Weather-resistant sea-island silk fabric and production method thereof

Abstract

The invention relates to the technical field of fabric production, and discloses a weather-resistant sea-island yarn fabric and a production method thereof.The weather-resistant sea-island yarn fabric comprises a sea-island yarn base cloth, the sea-island yarn base cloth is sequentially provided with a dye-nano zinc oxide composite layer, a cross-linking agent A bottom layer and a hybrid network layer, and the dye-nano zinc oxide composite layer is formed by dyeing of a dye bath containing 2.5-3.5 parts by weight of composite dispersion liquid; the cross-linking agent A bottom layer is formed by treating 15-25 parts by weight of a cross-linking agent A in a working bath; the hybrid network layer is formed by curing a hybrid finishing solution of 70-90 parts by weight of a weather-resistant finishing agent and 40-60 parts by weight of amino-functionalized silicon dioxide sol. The production method comprises the steps of dyeing, reduction cleaning, cross-linking agent A treatment, hybrid finishing liquid padding and baking curing. The ultraviolet aging resistance and color fastness to light of the sea-island silk fabric are improved through internal ultraviolet shielding of the nano zinc oxide, interface anchoring of the cross-linking agent and fixation of the weather-resistant finishing agent by a silicon dioxide hybrid network.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of fabric production, and in particular to a weather-resistant island silk fabric and a production method thereof. BACKGROUND

[0002] Island silk fabric (main component is polyester) is widely used due to its hand feeling and appearance characteristics. The polyester fiber macromolecular chain lacks active groups and has a dense structure. Under the action of light, heat and oxygen, the fiber is prone to aging, showing yellowing and mechanical property decline. If dyeing is performed, the dye molecules are also prone to photodegradation, resulting in fabric discoloration. Therefore, improving the weather resistance (including light color fastness and ultraviolet aging resistance) of the island silk fabric is a persistent technical problem in this field.

[0003] In the industry, to improve the weather resistance of the fabric, a functional finishing method is usually used. One common technical means is to mix ultraviolet absorbers (UVA) and hindered amine light stabilizers (HALS) with film-forming adhesives (such as acrylate) in the finishing stage. The finishing liquid is applied to the surface of the fabric by padding, and a protective coating is formed after drying. Another technical solution is to add inorganic shielding agents such as nano-zinc oxide or titanium dioxide to the polyester melt in the spinning stage to prepare fibers with ultraviolet resistance.

[0004] However, the existing fabric production technology has the following problems. The interface bonding force between the adhesives and the fibers is weak due to the hydrophobicity of the island silk fiber surface and the scarcity of functional groups. After finishing, the weather resistance additives are easily detached from the fiber surface after washing or rubbing, and the protective function is difficult to maintain. In addition, for the method of adding inorganic shielding agents in the spinning stage, the protective effect is mainly concentrated in the interior of the fiber, and the surface of the fabric, especially the dye molecules attached to the surface, is still exposed to the external environment, resulting in limited improvement in the light color fastness of the dye. Therefore, the present application provides a weather-resistant island silk fabric and a production method thereof to solve the problems existing in the prior art. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a weather-resistant island silk fabric and a production method thereof, which solves the problem that the existing island silk fabric is difficult to achieve excellent weather resistance while being dyed. Under the action of environmental factors such as light, heat and oxygen, the dye is prone to photodegradation, resulting in discoloration, and the fiber itself is also prone to yellowing and mechanical property decline, i.e., poor light color fastness and ultraviolet aging resistance.

[0006] To achieve the above purpose, the present application is implemented by the following technical solutions:

[0007] In a first aspect, the present application provides a weather-resistant island silk fabric, which adopts the following technical solutions:

[0008] A weather-resistant island-sea yarn fabric includes an island-sea yarn base fabric, on which a dye-nano zinc oxide composite layer, a crosslinking agent A bottom layer and a hybrid network layer are sequentially disposed.

[0009] The dye-nano zinc oxide composite layer is formed by dyeing with 2.5-3.5 parts by weight of dye-nano zinc oxide composite dispersion relative to 100 parts by weight of the island silk base fabric.

[0010] The crosslinking agent A bottom layer is formed by working bath treatment containing 15-25 parts by weight of crosslinking agent A and 975-985 parts by weight of deionized water;

[0011] The hybrid network layer is formed by treating and curing a hybrid finishing solution containing 70-90 parts by weight of weather-resistant finishing agent, 40-60 parts by weight of amine-functionalized SiO2 sol and 850-890 parts by weight of deionized water.

[0012] This technical solution improves the weather resistance of fabrics by constructing a multi-layered functional structure from the inside out, including:

[0013] Inner protective layer (dye-nano zinc oxide composite layer): This solution introduces nano zinc oxide during the dyeing process. Nano zinc oxide is a broad-spectrum inorganic ultraviolet shielding agent. By combining it with the dye during the dispersion preparation stage, it is fixed together with the dye to the interior and surface of the island-of-the-sea yarn fiber during the subsequent high-temperature dyeing process. This allows ultraviolet light to be scattered and absorbed by nano zinc oxide before it comes into contact with the dye molecules and the fiber itself, thereby reducing the damage of light energy to the dye chromophore and fiber macromolecules from the source, improving the lightfastness of the dye, and providing initial protection to the base fabric.

