CN111286980A - A kind of ultraviolet protective finishing agent, preparation method and application thereof - Google Patents

Abstract

The invention discloses an ultraviolet protective finishing agent. The finishing agent is, in parts by weight: gallic acid (3-9 parts), low-molecular polyvinyl alcohol (4-8 parts), 2-methacrylic acid (2- 6 parts), hydrogenated polydecene (2-5 parts), rutin (3-5 parts), catalyst (0.1-1 part), deionized water (70-90 parts). Also provided are a preparation method and application of a finishing agent. After the finishing agent of the present invention acts on the surface of the fabric, it can improve its ultraviolet absorption performance, so as to play a protective role; and the raw materials used and the production and application processes are free from harmful substances such as formaldehyde, and can also give the fabric excellent quality. It has antibacterial properties and is an environmentally friendly composite functional finishing agent.

Description

A kind of ultraviolet protective finishing agent, preparation method and application thereof

technical field

The invention relates to the technical field of textile processing, in particular to an ultraviolet-proof and bacteriostatic fabric finishing agent.

Background technique

UV protective finishing agents are often used finishing agents to improve the function of fabrics during textile processing. At present, the main principle of UV protection finishing is that the finished fabric can reflect ultraviolet rays. For example, some ceramic powders, metal oxides, etc. are used to treat the fabric to improve its ability to reflect ultraviolet rays. Second, the fabric is treated with protective finishing agents. These finishing agents Can absorb ultraviolet rays, making the fabric have the effect of anti-ultraviolet.

The existing finishing auxiliaries have a single function, or the anti-ultraviolet performance and antibacterial performance are low, the raw materials, the process are complex, and the safety problems. New finishing auxiliaries are urgently needed to improve the anti-ultraviolet and antibacterial properties of the finished fabrics. performance.

SUMMARY OF THE INVENTION

The present invention provides an ultraviolet protective finishing agent, which can solve the above-mentioned defects in the prior art.

The technical scheme of the present invention is as follows:

An ultraviolet protective finishing agent, the finishing agent is, in parts by weight: gallic acid (3-9 parts), low molecular polyvinyl alcohol (4-8 parts), 2-methacrylic acid (2-6 parts), Hydrogenated polydecene (homopolymer of hydrogenated-1-decene) (2-5 parts), rutin (3-5 parts), catalyst (0.1-1 part), deionized water (70-90 parts).

Preferably, the molar ratio of gallic acid: hydrogenated polydecene: rutin is 1-5:1-5:1-5, and the obtained finishing agent has high ultraviolet protection and antibacterial properties.

Preferably, the molar ratio of gallic acid:hydrogenated polydecene:rutin is 3:5:5.

Preferably, the catalyst is selected from at least one of ammonium persulfate and dibenzoyl peroxide.

The present invention also provides a preparation method of an ultraviolet protective finishing agent, which includes the steps of: (1) adding low molecular weight polyvinyl alcohol, gallic acid, deionized water, and a catalyst into a reaction vessel, and stirring thoroughly; (2) adding 2-methyl Acrylic acid, heat up and stir the reaction; (3) add a mixture of hydrogenated polydecene and deionized water, add rutin after at least 1 hour of reaction, and then stir for 2 hours; (4) after the reaction is completed, the temperature of the reaction solution is rapidly lowered in a cold water bath When the temperature is below 20°C, the finishing agent is obtained by adjusting the pH value between 6-8.

In the first step, gallic acid, low molecular weight polyvinyl alcohol, and 2-methacrylic acid are polymerized to obtain an intermediate product with better antibacterial effect. The phenolic hydroxyl structure in the product significantly improves the antibacterial performance, and hydrophilic groups such as hydroxyl group It also improves the hydrophilicity of the product, which is beneficial to the water solubility of the final synthetic product and improves the utilization efficiency. The second step is to add hydrogenated polydecene, and then use rutin with a slightly smaller molecular weight to participate in the synthesis, because the double bond of the olefin makes the molecular chain longer and reduces the steric hindrance between the benzene ring and the molecular branch. The structure greatly improves the ultraviolet protection performance of the synthesized product, and obtains a higher yield and better anti-ultraviolet and bacteriostatic effects.

Preferably, in step (1), the reaction temperature is 50-70°C, and the reaction time is 0.5-2h; in step (2), the temperature is raised to 80-90°C for 3-5h; in step (3), after adding rutin The reaction was stirred for 1-3h. If the temperature is too high or the reaction time is too long, the molecular weight of the polymer product is too large, and the binding fastness of the obtained finishing agent product to the fabric decreases; if the temperature is too low or the reaction time is too short, the molecular weight of the polymer product is too small, and the resulting finishing The UV protection and antibacterial properties of the antibacterial products cannot be obtained as expected.

