Process for the preparation of an antibacterial and aldehyde-removing colored fiber

Abstract

The present application relates to the technical field of functional fiber, in particular to a preparation method of colored fiber with sterilization and aldehyde removal, a composite photocatalyst is formed by using metal phthalocyanine dye, n-butyl titanate and trichloromethyl silane, taking metal phthalocyanine dye as the inner core, taking porous-mesoporous titanium dioxide as the intermediate layer, and taking mesoporous silicon dioxide as the shell layer, the composite photocatalyst is configured into dipping liquid, then the fiber is added and dipped, and the colored fiber is obtained through high-temperature baking, the present application solves the problem of fiber damage caused by the existing photocatalyst, the silicon-oxygen material is used as the wrapping barrier layer, the isolation effect is realized, the light requirement of titanium dioxide and metal phthalocyanine dye is ensured, and the fiber protection and the antibacterial and aldehyde removal performance are considered.

Description

Technical Field

[0001] This invention relates to the field of functional fiber technology, specifically to a method for preparing bactericidal and formaldehyde-removing colored fibers. Background Technology

[0002] The human environment is home to a variety of bacteria and fungi, including common ones such as Staphylococcus aureus, Bacillus subtilis, Escherichia coli, Aspergillus flavus, and Candida albicans. In hot and humid environments, bacteria can deposit on fibers and multiply rapidly. At this point, the fibers are affected by metabolites, leading to degradation and discoloration. Therefore, the requirements for the sterilization and antibacterial properties of textile products are constantly increasing to meet the demands for hygienic functions. Meanwhile, titanium dioxide, as an excellent photocatalyst, can exert good bactericidal and antibacterial effects; however, its own activity under light can degrade conventional dyes and fibers, reducing the fiber's lifespan. Summary of the Invention

[0003] To address the problems in existing technologies, this invention provides a method for preparing bactericidal and formaldehyde-removing colored fibers, which solves the problem of fiber damage caused by existing photocatalysts. By using silicon-oxygen materials as a coating barrier layer, the method achieves isolation while ensuring the light requirements of titanium dioxide and metal phthalocyanine dyes, thus achieving a balance between fiber protection and antibacterial and formaldehyde-removing properties.

[0004] To achieve the above technical objectives, the technical solution of the present invention is as follows:

[0005] A method for preparing a bactericidal and formaldehyde-removing colored fiber includes the following steps:

[0006] Step 1: Add the metal phthalocyanine dye to ethanol and stir until homogeneous. Then add tetrabutyl titanate and ethyl cellulose and ultrasonically disperse for 30-60 min. After filtration and drying, obtain the coating composite. The concentration of the metal phthalocyanine dye in ethanol is 200-500 g / L, the stirring speed is 1000-2000 r / min, the mass ratio of tetrabutyl titanate to ethyl cellulose is 3-5:1, and the concentration of tetrabutyl titanate in ethanol is 100-120 g / L. The ultrasonic dispersion frequency is 60-90 kHz, and the temperature is 40-60℃. The drying temperature is 90-100℃. In this step, the metal phthalocyanine dye is added to ethanol to form a suspension, and then tetrabutyl titanate and ethyl cellulose are added to form a mixed suspension. Then, the tetrabutyl titanate and ethyl cellulose are homogeneously dispersed on the surface of the metal phthalocyanine dye particles by high-frequency ultrasonic vibration to achieve an excellent liquid film coating system. After filtration, a surface liquid film is formed. Finally, the ethanol is evaporated during the drying process to obtain a composite film of tetrabutyl titanate and ethyl cellulose. The metal phthalocyanine dye used here can be selected from copper phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, and other series of dyes according to color requirements.