[0014] Intermediate interface (bottom layer of crosslinking agent A): This layer is a key transition layer connecting the fiber base fabric and the surface hybrid network. Crosslinking agent A (aziridine crosslinking agent) has a highly reactive aziridine ring. On the one hand, the active groups react with the terminal carboxyl or terminal hydroxyl groups on the surface of the island-sea yarn (polyester) fiber to achieve chemical grafting of the base fabric; on the other hand, it forms a dense layer of active sites on the fiber surface.

[0015] Surface anchoring (hybrid network layer): This layer is the core functional layer for achieving high weather resistance. During the baking and curing stage, complex chemical reactions occur in the system: the silanol groups (Si-OH) in the amino-functionalized SiO2 sol (prepared by hydrolysis of tetraethyl orthosilicate and co-hydrolysis of 3-aminopropyltriethoxysilane) undergo dehydration condensation polymerization to form an inorganic three-dimensional network framework of SiO2.

[0016] A multi-layered protection system is constructed through the physical shielding of the bottom ZnO layer, the interfacial bonding of the intermediate cross-linking agent, and the locking effect of the surface SiO2 inorganic network on the weather-resistant auxiliaries. This system enables the weather-resistant finishing agents to adhere firmly to the fabric surface, thereby improving the fabric's resistance to ultraviolet aging.

[0017] Preferably, the dye-nano zinc oxide composite dispersion is made from the following raw materials in parts by weight: 5.5 parts dye; 8-12 parts nano zinc oxide; 0.8-1.2 parts sodium lignosulfonate; and 190 parts deionized water.

[0018] By adopting the above technical solution, sodium lignosulfonate is used as a dispersant to ensure that the nano zinc oxide is maintained at the nanoscale dispersion in the composite dispersion, preventing agglomeration and ensuring the uniform fixation of ZnO during the dyeing process.

[0019] Preferably, the amino-functionalized SiO2 sol is made from the following raw materials in parts by weight: 9-12 parts of tetraethyl orthosilicate; 9-13 parts of 3-aminopropyltriethoxysilane; 45 parts of anhydrous ethanol; 7 parts of deionized water; and 0.1 parts of 1 mol / L hydrochloric acid.

[0020] By adopting the above technical solution, tetraethyl orthosilicate in this formulation provides the main body of the SiO2 network framework, while 3-aminopropyltriethoxysilane introduces the key amino group = reaction site for achieving chemical bonding with the bottom layer of crosslinking agent A.

[0021] Preferably, the dyes include CIDisperse Yellow 211, CIDisperse Blue 60, and CIDisperse Red 277.

[0022] By adopting the above technical solution, a disperse dye with a specific structure was selected that is compatible with the weather-resistant system of this solution.

[0023] Preferably, the crosslinking agent A is an aziridine crosslinking agent, and the weather-resistant finishing agent is a complex containing a benzotriazole ultraviolet absorber and a hindered amine light stabilizer.

[0024] By adopting the above technical solution, the chemical type of crosslinking agent A was clarified, and its high reactivity is the basis for achieving interfacial adhesion. Simultaneously, the components of the weather-resistant finishing agent were identified: benzotriazole UV absorbers absorb UV energy through intramolecular hydrogen bond rearrangement, and hindered amine light stabilizers quench free radicals generated during photoaging. The two are used in combination to provide synergistic protection for the material.

[0025] Secondly, this invention provides a method for producing weather-resistant island-sea fiber fabric, employing the following technical solution:

[0026] A method for producing weather-resistant island-island yarn fabric, used to prepare the weather-resistant island-island yarn fabric as described in any of the preceding claims, includes the following steps:

[0027] S1. Take 100 parts of island silk base fabric and add it to the dye bath, wherein the dye bath contains 2.5-3.5 parts of dye-nano zinc oxide composite dispersion, and dye it while keeping it warm.

[0028] S2. Perform a reduction cleaning and dry the dyed fabric;

[0029] S3. Immerse the cleaned and dried fabric in a working bath containing 15-25 parts of crosslinking agent A and 975-985 parts of deionized water and then dry it.

[0030] S4. Apply the hybrid finishing solution to the fabric after it has been immersed in the working bath by padding.

[0031] S5. After applying the hybrid finishing solution, the fabric is pre-dried and then cured at 145-155℃.

[0032] By adopting the above technical solution, this method performs dyeing, bottom layer preparation, and top layer finishing in separate steps, with a clear process logic. S1 achieves in-situ composite of dyeing and ZnO; S2 reduction cleaning ensures the removal of floating color; S3 applies crosslinking agent A as the bottom layer, providing a strong bonding interface for the finishing solution in S4; S4 applies a functional sol finishing solution; the high-temperature baking and curing step (145-155℃) in S5 is the key to forming the final hybrid network structure. This temperature can effectively initiate the condensation and network formation of amine-functionalized SiO2 sol, as well as the reaction between crosslinking agent A and the amine groups in SiO2 sol, thereby forming a strong, functional organic-inorganic hybrid weather-resistant layer on the fabric surface.

[0033] Preferably, in step S1, the preparation of the dye-nano zinc oxide composite dispersion includes: mixing 5.5 parts of dye, 8-12 parts of nano zinc oxide, 0.8-1.2 parts of sodium lignosulfonate and 190 parts of deionized water; subjecting the mixture to ultrasonic treatment at 400-500W for 30-40 minutes at room temperature, adjusting the pH of the system to 5.0-5.5, and mechanically stirring at 40-50℃ for 60-70 minutes.

