CN104562658A - Amino acid nano-silver modified finishing agent as well as preparation method of finishing agent and modified fishing shell fabric - Google Patents

Abstract

The application of the present invention provides an amino acid nano-silver modified finishing agent, a preparation method thereof and a modified finishing fabric. The amino acid nano-silver modified finishing agent is prepared by mixing a silver solution and an amino acid homogeneous solution, and stirring at a temperature of 95-100° C. for 30-45 minutes at the same time. The homogeneous amino acid solution is prepared by mixing an aqueous amino acid solution, a cross-linking agent and a surfactant. After the fibers or their fabrics are dipped and rolled twice, baked, washed, and dried, the modified finishing fabrics have been significantly improved and improved in terms of wrinkle resistance, shrinkage resistance, and dyeing and dyeing rate. It also has simplified procedures, environmentally friendly processes, and Close to nature, pollution-free, and short-term technical advantages.

Description

Amino acid nano silver modified finishing agent and its preparation method and modified finishing fabric

technical field

The patent application of the present invention relates to a modified finishing agent for fibers and their fabrics and a preparation method of the modified finishing agent, and functional fibers or fabrics obtained by finishing and modifying fibers or their fabrics.

Background technique

Technical research shows that because nano-silver has a high specific surface area and surface activity, its physical and chemical properties are stable, and it has super bactericidal and bacteriostatic activities. Based on this, silver ion modification is carried out to fiber or its fabric, and silver ion is attached and combined on the cotton fiber body, makes cotton fiber have antibacterial property, and this type of fabric modification, finishing technology have been seen in the related open technology, but these Modification technology only obtains a single antibacterial function, and is also accompanied by some other technical problems. For example, in the technical scheme disclosed in Chinese patent CN201320262131, the scheme first adopts methacrylamide grafting treatment to cotton fibers, and the polymethacrylamide molecules are used as grafts, and the electron-rich group amide bonds in its structure are then combined with silver ions The coordination effect can improve the adsorption of cotton fiber to silver ions, and obtain the modified cotton fiber with antibacterial properties. This solution also has the technical deficiency of a single modification function, and it also needs to pretreat the cotton fiber. The whole modification process is relatively cumbersome. The final silver content retention is only 75.23% of the original.

Nano-silver is prepared by reduction with a reducing agent. The reducing agents commonly used in the prior art include sodium borohydride, hydrazine hydrate, glucose, ascorbic acid, sodium hypophosphite, sodium citrate, etc., sodium borohydride, hydrazine hydrate, etc. There is a certain degree of toxicity and carcinogenicity, which is potentially harmful to the human body, other organisms and the environment. The nano-silver prepared by reduction with glucose, ascorbic acid, etc. only obtains antibacterial function in the functional finishing of the fabric, and the reducing agent does not play a functional role in the finished fabric.

The development of technology must cater to consumer demand and lead consumer orientation. With the deepening of people's understanding of the harmonious relationship between man and nature and the role of nature on human beings, natural material components are combined with fibers to produce, strengthen, extend and supplement beneficial functions, remove, transform and weaken unfavorable factors, and make them appear New functions close to the human body or other organisms are the development trend of textile processing technology.

Among them, a natural soluble bio-based material - amino acid, with its biocompatibility and affinity, contains natural moisturizing factors, has the effect of preventing skin aging and inhibiting melanin production, and is safe and non-toxic. In recent years, it has attracted more and more attention. If the fiber fabric is modified with amino acid, it can effectively protect the moisture in the fiber cuticle, moisturize the skin, and keep the skin tender, shiny and elastic for a long time. It can be used as a skin care finishing clothing fabric and applied to close-fitting clothing. Such as underwear, shirts, bedding, etc., showing good application prospects in the application of ecological and environmental protection finishing technology.

