阅读说明：本技术 一种改性纳米氧化锌及其制备方法和应用 (Modified nano zinc oxide and preparation method and application thereof ) 是由 廖师琴 杨陈 于 2021-08-24 设计创作，主要内容包括：本发明公开了一种改性纳米氧化锌,并公开了其制备方法和在配置成织物整理剂整理织物的应用。本发明以纳米氧化锌为核心,其本身,具有良好的紫外线屏蔽性和优越的抗菌、抑菌性能,添加入织物中,能赋予织物以防晒、抗菌、除臭等功能,同时能提供抗皱性和耐水洗性能。进行改性后,提高了防紫外线的效果,增强材料的弹性及持久耐用性,同时增大材料的可使用范围,增加抗菌性能。本发明制备方法简单,易于进行大规模生产使用。将本发明制得的改性纳米氧化锌应用于作为织物整理剂整理织物,整理后的织物的防紫外线性能、抗拉性和韧性均可以大幅提升,延长了织物的使用寿命。(The invention discloses modified nano zinc oxide, a preparation method thereof and application of the modified nano zinc oxide in finishing textiles prepared as a textile finishing agent. The nano zinc oxide is taken as a core, has good ultraviolet shielding property and excellent antibacterial and bacteriostatic properties, can be added into fabrics to endow the fabrics with sun-screening, antibacterial, deodorizing and other functions, and can provide wrinkle resistance and water washing resistance. After modification, the ultraviolet-proof effect is improved, the elasticity and the durability of the material are enhanced, the usable range of the material is enlarged, and the antibacterial performance is improved. The preparation method is simple and is easy to carry out large-scale production and use. The modified nano zinc oxide prepared by the invention is applied to finishing the fabric as a fabric finishing agent, the ultraviolet resistance, the tensile strength and the toughness of the finished fabric can be greatly improved, and the service life of the fabric is prolonged.)

1. The modified nano zinc oxide is characterized by comprising the following raw materials in parts by weight:

2. the modified nano zinc oxide of claim 1, which is prepared from the following raw materials in parts by weight:

40 parts of nano zinc oxide;

10 parts of a solvent;

9 parts of sodium bicarbonate;

6 parts of an antibacterial agent;

8 parts of nanocrystalline cellulose;

3 parts of an anti-ultraviolet agent;

6 parts of a composite modifier.

3. The modified nano zinc oxide according to claim 1 or 2, wherein the solvent is ethanol;

the antibacterial agent is chitosan;

the ultraviolet resistant agent consists of chloroethylene-vinyl acetate copolymer emulsion, 2, 4-dichlorobenzoic acid, microporous lignin and nano titanium dioxide;

the composite modifier consists of ricinoleic acid ester sodium sulfate, sodium aluminum sulfate dodecahydrate and graphene oxide-attapulgite.

4. The modified nano zinc oxide according to claim 3,

the mass ratio of the chloroethylene-vinyl acetate copolymer emulsion, the 2, 4-dichlorobenzoic acid, the microporous lignin and the nano titanium dioxide in the ultraviolet resistant agent is 3:2:2: 3;

the mass ratio of the ricinoleic acid ester sodium sulfate, the aluminum sodium sulfate dodecahydrate and the graphene oxide-attapulgite in the composite modifier is 0.5-1.5:0.5-1.5: 0.25-0.75.

5. The method for preparing the modified nano zinc oxide according to any one of claims 1 to 4, which is characterized by comprising the following steps:

s1: mixing nano zinc oxide, a solvent and sodium bicarbonate to obtain nano zinc oxide dispersion liquid;

s2: adding an antibacterial agent and nanocrystalline cellulose into the dispersion, fully mixing, and heating in a water bath to obtain a first mixed solution;

s3: adding a composite modifier into the first mixed solution, and then carrying out ultrasonic treatment to obtain a second mixed solution;

s4: adding an anti-ultraviolet agent into the second mixed solution, and mixing to obtain a modified nano zinc oxide solution;

s5: and finally, filtering, drying, crushing and sieving the modified nano zinc oxide solution to obtain the modified nano zinc oxide.