[0034] By adopting the above technical solution and using specific ultrasonic power and time, the agglomerates of nano-zinc oxide can be effectively opened, allowing them to be stably dispersed with the assistance of sodium lignosulfonate. Subsequent stirring at specific pH and temperature facilitates the interaction between dye molecules and the surface of nano-ZnO particles, forming a stable composite dispersion system.

[0035] Preferably, in step S4, the hybrid finishing solution includes an amino-functionalized sol, the preparation of which includes: mixing 9-12 parts of tetraethyl orthosilicate, 9-13 parts of 3-aminopropyltriethoxysilane, and 45 parts of anhydrous ethanol; slowly adding a mixed solution of 7 parts of deionized water and 0.1 parts of 1 mol / L hydrochloric acid, reacting at 30-40°C for 2-3 hours; subsequently adding 1 mol / L ammonia to adjust the pH of the system to 8-9; and finally sealing and aging at room temperature for 24 hours.

[0036] By employing the above technical solution, a two-step acid-base method is used to prepare highly active SiO2 sol. The first step, acid catalysis (hydrochloric acid), mainly promotes the hydrolysis reaction of silanes to generate silanol groups (Si-OH); the second step, base catalysis (ammonia water), mainly promotes the condensation reaction of silanol groups to form sol particles; the aging step makes the sol system homogeneous and stable.

[0037] Preferably, the heat preservation dyeing includes raising the temperature from 50°C to 120-140°C and maintaining the temperature for 50-70 minutes; the reduction cleaning includes a gradient cooling step before the reduction cleaning, and the reduction cleaning is a treatment with sodium hydrosulfite and sodium hydroxide at 70-90°C for 10-30 minutes.

[0038] By adopting the above technical solutions, a temperature range of 120-140℃ is a necessary condition for high-temperature and high-pressure dyeing of island-of-the-sea yarn (polyester), ensuring the dyeing of the dye and ZnO composite. Gradual cooling can prevent fabric creases. The reduction cleaning process at 70-90℃ can effectively remove floating dye and unfixed ZnO particles from the fiber surface, improving color fastness and the cleanliness of the finishing process.

[0039] Preferably, in step S3, the temperature of the working bath is 30-50℃, and the processing time is 10-30 minutes.

[0040] By adopting the above technical solution, at this temperature and time, it can be ensured that the aziridine crosslinking agent A has enough time to wet the fabric and react with the functional groups on the fiber surface to form a uniform and dense intermediate transition layer.

[0041] In summary, this application includes at least one of the following beneficial technical effects:

[0042] 1. The dye-nano zinc oxide composite layer of the present invention utilizes the ultraviolet shielding properties of nano zinc oxide to provide inner protection in the fiber matrix. The surface hybrid network layer fixes benzotriazole ultraviolet absorbers and hindered amine light stabilizers to the fabric surface, providing outer protection by absorbing ultraviolet rays and quenching free radicals, which helps to delay the photodegradation of dyes and the photoaging of fibers.

[0043] 2. This invention uses crosslinking agent A as an intermediate layer, whose active groups (aziridine rings) can react with the end groups of the island-sea fiber and the amine groups in the amine-functionalized SiO2 sol. This chemical bonding forms an interfacial connection between the fiber base fabric and the SiO2 hybrid network, making the weather-resistant finishing agent less likely to fall off during washing and helping to maintain long-term protective function.

[0044] 3. This invention integrates the introduction of some weather-resistant components (nano-ZnO) with the dyeing process. By composited with nano-zinc oxide during the dye dispersion preparation stage, it is fixed to the fiber along with the dye during high-temperature dyeing, simplifying the process and facilitating the distribution of ZnO inside and outside the fiber. Combined with surface finishing, this constitutes the aforementioned protective structure. Detailed Implementation

[0045] The main raw materials and reagents used in the following examples and comparative examples have the following sources and specifications. Reagents not specifically mentioned are all commercially available analytical grade or higher grade products.

[0046] CIDisperse Yellow 211 is a pyrazolone disperse dye, CAS No.: 86836-02-4;

[0047] CIDisperse Blue 60 is an anthraquinone disperse dye, CAS No.: 12217-80-0;

[0048] CIDisperse Red 277 is a copper-complex azo disperse dye, CAS No.: 70294-19-8;

[0049] The average particle size of nano zinc oxide is 30 nm, CAS number: 1314-13-2;

[0050] Tetraethoxysilane, CAS No.: 78-10-4;

[0051] 3-Aminopropyltriethoxysilane (APTES) is a silane coupling agent, CAS No.: 919-30-2;

[0052] Crosslinking agent A is an aziridine crosslinking agent, CAS number: 64265-57-2;

[0053] The weather-resistant finishing agent (UH) is an aqueous ultraviolet absorber microemulsion containing benzotriazole ultraviolet absorbers (CAS No.: 103597-45-1) and hindered amine light stabilizers (CAS No.: 70624-18-9).

[0054] Preparation Examples 1-6.

