Fluorine-free anti-sticking knitted fabric and preparation method thereof

Abstract

The invention discloses a fluoride-free anti-sticking knitted fabric and a preparation method thereof, and belongs to the field of textile and garment materials. The anti-sticking knitted fabric comprises knitted base cloth and a fluoride-free printed pattern layer printed on one surface of the knitted base cloth, the fluoride-free printed pattern layer is a micron-sized discontinuous pattern layer; the fluoride-free printed pattern layer is formed by fluoride-free printing paste through a printing process, and the fluoride-free printing paste comprises a fluoride-free waterproof agent, a cross-linking agent, an adhesive, a thickening agent and a wetting agent. In the invention, the micron-sized discontinuous pattern layer is formed on the surface of the knitted base cloth through the fluoride-free printing paste, discrete micron-sized three-dimensional'waterproof islands' can be constructed, the distance between the adjacent islands is smaller than the spreading critical length of sweat capillary tubes, a water film is broken, the phenomenon that the fabric is stuck to the body is reduced, and the wearing comfort is good. Meanwhile, in the fluoride-free printed pattern layer, a fluoride-free waterproof agent and a cross-linking agent form a three-dimensional network, so that the surface energy can be reduced, and the washing resistance and durability can be improved.

Description

Technical Field

[0001] The present invention relates to the field of textile clothing materials, and in particular to a fluorine-free anti-sticking knitted fabric and a preparation method thereof. Background Art

[0002] Nowadays, people's demands for clothing comfort are increasing. Textile technologies have been developed for summer clothing, featuring features such as moisture-wicking, quick-drying, and a cool feel. However, in hot summer environments or during exercise, the back, torso, and shoulders of the human body sweat noticeably. This sweat forms a water film between the fabric and the clothing, causing it to adhere to the body. This water film creates a sticky and stuffy feeling, leading to discomfort during daily wear. During exercise, the water film and adhesion increase the resistance between the skin and the fabric, affecting athletic performance. After exercise, or when experiencing environmental changes such as in an air-conditioned room, the damp fabric on the skin can easily cause colds.

[0003] Current common fabric development solutions fail to effectively address this pain point for summer knitwear. Using water-repellent yarn on the skin-facing side and hydrophilic yarn on the front can effectively wick away moisture, or employing a 3D concave-convex woven structure to improve adhesion. However, these methods rely on multi-layered fabrics, which are highly limited in texture and style, resulting in a narrow range of applications. Fluoride waterproofing padding can also be used to achieve full waterproofing, but this process compromises moisture permeability and skin-friendliness, resulting in a certain degree of stuffiness. Furthermore, the fluoride used is restricted under EU REACH regulations, making it less environmentally friendly. Summary of the Invention

[0004] In view of this, the present invention provides a fluorine-free anti-sticking knitted fabric and a preparation method thereof. The knitted fabric provided by the present invention can effectively improve the sticking performance and enhance the wearing comfort while maintaining the original texture of the fabric, and is also environmentally friendly.

[0005] The present invention provides a fluorine-free anti-sticking knitted fabric, comprising a knitted base fabric and a fluorine-free printed pattern layer printed on one surface of the knitted base fabric; the fluorine-free printed pattern layer is a micron-level non-continuous pattern layer; the fluorine-free printed pattern layer is formed by a fluorine-free printing paste through a printing process, and the fluorine-free printing paste comprises a fluorine-free waterproofing agent, a cross-linking agent, an adhesive, a thickener and a wetting agent.

[0006] In some embodiments, the fluorine-free waterproofing agent is selected from one or more of silicone, long-chain alkyl acrylate, polyurethane and bio-based waterproofing agents;

[0007] The adhesive is selected from one or more of acrylate copolymers, butadiene copolymers, vinyl acetate copolymers and polyurethane adhesives; the cross-linking agent is selected from aziridine compounds and / or self-cross-linking acrylic acid; the thickener is selected from one or more of alginates, anionic acrylic acid copolymers and starch thickeners; and the wetting agent is selected from polyoxyethylene ethers and / or glycol wetting agents.

[0008] In some embodiments, the micron-scale discontinuous pattern layer is a dot pattern and / or a spaced polygonal pattern, and the spacing between each pattern is 0.8-1.5 mm.