6. The method as claimed in claim 5, wherein the mixing in step S1 is performed by heating and dispersing in a stirring tank at 45-55 deg.C and stirring speed of 600-800 rpm for 12-22 min.

7. The method according to claim 5 or 6, wherein the water bath temperature in step S2 is 60-70 ℃ and the time is 10-18 min;

in the step S3, when ultrasonic treatment is carried out, the frequency is 60-80KHz, and the time is 20-40 min;

the temperature of the mixing in step S4 is normal temperature.

8. The preparation method according to any one of claims 5 to 7, wherein the particle size of the modified nano zinc oxide obtained in step S5 is 20 to 30 nm.

9. Use of the modified nano zinc oxide of any one of claims 1 to 4, characterized in that it is used for finishing textiles in a formulation as textile finishing agent.

Technical Field

The invention belongs to the technical field of textiles, and particularly relates to modified nano zinc and a preparation method and application thereof.

Background

With the development of technology and the continuous progress of society, the living standard of people is greatly improved, and the requirements on the living quality are higher and higher. Today, the global environment is damaged, the world returns to nature, the people become important standards for measuring the quality of life, and the people are more and more pursuing the multifunctionality of the fabric. In the open air environment, ultraviolet rays greatly damage human skins, and in high-intensity or long-time outdoor life, the skins have various problems due to the ultraviolet rays and even cause cancers.

The common technical means for manufacturing the ultraviolet-proof fabric in the current market mainly comprise two types: one is to mix the ultraviolet-proof material during spinning to achieve the effect of ultraviolet-proof; and the other method is to carry out ultraviolet-proof finishing on the fabric by using an after-finishing method. The most common after-finishing method is to coat a layer of material on the surface of the fabric by using a coating technology, wherein the coating material is generally black glue, silver glue or other materials with an ultraviolet-proof effect. However, the existing fabric has poor ultraviolet resistance and toughness after treatment, and cannot meet the use requirement.

Disclosure of Invention

Therefore, the invention aims to solve the technical problems of poor protection effect and poor toughness of the existing ultraviolet-proof fabric, and further provides modified nano-zinc, a preparation method thereof and application of the modified nano-zinc prepared into a fabric finishing agent for finishing fabric.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the invention provides modified nano zinc oxide, which comprises the following raw materials in parts by weight:

preferably, the feed consists of the following raw materials in parts by weight:

40 parts of nano zinc oxide;

10 parts of a solvent;

9 parts of sodium bicarbonate;

6 parts of an antibacterial agent;

8 parts of nanocrystalline cellulose;

3 parts of an anti-ultraviolet agent;

6 parts of a composite modifier.

Further, the solvent is ethanol;

the antibacterial agent is chitosan;

the ultraviolet resistant agent consists of chloroethylene-vinyl acetate copolymer emulsion, 2, 4-dichlorobenzoic acid, microporous lignin and nano titanium dioxide;

the composite modifier consists of ricinoleic acid ester sodium sulfate, sodium aluminum sulfate dodecahydrate and graphene oxide-attapulgite.

Preferably, the first and second electrodes are formed of a metal,

the mass ratio of the chloroethylene-vinyl acetate copolymer emulsion, the 2, 4-dichlorobenzoic acid, the microporous lignin and the nano titanium dioxide in the ultraviolet resistant agent is 3:2:2: 3;

the mass ratio of the ricinoleic acid ester sodium sulfate, the aluminum sodium sulfate dodecahydrate and the graphene oxide-attapulgite in the composite modifier is 0.5-1.5:0.5-1.5: 0.25-0.75.

The invention also provides a preparation method of the modified nano zinc oxide, which comprises the following steps:

s1: mixing nano zinc oxide, a solvent and sodium bicarbonate to obtain nano zinc oxide dispersion liquid;

s2: adding an antibacterial agent and nanocrystalline cellulose into the dispersion, fully mixing, and heating in a water bath to obtain a first mixed solution;

s3: adding a composite modifier into the first mixed solution, and then carrying out ultrasonic treatment to obtain a second mixed solution;

s4: adding an anti-ultraviolet agent into the second mixed solution, and mixing to obtain a modified nano zinc oxide solution;

s5: and finally, filtering, drying, crushing and sieving the modified nano zinc oxide solution to obtain the modified nano zinc oxide.

