Preparation method and application of efficient fluoride-free water-repellent dyeing finishing liquid

Abstract

The invention relates to a preparation method of a high-efficiency fluoride-free water-repellent dyeing finishing liquid, which comprises the following steps: preparing materials according to a ratio; the material comprises the following components in percentage by weight: 5%-8% of disperse dye, 8%-15% of long-chain alkane compound, 3%-8% of macromolecular wax, 3%-6% of cross-linking agent, 6%-15% of surfactant, 5%-15% of dispersing agent, 2%-5% of adhesive and the balance of water. Mixing and stirring the materials to obtain pre-finishing liquid; adding zirconium beads into the pre-finishing liquid and grinding to obtain a final dyeing finishing liquid. Through synergistic compounding of the long-chain alkane compound, the high-molecular wax and the cross-linking agent and in combination with a grinding process, the performance of the fluoride-free waterproof agent is remarkably improved. The prepared finishing liquid can form a film on the fiber surface, a long-chain alkane structure effectively reduces the surface energy, the excellent initial water repellent performance close to that of a traditional fluorine-containing product is achieved, a three-dimensional network structure is formed through reaction, and the durability and tolerance of a waterproof film are enhanced.

Description

Technical Field

[0001] This invention relates to the field of textile chemistry, and in particular to a method for preparing a highly efficient fluorine-free water-repellent dyeing and finishing solution and its application. Background Technology

[0002] With the rapid development of the outdoor sports and functional apparel market, consumers' demand for water-repellent properties in textiles is increasing daily. Traditional water-repellent finishing technologies heavily rely on fluorinated compounds (such as C8 / C6 fluorocarbon resins), which can form a barrier with extremely low surface energy on the fabric surface, thereby providing excellent and long-lasting water repellency.

[0003] However, perfluorinated and polyfluoroalkyl substances (PFAS) have been proven to be environmentally persistent, bioaccumulative, and potentially biotoxic. They are extremely difficult to degrade in the natural environment and can also pose a threat to human health through the food chain. In recent years, global environmental regulations have become increasingly stringent, imposing strict restrictions on the use and emission of PFAS, making the market demand for environmentally friendly, safe, and sustainable fluorine-free waterproofing solutions extremely urgent.

[0004] Currently, the industry has developed some fluorine-free waterproofing agents based on hydrocarbons, organosilicon, and wax emulsions as alternatives. However, these existing technologies generally suffer from the following technical bottlenecks: (a) Poor waterproofing performance: The initial water-repellent properties of most fluorine-free waterproofing agents, especially in high-pressure environments (such as heavy rain), are still difficult to compete with traditional fluorine-containing products. Their water contact angle is low, and water droplets easily wet the fabric.

[0005] (ii) Poor durability: After repeated washing or friction, the waterproof performance will decrease sharply, which cannot meet the service life requirements of high-end functional clothing.

[0006] (iii) Poor compatibility with dyeing processes: The traditional two-step process of "dyeing first and then finishing" is lengthy, energy-intensive, and water-intensive. Existing fluorine-free waterproofing agents are difficult to use simultaneously in the dyeing process because they easily interact with dyes, electrolytes, leveling agents, etc., which can lead to problems such as color difference, reduced color fastness, and uneven waterproofing distribution, seriously affecting production efficiency and product quality. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the purpose of this invention is to provide a method for preparing a highly efficient fluoride-free water-repellent dyeing and finishing liquid and its application, so as to solve one or more problems in the prior art.

[0008] To achieve the above objectives, the technical solution of the present invention is as follows: A method for preparing a highly efficient, fluorine-free, water-repellent dyeing and finishing solution includes the following steps: S1. Preparation of material proportions, wherein the materials include 5% to 8% disperse dye, 8% to 15% long-chain alkane compounds, 3% to 8% polymer wax, 3% to 6% crosslinking agent, 6% to 15% surfactant, 5% to 15% dispersant, 2% to 5% binder, and the remainder is water. S2. Mix and stir the materials to obtain a pre-finishing solution; S3. Add zirconium beads to the pre-finishing solution and grind to obtain the final dyeing solution.

[0009] Furthermore, the crosslinking agent is one or more combinations of polysiloxanes and epoxy compounds; the dispersant is one or more combinations of fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, naphthalene sulfonic acids, and polycarboxylic acids.