[0009] The present invention provides a method for preparing a fluorine-free anti-sticking knitted fabric, comprising the following steps:

[0010] S1. Providing a fluorine-free printing paste, wherein the fluorine-free printing paste comprises a fluorine-free waterproofing agent, a cross-linking agent, a binder, a thickener, a wetting agent and water;

[0011] S2. Using the fluorine-free printing paste, printing a non-continuous pattern on a knitted fabric, and curing it by baking to obtain a fluorine-free anti-sticking knitted fabric with a micron-level non-continuous pattern layer.

[0012] In some embodiments, the fluorine-free printing paste comprises: 18-22 wt% of fluorine-free waterproofing agent; 4-6 wt% of cross-linking agent; 12-18 wt% of adhesive; 1.2-1.8 wt% of thickener; 0.3-0.5 wt% of wetting agent; and the balance of water.

[0013] The fluorine-free waterproofing agent is selected from one or more of silicone, long-chain alkyl acrylate, polyurethane and bio-based waterproofing agents; the adhesive is selected from one or more of acrylate copolymers, butadiene copolymers, vinyl acetate copolymers and polyurethane adhesives; the cross-linking agent is selected from aziridine compounds and / or self-cross-linking acrylic acid; the thickener is selected from one or more of alginates, anionic acrylic acid copolymers and starch thickeners; the wetting agent is selected from polyoxyethylene ethers and / or glycol wetting agents.

[0014] In some embodiments, step S1 includes: adding a wetting agent and a thickener to water, stirring and dispersing, adding a premix of a fluorine-free waterproofing agent and a cross-linking agent, controlling the pH value to 6.5-7.0, adding an adhesive, and adjusting the room temperature viscosity to 6000-7000 mPa·s to obtain a fluorine-free printing paste.

[0015] In some embodiments, in step S2, the discontinuous pattern is a dot pattern and / or a spaced polygonal pattern, the spacing between each pattern is 0.8-1.5 mm, and the total coverage of all patterns is 35-65%.

[0016] In some embodiments, the printing is performed using a rotary screen printing plate with a mesh size of 100-125 meshes, a printing blade pressure of 2.5-3.2 Bar, a printing speed of 18-22 m / min, and pre-drying with hot air drying at 105-110°C.

[0017] In some embodiments, the printing is performed using a flat screen printing plate with a mesh size of 80-125, a printing scraper speed of 6-8 m / min, and pre-drying at 80-95° C. infrared drying.

[0018] In some embodiments, the curing temperature is 120-160° C., and the curing time is 1-3 minutes.

[0019] Compared to existing technologies, the anti-sticking knitted fabric provided by the present invention utilizes a fluorine-free waterproofing agent, meeting environmental protection requirements. The fabric comprises a knitted base fabric and a fluorine-free printed pattern layer printed on one surface of the knitted base fabric. The fluorine-free printed pattern layer is a micron-scale, non-continuous pattern layer formed through a printing process using a fluorine-free printing paste comprising a fluorine-free waterproofing agent, a cross-linking agent, an adhesive, a thickener, and a wetting agent. In the present invention, the micron-scale, non-continuous pattern layer formed on the surface of the knitted base fabric using the fluorine-free printing paste creates discrete, micron-scale, three-dimensional "waterproof islands." The spacing between adjacent islands is less than the critical length for sweat capillary spreading, breaking up the water film and reducing fabric sticking, resulting in improved wearer comfort.

[0020] At the same time, in the fluorine-free printed pattern layer, the fluorine-free waterproof agent and the cross-linking agent form a three-dimensional network, which can reduce surface energy and improve water resistance and durability. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is a photo of the finished fabric sample described in Example 1 of the present invention. DETAILED DESCRIPTION

[0022] The following is a clear and complete description of the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0023] The present invention provides a fluorine-free anti-sticking knitted fabric, comprising a knitted base fabric and a fluorine-free printed pattern layer printed on one surface of the knitted base fabric; the fluorine-free printed pattern layer is a micron-level non-continuous pattern layer; the fluorine-free printed pattern layer is formed by a fluorine-free printing paste through a printing process, and the fluorine-free printing paste comprises a fluorine-free waterproofing agent, a cross-linking agent, an adhesive, a thickener and a wetting agent.