Further, in step S1, the mixing is performed by heating and dispersing in a stirring tank, wherein the dispersing temperature is 45-55 ℃, the stirring speed is 600-800 rpm, and the time is 12min-22 min.

In the step S2, the water bath temperature is 60-70 ℃, and the time is 10-18 min;

in the step S3, when ultrasonic treatment is carried out, the frequency is 60-80KHz, and the time is 20-40 min;

the temperature of the mixing in step S4 is normal temperature.

Preferably, the particle size of the modified nano zinc oxide obtained in the step S5 is 20-30 nm.

The invention also discloses application of the modified nano zinc oxide, which is applied to preparing a fabric finishing agent for finishing fabrics.

The technical scheme of the invention has the following advantages:

(1) the nano zinc oxide is taken as a core, has good ultraviolet shielding property and excellent antibacterial and bacteriostatic properties, can be added into fabrics to endow the fabrics with sun-screening, antibacterial, deodorizing and other functions, and can provide wrinkle resistance and water washing resistance. The invention adds the anti-ultraviolet agent in the paint, which has the effect of compound anti-ultraviolet and achieves the effect of 1+1> 2. Meanwhile, the defect that the effect of selective absorption and reflection of the ultraviolet-proof wavelength is insufficient when the single nano zinc oxide is used for preventing ultraviolet rays is overcome. The absorption and reflection of ultraviolet rays at various wavelengths are increased; sodium bicarbonate is a raw material for preparing the nano zinc oxide, and the sodium bicarbonate added in the method is helpful for keeping the stability of the nano zinc oxide; the addition of the nanocrystalline cellulose helps to enhance the elasticity and the durability of the material and greatly improves the strength of the material, thereby enlarging the usable range of the material.

(2) The antibacterial agent is limited to be chitosan, the dissolved chitosan is in a gel state, and has strong adsorption capacity, the decomposition of zinc oxide can be relieved to a certain extent while the antibacterial effect of nano zinc oxide is improved, the service life of the material is prolonged, and the service life of the material is prolonged; the components of the composite modifier are limited, and after the graphene oxide component is added into the nano zinc oxide, the graphene oxide is in a regular structure, so that the specific surface area is large, the strength is high, and the strength of the whole material is improved.

(3) The application also defines the components in the ultraviolet resistant agent, wherein the vinyl chloride-vinyl acetate copolymer emulsion is a modified polyvinyl chloride emulsion, has the advantages of lower softening temperature, good fluidity, good flexibility, good solubility, good dimensional stability of products, certain internal reinforcement function and the like, and is only used as a solvent in the ultraviolet resistant agent; 2, 4-dichlorobenzoic acid exists as an intermediate for manufacturing the improved anti-ultraviolet agent; the microporous lignin and the titanium dioxide act on ultraviolet resistance, and the microporous lignin and the titanium dioxide supplement each other and are combined for use, so that the ultraviolet resistance effect is better; the microporous lignin mainly plays a role in absorbing ultraviolet rays, because the microporous lignin has a better adsorption and degradation function and assists the titanium dioxide to play a role in absorbing and decomposing residual ultraviolet rays alternatively after the titanium dioxide reflects and absorbs the ultraviolet rays to the limit, so that the ultraviolet-resistant safety of the whole reagent is improved; when the anti-ultraviolet agent with the limited components is applied to the nano zinc oxide, the surface properties of the nano zinc oxide can be changed, and the raw materials are matched with each other, so that the surface properties of the nano zinc oxide are improved, and the compatibility between nano particles and a matrix is increased.

(2) The preparation method is simple and is easy to carry out large-scale production and use.

(3) The modified nano zinc oxide prepared by the invention is applied to finishing the fabric as a fabric finishing agent, the ultraviolet resistance, the tensile strength and the toughness of the finished fabric can be greatly improved, and the service life of the fabric is prolonged.