[0055] Preparation Example 1:

[0056] This preparation example provides a method for preparing a dye-nano zinc oxide composite dispersion (DZ-1), including the following steps:

[0057] Weigh out 2 parts of CIDisperse Yellow 211, 1 part of CIDisperse Blue 60, 1.5 parts of CIDisperse Red 277 (total dye 5.5 parts), 8 parts of nano zinc oxide, 0.8 parts of sodium lignosulfonate, and 190 parts of deionized water; mix the above components and sonicate at room temperature (400W) for 30 minutes; then adjust the pH of the system to 5.0-5.5 with glacial acetic acid; finally, mechanically stir at 40℃ for 60 minutes to obtain dye-nano zinc oxide composite dispersion (DZ-1).

[0058] Preparation Example 2:

[0059] This preparation example provides a method for preparing a dye-nano zinc oxide composite dispersion (DZ-2), including the following steps:

[0060] Weigh out 2 parts of CIDisperse Yellow 211, 1 part of CIDisperse Blue 60, 1.5 parts of CIDisperse Red 277 (total dye 5.5 parts), 10 parts of nano zinc oxide, 1.0 part of sodium lignosulfonate, and 190 parts of deionized water; mix the above components and sonicate at room temperature (450W) for 35 minutes; then adjust the pH of the system to 5.0-5.5 with glacial acetic acid; finally, mechanically stir at 45℃ for 65 minutes to obtain dye-nano zinc oxide composite dispersion (DZ-2).

[0061] Preparation Example 3:

[0062] This preparation example provides a method for preparing a dye-nano zinc oxide composite dispersion (DZ-3), including the following steps:

[0063] Weigh out 2 parts of CIDisperse Yellow 211, 1 part of CIDisperse Blue 60, 1.5 parts of CIDisperse Red 277 (total dye 5.5 parts), 12 parts of nano zinc oxide, 1.2 parts of sodium lignosulfonate, and 190 parts of deionized water; mix the above components and sonicate at room temperature (500W) for 40 minutes; then adjust the pH of the system to 5.0-5.5 with glacial acetic acid; finally, mechanically stir at 50℃ for 70 minutes to obtain the dye-nano zinc oxide composite dispersion (DZ-3).

[0064] Preparation Example 4:

[0065] This preparation example provides a method for preparing amino-functionalized SiO2 sol (AS-1), including the following steps:

[0066] Weigh out 12 parts of tetraethyl orthosilicate (TEOS), 9 parts of 3-aminopropyltriethoxysilane (APTES), and 45 parts of anhydrous ethanol, and mix them thoroughly. Slowly add a mixed solution of 7 parts of deionized water and 0.1 parts of 1 mol / L hydrochloric acid, and react at 30°C for 2 hours. Then add 1 mol / L ammonia water to adjust the pH of the system to 8. Finally, seal and age at room temperature for 24 hours to obtain amino-functionalized SiO2 sol (AS-1).

[0067] Preparation Example 5:

[0068] This preparation example provides a method for preparing amino-functionalized SiO2 sol (AS-2), including the following steps:

[0069] Weigh out 10.5 parts of tetraethyl orthosilicate (TEOS), 11 parts of 3-aminopropyltriethoxysilane (APTES), and 45 parts of anhydrous ethanol, and mix them thoroughly. Slowly add a mixed solution of 7 parts of deionized water and 0.1 parts of 1 mol / L hydrochloric acid, and react at 35°C for 2.5 hours. Then add 1 mol / L ammonia water to adjust the pH of the system to 8.5. Finally, seal and age at room temperature for 24 hours to obtain amino-functionalized SiO2 sol (AS-2).

[0070] Preparation Example 6:

[0071] This preparation example provides a method for preparing amino-functionalized SiO2 sol (AS-3), including the following steps:

[0072] Weigh out 9 parts of tetraethyl orthosilicate (TEOS), 13 parts of 3-aminopropyltriethoxysilane (APTES), and 45 parts of anhydrous ethanol, and mix them thoroughly. Slowly add a mixed solution of 7 parts of deionized water and 0.1 parts of 1 mol / L hydrochloric acid, and react at 40°C for 3 hours. Then add 1 mol / L ammonia water to adjust the pH of the system to 9. Finally, seal and age at room temperature for 24 hours to obtain amino-functionalized SiO2 sol (AS-3).

[0073] Examples 1-3.

[0074] Example 1:

[0075] This embodiment provides a method for producing weather-resistant island silk fabric, including the following steps:

[0076] Take 100 parts of the base fabric and add it to a dye bath with a liquor ratio of 1:10. The dye bath contains: 3 parts of Preparation Example 2 (DZ-2), 1 part of high-temperature leveling agent, and adjust the pH of the dye bath to 4.5 with glacial acetic acid. Starting from 50°C, raise the temperature to 130°C and hold for 60 minutes.

[0077] Gradual cooling was used (130℃-120℃; 120℃-90℃ for 10 minutes; 90℃-60℃ for 10 minutes); then the liquid was drained, and the fabric was reduced and cleaned at 80℃ with 2 parts sodium hydrosulfite and 1 part sodium hydroxide for 20 minutes. After thorough washing with water, the fabric was dried to obtain the fabric.

[0078] The fabric obtained in step S3 is immersed in a working bath at 40°C. The working bath contains 20 parts of crosslinking agent A and 980 parts of deionized water. The fabric is treated for 20 minutes, then removed, rinsed with clean water, and dried.

[0079] A hybrid finishing solution was prepared, comprising 80 parts of weather-resistant finishing agent (UH), 50 parts of preparation example 5 (AS-2), and 870 parts of deionized water. The resulting fabric was treated with the hybrid finishing solution by padding (with a pick-up rate of 70%).