[0007] Step 2: The coating composite is placed in a reaction vessel and kept at a constant temperature for 1-3 hours. After purging and drying, the first hydrolysis composite is obtained. The atmosphere of the reaction vessel is a mixture of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 10-15:1. The constant temperature is 40-60℃, and the purging is carried out with nitrogen at 80-90℃ at a purging speed of 5-9 mL / min. This step utilizes the water vapor in the reaction vessel atmosphere to form the in-situ hydrolysis of tetrabutyl titanate, which is converted into a titanate structure. At the same time, water vapor forms a stable penetration in the gaps formed by the conversion of titanate and combines with the inner tetrabutyl titanate to achieve the effect of internal hydrolysis. In this system, ethyl cellulose is a barrier agent, and its water-insoluble properties ensure its stability during the in-situ hydrolysis process.

[0008] Step 3: Trichloroethylsilane is added to diethyl ether and stirred until homogeneous. Then, the first hydrolysis complex is added and rapidly stirred for 2-3 minutes, followed by rapid filtration and drying to obtain a liquid film complex. The volume ratio of trichloroethylsilane to diethyl ether is 1:1-2. The stirring speed for homogeneous stirring is 400-600 r / min. The amount of the first hydrolysis complex added is 200-300% of the mass of trichloroethylsilane. The rapid stirring speed is 2000-3000 min. The drying temperature is 40-50℃. This step utilizes the solubility of trichloroethylsilane in diethyl ether to form a dilution system. The addition of the second hydrolysis complex followed by rapid stirring and rapid filtration effectively reduces the dissolution of ethyl cellulose from the first hydrolysis complex by diethyl ether. This treatment method ensures that trichloroethylsilane forms a film on the surface of the first hydrolysis complex. During the drying process, diethyl ether is rapidly converted into vapor, achieving a separation effect. At this point, the surface of the liquid film complex is a trichloromethylsilane liquid film.

[0009] Step 4: The liquid film composite is sprayed into the reaction vessel and allowed to stand for 2-4 hours, followed by UV irradiation at a constant temperature for 2-4 hours. After purging, the composite photocatalyst is obtained. The reaction vessel atmosphere is a mixture of nitrogen and water vapor, with a nitrogen to water vapor volume ratio of 15-18:1. The standing temperature is 30-40℃. The UV irradiation temperature is 200-600W, and the constant temperature treatment temperature is 250-280℃. In this step, the liquid film composite is sprayed into the reaction vessel, and water molecules in the reaction vessel react with trichloromethylsilane to form methylsilicic acid, i.e., a methylsilicic acid film is formed on the surface of the liquid film composite, followed by UV irradiation under constant temperature conditions. At this point, methylsilicic acid and titanic acid are directly converted into silica and methylsiloxane films, while ethyl cellulose, acting as a barrier, is decomposed and removed. Therefore, this photocatalyst uses metal phthalocyanine dye as the core, porous-mesoporous titanium dioxide as the intermediate layer, and mesoporous silica as the shell to form a porous structure system. The silica in the shell is rich in surface-active hydroxyl groups, which can ensure that it forms a stable connection with the fiber. At the same time, titanium dioxide forms a connection with metal phthalocyanine dye. The photoactivation characteristics of titanium dioxide and the photosensitivity of metal phthalocyanine dye form a synergistic effect, effectively improving the photocatalytic performance of titanium dioxide, enhancing its antibacterial and bactericidal performance, and also achieving excellent formaldehyde removal performance.

[0010] Step 5: The composite photocatalyst is added to diethyl ether and ultrasonically dispersed to form an impregnation solution. Then, the fiber is added and impregnated, followed by high-temperature baking to obtain colored fiber. The concentration of the composite photocatalyst in diethyl ether is 100-200 g / L. The ultrasonic dispersion frequency is 50-80 kHz, and the temperature is 5-10℃. The high-temperature baking temperature is 135-145℃, and the time is 10-30 min. The fiber is a core-sheath structure fiber, with the core layer being high-melting-point polyester fiber and the sheath layer being low-melting-point polypropylene. This step utilizes diethyl ether as the dispersion solution for the composite photocatalyst, homogenizing it in the liquid. During the impregnation process, the composite photocatalyst is adhered to the fiber surface. Combined with the softening of the low-melting-point polypropylene on the fiber surface during baking, a penetrating curing effect is achieved, resulting in excellent curing performance. Simultaneously, the stability of the fiber is ensured by the polyester fiber in the core layer, maintaining the stability of the core-sheath structure fiber.