Detailed Description

The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

Nanocrystalline cellulose used in the examples was purchased from south-Henan Doxi chemical trade Co.

The vinyl chloride-vinyl acetate copolymer emulsion used in each example was purchased from shanghai okk chemical co.

The microporous lignin used in each example was purchased from Shanghai Aladdin Biotechnology Ltd.

The graphene oxide-attapulgite used in each example was purchased from basf, germany, and was model Attagel 50.

The fabric used in the test example was a 300D polyester fiber fabric produced by seine printing and dyeing group ltd.

Example 1

The embodiment provides modified nano zinc oxide, and raw materials of the modified nano zinc oxide comprise 20g of nano zinc oxide, 4g of ethanol, 3g of sodium bicarbonate, 2g of chitosan, 4g of nanocrystalline cellulose, 1g of ultraviolet resistant agent and 2g of composite modifier.

Wherein the ultraviolet resistant agent consists of 30 wt% of chloroethylene-vinyl acetate copolymer emulsion, 20 wt% of 2, 4-dichlorobenzoic acid, 20 wt% of microporous lignin and 20 wt% of nano titanium dioxide.

The composite modifier adopts ricinoleic acid ester sodium sulfate, sodium aluminum sulfate dodecahydrate and graphene oxide-attapulgite in a mass ratio of 1:1: 0.5.

The preparation method comprises the following steps:

(1) firstly, putting nano zinc oxide, ethanol and sodium bicarbonate into a stirring tank for heating and dispersing at the dispersion temperature of 45 ℃, the stirring speed of 600 revolutions per minute for 12min to obtain nano zinc oxide dispersion liquid;

(2) adding chitosan and nanocrystalline cellulose into the dispersion, mixing thoroughly, adding into a water bath kettle, heating in water bath at 60 deg.C for 10min to obtain mixed solution A;

(3) adding a composite modifier into the mixed solution A, adding the mixed solution into an ultrasonic generator after mixing, and carrying out ultrasonic treatment with the ultrasonic frequency of 60KHz for 20min to obtain a mixed solution B;

(4) adding an anti-ultraviolet agent into the mixed solution B, and fully mixing at normal temperature to obtain a modified nano zinc oxide solution;

(5) and finally, filtering, drying, crushing and sieving the modified nano zinc oxide solution to obtain the modified nano zinc oxide with the particle size of 20-30 nm.

Example 2

The embodiment provides modified nano zinc oxide, and raw materials of the modified nano zinc oxide comprise 40g of nano zinc oxide, 10g of ethanol, 9g of sodium bicarbonate, 6g of chitosan, 8g of nanocrystalline cellulose, 3g of an ultraviolet resistant agent and 6g of a composite modifier.

Wherein the ultraviolet resistant agent consists of 30 wt% of chloroethylene-vinyl acetate copolymer emulsion, 20 wt% of 2, 4-dichlorobenzoic acid, 20 wt% of microporous lignin and 20 wt% of nano titanium dioxide.

The composite modifier adopts ricinoleic acid ester sodium sulfate, sodium aluminum sulfate dodecahydrate and graphene oxide-attapulgite in a mass ratio of 1:1: 0.5.

The preparation method comprises the following steps:

(1) firstly, putting nano zinc oxide, ethanol and sodium bicarbonate into a stirring tank for heating and dispersing at the dispersion temperature of 55 ℃, the stirring speed of 800 revolutions per minute and the time of 22min to obtain nano zinc oxide dispersion liquid;

(2) adding chitosan and nanocrystalline cellulose into the dispersion, mixing thoroughly, adding into a water bath kettle, heating in water bath at 70 deg.C for 18min to obtain mixed solution A;

(3) adding a composite modifier into the mixed solution A, adding the mixed solution into an ultrasonic generator after mixing, and carrying out ultrasonic treatment with the ultrasonic frequency of 80KHz for 40min to obtain a mixed solution B;

(4) adding an anti-ultraviolet agent into the mixed solution B, and fully mixing at normal temperature to obtain a modified nano zinc oxide solution;

(5) and finally, filtering, drying, crushing and sieving the modified nano zinc oxide solution to obtain the modified nano zinc oxide with the particle size of 20-30 nm.

