CN115418851A - A kind of preparation method of graphene antibacterial composite fabric - Google Patents

Abstract

The present invention relates to a kind of preparation method of graphene antibacterial composite fabric, comprises the following steps: (1) pretreatment: the yarn of fabric is dipped in the tank containing pretreatment agent solution and carries out padding retention treatment to remove fabric yarn (2) ion grafting-antibacterial finishing padding: introduce ion grafting treatment into the solution containing quaternary ammonium salt cations, and introduce antibacterial finishing agent solution after drying to carry out padding treatment; antibacterial finishing agent Solution comprises graphene and copper-zinc particle; (3) to the fabric of natural fiber, after ion grafting-antibacterial finishing, carry out pre-drying earlier, then obtain graphene antibacterial composite fabric after carrying out wet short steam process; After ion grafting-antibacterial finishing, the fiber fabric is first subjected to four-stage baking treatment, then introduced into the softener solution for padding, and the graphene antibacterial composite fabric is obtained after setting. The method of the invention has the effect of high antibacterial fastness after repeated water washing.

Description

A kind of preparation method of graphene antibacterial composite fabric

technical field

The invention relates to the technical field of textile surface modification, in particular to a method for preparing a graphene antibacterial composite fabric.

Background technique

Today's growing inherent requirements for hygiene are driving the rapid development of the antimicrobial fabrics market. In the prior art, silver ions are usually used to sterilize antibacterial fabrics. By immersing them in silver ion finishing agents, the surface of fabric fibers absorbs silver ions to obtain antibacterial fabrics. However, this processing method is usually not washable and has poor fastness, and the antibacterial properties basically disappear after frequent washing. In the prior art, the surface of the fabric is usually coated to obtain a fabric with an antibacterial coating, but the application of the coating usually makes the air permeability of the fabric worse.

In addition, silver ions, especially nano-silver, will play a role in dissociation or release and have potential hazards. Once excessive, the human body cannot excrete it, which may cause poisoning and cause concerns about environmental safety and human health. Therefore, silver ions have been explicitly banned. Antimicrobials are used in medical devices. As an antibacterial fabric in contact with the human body, there will inevitably be potential hazards.

Therefore, for the antibacterial problem of fabrics, the main solutions are: 1. Find a finishing agent that can replace silver ion antibacterial agents; 2. How to make fabrics with high antibacterial fastness after washing under the premise of maintaining fabric air permeability.

Contents of the invention

In order to solve the above technical problems, a preparation method of graphene antibacterial composite fabric is provided. The method of the invention has the effect of high antibacterial fastness after repeated washing.

In order to achieve the above object, the present invention is realized through the following technical solutions:

A kind of preparation method of graphene antibacterial composite fabric, comprises the steps:

(1) Pretreatment: immerse the yarn of the fabric in a tank containing a pretreatment agent solution for padding retention treatment to remove impurities in the fabric yarn, then wash and dry;

(2) Ion grafting-antibacterial finishing padding: the yarn of the pretreated fabric is introduced into a cation solution containing a quaternary ammonium salt for ion grafting treatment, and after drying, it is introduced into an antibacterial finishing agent solution for padding treatment;

The antibacterial finishing agent solution includes the following 100% by weight materials: 3-10% of graphene, 1-15% of copper-zinc particles, 5-40% of crosslinking agent, 1-5% of hyperdispersant, 0.5% of surfactant -3%, the balance is water;

(3) after described ion grafting-antibacterial finishing to the fabric of natural fiber, carry out pre-drying first, then carry out after wet short steam process process promptly obtain graphene antibacterial composite fabric;

After the synthetic fiber fabric is subjected to the ion grafting-antibacterial finishing, it is first subjected to four-stage baking treatment, then introduced into the softener solution for padding, and the graphene antibacterial composite fabric is obtained after setting.