[0010] Furthermore, the adhesive is one or more combinations of polyurethane, polyvinyl acetate, polyacrylate, and butadiene.

[0011] Furthermore, during grinding, the grinding speed of the grinding machine is controlled at 6000 r / pm to 10000 r / pm, and the grinding time is controlled at 30 min to 90 min.

[0012] Furthermore, during the grinding process, the particle size of the dyeing and finishing solution is tested periodically to control the particle size to be between 300 nm and 500 nm. If the particle size is not met, water is added and grinding continues until the particle size is satisfied.

[0013] The dyeing and finishing solution prepared by the above method is used in water-repellent fabrics.

[0014] A method for processing water-repellent fabric, using a dyeing and finishing solution prepared by the above-described method, includes the following steps: Step 1: Prepare the materials, including the above-mentioned dyeing and finishing solution and the remainder is water, wherein the dyeing and finishing solution accounts for 15% to 25%; Step 2: Perform bath dyeing and finishing based on the two-dip and two-roll process.

[0015] Furthermore, the two dips and two rolls are dip, roll, dip, roll processes in sequence, and the rolling liquid rate is controlled to be 80% to 90%.

[0016] Furthermore, the bath dyeing and finishing process consists of drying, melting and drying, washing, and drying treatment in sequence.

[0017] Furthermore, during drying, the drying temperature is controlled at 80℃~85℃ and the drying time is 5min~10min; during melting and drying, the melting and drying temperature is controlled at 180℃~200℃ and the melting and drying time is 10min~15min; during washing, the washing temperature is controlled at 80℃~85℃ and the washing time is 15min~20min.

[0018] Compared with the prior art, the beneficial technical effects of the present invention are as follows: (I) This invention significantly improves the performance of fluorine-free waterproofing agents through the synergistic compounding of long-chain alkane compounds, polymer waxes, and crosslinking agents, combined with a grinding process. The prepared finishing liquid can form a continuous and dense film on the fiber surface. Its long-chain alkane structure can effectively reduce surface energy, thereby achieving excellent initial water-repellent performance close to that of traditional fluorine-containing products. Even under high water pressure, it can effectively prevent water droplets from wetting the fabric. At the same time, the three-dimensional network structure formed by the reaction also enhances the durability of the waterproof membrane, enabling it to withstand repeated washing and friction.

[0019] (ii) By combining dispersants and dispersant composite systems, the dyeing and waterproofing functions are achieved simultaneously, effectively solving the compatibility problem between fluorine-free waterproofing agents and components such as dyes and electrolytes in the dye bath, and preventing color difference, color fastness reduction or uneven waterproofing caused by interaction.

[0020] (III) In the application of dyeing and finishing solutions, the combination of "two dips and two pads" and precisely controlled baking and washing processes ensures the dyeing depth and uniformity, and simultaneously forms a stable waterproof membrane. Compared with the traditional two-step production method of "dyeing first and then finishing", the process flow is significantly shortened, and the energy and water consumption in the production process is significantly reduced. Attached Figure Description

[0021] Figure 1 The diagram shows a process flow chart of a method for preparing a highly efficient, fluoride-free, water-repellent dyeing and finishing solution according to an embodiment of the present invention, and its application.

[0022] Figure 2 This invention illustrates a method for preparing a highly efficient fluorine-free water-repellent dyeing and finishing liquid and its application in the production of water-repellent rice fabric. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of this invention clearer, the following detailed description, in conjunction with the accompanying drawings and specific embodiments, provides a method for preparing a highly efficient, fluoride-free, water-repellent dyeing and finishing liquid and its application. The advantages and features of this invention will become clearer from the following description. It should be noted that the accompanying drawings are in a very simplified form and use non-precise proportions, used only to facilitate and clearly illustrate the purpose of the embodiments of this invention. Please refer to the accompanying drawings to make the objectives, features, and advantages of this invention more apparent and understandable. It should be understood that the structures, proportions, sizes, etc., depicted in the accompanying drawings are only for illustrative purposes to aid those skilled in the art and are not intended to limit the implementation conditions of this invention. Therefore, they have no substantial technical significance. Any modifications to the structure, changes in proportions, or adjustments to the size, without affecting the effects and objectives achieved by this invention, should still fall within the scope of the technical content disclosed in this invention.

