CN103911851A - Method for preparing cotton fabric loaded with nano-zinc oxide - Google Patents

Abstract

The invention discloses a method for preparing cotton fabric loaded with nanometer zinc oxide, which belongs to the technical field of textile fabrics. The process is as follows: the scoured cotton fabric is ultrasonically cleaned in a deionized aqueous solution, dried, and then put into triethanolamine Immerse in diisopropyl titanate aqueous solution, take it out, squeeze and dry it on a paddle car, and then bake it; boil the mixed solution of masking agent and zinc acetate dihydrate, then add sodium hydroxide solution dropwise, and keep stirring until the pH is 12 , add the treated cotton fabric, stir for 5min~30min; take it out, wash it, and finally dry it. Its advantages are: the rapid growth of nano-zinc oxide on the surface of cotton fabric is realized, and the surface of zinc oxide grown on the surface of cotton fabric by this method has no coating, excellent performance, low ultraviolet transmittance, and good ultraviolet protection performance; and zinc oxide and Cotton fabrics have strong chemical bonds, strong bonding, and good durability. After repeated washing, they still maintain good UV protection performance.

Description

A kind of preparation method of cotton fabric loaded with nanometer zinc oxide

technical field

The invention relates to the technical field of textile fabrics, in particular to a method for preparing cotton fabrics loaded with nanometer zinc oxide.

Background technique

Cotton fabric is loved by people for its excellent softness, moisture absorption, breathability and other comfortable properties, but its lack of anti-ultraviolet properties and antibacterial properties limits its scope of use. Nano-zinc oxide has been widely concerned due to its excellent anti-ultraviolet properties, antibacterial properties, and photocatalytic properties. The use of nano-zinc oxide functionalized cotton fabrics will endow cotton fabrics with additional antibacterial properties and anti-ultraviolet properties, which is conducive to expanding cotton fabrics. The use of the fabric.

Nano-zinc dioxide is an inorganic oxide, and cotton fabric is an organic polymer compound. The combination of the two requires a strong chemical bond to have good fastness. In addition, when loading nano zinc dioxide on cotton fabrics, it is necessary to avoid particle agglomeration or severe coating of particles, which will lead to a significant reduction in antibacterial performance and anti-ultraviolet performance. Therefore, the preparation of nano zinc dioxide functionalized cotton fabrics with better fastness and excellent performance has become the direction of people's research.

At present, the methods for preparing nano-zinc dioxide functionalized cotton fabrics mainly include magnetron sputtering, finishing, sol-gel and hydrothermal methods. The feature of the magnetron sputtering method is that it is convenient to prepare thin films, but the investment in equipment and zinc oxide targets is large, and the prepared nano-zinc dioxide has no strong chemical bond with textile fibers and products, and its durability is poor. The post-finishing method is characterized by easy large-scale industrial production, but nano-zinc dioxide is not easy to disperse evenly, and will be wrapped by dispersant or adhesive when dispersed and fixed on the surface of cotton fabric, which affects the performance of nano-zinc oxide. The sol-gel method is characterized by low cost, but the decomposition of zinc oxide sol into zinc oxide with a regular structure requires a higher temperature, which will affect the performance of cotton fabrics. The characteristics of the hydrothermal method are that the prepared zinc oxide has regular grains, controllable shape, no wrapping and embedding, and excellent performance, but the reaction temperature is high and the time is long, and there is no strong chemical bond between zinc oxide and cotton.

For example, the Chinese patent with the patent number of 201310188503.1: a preparation method of flame-retardant/superhydrophobic cotton fabric, first cleaning and drying the cotton fabric; using ethanol as a solvent to prepare nano-zinc oxide particles, using aminopropyl methyl di Ethoxysilane is aminated, and magnetically stirred at room temperature to obtain an aminated zinc oxide/ethanol solution; configure an acetone solution containing epoxy resin, immerse clean cotton fabric in it, and epoxidize at room temperature for 2 to 4 hours , rinse with acetone, and dry; soak the epoxidized cotton fabric in zinc oxide/ethanol solution, take it out after 0.5 to 1.5 hours, place it in a clean watch glass, and dry it at room temperature; The cotton fabric is immersed in it for modification for 1 to 3 hours, rinsed with methanol, and dried to obtain a flame-retardant/super-hydrophobic cotton fabric, which has excellent waterproof performance; and its flame-retardant performance and thermal stability have also been greatly improved. The perfect combination of superhydrophobic properties and flame retardant properties of cotton fabrics.

