Self-cleaning antibacterial printing paste, preparation method and application thereof

Abstract

The present application relates to a kind of self-cleaning antibacterial printing paste and its preparation method and application, belong to textile printing and dyeing technical field, the preparation method of self-cleaning antibacterial printing paste, comprising the following steps: S1, under low speed stirring (300-500 rpm), slowly add thickening agent to deionized water, after stirring uniformly, form base material, S2, water-based acrylic resin or polyurethane emulsion, self-cleaning antibacterial nano composite paste, hand feel adjusting agent and color paste are sequentially added to base material, mix uniformly at medium speed stirring, time is about 20-30 minutes, S3, slowly add crosslinking agent, low speed stirring 10-15 minutes, avoid to produce too much bubble, S4, with appropriate amount of ammonia or pH regulator adjust system pH to 8-9, filter out material, the self-cleaning antibacterial printing paste of the application is obtained.The paste is made of modified nano composite photocatalytic material and water-based polymer colloidal stable composite, so that printing coating can efficiently degrade organic pollutants and kill microorganisms under visible light irradiation, while having excellent washability, hand feeling and fastness.

Description

Technical Field

[0001] This invention belongs to the field of textile printing and dyeing technology, specifically relating to a self-cleaning antibacterial printing paste, its preparation method, and its application. Background Technology

[0002] Traditional textile printing pastes are mainly used to achieve color and three-dimensional effects in patterns, offering limited functionality. With increasing awareness of health and hygiene, the demand for antibacterial properties in textiles is growing. Currently, most common antibacterial printing pastes achieve this by adding silver ions, quaternary ammonium salts, or natural antibacterial agents, but these technologies have the following shortcomings: 1. Poor antibacterial durability: Antibacterial agents are prone to migration and precipitation, and their antibacterial effect decreases significantly after repeated washing.

[0003] 2. Limited functionality: It only has antibacterial function and cannot degrade organic stains, oil stains and environmental pollutants attached to the surface of textiles.

[0004] 3. Potential risks: Some chemical antibacterial agents may cause skin allergies or lead to drug resistance in microorganisms.

[0005] 4. Environmental impact: Traditional adhesives and their additives have poor biodegradability.

[0006] Therefore, it is of great significance to develop a multifunctional printing paste that is durable, broad-spectrum, self-cleaning, and environmentally friendly. Summary of the Invention

[0007] The purpose of this invention is to provide a self-cleaning antibacterial printing paste with a simple structure and reasonable design, as well as its preparation method and application, in order to solve the above-mentioned problems.

[0008] The present invention achieves the above objectives through the following technical solutions: The purpose of this invention is to overcome the shortcomings of the prior art and provide a self-cleaning antibacterial printing paste and its preparation method. This paste achieves stable composite formation of modified nanocomposite photocatalytic materials and aqueous polymer colloids, enabling the printing coating to efficiently degrade organic pollutants and kill microorganisms under visible light irradiation, while also possessing excellent wash resistance, hand feel, and fastness.

[0009] The technical solution of the present invention is as follows: A self-cleaning antibacterial printing paste, comprising the following components by weight: • Water-based acrylic resin or polyurethane emulsion: 40-60 parts Self-cleaning antibacterial nanocomposite slurry: 5-15 parts Thickener: 1-3 parts Crosslinking agent: 1-2 parts • Hand feel modifier (silicone wax emulsion): 0.5-2 parts • Deionized water: 20-40 parts • Pigment paste: 0-10 parts The self-cleaning antibacterial nanocomposite slurry is prepared by the following method: 1. Preparation of nitrogen-doped titanium dioxide / silver nanoparticles / graphene oxide (N-TiO2 / Ag / GO) composite materials: • Graphene oxide (GO) was dispersed in ethylene glycol and ultrasonicated to obtain a uniform dispersion.

[0010] • Add tetrabutyl titanate and urea (nitrogen source), stir and hydrolyze, then transfer to a reactor for hydrothermal reaction (150-180°C, 6-12 hours) to allow TiO2 to grow in situ on the GO surface and achieve nitrogen doping, thus obtaining the N-TiO2 / GO precursor.