The finishing technology of amino acid on cellulose fiber fabric has appeared in the prior art. In the article "Preparation and Characterization of Cotton Fabric Amino Acid Adsorbable Materials", Li Shaoquan et al. proposed a modified finishing technology for the carboxylated cotton fabric to perform sericin amino acid adsorption treatment. Although this technology has completed the modification of sericin amino acid to cotton fiber, the moisture absorption rate of the modified and finished fabric has been greatly improved, but at the same time, it is found that the modified fabric has a technical problem of poor washing fastness, which is due to the amino acid. The amino group and the carboxyl group on the grafted cotton fiber are adsorbed by ionic bonds, which is caused by weak physical binding force. In addition, the breaking strength, mechanical properties and whiteness of the modified cotton fabric are significantly reduced, and the hand feeling is hard and the comfort is poor. Another main technical defect of the technical solution is that before the modification process, it is necessary to carry out carboxylation modification pretreatment on the cotton fiber, the process is complicated, the process is long, and the efficiency is low.

Chinese patent CN 200710049287 discloses a technical scheme for amino acid modification of synthetic fibers. In the scheme, amino acids are grafted, copolymerized, and blended into the molecular chain of synthetic fiber raw materials into the spinning stock solution, and the spun fiber silk material After setting treatment, a special-shaped fiber containing amino acid is prepared, and the amino acid is converted from protein. Amino acid and synthetic fiber are copolymerized and blended in the finished fiber, most of the amino acid is fused and distributed inside the fiber, and the contact with the skin is very limited, making it difficult to fully exert the health care function of amino acid.

To sum up, the existing technology generally has various technical problems such as single modification function, limited function, low natural attribution performance of the whole process method, cumbersome process, and unsatisfactory technical performance of the fabric itself.

Contents of the invention

The purpose of the invention of the patent application of the present invention is to provide a fiber body modified nano-silver preparation method that is closer to the natural properties and environmental protection requirements, and at the same time compatible with the natural affinity properties of amino acids, to achieve a variety of modification functions, and the modification process An amino acid nano-silver modified finishing agent that is environmentally friendly, close to nature, simplified, and effectively improves multiple technical indicators of the product, a preparation method thereof, and a modified finishing fabric.

The technical scheme of amino acid nano-silver modified finishing agent provided by the patent application of the present invention, its main technical content is: an amino acid nano-silver modified finishing agent, the modified finishing agent is composed of silver solution and amino acid homogeneous solution in a volume ratio of 1:1 Specific mixing, obtained after simultaneous stirring at 95-100°C for 30-45 minutes, the silver solution is an aqueous silver nitrate solution with a mass concentration range of 0.01-0.05g/L, and the amino acid homogeneous solution is an aqueous amino acid solution 1. A uniformly dispersed mixed solution of cross-linking agent and surfactant, wherein the mass concentration of the amino acid aqueous solution is 20-60 g/L, and the cross-linking agent is selected from one of fatty alcohol glycidyl ether or polycarboxylic acid, and the mass concentration is 20-60 g/L. 60 g/L, the surfactant is fatty alcohol polyoxyethylene ether, and its mass concentration is 2~6 g/L.

The patent application of the present invention also provides a technical scheme for the preparation method of the amino acid nano-silver modified finishing agent. The method is: the amino acid homogeneous solution and the silver solution are mixed at a volume ratio of 1:1, and stirred simultaneously at a temperature of 95-100°C 30～45 minutes, make, wherein, described silver solution is the silver nitrate aqueous solution of 0.01～0.05g/L mass concentration range, and described amino acid homogeneous solution is the dispersion of amino acid aqueous solution, cross-linking agent and tensio-active agent Uniformly mixed solution, wherein the mass concentration of the amino acid aqueous solution is 20-60 g/L, the cross-linking agent is fatty alcohol glycidyl ether or one of polycarboxylic acids, the mass concentration is 20-60 g/L, and the surfactant is fat Alcohol polyoxyethylene ether, its mass concentration is 2~6 g/L.

In the above technical solution, the fatty alcohol glycidyl ether is any one of hexylene glycol diglycidyl ether, butanediol diglycidyl ether, propylene glycol diglycidyl ether, and ethylene glycol diglycidyl ether.

In the above technical solution, the polycarboxylic acid is any one of butane tetracarboxylic acid, citric acid and polymaleic acid.

In the above technical scheme, the surfactant is any one of Span-80, Tween80, JFC, and Pingping plus O.

In the above technical solution, the amino acid aqueous solution is selected from any one of lysine aqueous solution, glutamic acid aqueous solution or methionine aqueous solution with good cost performance.

