.6% to 99.9%, and excellent conductivity, with a sheet resistance of 0.0183–0.0215 MΩ. In contrast, the comparative example, due to the absence of a certain component, suffers from poor stability or the inability of certain reactions to occur in its modified conductive carbon black dispersion, affecting its multi-peaked particle size distribution and leading to a decrease in conductivity and antibacterial rate. For example, the antibacterial rate is approximately 50.6–80.8%, and the sheet resistance is 0.0624–0.0872 MΩ. This is because coffee grounds themselves possess a polyphenol molecular structure, which can effectively support nano-silver iodide and nano-palladium. Nano-palladium, as a catalyst, may be indispensable for driving the efficient and directional conversion of AgI under alkaline conditions and forming high-performance Ag-Pd conductive materials. The interaction between nano-AgI and hydrophobic carbon black is primarily physical adsorption (van der Waals forces). In the absence of anchoring agents (such as Pd nanoparticles or polyphenols found in coffee), the ability of nano-AgI to support carbon black is weak. Furthermore, the catalytic effect of a small amount of nano-Pd facilitates the formation of a coexisting Ag and AgI structure, allowing dissolved or surface-adsorbed Ag to... + / Complexing Ag + It may be reduced to elemental Ag by reducing substances present in the system. 0 These components are fixed and loaded onto the carbon black dispersion. These structural changes significantly improve the performance of the modified nano-conductive carbon black.

[0154] It should be understood that any parts not described in detail in this specification belong to the prior art.

[0155] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a modified conductive carbon black dispersion, characterized in that, The method includes the following steps: (1) The conductive carbon black, coffee grounds, abrasive and water are mixed, and the pH of the mixture is adjusted to alkaline. The mixture is then ground at room temperature to obtain a primary carbon black dispersion, wherein the abrasive contains a dispersant and a nonionic surfactant. (2) The nano-silver iodide, nano-palladium and the primary carbon black dispersion are subjected to a second grinding at room temperature to obtain a carbon black composite dispersion modified in situ with silver and palladium; (3) The aqueous polyurethane and the in-situ modified carbon black with silver and palladium are dispersed in a third grinding at room temperature to obtain a modified conductive carbon black dispersion. In step (1), the first grinding rate is 1200-2500 rpm and the time is 1-2 hours.

2. The method according to claim 1, characterized in that, Based on a total mass percentage of conductive carbon black, coffee grounds, abrasive, nano silver iodide, nano palladium, waterborne polyurethane, and water, the amount of conductive carbon black is 1-5% by mass, the amount of coffee grounds is 3-5% by mass, the amount of abrasive is 1-3% by mass, the amount of nano silver iodide is 3-5% by mass, the amount of nano palladium is 0.5-3% by mass, the amount of waterborne polyurethane is 1-3% by mass, and water is the balance. And / or, coffee grounds are coffee grounds that have been dried, crushed and passed through a 100-mesh sieve.

3. The method according to claim 1 or 2, characterized in that, In step (1), the mass ratio of the dispersant to the nonionic surfactant is 2:(0.5-2). And / or, the dispersant is sodium methylene dimethylnaphthalene sulfonate and / or sodium methylene dinaphthalene sulfonate; And / or, the nonionic surfactant is styrene-based phenol polyoxyethylene ether.

4. The method according to any one of claims 1-3, characterized in that, In step (1), the pH value of the mixture is adjusted to alkaline using an alkaline solution; And / or, in step (1), the alkaline pH value is 10-12; And / or, in step (1), the conditions for the first grinding include: a temperature of 10-40°C.

5. The method according to any one of claims 1-4, characterized in that, In step (2), the mass ratio of the nano-silver iodide to the nano-palladium is (15-35):1; And / or, the conditions for the second grinding include: a temperature of 10-40°C and a time of 1-2 hours.

6. The method according to any one of claims 1-5, characterized in that, In step (3), the conditions for the third grinding include: a temperature of 10-40°C and a time of 0.5-2 hours.

7. The modified conductive carbon black dispersion prepared by the method according to any one of claims 1-6.

8. The application of the modified conductive carbon black dispersion according to claim 7 in the preparation of multifunctional textiles.

9. A functional textile fabric, characterized in that, The preparation process of this functional textile fabric includes: The textile fabric is immersed in the modified conductive carbon black dispersion of claim 7, and then dried and baked.

10. The functional textile fabric according to claim 9, characterized in that, The conditions for immersion include: a liquid yield of 75-85% and an immersion temperature of 10-40℃; And / or, the baking conditions include: a temperature of 130-160°C and a time of 1-5 min.

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