Further, the fabric is a natural fiber or a synthetic fiber, and the impurities in the yarn of the natural fiber are pectin, cotton wax, cottonseed husk, hemp husk, etc., and the impurities in the yarn of the synthetic fiber are slurry, spinning Silk oil agent etc.; The pretreatment agent solution that the fabric of described natural fiber is used comprises following 100% weight percent material: Refining enzyme 2-20%, sodium hydroxide 25-55%, dimethyltetramethylene phosphoric acid 0.5-2% of sodium, 1-5% of refining penetrating agent, and the balance is water. For the fabric of the natural fiber, the pretreatment process is a padding retention treatment or an ultrasonic padding retention treatment; The pretreatment agent solution for natural fiber fabrics is water and/or alcohol, and the pretreatment process must cooperate with ultrasonic padding retention treatment; the frequency of the ultrasonic waves is 2-5 MHz.

Further, the ion grafting-antibacterial finishing and padding process also includes the use of ultrasonic assistance; the ultrasonic frequency of the ultrasonic assistance is 2-5 MHz.

Further, the pretreatment agent solution for the natural fiber includes the following 100% by weight materials: refining enzyme 2-20%, sodium hydroxide 25-55%, sodium dimethyl tetramethylene phosphate 0.5-2 %, refined penetrant 1-5%, and the balance is water.

Further, the drying temperature in step (1) and step (2) is 50-100°C; the solution containing quaternary ammonium salt cations is obtained by dissolving the quaternary ammonium salt surfactant in water and/or ethanol, The concentration of the described quaternary ammonium salt cationic solution is (5-12) g/L; The quaternary ammonium salt surfactant is dialkyl dimethyl ammonium salt, alkyl trimethyl ammonium salt, benzyl chloride One or more of pyridinium salts.

Further, the graphene is graphene oxide of 500-800 nanometers; the zinc-copper particle is a mixture of at least one of nano-copper oxide and nano-cuprous oxide mixed with nano-zinc oxide in any mass ratio;

Further, the crosslinking agent is an acrylate; the hyperdispersant is an acrylate water-soluble polymer dispersant; the surfactant is a nonionic surfactant, and the nonionic surfactant is One or more of JFC, JFC-1, JFC-2, JFC-E, JFC-S. The cross-linking agent has a cross-linking function that can make the antibacterial material more firmly attached to the fiber, and can also make the fabric have a better hand feeling; the function of the non-ionic surfactant is to penetrate the antibacterial material into the gap of the fiber go.

Further, the pre-drying temperature is 85-102°C and the time is 1-2min; the wet short steaming process is at 140°C for 0.5-1.5min.

Further, the four-stage baking treatment is a four-stage temperature treatment, which is 90±5°C for 1-2min, 160±5°C for 1-2min, 190±5°C for 1-2min, and 120±5°C. ℃ for 1-2 minutes; the softener solution is an organosilicon softener with a mass concentration of 2-10%. The four-stage baking treatment is more evenly heated and causes less damage to the fiber.

Beneficial technical effects:

In the present invention, the fabric is grafted with quaternary ammonium salt cations first, so that the ionic bond is anchored on the yarn fiber of the fabric, and then the antibacterial finishing of the formula of the present invention is carried out, so that the antibacterial material is anchored deep into the fiber gap through the ionic bond. This obtains long-acting antibacterial and water-resistant effects, and the antibacterial fabric prepared by the method of the invention is repeatedly washed with water, and the antibacterial effect decays less than 2%, and has better antibacterial and water-resistant properties. The invention adopts graphene and zinc-copper particles as the antibacterial material, so that the antibacterial rate of the finished fabric against Candida albicans can reach over 98%, and the antibacterial rate against Staphylococcus aureus can reach over 99.5%.

detailed description

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. The following description of at least one exemplary embodiment is merely illustrative in nature and in no way taken as limiting the invention, its application or uses. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

The numerical values set forth in these examples do not limit the scope of the invention unless specifically stated otherwise. Techniques and methods known to those of ordinary skill in the related art may not be discussed in detail, but under appropriate circumstances, the techniques and methods should be regarded as a part of the specification. In all examples shown and discussed herein, any specific values should be construed as exemplary only, and not as limitations. Therefore, other examples of the exemplary embodiment may have different values.