[0080] The impregnated fabric is placed in a setting machine and pre-dried at 110°C for 2 minutes. Then, the temperature is raised to 150°C and baked for 3 minutes to cure. After cooling, the finished product is obtained.

[0081] Example 2:

[0082] This embodiment provides a method for producing weather-resistant island silk fabric, including the following steps:

[0083] Take 100 parts of the base fabric and add it to a dye bath with a liquor ratio of 1:10. The dye bath contains: 2.5 parts of Preparation Example 1 (DZ-1), 1 part of high-temperature leveling agent, and adjust the pH of the dye bath to 4.5 with glacial acetic acid. Starting from 50°C, raise the temperature to 120°C and hold for 50 minutes.

[0084] Gradual cooling was used (130℃-120℃; 120℃-90℃ for 10 minutes; 90℃-60℃ for 10 minutes); then the liquid was drained, and the fabric was reduced and cleaned for 10 minutes at 70℃ using 2 parts sodium hydrosulfite and 1 part sodium hydroxide. After thorough washing with water, the fabric was dried to obtain the fabric.

[0085] The fabric obtained in step S3 is immersed in a working bath at 30°C, which contains 15 parts of crosslinking agent A and 985 parts of deionized water, and treated for 10 minutes. The fabric is then removed, rinsed with clean water, and dried.

[0086] A hybrid finishing solution was prepared, comprising 70 parts of weather-resistant finishing agent (UH), 40 parts of preparation example 4 (AS-1), and 890 parts of deionized water. The fabric obtained in step 3 was subjected to the hybrid finishing solution by padding (with a pick-up rate of 70%).

[0087] The impregnated fabric is placed in a setting machine and pre-dried at 110°C for 2 minutes. Then, the temperature is raised to 145°C and baked for 3 minutes to cure. After cooling, the finished product is obtained.

[0088] Example 3:

[0089] This embodiment provides a method for producing weather-resistant island silk fabric, including the following steps:

[0090] Take 100 parts of the base fabric and add it to a dye bath with a liquor ratio of 1:10. The dye bath contains: 3.5 parts of Preparation Example 3 (DZ-3), 1 part of high-temperature leveling agent, and adjust the pH of the dye bath to 4.5 with glacial acetic acid. Starting from 50°C, raise the temperature to 140°C and hold for 70 minutes.

[0091] Gradual cooling was employed (130℃-120℃; 120℃-90℃ for 10 minutes; 90℃-60℃ for 10 minutes); followed by draining the liquid, and then reducing cleaning was performed at 90℃ using 2 parts sodium hydrosulfite and 1 part sodium hydroxide for 30 minutes. After thorough washing with water, the fabric was dried to obtain the final product.

[0092] The resulting fabric was immersed in a working bath at 50°C, which contained 25 parts of crosslinking agent A and 975 parts of deionized water. The treatment lasted for 30 minutes. The fabric was then removed, rinsed with clean water, and dried.

[0093] Prepare a hybrid finishing solution containing 90 parts of weather-resistant finishing agent (UH), 60 parts of preparation example 6 (AS-3), and 850 parts of deionized water. Apply the hybrid finishing solution to the fabric obtained in step S3 by padding (setting the padding rate to 70%).

[0094] The impregnated fabric is placed in a setting machine and pre-dried at 110°C for 2 minutes. Then, the temperature is raised to 155°C and baked for 3 minutes to cure. After cooling, the finished product is obtained.

[0095] Comparative Examples 1-6.

[0096] Comparative Example 1:

[0097] Compared with Example 1, the difference is that only conventional disperse dyes (without nano ZnO) are used for dyeing and cleaning, and no primer or hybrid finishing is performed, while the rest of the steps are the same.

[0098] Comparative Example 2:

[0099] Compared to Example 1, the difference is that 5.5 parts of the dye combination (without nano-ZnO) were used instead of Preparation Example 2 (DZ-2) for staining, while the other steps were the same.

[0100] Comparative Example 3:

[0101] Compared with Example 1, the difference is that the base coating step is skipped and the dried fabric is directly subjected to hybrid finishing, while the remaining steps are the same.

[0102] Comparative Example 4:

[0103] Compared with Example 1, the difference is that only the dyeing step to the base coat step is performed, and the hybrid finishing step and baking step are not performed, while the remaining steps are the same.

[0104] Comparative Example 5:

[0105] Compared with Example 1, the difference is that in the hybrid finishing step, the prepared hybrid finishing solution contains only 80 parts of weather-resistant finishing agent (UH) and 920 parts of deionized water, and does not include Preparation Example 5 (AS-2), while the other steps are the same.

[0106] Comparative Example 6:

[0107] Compared with Example 1, the difference is that in the hybrid finishing step, the prepared hybrid finishing solution only contains 50 parts of Preparation Example 5 (AS-2) and 950 parts of deionized water, and does not contain weather-resistant finishing agent (UH), while the other steps are the same.

[0108] Test Case 1-Test Case 4.

[0109] Test Example 1:

[0110] Experimental description:

[0111] This test aims to evaluate the color stability of various fabrics under simulated sunlight, temperature, and humidity conditions. The experiment was conducted according to Method 3 (Test Conditions for Exposed Textiles to Artificial Weather) in GB / T 8427-2019 "Textiles - Tests for Color Fastness to Artificial Light: Xenon Arc".