[0011] As can be seen from the above description, the present invention has the following advantages:

[0012] 1. This invention solves the problem of fiber damage caused by existing photocatalysts. It uses silicon-oxygen materials as a barrier layer to achieve isolation while ensuring the light requirements of titanium dioxide and metal phthalocyanine dyes, thus achieving a balance between fiber protection and antibacterial and formaldehyde removal performance.

[0013] 2. This invention utilizes the porous encapsulation structure of titanium dioxide to ensure the amount of light irradiated on the surface of the metal phthalocyanine dye, forming a photocatalytic synergistic effect between titanium dioxide and the metal phthalocyanine dye. At the same time, the titanium dioxide is treated with a surface liquid film to form a porous thin layer on the metal phthalocyanine dye without obscuring the internal color, thus maintaining the color of the fiber.

[0014] 3. In this invention, the composite photocatalyst is coated onto the fiber surface based on impregnation, and the high-temperature baking softening properties of polypropylene are used to achieve physical penetration and fixation of the composite photocatalyst. At the same time, the softened polypropylene material forms a permeable clamping effect on the mesoporous silica layer on the surface of the composite photocatalyst, which greatly improves the stability of the composite photocatalyst. Attached Figure Description

[0015] Figure 1 These are photographs of the composite photocatalysts prepared according to embodiments of the present invention; wherein, a is a composite photocatalyst based on a copper phthalocyanine / titanium dioxide system; b is a composite photocatalyst based on a copper phthalocyanine / titanium dioxide system; and c is a composite photocatalyst based on a ferrous phthalocyanine / titanium dioxide system. Detailed Implementation

[0016] The present invention will be described in detail with reference to the embodiments, but the claims of the present invention are not intended to limit the scope of the invention.

[0017] Example 1

[0018] A method for preparing a bactericidal and formaldehyde-removing colored fiber includes the following steps:

[0019] Step 1: Add copper phthalocyanine dye to ethanol and stir until homogeneous. Then add tetrabutyl titanate and ethyl cellulose and ultrasonically disperse for 30 min. After filtration and drying, obtain the coating composite. The concentration of the metallic phthalocyanine dye in ethanol is 200 g / L, the stirring speed is 1000 r / min, the mass ratio of tetrabutyl titanate to ethyl cellulose is 3:1, and the concentration of tetrabutyl titanate in ethanol is 100 g / L. The ultrasonic dispersion is performed at a frequency of 60 kHz and a temperature of 40 °C. The drying temperature is 90 °C.

[0020] Step 2: Place the coating composite in a reaction vessel and let it stand at a constant temperature for 1 hour. Then, purge and dry to obtain the first hydrolysis composite. The atmosphere of the reaction vessel is a mixture of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 10:1. The temperature of the constant temperature standing is 40°C. The purging uses nitrogen at 80°C and the purging speed is 5 mL / min.

[0021] Step 3: Trichloroethylsilane is added to diethyl ether and stirred until homogeneous. Then, the first hydrolysis complex is added and rapidly stirred for 2 minutes, followed by rapid filtration and drying to obtain a liquid film complex. The volume ratio of trichloroethylsilane to diethyl ether is 1:1. The stirring speed for homogeneous stirring is 400 r / min. The amount of the first hydrolysis complex added is 200% of the mass of trichloroethylsilane. The rapid stirring speed is 2000 min. The drying temperature is 40℃.

[0022] Step 4: The liquid film composite is sprayed into the reaction vessel and left to stand for 2 hours, then treated with ultraviolet light at a constant temperature for 2 hours. After purging, the composite photocatalyst is obtained. The atmosphere of the reaction vessel is a mixture of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 15:1. The standing temperature is 30°C. The ultraviolet light irradiation temperature is 200W, and the constant temperature treatment temperature is 250°C.