The experimental methods without specific conditions indicated in the following examples are usually measured according to national standards; if there is no corresponding national standard, then the general international standards or the standard requirements proposed by relevant enterprises are followed. All parts are by weight and all percentages are by weight unless otherwise indicated.

Refining enzymes, refining enzyme penetrating agents, silicone softeners, etc. used in the following examples are regarded as substances used in conventional technical means unless otherwise specified. Those skilled in the art know the above types of substances routinely used in the industry.

Example 1

A kind of preparation method of graphene antibacterial composite fabric, comprises the steps:

(1) Pre-treatment: immerse the yarn of cotton and hemp fiber in a tank containing a pre-treatment agent solution for padding retention treatment to remove impurities such as pectin, cotton wax, cotton seed hulls, and hemp husks in the fiber yarn, and then wash with water , drying below 100 ℃;

The pretreatment agent solution includes the following 100% by weight materials: 10% refining enzyme, 35% sodium hydroxide, 1% sodium dimethyl tetramethylene phosphate, 3% refining penetrating agent, and the balance is water.

(2) Ion grafting-antibacterial finishing and padding: the quaternary ammonium salt surfactant is dissolved in water and ethanol (water and ethanol volume ratio is 2:1) to obtain a concentration of 10g/L containing the quaternary ammonium salt cationic solution , the quaternary ammonium salt surfactant is benzyl chloride pyridinium salt; the pretreated cotton and linen fiber yarn is immersed in the above-mentioned cation solution containing quaternary ammonium salt to carry out ion grafting treatment, and the fiber fabric and the quaternary ammonium The salt cation solution is dipped and mixed according to 1g:10mL, dried below 100°C, and then introduced into the antibacterial finishing agent solution and assisted by 2-5 MHz ultrasonic waves for 12 seconds of padding treatment;

The antibacterial finishing agent solution includes the following 100% by weight materials: 5% graphene, 12% zinc-copper particles, 10% crosslinking agent sodium acrylate, acrylic acid-butyl acrylate-acrylamide terpolymer water-soluble polymer Dispersant 2%, JFC-2 non-ionic surfactant 0.8%, the balance is water;

Wherein the graphene is graphene oxide with an average particle diameter of 500-800nm; the zinc-copper particles are nano-zinc oxide and nano-copper oxide (equal mass ratio).

(3) After the ion grafting-antibacterial finishing and padding in the previous step, the cotton and linen fibers are pre-dried at 100°C for 1-2min, and then wet short-steamed at 140°C for 1min to obtain graphene antibacterial Composite cotton and linen fabric.

Example 2

The preparation method of this example is the same as that of Example 1, except that the zinc-copper particles in the antibacterial finishing agent solution are a mixture of nano-zinc oxide and nano-cuprous oxide prepared in equal proportions.

Example 3

The preparation method of this example is the same as that of Example 1, except that the zinc-copper particles in the antibacterial finishing agent solution are a mixture of nano-zinc oxide, nano-copper oxide, and nano-cuprous oxide prepared in equal proportions.

Example 4

A kind of preparation method of graphene antibacterial composite fabric, comprises the steps:

(1) Pretreatment: Immerse the yarn of polyester fiber in the tank containing the solution of pretreatment agent, and use 2-5 MHz ultrasonic wave to assist padding and retention treatment for 12 seconds to remove the size, oil, etc. in the polyester fiber yarn Impurities, then washed with water and dried below 100°C;

The pretreatment agent solution is a mixed solution of water and ethanol (volume ratio is 2:1).