[0112] Experimental steps:

[0113] Sample preparation: Cut 100mm × 60mm specimens from the fabrics obtained in Examples 1-3 and Comparative Examples 1-6, and prepare three parallel samples for each specimen. Place the specimens under standard atmospheric conditions (temperature (20±2)℃, relative humidity (65±4)%) for at least 4 hours to condition them.

[0114] Equipment and parameter settings: A standard-compliant water-cooled xenon arc lamp aging test chamber was used. The black plate temperature (BPT) was set to (65±3)℃, the chamber temperature to (40±2)℃, the relative humidity to (50±10)%, and the irradiance to be controlled at (60±2) W / m² within the 300nm to 400nm wavelength range. 2 .

[0115] Exposure procedure: Fix the conditioned sample onto the sample holder, ensuring the exposure surface is flat. Place the sample holder inside the test chamber and begin continuous exposure for 200 hours.

[0116] Result assessment: After exposure, the sample was removed and allowed to recover under standard atmospheric conditions for at least 4 hours.

[0117] Lightfastness rating: Using a gray scale conforming to GB / T 251-2008 for assessing color change, three ratingrs independently rated the color change of the sample before and after exposure under a standard color matching light box (D65 light source). The average of the three ratings was taken as the final result, accurate to 0.5.

[0118] Color difference measurement: Using a spectrophotometer, under the conditions of D65 light source and 10° field of view, the color values ​​of the sample before and after exposure were measured, and the average value of three parallel samples was taken as the final color difference.

[0119] The experimental data are shown in Table 1:

[0120] Table 1: Color fastness test results of each fabric sample after 200 hours of xenon arc lamp exposure

[0121] Test sample Sunlight color fastness (grade) Color difference after exposure Example 1 5 1.15 Example 2 4-5 1.48 Example 3 5 0.96 Comparative Example 1 2-3 18.72 Comparative Example 2 3 12.35 Comparative Example 3 3-4 9.81 Comparative Example 4 3 11.94 Comparative Example 5 4 5.16 Comparative Example 6 3-4 8.63

[0122] in conclusion:

[0123] Table 1 shows that Comparative Example 1 (blank) faded severely (color difference value after exposure: 18.72). The color difference value of Comparative Example 2 (without ZnO) after exposure (12.35) is still different from that of Example 1 (1.15), indicating that the nano ZnO in the DZ dispersion has a preliminary light-shielding effect.

[0124] The results of Comparative Example 4 (without hybrid network) and Comparative Example 3 (without aziridine primer) were used to analyze the coating structure. The performance of Comparative Example 4 was similar to that of Comparative Example 2, indicating that the lack of hybrid network coverage meant that the protective effect could not be achieved. Comparative Example 3, after exposure, had a color difference value of 9.81, which was inferior to Comparative Examples 5 and 6, indicating the lack of covalent bonding anchors in the aziridine primer, resulting in weak adhesion between the finishing layer and the fibers, and failure under humid, hot, and light-exposed conditions.

[0125] Comparative Example 5 (without AS sol, color difference value 5.16 after exposure) and Comparative Example 6 (without UH, color difference value 8.63 after exposure) demonstrate the synergistic effect of the hybrid finishing liquid components. UH (Comparative Example 5) provides the main photoprotection, but lacks AS inorganic network coating, limiting its durability and efficiency. The inorganic network physical barrier formed by AS alone (Comparative Example 6) has limited effect.

[0126] The lightfastness of Examples 1-3 all reached level 4-5 or higher, with a color difference value of less than 1.5 after exposure, which is superior to all comparative examples. This is because the scheme constructs a multi-layer protective system: DZ composite enhances the photostability of the dye; the aziridine base coating introduces reaction sites; the hybrid finishing layer formed by AS and UH is covalently bonded to the fiber through an amine-aziridine ring-opening reaction. The Si−O−Si network coats UH and is firmly fixed by covalent bonds, integrating UV shielding, absorption, and free radical quenching functions, thus inhibiting dye photodegradation.

[0127] Test Example 2:

[0128] Experimental description:

[0129] This test aims to evaluate the UV protection capability of various fabric samples. The experiment was conducted in accordance with GB / T 18830-2009 "Evaluation of UV Protection Performance of Textiles".

[0130] Experimental steps:

[0131] Sample preparation: From the fabrics obtained in Examples 1-3 and Comparative Examples 1-6 (all original unwashed samples), four samples (10cm × 10cm) were randomly cut, avoiding creases and areas 5cm from the edge. The samples were placed under standard atmospheric conditions (temperature (20±2)℃, relative humidity (65±4)%) for at least 4 hours to condition them.

[0132] Equipment and parameter settings: Use an ultraviolet spectrophotometer equipped with an integrating sphere (or a dedicated fabric UPF tester). Set the test wavelength range to 290 nm to 400 nm, with wavelength intervals of 5 nm.

[0133] Spectral transmittance measurement: Place the sample flat at the test aperture of the instrument, ensuring no tension. Measure the spectral transmittance of each sample in the range of 290 nm to 400 nm. To eliminate the influence of uneven fabric structure, each sample was rotated four times (0°, 90°, 180°, 270°) for measurement, and the arithmetic mean of the four measurements was taken as the spectral transmittance of the sample.

[0134] Data calculation:

[0135] UPF value calculation: According to the formula Calculate the UPF value. Wherein, Solar spectral irradiance, The spectral function of the erythema effect, The spectral transmittance of the sample is given. The wavelength interval is denoted as .