[0023] Step 5: The composite photocatalyst is added to diethyl ether and ultrasonically dispersed to form an impregnation solution. Then, the fiber is added and impregnated, followed by high-temperature baking to obtain colored fiber. The concentration of the composite photocatalyst in diethyl ether is 100 g / L. The ultrasonic dispersion frequency is 50 kHz and the temperature is 5 °C. The high-temperature baking temperature is 135 °C and the time is 10 min. The fiber is a core-sheath structure fiber, with the core layer being high-melting-point polyester fiber and the sheath layer being low-melting-point polypropylene. The impregnation adopts a two-dip two-roll process, with a pressure of 0.2 MPa between the two rollers and a roller speed of 20 rpm. The impregnation equipment is a Foshan Jingke P-AO vertical pneumatic electric small rolling mill.

[0024] Example 2

[0025] A method for preparing a bactericidal and formaldehyde-removing colored fiber includes the following steps:

[0026] Step 1: Add copper phthalocyanine dye to ethanol and stir until homogeneous. Then add tetrabutyl titanate and ethyl cellulose and ultrasonically disperse for 60 min. After filtration and drying, obtain the coating composite. The concentration of the metallic phthalocyanine dye in ethanol is 500 g / L, the stirring speed is 2000 r / min, the mass ratio of tetrabutyl titanate to ethyl cellulose is 5:1, and the concentration of tetrabutyl titanate in ethanol is 120 g / L. The ultrasonic dispersion is performed at a frequency of 90 kHz and a temperature of 60 °C. The drying temperature is 100 °C.

[0027] Step 2: Place the coating composite in a reaction vessel and let it stand at a constant temperature for 3 hours. Then, purge and dry to obtain the first hydrolysis composite. The atmosphere of the reaction vessel is a mixture of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 15:1. The temperature of the constant temperature standing is 60°C. The purging uses nitrogen at 90°C and the purging speed is 9 mL / min.

[0028] Step 3: Trichloroethylsilane is added to diethyl ether and stirred until homogeneous. Then, the first hydrolysis complex is added and stirred rapidly for 3 minutes, followed by rapid filtration and drying to obtain a liquid film complex. The volume ratio of trichloroethylsilane to diethyl ether is 1:2. The stirring speed for homogeneous mixing is 600 r / min. The amount of the first hydrolysis complex added is 300% of the mass of trichloroethylsilane. The stirring speed for rapid mixing is 2000-3000 min. The drying temperature is 50°C.

[0029] Step 4: The liquid film composite is sprayed into the reaction vessel and left to stand for 4 hours, then treated with ultraviolet light at a constant temperature for 4 hours. After purging, the composite photocatalyst is obtained. The atmosphere of the reaction vessel is a mixture of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 18:1. The standing temperature is 40°C. The ultraviolet light irradiation temperature is 600W, and the constant temperature treatment temperature is 280°C.

[0030] Step 5: The composite photocatalyst is added to diethyl ether and ultrasonically dispersed to form an impregnation solution. Then, the fiber is added and impregnated, followed by high-temperature baking to obtain colored fiber. The concentration of the composite photocatalyst in diethyl ether is 200 g / L. The ultrasonic dispersion frequency is 80 kHz and the temperature is 10 ℃. The high-temperature baking temperature is 145 ℃ and the time is 30 min. The fiber is a core-sheath structure fiber, with the core layer being high-melting-point polyester fiber and the sheath layer being low-melting-point polypropylene. The impregnation adopts a two-dip two-roll process, with a pressure of 0.2 MPa between the two rollers and a roller speed of 20 rpm. The impregnation equipment is a Foshan Jingke P-AO vertical pneumatic electric small rolling mill.