The patent application of the present invention also provides a modified finishing fabric obtained by applying the amino acid nano-silver modified finishing agent. The fiber body or fiber body fabric referred to below is cotton fiber, viscose fiber, tencel fiber, modal fiber, bamboo fiber, hemp fiber or its fiber fabric. The modified finishing method provided by the application of the present invention is: the fiber body or fiber body fabric is immersed in the amino acid nano-silver modified finishing agent, and its bath ratio is 1:30. 70~90%, then pre-baked at 40~80°C for 5 minutes, then baked at 80~160°C for 3 minutes, washed with water until neutral, and dried.

The amino acid nano-silver modified finishing agent disclosed in the patent application of the present invention uses amino acid as a reducing agent to reduce nano-silver and at the same time introduces it into the modified finishing agent to obtain an amino acid-modified finishing solution containing nano-silver. The particle size of nano-silver is generally It is less than 30nm, and it is applied to the modification of fibers or their fabrics, so that the surface of fibers or their fabrics is uniformly fixed with nano-silver and covalently cross-linked amino acids. Figure 2 shows the modified finishing with lysine as a reducing agent Modified finishing fabrics, the covalently cross-linked microstructure between the cellulose fibers and the cross-linking agent and lysine makes the modified fibers or their fabrics have antibacterial, moisturizing, moisture-wicking, and skin-friendly properties at the same time The multiple modification functions of health care have changed the technical problem of the single modification function of the existing modification technology, and have the technical advantages of strong adsorption and fixation with the fiber body, and its washing fastness is greatly improved, which overcomes the existing technical problems. The technical problems of unsatisfactory antibacterial performance and poor wash fastness, after 50 times of water washing, the antibacterial rate of Escherichia coli and Staphylococcus aureus can still reach more than 95%; Overcome the technical problems of cotton fiber, viscose fiber, tencel fiber, modal fiber, bamboo fiber, hemp fiber or their fiber fabrics, such as easy to wrinkle, easy to shrink, unsatisfactory dye uptake rate, etc., the modified Fiber or its fabric, wrinkle resistance, shrinkage, dyeing and dyeing rate and other technical performance indicators have been significantly improved and improved, the wrinkle recovery angle increased by more than 50°, and the dye uptake rate of the dye was increased by more than 5%. The antibacterial rate of the modified fabric reaches more than 99%, which makes the health care, comfort and appearance of the modified fabric more in line with the needs of the human body or other organisms. The preparation method and modification method of the modified finishing agent disclosed in the technical scheme have the technical advantages of simplified process, environmentally friendly process, close to nature and no pollution, short time consumption, low process cost and high added value of the product.

Description of drawings

Fig. 1 is a dyeing process curve diagram.

Figure 2 is a schematic diagram of the microscopic state of crosslinking agent covalently crosslinked with amino acid and cellulose fiber, wherein the long wave curve shows the cellulose fiber, and the crosslinking agent BTCA and lysine are formed between the two cellulose fiber macromolecules The acid LYS is covalently cross-linked, and the black spots between the two cellulose fiber macromolecules are evenly attached nano-silver.

Detailed ways

The technical content of the application of the present invention will be described in detail below through the following examples. Wherein, the cotton fiber or its fabric in each embodiment can also be replaced by viscose fiber, tencel fiber, modal fiber, bamboo fiber, hemp fiber or its fiber fabric, and the effect is the same; Span-80, JFC, and Pingping plus O replace the Tween80 in the embodiment, and the effect is also the same.

Example 1

Step 1. Preparation of amino acid nano-silver modified finishing agent:

Silver solution is the silver nitrate aqueous solution that mass concentration is 0.01g/L;

Amino acid homogeneous solution is a homogeneously dispersed mixed solution of the following components, including amino acid aqueous solution with a mass concentration of 20g/L, including a glycol glycidyl ether crosslinking agent with a mass concentration of 20g/L, including a mass concentration of 2g/L Tween-80 surfactant; for cost considerations, amino acid aqueous solution can choose lysine, glutamic acid, methionine and other aqueous solutions that are more cost-effective;

The silver solution and the amino acid homogeneous solution are mixed at a volume ratio of 1:1, and the amino acid nano-silver modified finishing agent is prepared at a temperature of 95° C. with a stirring speed of not lower than 200 rpm for 30 minutes.