Another example is the Chinese patent No. 201310261816.5: a method for preparing hydrophobic and lipophilic cotton fabric materials by constructing zinc oxide microstructures. The specific steps are:

a. Prepare 0.05mol/L zinc acetate alcohol solution at 60-65℃, add 0.10-0.15mol/L sodium hydroxide alcohol solution drop by drop under stirring until a transparent colloid of zinc oxide with Tyndall phenomenon is formed solution;

b. Soak the cleaned cotton fabric in the colloidal solution of zinc oxide obtained in step a for 2 to 5 minutes, then lightly paddle the cotton fabric and dry it, then solidify it at 170 to 175°C for 3 to 5 minutes;

c. repeat step b3 times, thereby form zinc oxide nano-crystal seed film on the cotton fabric surface;

d. Dissolve zinc nitrate and hexamethylenetetramine equimolarly in water, and prepare a mixed solution with a concentration of 2.9 to 3 mol/L; immerse the cotton fabric covered with the zinc oxide seed film obtained in step c in the mixed solution After reacting in the solution for 3-3.5 hours at 90 DEG C and 120 DEG C respectively, the cotton fabric is taken out, rinsed with deionized water and then dried to obtain the cotton fabric with fine zinc oxide structure grown on the surface.

Prepare an ethanol solution of 1.0-1.5mmol/L palmitic acid; irradiate the cotton fabric substrate with zinc oxide microstructure on the surface obtained in step 2d for 10min under a UV lamp, and then put it flat into the ethanol solution of palmitic acid prepared above. Stand in the solution to react for 48-50 hours; finally take it out, wash it with ethanol for several times, and dry it at low temperature to obtain a hydrophobic and lipophilic cotton fabric material.

The prepared cotton fabric is lipophilic and has good oil absorption capacity after wrapping cotton, and will have good practical application value in the restoration of oil-polluted water bodies.

Contents of the invention

The object of the present invention is to provide a method for preparing cotton fabric loaded with nano-zinc oxide, which realizes rapid growth of nano-zinc oxide on the surface of cotton fabric and greatly improves the ultraviolet protection performance of cotton fabric.

In order to achieve the purpose of the present invention, technical scheme is as follows:

A method for preparing cotton fabrics loaded with nanometer zinc oxide, comprising the following steps:

1) Ultrasonic cleaning the scoured cotton fabric in deionized aqueous solution for 5-15 minutes, then drying at 60°C for use;

2) Dissolve triethanolamine diisopropyl titanate in 100ml of water, stir for 5 minutes, and prepare a triethanolamine diisopropyl titanate solution with a concentration of 2-5g/L;

3) Take 0.5g to 5g of the cotton fabric in step 1) and put it into the aqueous solution of triethanolamine diisopropyl titanate in step 2), soak it for 2 to 5 minutes, and squeeze it on a paddle after taking it out;

4), repeat the step 3) 1 to 3 times;

5) Dry the cotton fabric at 60°C, and then bake it at a temperature of 160°C to 180°C for 3 to 5 minutes;

6) Prepare a sodium hydroxide solution with a concentration of 10g/L-40g/L;

7) Take 0.005mol～0.02mol of masking agent, and dissolve it in 100ml of water together with zinc acetate dihydrate whose molar ratio is 2:1～4:1, and heat the mixed solution on the electric stove to boil, then Add the sodium hydroxide solution in step 6) dropwise, and stir continuously until the pH is 12, add the cotton fabric treated in step 5), and stir for 5 minutes to 30 minutes;

8) Take out the cotton fabric, wash it with water for 2 to 4 times, each time for 2 minutes, and finally dry it at 60°C.

As a preferred technical solution: in the step 3), the excess rate of the cotton fabric after being squeezed by the padder is 70%-85%.

As a preferred technical solution: the masking agent shown is any one of citric acid monohydrate, sodium potassium tartrate, and sodium edetate.

The function of adding the masking agent is to use it to complex zinc ions to control the formation rate of zinc hydroxide.

Triethanolamine diisopropyl titanate acts as a coupling agent, and can also be replaced by other coupling agents. The inorganic and organophilic groups on it can form strong chemical bonds with zinc oxide and cotton fabrics respectively. Improved durability.