[0024] The knitted fabric provided by the present invention can maintain the original texture of the fabric, while effectively improving the adhesion performance, enhancing wearing comfort, and is also environmentally friendly.

[0025] The anti-stick knitted fabric described in the embodiments of the present invention includes a knitted base fabric having any knitted fabric structure, and the fiber material and color are not particularly limited, and has a wide range of uses. In specific embodiments of the present invention, the knitted base fabric can be a combed cotton knitted fabric (such as a single-sided jersey structure, specification 32S) or a polyester-cotton blend or other knitted fabric type; the weight is preferably 170-185g / m2. 2 .

[0026] Furthermore, one surface of the knitted base fabric (which may be the skin-facing surface) is printed with a micron-scale, discontinuous, fluorine-free printed pattern layer, primarily comprising a fluorine-free water repellent. The dispersed, microscopically three-dimensional, water-repellent and hydrophobic printed areas can be dot patterns or spaced polygonal patterns (the spacing between patterns is preferably 0.8-1.5 mm). This pattern disrupts the continuous water film formed between skin sweat and the fabric, while retaining some unprinted areas for moisture absorption and breathability, thereby imparting excellent anti-sticking properties, environmental advantages, and wearing comfort to the knitted fabric.

[0027] Wherein, the fluorine-free waterproofing agent is selected from one or more of silicone, long-chain alkyl acrylate, polyurethane and bio-based waterproofing agents, preferably a combination of two types. For example, the silicone waterproofing agent includes: methyl hydrogen polysiloxane (MHPS), amino-modified polysiloxane, epoxy-modified polysiloxane, amino silicone oil, etc. The long-chain alkyl acrylate waterproofing agent includes: stearic acid acrylate copolymer (C18 acrylate, which can be a hyperbranched macromolecular polymer, using the C18 long chain to achieve a fluorine-free hydrophobic effect), behenic acid acrylate copolymer, etc.; polyurethane waterproofing agents such as long-chain alkyl modified polyurethane, etc.; bio-based waterproofing agents include: methyl palmitate derivatives, chitosan hydrophobic modification, etc.

[0028] The above fluorine-free waterproofing agent is selected to utilize the arrangement of long-chain alkyl groups to reduce the surface energy of the fiber and form a hydrophobic effect, wherein the carbon chain length is preferably between C8-C22, and further C15-C20. A carbon chain that is too short will lead to weak alkyl crystallinity, a large critical surface tension, and insufficient water resistance; a carbon chain that is too long may lead to decreased mobility, poor synergy with the cross-linking agent, and the carbon chain cannot be effectively arranged in the air, resulting in insufficient water resistance. The molecular weight range of the fluorine-free waterproofing agent is preferably: 50,000-200,000 Da. When the molecular chain is too short, such as less than 50,000 Da, the intermolecular force requirements are high, the printing points are fragile, and the wash resistance is poor; when the molecular weight is too high to greater than 200,000 Da, the slurry permeability is poor and the printing effect is poor.

[0029] The fluorine-free printing pattern layer is formed by a fluorine-free printing paste through a printing process. In addition to the main component of the fluorine-free waterproofing agent, the fluorine-free printing paste includes a cross-linking agent, an adhesive, a thickener and a wetting agent. The adhesive is selected from one or more of acrylate copolymers, butadiene copolymers, vinyl acetate copolymers and polyurethane adhesives; the adhesive preferably has a molecular weight of 100,000-300,000. If the molecular weight is too low (<50,000), the film will be fragile; if it is too high (>500,000), the permeability will be poor. Its solid content is preferably 40%-50%. If the solid content is too low (<40%), multiple coatings are required; if the solid content is too high (>50%), the leveling property will be poor. The glass transition temperature (Tg) is between -10°C and 30°C. If Tg is too high, the printing will be hard and have a poor touch; if Tg is too low, the heat resistance will be insufficient.

[0030] The cross-linking agent is selected from aziridine compounds and / or self-cross-linking acrylic acid; the thickener is selected from one or more of alginate, anionic acrylic copolymer and starch thickeners, such as sodium alginate, starch, etc., or anionic acrylic copolymers with a molecular weight between 200,000 and 300,000, all of which are conventional printing thickeners available on the market; the wetting agent is selected from polyoxyethylene ethers and / or glycol wetting agents, further including octylphenol polyoxyethylene ether, nonylphenol polyoxyethylene ether, acetylene glycol, ethylene glycol, etc.