Example 3

The embodiment provides modified nano zinc oxide, and raw materials of the modified nano zinc oxide comprise 25g of nano zinc oxide, 5g of ethanol, 4g of sodium bicarbonate, 3g of chitosan, 5g of nanocrystalline cellulose, 2g of an ultraviolet resistant agent and 3g of a composite modifier.

Wherein the ultraviolet resistant agent consists of 30 wt% of chloroethylene-vinyl acetate copolymer emulsion, 20 wt% of 2, 4-dichlorobenzoic acid, 20 wt% of microporous lignin and 20 wt% of nano titanium dioxide.

The composite modifier adopts ricinoleic acid ester sodium sulfate, sodium aluminum sulfate dodecahydrate and graphene oxide-attapulgite in a mass ratio of 1:1: 0.5.

The preparation method comprises the following steps:

(1) firstly, putting nano zinc oxide, ethanol and sodium bicarbonate into a stirring tank for heating and dispersing at the dispersion temperature of 46 ℃, the stirring speed of 650 revolutions per minute and the stirring time of 13min to obtain nano zinc oxide dispersion liquid;

(2) adding chitosan and nanocrystalline cellulose into the dispersion, mixing thoroughly, adding into a water bath kettle, heating in water bath at 62 deg.C for 12min to obtain mixed solution A;

(3) adding a composite modifier into the mixed solution A, adding the mixed solution into an ultrasonic generator after mixing, and carrying out ultrasonic treatment with the ultrasonic frequency of 65KHz for 25min to obtain a mixed solution B;

(4) adding an anti-ultraviolet agent into the mixed solution B, and fully mixing at normal temperature to obtain a modified nano zinc oxide solution;

(5) and finally, filtering, drying, crushing and sieving the modified nano zinc oxide solution to obtain the modified nano zinc oxide with the particle size of 20-30 nm.

Example 4

The embodiment provides modified nano zinc oxide, and raw materials of the modified nano zinc oxide comprise 35g of nano zinc oxide, 8g of ethanol, 8g of sodium bicarbonate, 5g of chitosan, 7g of nanocrystalline cellulose, 2g of an ultraviolet resistant agent and 5g of a composite modifier.

Wherein the ultraviolet resistant agent consists of 30 wt% of chloroethylene-vinyl acetate copolymer emulsion, 20 wt% of 2, 4-dichlorobenzoic acid, 20 wt% of microporous lignin and 20 wt% of nano titanium dioxide.

The composite modifier adopts ricinoleic acid ester sodium sulfate, sodium aluminum sulfate dodecahydrate and graphene oxide-attapulgite in a mass ratio of 1:1: 0.5.

The preparation method comprises the following steps:

(1) firstly, putting nano zinc oxide, ethanol and sodium bicarbonate into a stirring tank for heating and dispersing at the dispersion temperature of 52 ℃, the stirring speed of 750 revolutions per minute and the stirring time of 20min to obtain nano zinc oxide dispersion liquid;

(2) adding chitosan and nanocrystalline cellulose into the dispersion, mixing thoroughly, adding into a water bath kettle, heating in water bath at 68 deg.C for 16min to obtain mixed solution A;

(3) adding a composite modifier into the mixed solution A, adding the mixed solution into an ultrasonic generator after mixing, and carrying out ultrasonic treatment with the ultrasonic frequency of 75KHz for 35min to obtain a mixed solution B;

(4) adding an anti-ultraviolet agent into the mixed solution B, and fully mixing at normal temperature to obtain a modified nano zinc oxide solution;

(5) and finally, filtering, drying, crushing and sieving the modified nano zinc oxide solution to obtain the modified nano zinc oxide with the particle size of 20-30 nm.

Example 5

The embodiment provides modified nano zinc oxide, and raw materials of the modified nano zinc oxide comprise 30g of nano zinc oxide, 7g of ethanol, 6g of sodium bicarbonate, 4g of chitosan, 6g of nanocrystalline cellulose, 2g of an ultraviolet resistant agent and 4g of a composite modifier.