Step 2, the modified finishing method of cotton fiber or its fabric:

Immerse the cotton fiber or its fabric in the amino acid nano-silver modified finishing agent, the bath ratio is 1:30, after two dipping and two padding, each dipping is 15 minutes at room temperature, and the rolling pressure is 0.9kg/cm ² , with liquid The rate is 70%, and then placed in an oven, pre-baked at 40°C for 5 minutes, then baked at 80°C for 3 minutes, washed to neutral, and then dried at 40°C to obtain a modified finished fabric .

Example 2

Step 1. Preparation of Amino Acid Nano Silver Modified Finishing Agent

Silver solution is the silver nitrate aqueous solution that mass concentration is 0.03g/L;

Amino acid homogeneous solution is a homogeneously dispersed mixed solution of the following components: amino acid aqueous solution with a mass concentration of 40g/L, butanetetracarboxylic acid crosslinking agent with a mass concentration of 40g/L, and Tween with a mass concentration of 4g/L -80 Surfactant. Among them, due to cost considerations, the amino acid aqueous solution can choose aqueous solutions such as lysine, glutamic acid, and methionine, which are more cost-effective;

The silver solution and the amino acid homogeneous solution are mixed according to the volume ratio of 1:1, heated to 100° C., stirred vigorously for 30 minutes, and the stirring speed is not lower than 200 rpm, and the amino acid nano-silver modified finishing solution is obtained.

Step 2, the modified finishing method of cotton fiber or its fabric

Immerse the cotton fiber or its fabric in the amino acid nano-silver modified finishing solution, the bath ratio is 1:30, two dipping and two rolling at room temperature, each dipping is 15 minutes, the rolling pressure is 0.9kg/cm ² , the liquid carrying rate 70%, pre-baked in an oven at 80°C for 5 minutes, then baked at 160°C for 3 minutes, washed with water until neutral, and then dried at 80°C to obtain a modified finished product.

Example 3

Step 1. Preparation of Amino Acid Nano Silver Modified Finishing Agent

Silver solution is the silver nitrate aqueous solution that mass concentration is 0.05g/L;

Amino acid homogeneous solution is a uniformly dispersed mixed solution of the following raw materials: amino acid aqueous solution with a mass concentration of 60g/L, butanetetracarboxylic acid crosslinking agent with a mass concentration of 60g/L, and Tween- 80 surfactant; for cost considerations, the amino acid aqueous solution can be selected from aqueous solutions such as lysine, glutamic acid, and methionine, which are more cost-effective;

The silver solution and the amino acid homogeneous solution are mixed at a volume ratio of 1:1, and the amino acid nano-silver modified finishing agent is prepared at a temperature of 95° C. with a stirring speed of not lower than 200 rpm for 30 minutes.

Step 2, the modified finishing method of cotton fiber or its fabric

Immerse the cotton fiber or its fabric in the amino acid nano-silver modified finishing agent, the bath ratio is 1:30, at room temperature, go through two dipping and two rolling, each soaking for 15 minutes, the rolling pressure is 0.9kg/cm ² , the liquid carrying rate 70%, pre-baked in an oven at 80°C for 5 minutes, then baked at 160°C for 3 minutes, washed with water until neutral, and dried at 80°C.

The following table is the detection data table of the modified finishing fabric sample of the above-mentioned embodiment through dyeing, anti-wrinkle and antibacterial experiments, .

Among them, the dyeing performance test is:

Wherein the dyeing prescription of reactive dyes is:

Argosol Red BF-3B 2% (o.w.f.)

Soda ash Na ₂ CO ₃ 20g/L

Yuanming powder Na ₂ SO ₄ 30g/L

Bath ratio 30:1

Dyeing with the dyeing process curve shown in Figure 1, the post-washing treatment is: add 3g/l soap flakes, cook at a temperature of 95°C for 5 minutes, wash with water and dry to obtain a test sample.