[0031] Accordingly, an embodiment of the present invention provides a method for preparing a fluorine-free anti-sticking knitted fabric, comprising the following steps:

[0032] S1. Providing a fluorine-free printing paste, wherein the fluorine-free printing paste comprises a fluorine-free waterproofing agent, a cross-linking agent, a binder, a thickener, a wetting agent and water;

[0033] S2. Using the fluorine-free printing paste, printing a non-continuous pattern on a knitted fabric, and curing it by baking to obtain a fluorine-free anti-sticking knitted fabric with a micron-level non-continuous pattern layer.

[0034] In the embodiment of the present invention, a fluorine-free printing paste system with anti-sticking properties is first prepared: the fluorine-free waterproofing agent, cross-linking agent, adhesive, thickener, wetting agent and water can be compounded according to the proportions in the table below. The specific types of each component are as described above. After uniform mixing, the printing paste is obtained. Preferably, water is added to a stirring kettle, the temperature is raised to 40-60°C, the wetting agent and thickener are added according to the process formula requirements, and the mixture is stirred and dispersed at 600-3000 rpm. After 10-30 minutes, the premix of the fluorine-free waterproofing agent and the cross-linking agent is slowly added, the pH is controlled to 6.5-7.0, and finally the adhesive is added to adjust the viscosity to 6500±500mPa·s (room temperature) to obtain the anti-sticking fluorine-free printing paste.

[0035] Table 1 Formula of fluorine-free anti-sticking printing paste system

[0036] Components Mass percentage Fluorine-free waterproofing agent 18-22％ crosslinking agent 4-6％ Adhesives 12-18％ thickener 1.2-1.8％ Wetting agent 0.3-0.5％ water margin

[0037] The embodiments of the present invention utilize the aforementioned fluorine-free printing paste in a non-stick fluorine-free printing process. Depending on product requirements, the formulated fluorine-free printing paste is selectively printed onto the skin-contacting surface (generally the reverse side) of knitted fabric using rotary screen printing or flat screen printing. After pre-drying and curing, a water-repellent, micron-scale, non-continuous pattern layer is formed, resulting in a fluorine-free, non-stick knitted fabric.

[0038] In an embodiment of the present invention, the discontinuous pattern is a dot pattern and / or a spaced polygonal pattern, the spacing between each pattern is 0.8-1.5 mm, and the total coverage (distribution density) of all patterns is 35-65%.

[0039] In some embodiments, the printing is performed using a rotary screen printing plate, that is, a rotary screen printing process, and the specific process is shown in Table 2 below; in other embodiments, the printing is performed using a flat screen printing plate, that is, a flat screen printing process, and the specific process is shown in Table 3 below.

[0040] Table 2 Fluorine-free anti-stick rotary screen printing process

[0041] parameter Setting value Mesh number 100-125 mesh Scraper pressure 2.5-3.2 Bar Printing speed 18-22m / min Pre-baking temperature 105-110℃ (hot air)

[0042] Table 3 Fluorine-free anti-stick flat screen printing process

[0043] parameter Setting value Mesh number 80-125 mesh Scraper speed 6-8m / min Scraper angle 75° Scraper reciprocating 2 times Pre-baking temperature 80-95℃(infrared)

[0044] After printing, the semi-finished fabric in this embodiment of the present invention can be transferred to a hot air circulation drying machine for curing. The drying time can be 1-3 minutes, and the temperature is preferably 120-160°C. This curing process produces a non-sticky, fluorine-free printed knitted fabric. The knitted fabric obtained through this printing process exhibits excellent anti-sticking properties, environmental advantages, and wearer comfort.

[0045] To better understand the technical content of this invention, the following specific examples are provided to further illustrate the invention. The raw materials used in these examples are commercially available. The fluorine-free water repellent used has a molecular weight of 50,000-100,000 Da; the binder has a molecular weight of 150,000-200,000 Da, and a solids content of 40%-50%.