(2) Ion grafting-antibacterial finishing and padding: the quaternary ammonium salt surfactant is dissolved in water and ethanol (water and ethanol volume ratio is 2:1) to obtain a concentration of 10g/L containing the quaternary ammonium salt cationic solution , the quaternary ammonium salt surfactant is benzyl chloride pyridinium salt; the pretreated polyester fiber yarn is immersed in a solution containing quaternary ammonium salt cations to carry out ion grafting treatment, and the fiber fabric and the quaternary ammonium salt cations The solution is dipped and mixed according to 1g:10mL, dried below 100°C, and then introduced into the antibacterial finishing agent solution and assisted by 2-5 MHz ultrasonic waves for padding treatment for 12 seconds;

The antibacterial finishing agent solution includes the following 100% by weight materials: 10% graphene, 3% zinc-copper particles, 35% crosslinking agent sodium acrylate, acrylic acid-butyl acrylate-acrylamide terpolymer water-soluble polymer Dispersant 3%, JFC-2 non-ionic surfactant 3%, the balance is water;

Wherein the graphene is graphene oxide with an average particle diameter of 500-800nm; the zinc-copper particles are nano-zinc oxide and nano-copper oxide (equal mass ratio).

(3) After the polyester fiber has undergone ion grafting-antibacterial finishing and padding in the previous step, it is then subjected to four-stage baking treatment: 90±5°C for 2 minutes, 160±5°C for 1 minute, 190±5°C for 1 minute, 120±5°C ℃ treatment for 2 minutes, and then introduced into a 5% silicone softener solution for padding treatment, and the graphene antibacterial composite fabric was obtained after setting at 180±5 ℃.

Comparative example 1

The preparation method of this comparative example is the same as that of Example 1, except that in step (2), the cation solution containing quaternary ammonium salt and the antibacterial finishing agent solution are first mixed, and then the fabric is subjected to ultrasonic-assisted padding treatment.

Comparative example 2

The preparation method of this comparative example is the same as that of Example 1, except that the zinc-copper particles in the antibacterial finishing agent solution only have nanometer zinc oxide.

Comparative example 3

The preparation method of this comparative example is the same as that of Example 1, except that the zinc-copper particles in the antibacterial finishing agent solution only have nano-copper oxide.

Comparative example 4

The preparation method of this comparative example is the same as that of Example 1, except that the antibacterial finishing agent solution does not contain graphene, and zinc and copper particles are added according to the weight percentage of graphene.

The antibacterial fabric obtained in the above examples and comparative examples is tested for antibacterial performance before washing, and then it is washed for 30 times to test the antibacterial performance. The washing procedure is carried out according to FZ/T 73023-2006 Appendix C, and the antibacterial performance test is with reference to GB/T 20944.3-2008 Textile antibacterial performance evaluation part 3 was tested by oscillation method, and the test results are shown in Table 1.

The antibacterial property before and after the antibacterial fabric washing that table 1 embodiment and comparative example obtain

As can be seen from Table 1, the antibacterial fabric prepared by the inventive method is washed repeatedly, and the antibacterial effect attenuation is less than 1%. The antibacterial rate of Staphylococcus aureus can reach more than 99.5%, which can fully meet the standard of AA grade antibacterial fabric. However, in the preparation method of Comparative Example 1, the grafting of quaternary ammonium salt cations was not carried out first, resulting in a very serious decline in the antibacterial properties of the fabric after repeated washing. In Comparative Examples 2 and 3, only nano-zinc oxide and nano-copper oxide were used respectively, and the resistance of the fabric after repeated washing, especially the resistance to the fungus Candida albicans, decreased by more than 2%. Comparative example 4 does not contain graphene and only has nano-copper oxide and nano-zinc oxide. The fabric has poor resistance to fungi in an unwashed state, and is still good to bacteria resistance, but the resistance to fungi after repeated washing The decline is also greater. The invention adds graphene, nano-zinc oxide and nano-copper oxide to play a synergistic antibacterial effect on bacteria and fungi, and the method of the invention has a very good washing resistance effect.