[0011] • Disperse the above precursor in water, add silver nitrate solution, and under ultraviolet light irradiation or sodium borohydride reduction, react Ag... + Ag nanoparticles are reduced to Ag nanoparticles and loaded onto N-TiO2 / GO composite material to obtain N-TiO2 / Ag / GO composite powder.

[0012] 2. Surface modification: The above composite powder is dispersed in an ethanol solution containing a silane coupling agent (such as KH-550) to perform surface modification, so as to improve its dispersion stability in polymer colloids.

[0013] 3. Pulping: The modified composite powder, dispersant (sodium polyacrylate) are mixed with deionized water and subjected to high-speed shearing and ball milling to produce a stable nanocomposite slurry with a solid content of 10-20%.

[0014] The preparation method of the self-cleaning antibacterial printing paste includes the following steps: 1. While stirring at low speed (300-500 rpm), slowly add the thickener to the deionized water and stir until it is evenly mixed to form a base.

[0015] 2. Add water-based acrylic resin or polyurethane emulsion, self-cleaning antibacterial nanocomposite slurry, hand feel modifier and color paste (if coloring is required) to the base material in sequence, and stir at medium speed (800-1200 rpm) until evenly mixed, for about 20-30 minutes.

[0016] 3. Slowly add the crosslinking agent and stir at low speed (300-500 rpm) for 10-15 minutes to avoid generating too many bubbles.

[0017] 4. Adjust the pH of the system to 8-9 with an appropriate amount of ammonia or pH adjuster, filter and discharge to obtain the self-cleaning antibacterial printing paste.

[0018] The beneficial effects of this invention are as follows: 1. Highly efficient broad-spectrum antibacterial and self-cleaning: Nano-silver (Ag) provides rapid contact sterilization; nitrogen-doped TiO2 (N-TiO2) extends the photoresponse range to the visible light region, generating highly oxidizing reactive oxygen species (ROS) under light irradiation, which can destroy the microbial cell structure and degrade organic stains, achieving self-cleaning; graphene oxide (GO) not only enhances the conductivity and mechanical strength of the material, but its huge specific surface area can also adsorb pollutants, producing a synergistic effect with N-TiO2 and Ag, greatly improving photocatalytic and antibacterial efficiency.

[0019] 2. Long-lasting and washable: Nanomaterials are stably fixed in the polymer cross-linked network through chemical bonding and physical coating, making them difficult to fall off. Photocatalysis can continuously regenerate antibacterial active sites, making the function lasting.

[0020] 3. Environmental friendliness and safety: Based on an aqueous system, it has low VOC content, and the final photocatalytic products are CO2 and H2O, with no secondary pollution. The slow-release effect of nano-silver reduces potential cytotoxicity.

[0021] 4. Excellent application performance: The printed patterns are clear, the hand feel is soft, and the dry / wet rubbing fastness and washing fastness are excellent. It is suitable for printing on a variety of fabrics such as cotton, polyester, and blended fabrics. Detailed Implementation

[0022] The present application will now be described in further detail. It should be noted that the following specific embodiments are only used to further illustrate the present application and should not be construed as limiting the scope of protection of the present application. Those skilled in the art can make some non-essential improvements and adjustments to the present application based on the above application content.

[0023] Example 1: 1. Preparation of self-cleaning antibacterial nanocomposite slurry: Disperse 0.1 g of GO in 50 mL of ethylene glycol and sonicate for 2 hours. Add 5 mL of tetrabutyl titanate and 2 g of urea, stir for 2 hours, then transfer to a 100 mL hydrothermal reactor and react at 180°C for 12 hours. After cooling, centrifuge, wash, and dry to obtain N-TiO2 / GO.

[0024] Disperse 0.5g of N-TiO2 / GO in 50mL of water, add 10mL of 0.1M AgNO3 solution, and reduce under UV light for 1 hour. After centrifugation and washing, redisperse in an ethanol solution containing 1wt% KH-550 and modify for 12 hours. After drying, mix with 2g of sodium polyacrylate and 47g of water, and ball mill for 4 hours to obtain composite slurry A with a solid content of approximately 10%.