[0046] Example 1

[0047] 1. Fabric type: 32S combed cotton knit fabric (single-sided jersey structure), weight: 180±5g / m 2 The printing paste formula is as follows:

[0048] Table 4 Slurry formula

[0049]

[0050] 2. Slurry preparation process

[0051] 2.1 Premixed crosslinking system:

[0052] The aziridine crosslinker was pre-mixed with the amino silicone oil fluorine-free waterproofing agent 1 and the C18 acrylate copolymer fluorine-free waterproofing agent 2 in a mass ratio of 3:15:8, and stirred in a 50°C water bath for 15 min.

[0053] 2.2 Preparation of main slurry:

[0054] Deionized water (60% total mass), wetting agent Surfynol 104 (0.5%), and PTF-3 thickener (added three times with an interval of 5 minutes) were added to a stainless steel reactor in sequence, and the mixture was dispersed at 1200 rpm for 30 minutes until a uniform colloid was obtained.

[0055] 2.3 Final mixing process:

[0056] Slowly add the premixed cross-linking system, control the temperature ≤ 45 ° C, and finally add the adhesive acrylate TF-306, adjust the pH to 6.8 ± 0.2, and control the viscosity to 6500 ± 200 mPa·s.

[0057] 3. Rotary screen printing process

[0058] 3.1 Use 110 mesh rotary screen, the equipment is Stoke RD-IV rotary screen printing machine, set the scraper pressure to 3.0 Bar, printing speed to 20m / min, and slurry application amount to 38g / m 2 The non-continuous pattern is a dot pattern, the spacing between each pattern is 0.8-1.5 mm, and the total coverage (distribution density) of all patterns is 55-65%.

[0059] 3.2 Pre-drying: After printing, pre-dry in a Monfongs 3280 dryer at 105°C for 2 minutes using hot air circulation to make the residual moisture content 12-15%.

[0060] 3.3 Baking and curing: After pre-drying, transfer the fabric to the Brückner Thermex 6500 heat setting machine and use 150℃×2.5min hot air drying to ensure that the surface temperature of the fabric is ≥140℃. After baking, the finished product of fluorine-free anti-sticking printed knitted cotton fabric is obtained. Figure 1 shown.

[0061] Example 2

[0062] 1. Fabric type: 32S combed cotton knit fabric (single-sided jersey structure), weight: 180±5g / m2. The printing paste formula is as follows:

[0063] Table 5 Slurry formula

[0064]

[0065] 2. Slurry preparation process

[0066] 2.1 Premixed crosslinking system:

[0067] The aziridine crosslinking agent and the fluorine-free waterproofing agent epoxy-modified polysiloxane were pre-mixed in a ratio of 3:23 and stirred in a 50°C water bath for 15 minutes.

[0068] 2.2 Preparation of main slurry:

[0069] Deionized water (60% total mass), Surfynol 104 (0.5%), and PTF-3 thickener (added three times with an interval of 5 minutes) were added sequentially into a stainless steel reactor, and the mixture was dispersed at 1200 rpm for 30 minutes until a uniform colloid was obtained.

[0070] 2.3 Final mixing process:

[0071] Slowly add the premixed crosslinking system, control the temperature ≤45°C, and finally add the butadiene copolymer Wingtack STS adhesive, adjust the pH to 6.8±0.2, and control the viscosity to 6200±200mPa·s.

[0072] 3. Rotary screen printing process

[0073] 3.1. Use a 110 mesh rotary screen with a non-hexagonal honeycomb pattern, a distribution density of 45% coverage, and a pattern spacing of 0.8-1.5 mm. Print according to Table 2. The equipment is a Stock RD-IV rotary screen printer, with a blade pressure of 3.0 bar, a printing speed of 20 m / min, and a slurry application rate of 38 g / m 2 , for printing.

[0074] 3.2. Pre-drying: After printing, pre-dry in a Monfongs 3280 dryer at 105°C for 2 minutes with hot air circulation to make the residual moisture content 12-15%.

[0075] 3.3 Baking and curing: After pre-drying, the fabric was transferred to a Brückner Thermex 6500 heat setting machine and dried with hot air at 150°C × 2.5min to ensure that the surface temperature of the fabric was ≥140°C. After baking, the finished fluorine-free anti-sticking printed knitted cotton fabric was obtained.