The above is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto, any person familiar with the technical field within the technical scope disclosed in the present invention, according to the technical solution of the present invention Any equivalent replacement or change of the inventive concepts thereof shall fall within the protection scope of the present invention.

Claims (8)

1. A preparation method of a graphene antibacterial composite fabric is characterized by comprising the following steps:

(1) Pretreatment: immersing the yarns of the fabric into a groove containing a pretreatment agent solution for padding retention treatment to remove impurities in the yarns of the fabric, and then washing and drying;

(2) Ion grafting-antibacterial finishing padding: introducing the yarn of the pretreated fabric into a cationic solution containing quaternary ammonium salt for ion grafting treatment, drying, and introducing into an antibacterial finishing agent solution for padding treatment;

the antibacterial finishing agent solution comprises the following materials in 100% by weight: 3-10% of graphene, 1-15% of copper-zinc particles, 5-40% of a cross-linking agent, 1-5% of a hyperdispersant, 0.5-3% of a surfactant and the balance of water;

(3) After the ion grafting-antibacterial finishing is carried out on the fabric of the natural fiber, pre-drying is carried out, and then the wet short steaming process treatment is carried out, so that the graphene antibacterial composite fabric is obtained;

after the ion grafting-antibacterial finishing is carried out on the synthetic fiber fabric, four-stage baking treatment is carried out, then the synthetic fiber fabric is introduced into a softening agent solution for padding, and the graphene antibacterial composite fabric is obtained after shaping.

2. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the fabric is a fabric of natural fibers or a fabric of synthetic fibers; the pretreatment agent solution for the fabric of the natural fiber comprises the following materials in percentage by weight of 100 percent: 2-20% of refined enzyme, 25-55% of sodium hydroxide, 0.5-2% of dimethyl tetramethylidene sodium phosphate, 1-5% of refined penetrating agent and the balance of water, wherein the pretreatment process for the natural fiber fabric is padding retention treatment or ultrasonic padding retention treatment; the pretreatment agent solution for the fabric of the natural fiber is water and/or alcohol, and the pretreatment process must be matched with ultrasonic padding retention treatment; the frequency of the ultrasonic wave is 2-5 MHz.

3. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the ion grafting-antibacterial finishing padding process further comprises the steps of adopting ultrasonic assistance; the ultrasonic wave frequency of the ultrasonic wave assistance is 2-5 MHz.

4. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the drying temperature in the steps (1) and (2) is 50-100 ℃; the quaternary ammonium salt cation-containing solution is obtained by dissolving a quaternary ammonium salt surfactant in water and/or ethanol, and the concentration of the quaternary ammonium salt cation-containing solution is (5-12) g/L; the quaternary ammonium salt surfactant is one or more of dialkyl dimethyl ammonium salt, alkyl trimethyl ammonium salt and benzyl chloride pyridinium salt.

5. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the graphene is graphene oxide of 500-800 nm; the zinc-copper particles are a mixture of at least one of nano copper oxide and nano cuprous oxide and nano zinc oxide in any mass ratio.

6. The method for preparing the graphene antibacterial composite fabric according to claim 1, wherein the cross-linking agent is acrylate; the hyper-dispersant is an acrylate water-soluble polymer dispersant; the surfactant is a nonionic surfactant.

7. The preparation method of the graphene antibacterial composite fabric according to claim 1, wherein the pre-drying temperature is 85-102 ℃, and the time is 1-2min; the wet short steaming process treatment is carried out at 140 ℃ for 0.5-1.5min.

8. The method for preparing the graphene antibacterial composite fabric according to claim 1, wherein the four-stage baking treatment is a temperature treatment in four stages, namely 90 ± 5 ℃ treatment for 1-2min, 160 ± 5 ℃ treatment for 1-2min, 190 ± 5 ℃ treatment for 1-2min, and 120 ± 5 ℃ treatment for 1-2min; the softening agent solution is an organic silicon softening agent with the mass concentration of 2-10%.