[0024] Please see Figure 1 A method for preparing a highly efficient fluoride-free, water-repellent dyeing and finishing solution includes the following steps: S1. Material Proportioning Preparation: During proportioning, precise weighing of each component must strictly adhere to the specified mass percentage range, especially ensuring the proportion of functional components falls within the required process range. The materials include: Disperse dyes, accounting for 5% to 8%, are used to ensure the depth and uniformity of dyeing.

[0025] Long-chain alkane compounds, accounting for 8% to 15%, serve as the core waterproofing component.

[0026] A 3% to 8% polymer wax is used to synergistically enhance surface smoothness and water repellency.

[0027] A crosslinking agent comprising 3% to 6% is used to enhance the crosslinking density of the finishing solution after film formation.

[0028] A composite system is formed by surfactants accounting for 6% to 15% and dispersants accounting for 5% to 15%. The proportions are optimized according to the characteristics of the raw materials to ensure the dispersion stability of each component.

[0029] An adhesive comprising 2% to 5% is used to balance the bonding strength with fibers and the rheological properties of the finishing solution.

[0030] The remainder is water, which, as a dispersion medium, needs to be deionized to avoid impurity ions interfering with the stability of the system.

[0031] Furthermore, the crosslinking agent is one or more combinations of polysiloxanes and epoxy compounds. Polysiloxanes impart good flexibility and weather resistance to the membrane, while epoxy compounds can crosslink with the active groups of other components through epoxy groups, improving the membrane's density. The dispersant is one or more combinations of fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, naphthalene sulfonic acids, and polycarboxylic acids. Fatty alcohol polyoxyethylene ethers have good emulsifying and dispersing abilities, effectively reducing the surface tension of the system. Fatty acid polyoxyethylene esters can improve the wettability of the finishing solution on the fibers. Naphthalene sulfonic acid dispersants are particularly effective at dispersing dispersed dyes, preventing dye particle aggregation. Polycarboxylic acid dispersants possess excellent anti-electrolyte properties, maintaining a stable dispersion in complex systems. Through the combined use of the above dispersants, synergistic effects can be achieved based on the characteristics of different raw materials, ensuring that components such as dispersed dyes and long-chain alkane compounds form a uniform and stable dispersion system in water, avoiding color differences or fluctuations in waterproof performance due to uneven dispersion.

[0032] Furthermore, the adhesive is one or a combination of polyurethane, polyvinyl acetate, polyacrylate, and butadiene adhesives. Polyurethane adhesives possess excellent elasticity and weather resistance, imparting good flexibility to the finishing film. Polyvinyl acetate adhesives have good film-forming properties, enhancing the adhesion strength of the finishing solution to the fabric surface. Polyacrylate adhesives exhibit excellent wash resistance, enhancing the durability of the finishing effect. Butadiene adhesives improve the mechanical properties of the finishing film and increase the tear resistance of the fabric. By rationally compounding the above adhesives, the bonding force between the finishing solution and the fibers can be synergistically optimized, ensuring that the water-repellent components do not easily detach during subsequent use of the fabric, thereby maintaining a long-term stable waterproof effect.

[0033] S2. Mix and stir the materials to obtain a pre-finishing solution.

[0034] Mix disperse dyes, long-chain alkane compounds, polymeric waxes, crosslinking agents, surfactants, dispersants, binders, and a portion of water in appropriate mass ratios, and stir until homogeneous. During stirring, maintain a stirring speed of 450–550 rpm for 20–40 minutes to ensure complete dissolution of all solid materials and formation of a preliminary dispersion with the liquid components. Monitor the uniformity of the mixture in real time; if stratification or precipitation occurs, adjust the stirring parameters promptly.

[0035] S3. Add zirconium beads to the pre-finishing solution and grind to obtain the final dyeing solution.

[0036] Zirconium beads are added to the pre-treatment solution obtained by stirring in S2 for grinding. The diameter and amount of zirconium beads are controlled based on the quality of the pre-treatment solution to ensure shear efficiency during the grinding process. During grinding, a circulating grinding method is used to ensure full contact between the pre-treatment solution and the zirconium beads. The grinding speed of the grinder is controlled at 6000r~10000r / pm, and the grinding time is 30min~90min. The shear force generated by the collision and friction between the zirconium beads refines and uniformly disperses the particles in the system.