[0076] Example 3

[0077] 1. Fabric Specifications Material: 32S combed cotton knitted fabric (single-sided jersey structure), weight: 180±5g / m2. The printing paste formula is as follows:

[0078] Table 6 Slurry formula

[0079]

[0080] 2. Slurry preparation process

[0081] 2.1 Premixed crosslinking system:

[0082] Premix the self-crosslinking acrylic acid 728M and the long-chain alkyl acrylate waterproofing agent in a ratio of 1:4 and stir in a 50°C water bath for 15 minutes.

[0083] 2.2 Preparation of main slurry:

[0084] Deionized water (58.1% total mass), acetylene glycol (0.4%), and sodium alginate thickener (added three times with an interval of 5 minutes) were added sequentially into a stainless steel reactor, and the mixture was dispersed at 1500 rpm for 30 minutes until a uniform colloid was obtained.

[0085] 2.3 Final mixing process:

[0086] Slowly add the premixed cross-linking system, control the temperature ≤ 45 ° C, and finally add the modified polyurethane AH-1207 adhesive, adjust the pH to 6.8 ± 0.2, and control the viscosity to 6500 ± 200 mPa·s

[0087] 3. Rotary screen printing process

[0088] 3.1. Use a 110 mesh rotary screen with a non-hexagonal honeycomb pattern, a distribution density of 45% coverage, a Stokes RD-IV rotary screen printer, set the scraper pressure to 3.0 Bar, the printing speed to 20 m / min, and the slurry application amount to 38 g / m 2 , for printing.

[0089] 3.2. Pre-drying: After printing, pre-dry in a Monfongs 3280 dryer at 105°C for 2 minutes with hot air circulation to make the residual moisture content 12-15%.

[0090] 3.3. Curing: After pre-drying, the fabric was transferred to a Brückner Thermex 6500 heat setting machine and dried using hot air at 150°C for 2.5 min to ensure that the fabric surface temperature was ≥145°C. After curing, the finished product, fluorine-free, anti-sticking printed knitted cotton fabric, was obtained.

[0091] Example 4

[0092] 1. Fabric Specifications Material: 32S combed cotton knitted fabric (single-sided jersey structure), weight: 180±5g / m2. The printing paste formula is as follows:

[0093] Table 7 Slurry formula

[0094]

[0095] 2. Slurry preparation process

[0096] 2.1 Premixed crosslinking system:

[0097] Premix the self-crosslinking acrylic acid crosslinker 728M and the fluorine-free waterproofing agent methyl hydrogen polysiloxane DK-301 in a ratio of 1:4 and stir in a 60°C water bath for 15 minutes.

[0098] 2.2 Preparation of main slurry:

[0099] Deionized water (58.1% total mass), wetting agent ethylene glycol (0.4%), and sodium alginate thickener (added three times with an interval of 5 minutes) were added in sequence to a stainless steel reactor, and the mixture was dispersed at 1200 rpm for 30 minutes until a uniform colloid was obtained.

[0100] 2.3 Final mixing process:

[0101] Slowly add the premixed cross-linking system, control the temperature ≤ 45 ° C, and finally add the acrylate TF306 adhesive, adjust the pH to 6.8 ± 0.2, and control the viscosity to 6500 ± 200 mPa·s.

[0102] 3. Flat screen printing

[0103] The adjusted printing paste was placed on a 110-mesh flat screen, and a non-continuous honeycomb pattern was used with a coverage rate of 45%. Printing was performed at a speed of 7 m / min with two reciprocating scraping strokes to ensure that the mesh penetration rate was ≥ 90%. Subsequently, infrared drying was performed at 90°C × 2 min to make the surface moisture content of the fabric ≤ 15%, and then hot air circulation baking was performed at 140°C × 2 min to obtain a fluorine-free anti-sticking printed fabric.

[0104] Comparative Example 1

[0105] 1. Fabric type: 32S combed cotton knit fabric (single-sided jersey structure), weight: 180±5g / m2. The printing paste formula is as follows:

[0106] Table 8 Slurry formula

[0107]

[0108] 2. Slurry preparation process

[0109] 2.1 Premixed crosslinking system:

[0110] Premix the aziridine crosslinker XL-12 and the fluorine-free waterproofing agent epoxy-modified polysiloxane in a ratio of 1:5 and stir in a 50°C water bath for 15 minutes.