The beneficial effect that the present invention has:

The rapid growth of nano-zinc oxide on the surface of cotton fabric is realized, and the surface of zinc oxide grown on the surface of cotton fabric by this method has no coating, excellent performance, low ultraviolet transmittance, and good ultraviolet protection performance; and the relationship between zinc oxide and cotton fabric It has a strong chemical bond, strong binding force, and good durability. After repeated washing, it still maintains good UV protection performance. The method is simple and easy to control, and common raw materials can be used, and the preparation cost is low.

Description of drawings

Fig. 1 is the X-ray diffraction pattern of the cotton fabric of Example 2 of the present invention.

Detailed ways

The present invention will be further described below in conjunction with the examples, but the protection scope of the present invention is not limited only to the examples.

Example 1

A method for preparing cotton fabrics loaded with nanometer zinc oxide, comprising the following steps:

1) Ultrasonic cleaning of the scoured cotton fabric in deionized aqueous solution for 5 minutes, and then drying at 60°C for use;

2) Dissolve triethanolamine diisopropyl titanate in 100ml of water, stir for 5 minutes, and prepare a triethanolamine diisopropyl titanate solution with a concentration of 2g/L;

3) Take 0.5g of the cotton fabric in the step 1) and put it into the triethanolamine diisopropyl titanate aqueous solution in the step 2), soak it for 2 minutes, squeeze it on the paddle after taking it out, and squeeze it on the paddle The excess rate of cotton fabric after pressing is 70%;

4), repeat the step 3) once;

5) Dry the cotton fabric at 60°C, and then bake it at 160°C for 3 minutes;

6) Prepare a sodium hydroxide solution with a concentration of 10g/L;

7) Dissolve 0.005mol of sodium ethylenediaminetetraacetic acid (EDTA) and 0.01mol of zinc acetate dihydrate in 100ml of water, heat the mixed solution on an electric stove until it boils, and then add dropwise the sodium hydroxide in the above step 6) Solution, stirring continuously until the pH is 12, adding the cotton fabric treated in step 5) and stirring for 5min to 10min;

8) Take out the cotton fabric, wash it twice with water for 2 minutes each time, and finally dry it at 60°C.

Example 2

A method for preparing cotton fabrics loaded with nanometer zinc oxide, comprising the following steps:

1) Clean the scoured cotton fabric ultrasonically for 10 minutes in a deionized aqueous solution, then dry it at 60°C for use;

2) Dissolve triethanolamine diisopropyl titanate in 100ml of water, stir for 5 minutes, and prepare a triethanolamine diisopropyl titanate solution with a concentration of 3g/L;

3) Take 3g of the cotton fabric in the step 1) and put it into the triethanolamine diisopropyl titanate aqueous solution in the step 2), soak it for 2 minutes, squeeze it on the paddle after taking it out, and squeeze it on the paddle The excess rate of cotton fabric is 80%;

4), repeat the step 3) 2 times;

5) Dry the cotton fabric at 60°C, and then bake it at 170°C for 4 minutes;

6) Prepare a sodium hydroxide solution with a concentration of 20g/L;

7) Dissolve 0.01mol of potassium sodium tartrate and 0.03mol of zinc acetate dihydrate in 100ml of water, heat the mixed solution on an electric stove to boil, then add the sodium hydroxide solution in the above step 6) dropwise, and keep stirring until When the pH is 12, add the cotton fabric treated in step 5) and stir for 15 minutes to 30 minutes;

8) Take out the cotton fabric, wash it with water for 3 times, each time for 2 minutes, and finally dry it at 60°C.

Example 3

A method for preparing cotton fabrics loaded with nanometer zinc oxide, comprising the following steps:

1) Ultrasonic cleaning of the scoured cotton fabric in deionized aqueous solution for 15 minutes, and then drying at 60°C for use;

2) Dissolve triethanolamine diisopropyl titanate in 100ml of water, stir for 5 minutes, and prepare a triethanolamine diisopropyl titanate solution with a concentration of 5g/L;

3) Take 5g of the cotton fabric in the step 1) and put it into the triethanolamine diisopropyl titanate aqueous solution in the step 2), soak it for 2 minutes, squeeze it on the paddle after taking it out, and squeeze it on the paddle The excess rate of cotton fabric is 85%;

4), repeat the step 3) 3 times;

5) Dry the cotton fabric at 60°C, and then bake it at 180°C for 5 minutes;

6) Prepare a sodium hydroxide solution with a concentration of 40g/L;

7) Dissolve 0.02mol of citric acid and 0.08mol of zinc acetate dihydrate in 100ml of water, heat the mixed solution on an electric stove to boil, then add the sodium hydroxide solution in the above step 6) dropwise, and keep stirring until the pH 12, add the cotton fabric treated in step 5) and stir for 20-30 minutes;

8) Take out the cotton fabric, wash it with water for 4 times, each time for 2 minutes, and finally dry it at 60°C.