[0031] Example 3

[0032] A method for preparing a bactericidal and formaldehyde-removing colored fiber includes the following steps:

[0033] Step 1: Ferrous phthalocyanine dye was added to ethanol and stirred until homogeneous. Then, tetrabutyl titanate and ethyl cellulose were added and ultrasonically dispersed for 50 min. After filtration, the mixture was dried to obtain the coating composite. The concentration of the metallic phthalocyanine dye in ethanol was 400 g / L, the stirring speed was 1500 r / min, the mass ratio of tetrabutyl titanate to ethyl cellulose was 4:1, and the concentration of tetrabutyl titanate in ethanol was 110 g / L. The ultrasonic dispersion was performed at a frequency of 80 kHz and a temperature of 50 °C. The drying temperature was 95 °C.

[0034] Step 2: Place the coating composite in a reaction vessel and let it stand at a constant temperature for 2 hours. Then, purge and dry to obtain the first hydrolysis composite. The atmosphere of the reaction vessel is a mixture of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 13:1. The temperature of the constant temperature standing is 50°C. The purging uses nitrogen at 85°C and the purging speed is 7 mL / min.

[0035] Step 3: Trichloroethylsilane is added to diethyl ether and stirred until homogeneous. Then, the first hydrolysis complex is added and rapidly stirred for 2 minutes, followed by rapid filtration and drying to obtain a liquid film complex. The volume ratio of trichloroethylsilane to diethyl ether is 1:1. The stirring speed for homogeneous stirring is 500 r / min. The amount of the first hydrolysis complex added is 250% of the mass of trichloroethylsilane. The rapid stirring speed is 2500 min. The drying temperature is 45℃.

[0036] Step 4: The liquid film composite is sprayed into the reaction vessel and left to stand for 3 hours, then treated with ultraviolet light at a constant temperature for 3 hours. After purging, the composite photocatalyst is obtained. The atmosphere of the reaction vessel is a mixture of nitrogen and water vapor, and the volume ratio of nitrogen to water vapor is 16:1. The standing temperature is 35°C. The ultraviolet light irradiation temperature is 400W, and the constant temperature treatment temperature is 270°C.

[0037] Step 5: The composite photocatalyst is added to diethyl ether and ultrasonically dispersed to form an impregnation solution. Then, the fiber is added and impregnated, followed by high-temperature baking to obtain colored fiber. The concentration of the composite photocatalyst in diethyl ether is 150 g / L. The ultrasonic dispersion frequency is 70 kHz and the temperature is 8 ℃. The high-temperature baking temperature is 140 ℃ and the time is 20 min. The fiber is a core-sheath structure fiber, with the core layer being high-melting-point polyester fiber and the sheath layer being low-melting-point polypropylene. The impregnation adopts a two-dip two-roll process, with a pressure of 0.2 MPa between the two rollers and a roller speed of 20 rpm. The impregnation equipment is a Foshan Jingke P-AO vertical pneumatic electric small rolling mill.

[0038] The colored fibers prepared in Examples 1-3 were used as test examples for the following tests:

[0039] Test 1: Antibacterial test (Standard: GB / T 30706-2014 Test method and evaluation of antibacterial properties of photocatalytic antibacterial materials and products under visible light irradiation). The antibacterial rates of Examples 1-3 are shown below:

[0040] Example 1 Example 2 Example 3 E. coli 99.99％ 99.99％ 99.99％ Staphylococcus aureus 99.89％ 99.96％ 99.92％

[0041] Test 2: Formaldehyde removal performance (Standard: GB / T 23761-2020 Test method for air purification performance of photocatalytic materials and products - degradation of acetaldehyde (or formaldehyde)). The acetaldehyde removal performance of Examples 1-3 is shown below:

[0042] Example 1 Example 2 Example 3 Acetaldehyde removal rate 98.96％ 99.98％ 99.91％ stability 93.87％ 96.57％ 95.18％

[0043] The above tests showed that the colored fibers prepared in Examples 1-3 all had good killing properties against Escherichia coli and Staphylococcus aureus, exhibiting excellent antibacterial effects. At the same time, they also showed excellent acetaldehyde degradation and stability in acetaldehyde removal, demonstrating excellent acetaldehyde removal effects.