Wherein the ultraviolet resistant agent consists of 30 wt% of chloroethylene-vinyl acetate copolymer emulsion, 20 wt% of 2, 4-dichlorobenzoic acid, 20 wt% of microporous lignin and 20 wt% of nano titanium dioxide.

The composite modifier adopts ricinoleic acid ester sodium sulfate, sodium aluminum sulfate dodecahydrate and graphene oxide-attapulgite in a mass ratio of 1:1: 0.5.

The preparation method comprises the following steps:

(1) firstly, putting nano zinc oxide, ethanol and sodium bicarbonate into a stirring tank for heating and dispersing at the dispersion temperature of 50 ℃, the stirring speed of 700 revolutions per minute and the time of 17min to obtain nano zinc oxide dispersion liquid;

(2) adding chitosan and nanocrystalline cellulose into the dispersion, mixing thoroughly, adding into a water bath kettle, heating in water bath at 65 deg.C for 14min to obtain mixed solution A;

(3) adding a composite modifier into the mixed solution A, adding the mixed solution into an ultrasonic generator after mixing, and carrying out ultrasonic treatment with the ultrasonic frequency of 70KHz for 30min to obtain a mixed solution B;

(4) adding an anti-ultraviolet agent into the mixed solution B, and fully mixing at normal temperature to obtain a modified nano zinc oxide solution;

(5) and finally, filtering, drying, crushing and sieving the modified nano zinc oxide solution to obtain the modified nano zinc oxide with the particle size of 20-30 nm.

Comparative example 1

The comparative example differs from example 1 in that the nano zinc oxide is not modified.

Comparative example 2

The comparative example differs from example 1 in that no uv-resistant agent is added.

Test examples

The performance tests were conducted on the examples of the present invention and the comparative examples, and the obtained nano zinc oxide prepared dispersion having a content of 5 wt% was used as a raw material of a textile finishing agent comprising 2.5 wt% of the nano zinc oxide dispersion and 50 wt% of PVA. The fabric finishing agent is used for spraying the fabric, 2 layers of the fabric are sprayed by adopting a two-step spraying method, the thickness of a formed film is 0.05mm, performance tests are carried out after 12 times of washing, the performance test results are shown in table 1, wherein the fracture strength is measured according to the following steps: GB/T3923.1-2013 part 1 of tensile Properties of textile fabrics: determination of breaking strength and elongation at break (bar method); the wear resistance was determined as follows: GB/T21196.2-2007 determination of abrasion resistance of fabrics by Martindale method part 2: measurement of specimen breakage "; reference for antibacterial property measurement of antibacterial fabric: AATCC 100-; the ultraviolet resistance was measured as follows: GB/T18830-2009 evaluation of ultraviolet resistance of textiles;

TABLE 1 Performance Effect of the textile finishing of the examples and comparative examples

As can be seen from the above table, in example 2, which is preferred to be in a specific ratio, the performance of each aspect is the best, and in comparative example 1, which is not modified by nano zinc oxide, the performance of each aspect is greatly reduced compared with that of example 1; in the comparative example 2, the anti-ultraviolet agent defined in the application is not added, compared with the example 1, except that the ultraviolet shielding rate is not good, the elongation at break, the bacteriostasis rate, the breaking strength and the friction times when the fabric is damaged are all reduced in different degrees, because the toughness of the whole fabric is not enhanced after the anti-ultraviolet agent is not added, and because of the lack of the toughness, the direct impact force between the fabric and the outside is increased when the fabric is rubbed, so that the fabric is damaged early, and the anti-friction performance is reduced; meanwhile, the nano titanium dioxide has an auxiliary antibacterial effect and can be tough, and after the ultraviolet resistant agent is not added, the antibacterial property and the toughness of the whole fabric are not enhanced, so that the strength is directly reduced, the elongation at break is reduced, and the antibacterial rate is reduced; meanwhile, the strength is reduced, the friction resistance is reduced and the elongation at break is reduced due to less spraying of the ultraviolet resistant agent layer.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.