Among them, the anti-wrinkle performance test:

Use YG(B)541E automatic digital fabric crease elasticity tester. Test method: the anti-wrinkle performance of the fabric is expressed by the wrinkle recovery angle. This experiment adopts the determination method of wrinkle recovery angle according to the vertical method in GB/T 3819-1997, "Textiles - Determination of Wrinkle Recovery of Fabrics - Recovery Angle Method".

Among them, the antibacterial performance test: the national standard GB/T20944.3-2008 "Evaluation of the Antibacterial Performance of Textiles Part 3: Oscillating Method" is used for testing, and the test bacteria are Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria coli. The formula for calculating the antibacterial rate of the sample is as follows:

In the formula: Y is the antibacterial rate (%); Wb is the concentration of viable bacteria in the flask after the blank sample was shaken and contacted for 18 hours (CFU/mL); Wc is the viable bacteria in the flask after the fabric sample to be tested was shaken and contacted for 18 hours Concentration (CFU/mL).

Claims (8)

1. amino acid nano-silver modification agent, it is characterized in that the agent of this modification is mixed by 1:1 volume ratio by silver-colored solution and the equal miscible fluid of amino acid, obtained after stirring 30 ~ 45 minutes at 95 ~ 100 DEG C of temperature simultaneously, described silver-colored solution is the silver nitrate aqueous solution of 0.01 ~ 0.05g/L mass concentration scope, the equal miscible fluid of described amino acid is amino acid solution, the mixed solution that is uniformly dispersed of crosslinking agent and surfactant, the mass concentration of amino acid solution is wherein 20 ~ 60 g/L, crosslinking agent selects one of fatty alcohol glycidol ether or polybasic carboxylic acid, mass concentration is 20 ~ 60 g/L, surfactant is fatty alcohol-polyoxyethylene ether, its mass concentration is 2 ~ 6 g/L.

2. amino acid nano-silver modification according to claim 1 agent, is characterized in that described fatty alcohol glycidol ether is one of any in hexylene glycol glycidol ether, butanediol diglycidyl ether, propylene glycol diglycidylether, ethylene glycol diglycidylether.

3. amino acid nano-silver modification according to claim 1 agent, is characterized in that described polybasic carboxylic acid is one of any in BTCA, citric acid, poly.

4. amino acid nano-silver modification according to claim 1 agent, is characterized in that described surfactant is one of any in Span-80, Tween80, JFC, paregal O.

5. amino acid nano-silver modification according to claim 1 agent, it is characterized in that described amino acid solution be in lysine solution, glutamic acid aqueous solution or the methionine aqueous solution any one.

6. the preparation method of one of any described amino acid nano-silver modification agent in a claim 1 to 5, it is characterized in that the method is: the equal miscible fluid of amino acid mixes by 1:1 volume ratio with silver-colored solution, stir 30 ~ 45 minutes at 95 ~ 100 DEG C of temperature simultaneously, obtained, wherein, described silver-colored solution is the silver nitrate aqueous solution of 0.01 ~ 0.05g/L mass concentration scope, the equal miscible fluid of described amino acid is amino acid solution, the mixed solution that is uniformly dispersed of crosslinking agent and surfactant, the mass concentration of amino acid solution is wherein 20 ~ 60 g/L, crosslinking agent selects one of fatty alcohol glycidol ether or polybasic carboxylic acid, mass concentration is 20 ~ 60 g/L, surfactant is fatty alcohol-polyoxyethylene ether, its mass concentration is 2 ~ 6 g/L.

7. an application rights requires the modification fabric that in 1 to 5, one of any described amino acid nano-silver modification agent obtains, it is characterized in that this modification fabric obtains by the following method: corpus fibrosum or corpus fibrosum fabric immerse in the agent of amino acid nano-silver modification, its bath raio is 1: 30, roll through two leachings two, each dipping 15 minutes, liquid carrying rate was 70 ~ 90%, by preliminary drying in 40 ~ 80 DEG C of temperature 5 minutes, bake 3 minutes through 80 ~ 160 DEG C of temperature again, be washed to neutrality, oven dry.

8. modification fabric according to claim 7, is characterized in that described corpus fibrosum or corpus fibrosum fabric are cotton fiber, viscose acetal fibre, tencel fiber, Modal fibre, bamboo fibre, flax fibre or its fabric.