[0044] It is understood that the above detailed description of the present invention is for illustrative purposes only and is not intended to limit the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention to achieve the same technical effects; as long as the usage requirements are met, they are all within the protection scope of the present invention.

Claims

1. A method for preparing a bactericidal and formaldehyde-removing colored fiber, characterized in that: Includes the following steps: Step 1: Add the metal phthalocyanine dye to ethanol and stir until homogeneous. Then add tetrabutyl titanate and ethyl cellulose and ultrasonically disperse for 30-60 minutes. After filtration, dry to obtain the coating composite. Step 2: Place the coating composite in a reaction vessel and let it stand at a constant temperature for 1-3 hours, then blow it dry to obtain the first hydrolysis composite. Step 3: Add trichloroethylsilane to diethyl ether and stir until homogeneous. Then add the first hydrolysis complex and stir rapidly for 2-3 minutes. Filter quickly and dry to obtain the liquid film complex. Step 4: Spray the liquid film composite into the reaction vessel and let it stand for 2-4 hours, then treat it with ultraviolet light at a constant temperature for 2-4 hours, and then purge to obtain the composite photocatalyst; the ultraviolet light temperature is 200-600W, and the constant temperature treatment temperature is 250-280℃. Step 5: The composite photocatalyst is added to diethyl ether and ultrasonically dispersed to form an impregnation solution. Then, the fiber is added and impregnated, and then baked at high temperature to obtain colored fiber. The fiber is a core-sheath structure fiber, and the core layer of the core-sheath structure is a high-melting-point polyester fiber, and the sheath layer is a low-melting-point polypropylene fiber.

2. The method for preparing bactericidal and formaldehyde-removing colored fibers according to claim 1, characterized in that: In step 1, the concentration of the metal phthalocyanine dye in ethanol is 200-500 g / L, and the stirring speed is 1000-2000 r / min.

3. The method for preparing bactericidal and formaldehyde-removing colored fibers according to claim 1, characterized in that: In step 1, the mass ratio of tetrabutyl titanate to ethyl cellulose is 3-5:1, and the concentration of tetrabutyl titanate in ethanol is 100-120 g / L. The ultrasonic dispersion is performed at a frequency of 60-90 kHz and a temperature of 40-60 °C. The drying temperature is 90-100 °C.

4. The method for preparing bactericidal and formaldehyde-removing colored fibers according to claim 1, characterized in that: The atmosphere of the reactor in step 2 is a mixture of nitrogen and water vapor, with a volume ratio of nitrogen to water vapor of 10-15:

1. The constant temperature settling temperature is 40-60℃. The purging uses nitrogen at 80-90℃ and the purging speed is 5-9 mL / min.

5. The method for preparing bactericidal and formaldehyde-removing colored fibers according to claim 1, characterized in that: In step 3, the volume ratio of trichloroethylsilane to diethyl ether is 1:1-2, the stirring speed for uniform mixing is 400-600 r / min, the amount of the first hydrolysis complex added is 200-300% of the mass of trichloroethylsilane, the stirring speed for rapid mixing is 2000-3000 min, and the drying temperature is 40-50℃.

6. The method for preparing bactericidal and formaldehyde-removing colored fibers according to claim 1, characterized in that: The atmosphere of the reactor in step 4 is a mixture of nitrogen and water vapor, with a volume ratio of nitrogen to water vapor of 15-18:1, and the settling temperature is 30-40℃.

7. The method for preparing bactericidal and formaldehyde-removing colored fibers according to claim 1, characterized in that: The concentration of the composite photocatalyst in diethyl ether in step 5 is 100-200 g / L, and the ultrasonic dispersion is performed at an ultrasonic frequency of 50-80 kHz and a temperature of 5-10 °C.

8. The method for preparing bactericidal and formaldehyde-removing colored fibers according to claim 1, characterized in that: The high-temperature baking in step 5 is at a temperature of 135-145℃ for 10-30 minutes.

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