[0111] 2.2 Slurry preparation:

[0112] In a stainless steel reactor, add the following ingredients in sequence: deionized water (57% total mass), Surfynol 104 (1%), and PTF-3 thickener (added in three additions, 5 min apart). Disperse at 1200 rpm for 30 min until a uniform colloid is obtained. Slowly add the premixed crosslinking system. Control the temperature to ≤45°C, adjust the pH to 6.8±0.2, and control the viscosity to 6000±200 mPa·s.

[0113] 3. Rotary screen printing process

[0114] 3.1. Use a 110 mesh rotary screen with a non-hexagonal honeycomb pattern, a distribution density of 45% coverage, a Stokes RD-IV rotary screen printer, set the scraper pressure to 3.0 Bar, the printing speed to 20 m / min, and the slurry application amount to 38 g / m 2 , for printing.

[0115] 3.2. Pre-drying: After printing, pre-dry in a Monfongs 3280 dryer at 105°C for 2 minutes with hot air circulation to make the residual moisture content 12-15%.

[0116] 3.3. Curing: After pre-drying, the fabric was transferred to a Brückner Thermex 6500 heat setting machine and dried using hot air at 150°C for 2.5 min, ensuring that the fabric surface temperature was ≥140°C. After curing, the finished printed knitted cotton fabric was obtained.

[0117] Comparative Example 2

[0118] 1. Fabric material: 32S combed cotton knitted fabric (single-sided jersey structure), weight: 180±5g / m2. Printing paste formula is as follows:

[0119] Table 9 Slurry formula

[0120]

[0121] 2. Slurry preparation process

[0122] 2.1 Premixed crosslinking system:

[0123] Premix the self-crosslinking acrylic crosslinker 728M and the C6 fluorinated waterproofing agent FCB060 in a ratio of 5:22 and stir in a 60°C water bath for 15 min.

[0124] 2.2 Preparation of main slurry:

[0125] In a stainless steel reactor, add the following: deionized water (59.4% total mass), wetting agent ethylene glycol (0.6%), and sodium alginate thickener (added in three times, with an interval of 5 minutes). Disperse at a high speed of 1200 rpm for 30 minutes until a uniform colloid is obtained. Adjust the pH to 6.8±0.2 and control the viscosity to 6500±200 mPa·s.

[0126] 3. Flat screen printing

[0127] The adjusted printing paste was placed on a 110-mesh flat screen, and a non-continuous honeycomb pattern was used with a coverage rate of 45%. Printing was performed at a speed of 7 m / min with two reciprocating scraping strokes to ensure that the mesh penetration rate was ≥ 90%. Subsequently, infrared drying was performed at 90°C × 2 min to make the surface moisture content of the fabric ≤ 15%, and then hot air circulation baking was performed at 140°C × 2 min to obtain a fluorine-free anti-sticking printed fabric.

[0128] The above embodiments and comparative examples were tested according to the test items and test methods in Table 10 below, and the test results were obtained, see Table 11.

[0129] Table 10 Test methods

[0130] Test items Test Method Skin adhesion (before washing) T / CNGA 64-2024 (water absorption 300%) Skin adhesion (after washing) T / CNGA 64-2024 (water absorption 300%) 4N 10 washes Dynamic moisture permeability GB / T 12704-2019 Method B Total organic fluorine TOF OEKO-TEX Standard 100

[0131] Table 11 Performance test results

[0132]

[0133] Comparative Example 1 shows that, in the absence of an adhesive, poor adhesion and the inability to form effective, three-dimensional, island-like isolation points result in insufficient water film penetration, and unsatisfactory anti-stick performance both before and after washing. Comparative Example 2 also demonstrates that printed fabrics using a fluorine-containing water repellent contain residual fluorine, posing a health hazard.

[0134] Examples 1, 2, 3, and 4, by creating micro-stereoscopic hydrophobic printed areas, break up water films, effectively improving the fabric's adhesion and enhancing wearing comfort. Among them, Example 1 utilizes a combination of multiple fluorine-free waterproofing agents, creating a synergistic effect and exhibiting stronger isolation properties, better anti-adhesion effects, and improved breathability, making it the preferred solution.

[0135] This article uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only used to help understand the method of the present invention and its core ideas. The above is only a preferred implementation method of the present invention. It should be pointed out that due to the limitations of textual expression, there are objectively infinite specific structures. For ordinary technicians in this technical field, without departing from the principles of the present invention, they can make several improvements, modifications or changes, and can also combine the above technical features in an appropriate manner; these improvements, modifications, changes or combinations, or the direct application of the inventive concept and technical solution to other occasions without improvement, should be regarded as the scope of protection of the present invention.