[0136] Average transmittance calculation: Calculate the average transmittance for the ultraviolet A band (UVA, 315-400nm). Average transmittance of UVB band (290-315nm) .

[0137] Results Report: Report the arithmetic mean of the UPF values ​​measured for the four samples, and assess the UPF rating according to the standard. and The average value.

[0138] The experimental data are shown in Table 2:

[0139] Table 2: UV protection performance test results of fabrics from the examples and comparative examples

[0140] Test sample UPF (calculated value) UPF grade Example 1 165 1.12 0.85 50+ Example 2 138 1.45 1.10 50+ Example 3 189 0.94 0.73 50+ Comparative Example 1 22 4.88 3.91 20 Comparative Example 2 43 2.51 1.98 40 Comparative Example 3 48 2.20 1.76 45 Comparative Example 4 36 3.15 2.64 35 Comparative Example 5 45 2.39 1.90 40 Comparative Example 6 41 2.76 2.25 40

[0141] in conclusion:

[0142] Table 2 shows that the UPF of Examples 1-3 all reached 50+, with average transmittance in the UVA band (315-400nm) and UVB band (290-315nm) below 1.5%. Comparative Example 1 (conventional staining) had a UPF of only 22. Comparative Example 4 (containing DZ and primer) showed a UPF increase to 36, indicating that nano-ZnO has both scattering and absorption effects on ultraviolet light.

[0143] The UPF values ​​of Comparative Example 5 (without AS sol) and Comparative Example 6 (without UH) were 45 and 41, respectively, both higher than Comparative Example 4, but lower than Example 1 (UPF 165). This indicates that UH (ultraviolet absorber) and AS (Si−O−Si network) contribute to the absorption of UV light when applied individually, but lack synergy: Comparative Example 6 (AS only) lacks the efficient chemical absorption of UH; Comparative Example 5 (UH only) lacks the coating and fixation of the AS network, resulting in limited UH distribution efficiency and concentration.

[0144] Comparative Example 3 (aziridine-free primer) had a UPF of 48, which was lower than that of Example 1, indicating that the lack of covalent bonding sites and insufficient density of the physically adsorbed finishing layer structure led to a decrease in UV attenuation efficiency.

[0145] The high UPF values ​​(>130) in Examples 1-3 are due to the dual attenuation achieved by nano-ZnO, the AS inorganic network, and the UH ultraviolet absorber through "physical scattering + chemical absorption". The Si−O−Si network coats ZnO and UH and is covalently bonded to the fiber through an amine-aziridine reaction, forming a high-density protective layer that reduces the ultraviolet transmittance.

[0146] Test Example 3:

[0147] Experimental description:

[0148] This test aims to evaluate the ability of various fabrics to retain their mechanical strength after exposure to artificial climate (xenon arc lamp), in order to characterize the light aging resistance of the fabric's polymer materials. The experiment was conducted according to GB / T 3923.1-2013 "Textiles - Tensile Properties of Fabrics - Part 1: Determination of Breaking Strength and Elongation at Break - Strip Method".

[0149] Experimental steps:

[0150] Sample preparation: Take the original unexposed fabrics of Examples 1-3 and Comparative Examples 1-6, as well as the fabrics after being exposed to sunlight for 200 hours in "Test Example 1".

[0151] Sample cutting: Cut 50mm×300mm samples along the warp of the fabric, and cut 5 samples of each type (raw / exposed).

[0152] Conditioning: Place all samples under standard atmospheric conditions (temperature (20±2)℃, relative humidity (65±4)%) for at least 24 hours.

[0153] Equipment and parameter settings: Use a constant rate of elongation (CRE) universal testing machine. Set the gauge length to 200 mm and the tensile speed to a constant 100 mm / min.

[0154] Strength test: After conditioning, the samples (original sample and exposed sample) are clamped sequentially between the upper and lower clamps of the testing machine to ensure uniform force on the sample. Start the testing machine to perform tensile testing until the sample breaks, and record its breaking strength (N).

[0155] Data calculation: Calculate the average breaking strength of 5 original specimens and 5 specimens after exposure for each sample.

[0156] The experimental data are shown in Table 3:

[0157] Table 3: Strength retention rate of each fabric sample after 200 hours of xenon arc lamp exposure

[0158] Test sample Strength retention rate (%) Example 1 92.6 Example 2 89.6 Example 3 93.9 Comparative Example 1 38.8 Comparative Example 2 52.8 Comparative Example 3 63.9 Comparative Example 4 55.7 Comparative Example 5 74.8 Comparative Example 6 66.1

[0159] in conclusion:

[0160] Table 3 shows that the decrease in fabric strength is attributed to the photodegradation of polymer materials. The strength retention rate of Comparative Example 1 (blank) was only 38.8%, indicating that the PET / PA6 substrate is prone to photo-oxidative aging.

[0161] Comparative Example 5 (without AS sol) had a retention rate of 74.8%, indicating that UH (containing HALS) provided photoprotection. Comparative Example 6 (without UH) had a retention rate of 66.1%, indicating that the AS inorganic network provided a physical barrier, but its efficiency was lower than that of UH. Example 1 (92.6%) was higher than Comparative Examples 5 and 6, indicating a synergistic effect between AS and UH: the Si−O−Si network encapsulates and fixes UH, preventing its migration and loss, and improving the dispersibility and stability of the light stabilizer.