[0025] 2. Preparation of printing paste: Add 1.5 parts of polyacrylic acid thickener to 20 parts of deionized water while stirring at 400 rpm, and stir well.

[0026] Add 50 parts of water-based acrylic resin, 8 parts of composite slurry A, 1 part of silicone wax emulsion and 5 parts of blue pigment, increase the speed to 1000 rpm and stir for 25 minutes.

[0027] Slowly add 1.5 parts of aziridine crosslinking agent and stir at 400 rpm for 12 minutes.

[0028] Adjust the pH to 8.5 with ammonia water, filter, and obtain a blue self-cleaning antibacterial printing paste.

[0029] Example 2: In Example 1, the waterborne acrylic resin was replaced with 55 parts of waterborne polyurethane emulsion, the amount of composite paste A was increased to 12 parts, and no color paste was added to prepare a transparent, self-cleaning, antibacterial printing paste. Other steps were the same as in Example 1.

[0030] Application example: The adhesive pastes obtained in Examples 1 and 2 were printed onto pure cotton knitted fabric using a flatbed printing method, pre-baked at 100°C for 2 minutes, and then baked at 150°C for 3 minutes to fix the color.

[0031] • Antibacterial test: The printed fabrics were tested according to GB / T20944.3-2008 (oscillation method). The antibacterial rate against Staphylococcus aureus and Escherichia coli was greater than 99.9% (>99% after 50 washes).

[0032] • Self-cleaning test: A methylene blue solution (simulating organic stains) was applied to the printed surface and irradiated under a fluorescent lamp (simulating visible light) for 6 hours. The methylene blue fading rate on the sample surfaces of Examples 1 and 2 both exceeded 95%, while the control sample without the added composite paste showed almost no change.

[0033] • Fastness test: Dry rubbing fastness is grade 4-5, wet rubbing fastness is grade 4, and soap washing fastness (color change, staining) is grade 4 or above.

[0034] The embodiments described above are merely examples of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention.

Claims

1. A self-cleaning antibacterial printing paste, characterized in that: By weight, it comprises the following components: 40-60 parts of aqueous resin emulsion, 5-15 parts of self-cleaning antibacterial nanocomposite slurry, 1-3 parts of thickener, 1-2 parts of crosslinking agent, 0.5-2 parts of hand feel modifier, 20-40 parts of deionized water, and 0-10 parts of color paste; the self-cleaning antibacterial nanocomposite slurry comprises a composite material of nitrogen-doped titanium dioxide, nano silver, and graphene oxide.

2. The self-cleaning antibacterial printing paste according to claim 1, characterized in that: The aqueous resin emulsion is at least one of an aqueous acrylic resin emulsion or an aqueous polyurethane emulsion.

3. The self-cleaning antibacterial printing paste according to claim 1, characterized in that: In the self-cleaning antibacterial nanocomposite slurry, nitrogen-doped titanium dioxide, nano-silver and graphene oxide are composited by hydrothermal method and in-situ reduction method, and its surface is modified by silane coupling agent.

4. The self-cleaning antibacterial printing paste according to claim 3, characterized in that: The silver nanoparticles are loaded in particulate form on a composite carrier of nitrogen-doped titanium dioxide and graphene oxide.

5. A method for preparing the self-cleaning antibacterial printing paste as described in any one of claims 1-4, characterized in that: Includes the following steps: S1: Add the thickener to deionized water while stirring to form a base material; S2: Add water-based resin emulsion, self-cleaning antibacterial nanocomposite slurry, hand feel modifier and color paste to the base material in sequence, and stir evenly; S3: Add crosslinking agent and stir at low speed until homogeneous; S4: Adjust the pH to 8-9, filter, and you have the product.

6. The application of a self-cleaning antibacterial printing paste as described in any one of claims 1-4 in textile printing.