[0037] Furthermore, during grinding, the particle size of the dyeing and finishing solution is tested periodically. Preferably, a laser particle size analyzer can be used for testing to control the particle size to 300nm to 500nm. If the requirement is not met, water is added to adjust the system concentration and grinding continues until the particle size is met to comply with the process standards.

[0038] This grinding process, by strictly controlling the particle size after grinding, can refine the solid particles in the system to a nanoscale dispersion state, significantly improving the stability of the finishing solution. When applied to fabric processing in the future, it can more effectively form a continuous and dense film on the fiber surface, thereby ensuring the water-repellent performance and dyeing uniformity of the fabric.

[0039] Furthermore, the aforementioned disperse dyes, long-chain alkane compounds, polymeric waxes, and crosslinking agents are mixed and ground to allow the finishing solution to form a continuous, dense, and soft film on the fiber surface. This film itself is water-repellent and simultaneously fixes other waterproof components, achieving an optimal balance in film-forming properties, durability, and hand feel. The molecular structure of long-chain alkanes can mimic fluorocarbon chains, arranging on the fabric surface to form a low surface energy layer, making it difficult for water droplets to penetrate. The crosslinking agent reacts with the long-chain alkane compounds and polymeric waxes to form a three-dimensional network structure, greatly improving the durability of the waterproof film, including its resistance to washing, dry cleaning, and abrasion. The dispersant ensures that the aforementioned active ingredients form a stable and uniform dispersion in water, preventing precipitation and guaranteeing product consistency during application. Therefore, the application of the dyeing and finishing solution prepared by the above method in water-repellent fabrics is proposed.

[0040] Please refer to the following: Figure 2 A method for processing a water-repellent fabric includes the following steps: Step 1: Material preparation, including the dyeing and finishing solution prepared as described above, and the remainder being water, with the dyeing and finishing solution comprising 15%–25%. The ratio of dyeing and finishing solution to water can be precisely controlled within this range according to the fabric material and the target water-repellent rating. When the fabric is a lightweight polyester fiber, a dyeing and finishing solution ratio of 15%–20% can be used to avoid excessive finishing solution leading to increased fabric stiffness. When the fabric is a heavy cotton fabric, the ratio can be increased to 20%–25% to ensure sufficient adhesion of the waterproof components.

[0041] Step 2: Perform bath dyeing and finishing based on the two-dip and two-roll process.

[0042] The two dips and two rubs are dip, rub, dip, rub treatments in sequence, with the rub rate controlled at 80% to 90% to ensure that the fabric fully absorbs the finishing liquid during the dip and rub process. Through the synergistic effect of two dips and two rubs, the adsorption amount and uniformity of the finishing liquid on the fabric can be significantly improved, laying a good foundation for subsequent bath dyeing and finishing.

[0043] The bath dyeing and finishing process consists of drying, melt drying, washing, and drying again. The first drying stage aims to remove excess moisture from the fabric surface, controlling the drying temperature at 80-85℃ and the drying time at 5-10 minutes. This ensures the fabric is initially set while preventing premature reaction of the effective components in the finishing solution due to high temperatures, and avoids migration of the finishing solution due to uneven moisture evaporation during the subsequent melt drying process. The melt drying stage, controlled at 180-200℃ and for 10-15 minutes, uses high temperature to promote a chemical reaction between long-chain alkane compounds and cross-linking agents, forming a dense, three-dimensional network structure of waterproof film on the fiber surface. Simultaneously, the polymer wax and adhesive work synergistically to enhance the bonding strength between the film and the fiber. The washing stage, controlled at 80-85℃ and for 15-20 minutes, effectively removes unreacted free components and impurities, preventing residual substances from affecting the fabric's feel and colorfastness. The second drying stage, similar to the first, further solidifies the waterproof film structure, ensuring the fabric achieves stable water-repellent properties.