The ordinary cotton fabric not loaded with zinc oxide, the cotton fabric of the above embodiments and the loaded zinc oxide cotton fabric washed 10 times in each embodiment are detected simultaneously. The detection standard refers to GB/T18830, and the detection indicators are UPF value and T (UVA ) value, and the test results are shown in Table 1 below. UPF is the ultraviolet protection factor. UPF specifically refers to "the ratio of the average effect of ultraviolet radiation calculated when the skin is not protected to the average effect of ultraviolet radiation calculated when the skin is protected by fabric". T(UVA) represents the transmittance of UVA, and UVA represents the solar ultraviolet radiation with a wavelength of 315-400nm.

In addition, X-ray diffraction analysis was carried out on the cotton fabric prepared in Example 2, and the results are shown in Figure 1. From Figure 1, it can be seen that there are obvious and large-scale ZnO peaks on the cotton fabric.

Table 1 Detection of anti-ultraviolet properties of cotton fabrics

Note: The washing conditions are temperature 40°C, bath ratio 50:1, standard detergent 5g/l, 5 minutes as one time, and water for 2 minutes after washing.

It can be seen from Table 1 that compared with ordinary cotton fabrics, the cotton fabrics of the present invention have greatly improved the ultraviolet protection performance, and there is a strong chemical bond between zinc oxide and cotton fabrics, with strong binding force and good durability. After several washes, it still maintains good UV protection performance.

Finally, it should be noted that: the above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention. Therefore, although the specification has described the present invention in detail with reference to the above-mentioned various embodiments, the skilled artisan Those of ordinary skill in the art should understand that the present invention can still be modified or equivalently replaced, and all technical solutions and improvements that do not depart from the spirit and scope of the present invention should be included in the claims of the present invention.

Claims (3)

1. a COTTON FABRIC preparation method for supported nano zinc oxide, is characterized in that: comprise the following steps:

1), by the COTTON FABRIC that kiering was processed ultrasonic cleaning 5～15min in deionized water solution, then stand-by 60 ℃ of oven dry;

2), get triethanolamine metatitanic acid diisopropyl ester and be dissolved in 100ml water, stir 5min, being mixed with concentration is the triethanolamine metatitanic acid diisopropyl ester solution of 2 ~ 5g/L;

3), COTTON FABRIC 0.5g ~ 5g of getting described step 1) puts into described step 2) in the triethanolamine metatitanic acid diisopropyl ester aqueous solution in, dipping 2～5min, pushes at padding machine after taking-up;

4), repeating said steps 3) 1～3 time;

5), by COTTON FABRIC 60 ℃ of oven dry, be then placed at the temperature of 160 ℃～180 ℃ and bake 3～5min;

6) sodium hydroxide solution that, configuration concentration is 10g/L ~ 40g/L;

7), get 0.005mol ~ 0.02 mol screening agent, and be jointly dissolved in 100ml water with the two water zinc acetates that described screening agent mol ratio is 2:1 ~ 4:1, mixed solution is heated to and is boiled on electric furnace, then drip the sodium hydroxide solution of described step 6), constantly stir, until pH is 12, add described step 5) COTTON FABRIC after treatment, stir 5 min ~ 30min;

8), take out COTTON FABRIC, water cleaning 2～4 times, each 2min, finally oven dry at 60 ℃.

2. the COTTON FABRIC preparation method of supported nano zinc oxide according to claim 1, is characterized in that: in described step 3), after padding machine extruding, the pick-up of COTTON FABRIC is 70% ~ 85%.

3. the COTTON FABRIC preparation method of supported nano zinc oxide according to claim 1, is characterized in that: shown in screening agent be any one in Citric Acid Mono, sodium potassium tartrate tetrahydrate, sodium ethylene diamine tetracetate.