Claims

1. A fluorine-free anti-stick knitted fabric, characterized in that: The invention comprises a knitted base fabric and a fluorine-free printed pattern layer printed on one surface of the knitted base fabric; The fluorine-free printing pattern layer is a micron-level non-continuous pattern layer; the fluorine-free printing pattern layer is formed by a fluorine-free printing paste through a printing process, and the fluorine-free printing paste includes a fluorine-free waterproofing agent, a cross-linking agent, an adhesive, a thickener and a wetting agent.

2. The anti-sticking knitted fabric according to claim 1, characterized in that: The fluorine-free waterproofing agent is selected from one or more of silicone, long-chain alkyl acrylate, polyurethane and bio-based waterproofing agents; The adhesive is selected from one or more of acrylate copolymers, butadiene copolymers, vinyl acetate copolymers and polyurethane adhesives; the cross-linking agent is selected from aziridine compounds and / or self-cross-linking acrylic acid; the thickener is selected from one or more of alginates, anionic acrylic acid copolymers and starch thickeners; and the wetting agent is selected from polyoxyethylene ethers and / or glycol wetting agents.

3. The anti-sticking knitted fabric according to claim 1, characterized in that: The micron-scale discontinuous pattern layer is a dot matrix pattern and / or a spaced polygonal pattern, and the spacing between each pattern is 0.8-1.5 mm.

4. A method for preparing a fluorine-free anti-sticking knitted fabric, characterized in that: The following steps are involved: S1. Providing a fluorine-free printing paste, wherein the fluorine-free printing paste comprises a fluorine-free waterproofing agent, a cross-linking agent, a binder, a thickener, a wetting agent and water; S2. Using the fluorine-free printing paste, printing a non-continuous pattern on a knitted fabric, and curing it by baking to obtain a fluorine-free anti-sticking knitted fabric with a micron-level non-continuous pattern layer.

5. The preparation method according to claim 4, characterized in that The fluorine-free printing paste comprises: 18-22 wt% of fluorine-free waterproofing agent; 4-6 wt% of cross-linking agent; 12-18 wt% of adhesive; 1.2-1.8 wt% of thickener; 0.3-0.5 wt% of wetting agent; and the balance of water. The fluorine-free waterproofing agent is selected from one or more of silicone, long-chain alkyl acrylate, polyurethane and bio-based waterproofing agents; the adhesive is selected from one or more of acrylate copolymers, butadiene copolymers, vinyl acetate copolymers and polyurethane adhesives; the cross-linking agent is selected from aziridine compounds and / or self-cross-linking acrylic acid; the thickener is selected from one or more of alginates, anionic acrylic acid copolymers and starch thickeners; the wetting agent is selected from polyoxyethylene ethers and / or glycol wetting agents.

6. The preparation method according to claim 5, characterized in that Step S1 includes: adding a wetting agent and a thickener to water, stirring and dispersing, adding a premix of a fluorine-free waterproofing agent and a cross-linking agent, controlling the pH value to 6.5-7.0, adding an adhesive, and adjusting the room temperature viscosity to 6000-7000 mPa·s to obtain a fluorine-free printing paste.

7. The preparation method according to claim 4, characterized in that In step S2, the discontinuous pattern is a dot pattern and / or a spaced polygonal pattern, the spacing between each pattern is 0.8-1.5 mm, and the total coverage of all patterns is 35-65%.

8. The preparation method according to claim 5, characterized in that The printing is performed using a rotary screen printing plate with a mesh size of 100-125 meshes, a printing scraper pressure of 2.5-3.2 Bar, a printing speed of 18-22 m / min, and pre-drying with hot air drying at 105-110°C.

9. The preparation method according to claim 5, characterized in that The printing is carried out using a flat screen printing plate with a mesh number of 80-125 meshes, a printing scraper speed of 6-8 m / min, and pre-drying with infrared drying at 80-95° C.

10. The preparation method according to any one of claims 4 to 9, characterized in that: The baking and curing temperature is 120-160° C. and the time is 1-3 minutes.

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