[0044] To further demonstrate the feasibility of the method of the present invention, different proportions of finishing liquid components were used in Examples 1-3 of the present invention and other comparative examples 1-3. After water-repellent fabrics were made based on the finishing liquids, water-repellent performance level tests were conducted, as shown in Tables 1 and 2 below: Table 1

[0045] Table 2

[0046] As shown in Tables 1 and 2, the water-repellent properties of the fabric are significantly improved by adjusting the material ratio of the finishing liquid of this invention, namely the synergistic compounding of long-chain alkane compounds and polymeric waxes. In Examples 1-3, when the proportion of long-chain alkane compounds is 8%-13% and the proportion of polymeric waxes is 3%-8%, the water-repellent performance of the fabric before washing reaches level 5. In contrast, the water-repellent performance before washing in Comparative Example 1 (without long-chain alkane compounds) and Comparative Example 2 (without polymeric waxes) is only level 4-5 and level 4, respectively, and in Comparative Example 3 (without both), it is as low as level 2, fully demonstrating the necessity of the synergistic effect of the two. In terms of durability, Example 1 maintains a level of 4-5 after 20 washes, level 4 after 50 washes, and drops to level 3-4 after 100 washes, which is far better than the degradation rate of Comparative Examples 1-3. This is due to the three-dimensional network structure formed by the reaction of the crosslinking agent with long-chain alkane compounds and polymeric waxes, which enhances the water-repellent membrane's wash resistance. In summary, the effectiveness and superiority of the preparation method and application process of this invention have been verified. It enables the simultaneous completion of dyeing and water-repellent finishing, significantly shortens the traditional process flow, and reduces production energy and water consumption.

[0047] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0048] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing a highly efficient, fluorine-free, water-repellent dyeing and finishing solution, characterized in that: Includes the following steps: S1. Preparation of material proportions: the materials include 5% to 8% disperse dye, 8% to 15% long-chain alkane compounds, 3% to 8% polymer wax, 3% to 6% crosslinking agent, 6% to 15% surfactant, 5% to 15% dispersant, 2% to 5% binder, and the remainder is water. S2. Mix and stir the materials to obtain a pre-finishing solution; S3. Add zirconium beads to the pre-finishing solution and grind to obtain the final dyeing solution.

2. The preparation method of the highly efficient fluoride-free water-repellent dyeing and finishing solution as described in claim 1, characterized in that: The crosslinking agent is one or more combinations of polysiloxanes and epoxy compounds; the dispersant is one or more combinations of fatty alcohol polyoxyethylene ethers, fatty acid polyoxyethylene esters, naphthalene sulfonic acids, and polycarboxylic acids.

3. The preparation method of a highly efficient fluoride-free water-repellent dyeing and finishing solution as described in claim 1, characterized in that: The adhesive is one or a combination of polyurethane, polyvinyl acetate, polyacrylate, and butadiene.

4. The preparation method of a highly efficient fluoride-free water-repellent dyeing and finishing solution as described in claim 1, characterized in that: During grinding, control the grinding speed of the grinder to be 6000r~10000r / pm and the grinding time to be 30min~90min.

5. The preparation method of a highly efficient fluoride-free water-repellent dyeing and finishing solution as described in claim 1, characterized in that: During grinding, the particle size of the dyeing and finishing solution is tested periodically to control the particle size to be between 300nm and 500nm. If the particle size is not met, water is added and grinding is continued until the particle size is met.

6. The application of the dyeing and finishing solution prepared by any one of claims 1 to 5 in water-repellent fabrics.

7. A method for processing a water-repellent fabric, using a dyeing and finishing solution prepared by any one of claims 1 to 5, characterized in that: Includes the following steps: Step 1: Prepare the materials, including the above-mentioned dyeing and finishing solution and the remainder is water, wherein the dyeing and finishing solution accounts for 15% to 25%; Step 2: Perform bath dyeing and finishing based on the two-dip and two-roll process.

8. The processing method of a water-repellent fabric as described in claim 7, characterized in that: The two dips and two rolls are dip, roll, dip, roll processes in sequence, with the rolling liquid rate controlled at 80% to 90%.

9. The processing method of a water-repellent fabric as described in claim 8, characterized in that: The bath dyeing and finishing process consists of drying, melting and drying, washing, and drying treatment in sequence.

10. The processing method of a water-repellent fabric as described in claim 9, characterized in that: During drying, the drying temperature is controlled at 80℃~85℃ and the drying time is 5min~10min; during melting and drying, the melting and drying temperature is controlled at 180℃~200℃ and the melting and drying time is 10min~15min; during washing, the washing temperature is controlled at 80℃~85℃ and the washing time is 15min~20min.

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