[0162] Comparative Example 3 (without aziridine primer) had a retention rate of 63.9%, lower than Comparative Examples 5 and 6. This indicates that the lack of covalent bonding sites caused the physically adsorbed finishing layer to detach and fail during humid heat aging, resulting in substrate exposure. Comparative Example 4 (DZ and aziridine only) also confirmed the lack of host protection from the hybrid network with a retention rate of 55.7%.

[0163] The strong retention rate of >89% in Examples 1-3 indicates that this protective system blocks ultraviolet light through "absorption + scattering" and inhibits polymer chain breakage by utilizing HALS to quench free radicals. The covalent bonding between aziridine and AS sol ensures the adhesion stability of the protective system under aging conditions.

Claims

1. A weather-resistant island-sea silk fabric, characterized in that, The fabric includes a sea-island filament base, on which a dye-nano zinc oxide composite layer, a crosslinking agent A bottom layer, and a hybrid network layer are sequentially disposed. The sea-island filament fabric is composed of the following raw materials in parts by weight: The dye-nano zinc oxide composite layer is formed by dyeing with 2.5-3.5 parts by weight of dye-nano zinc oxide composite dispersion; The crosslinking agent A bottom layer is formed by working bath treatment of 15-25 parts by weight of crosslinking agent A and 975-985 parts by weight of deionized water; The hybrid network layer is formed by treating and curing a hybrid finishing solution consisting of 70-90 parts by weight of weather-resistant finishing agent, 40-60 parts by weight of amine-functionalized SiO2 sol, and 850-890 parts by weight of deionized water.

2. The weather-resistant island-sea yarn fabric according to claim 1, characterized in that, The dye-nano zinc oxide composite dispersion is made from the following raw materials in parts by weight: 5.5 parts dye; 8-12 parts of nano zinc oxide; Sodium lignosulfonate 0.8-1.2 parts; 190 portions of deionized water.

3. The weather-resistant island-sea yarn fabric according to claim 1, characterized in that, The amino-functionalized SiO2 sol is made from the following raw materials in parts by weight: 9-12 parts of tetraethyl orthosilicate; 9-13 parts of 3-aminopropyltriethoxysilane; 45 parts of anhydrous ethanol; 7 parts deionized water; 0.1 part of 1 mol / L hydrochloric acid.

4. The weather-resistant island-sea yarn fabric according to claim 1, characterized in that, The dyes include CIDisperseYellow 211, CIDisperseBlue 60, and CIDisperseRed 277.

5. The weather-resistant island-sea yarn fabric according to claim 1, characterized in that, The crosslinking agent A is a aziridine crosslinking agent, and the weather-resistant finishing agent is a complex containing a benzotriazole ultraviolet absorber and a hindered amine light stabilizer.

6. A method for producing weather-resistant island-island yarn fabric, used to prepare the weather-resistant island-island yarn fabric according to any one of claims 1-5, characterized in that, Includes the following steps: S1. Take 100 parts of island silk base fabric and add it to the dye bath, wherein the dye bath contains 2.5-3.5 parts of dye-nano zinc oxide composite dispersion, and dye at 130℃. S2. Perform a reduction cleaning and dry the dyed fabric; S3. Immerse the cleaned and dried fabric in a working bath containing 15-25 parts of crosslinking agent A and 975-985 parts of deionized water and then dry it. S4. Apply the hybrid finishing solution to the fabric after it has been immersed in the working bath by padding. S5. After applying the hybrid finishing solution, the fabric is pre-dried and then cured at 145-155℃.

7. The method for producing weather-resistant island-sea yarn fabric according to claim 6, characterized in that, In step S1, the preparation of the dye-nano zinc oxide composite dispersion includes: Mix 5.5 parts of dye, 8-12 parts of nano zinc oxide, 0.8-1.2 parts of sodium lignosulfonate and 190 parts of deionized water; Perform ultrasonic treatment at 400-500W for 30-40 minutes at room temperature, adjust the pH of the system to 5.0-5.5, and mechanically stir at 40-50℃ for 60-70 minutes.

8. The method for producing weather-resistant island-sea yarn fabric according to claim 6, characterized in that, In step S4, the hybrid finishing solution includes an amino-functionalized sol, and the preparation of the amino-functionalized sol includes: Mix 9-12 parts of tetraethyl orthosilicate, 9-13 parts of 3-aminopropyltriethoxysilane, and 45 parts of anhydrous ethanol; Slowly add a mixed solution of 7 parts deionized water and 0.1 parts 1 mol / L hydrochloric acid, and react at 30-40℃ for 2-3 hours; Then, 1 mol / L ammonia was added dropwise to adjust the pH of the system to 8-9; finally, the system was sealed and aged at room temperature for 24 hours.

9. The method for producing weather-resistant island-sea yarn fabric according to claim 6, characterized in that, The heat preservation staining process involves raising the temperature from 50°C to 120-140°C and maintaining the temperature for 50-70 minutes; the reduction cleaning process includes a gradient cooling step before the reduction cleaning process, and the reduction cleaning process involves treating with sodium hydrosulfite and sodium hydroxide at 70-90°C for 10-30 minutes.

10. The method for producing weather-resistant island-sea yarn fabric according to claim 6, characterized in that, In step S3, the temperature of the working bath is 30-50℃, and the processing time is 10-30 minutes.