Preferably, the molar ratio of gallic acid: hydrogenated polydecene: rutin is 1-5:1-5:1-5.

An application of the above-mentioned UV protective finishing agent, the finishing agent is finished on the surface of the fabric by the dipping method or the padding method.

Preferably, the dosage of the finishing agent in the dipping method is 5mL/L-30mL/L, the finished fabric can obtain high UV protection performance and antibacterial performance, and the dosage of the finishing agent can be reduced.

The fabrics mentioned above are those made of cotton, hemp, silk, wool or regenerated fibers.

Compared with the prior art, the beneficial effects of the present invention are as follows:

The invention uses environment-friendly gallic acid, rutin and hydrogenated polydecene as the raw materials of the finishing agent, and has excellent ultraviolet protection performance and antibacterial performance; The acid contains a benzene ring and a hydroxyl structure, which can not only improve the hydrophilicity of the finishing agent, but also give the finishing agent certain UV protection performance and bacteriostatic performance; the increase of rutin is mainly because the molecular size of rutin is moderate and has more The benzene ring structure and phenolic hydroxyl structure have a better strengthening effect on the anti-ultraviolet performance and antibacterial performance of the finishing agent; 2-methacrylic acid is mainly used as a bridging agent to improve the effect of combining the reactions of various raw materials, and the by-products generated by rutin The product also has a certain anti-ultraviolet effect; the addition of hydrogenated polydecene can improve the ultraviolet protection performance and durability of the finishing agent.

In the preparation method of the present invention, in the first step, gallic acid, low-molecular-weight polyvinyl alcohol and 2-methacrylic acid are polymerized to obtain an intermediate product with better antibacterial effect, the phenolic hydroxyl structure in the product makes the antibacterial performance significantly improved, and the hydroxyl group and other hydrophilic groups also improve the hydrophilicity of the product, which is beneficial to the water solubility of the final synthetic product and improves the utilization efficiency; the second step is to add hydrogenated polydecene, and then use rutin with a slightly smaller molecular weight to participate in the synthesis, because the olefin di The bond makes the molecular chain longer and reduces the steric hindrance between the benzene ring and the molecular branch. The benzene ring structure on the molecule greatly improves the UV protection performance of the synthesized product, and obtains a higher yield and better UV protection. Bacteriostatic effect.

Of course, it is not necessary for any product embodying the present invention to achieve all of the above-described advantages simultaneously.

Detailed ways

The invention provides an ultraviolet protective finishing agent, which in parts by weight is: gallic acid (3-9 parts), low molecular polyvinyl alcohol (4-8 parts), 2-methacrylic acid (2- 6 parts), hydrogenated polydecene (homopolymer of hydrogenated-1-decene) (2-5 parts), rutin (3-5 parts), catalyst (0.1-1 part), deionized water (70- 90 servings). The catalyst may be at least one of ammonium persulfate and dibenzoyl peroxide.

Low-molecular-weight polyvinyl alcohol is used as the main chain of the finishing agent molecule, and the small molecule gallic acid can endow the finishing agent with certain UV protection and antibacterial properties. Rutin can better enhance the UV protection and bacteriostatic properties of the finishing agent. 2-methacrylic acid is mainly used as a bridging agent to improve the effect of combining the reactions of various raw materials, and the by-products generated with rutin also have a certain anti-ultraviolet effect. Hydrogenated polydecene can improve the UV protection performance and durability of the finishing agent. , ammonium persulfate is the reaction catalyst.

The UV protection principle of the present invention is mainly that after the finishing agent acts on the surface of the fabric, it can improve its UV absorption performance, thereby playing a protective role. However, the anti-ultraviolet effect of the finishing agent of the present invention is not only better than that of the same kind of anti-ultraviolet finishing agents, but also the raw materials used and the production and application processes are free from harmful substances such as formaldehyde, and can also endow the fabric with excellent antibacterial properties. An environmentally friendly composite functional finishing agent.

As used herein, a range represented by "one value to another value" is a general representation that avoids listing all the values in the range in the specification. Therefore, the recitation of a specific numerical range includes any numerical value within the numerical range and a smaller numerical range defined by any numerical value within the numerical range, as if the arbitrary numerical value and the smaller numerical value were expressly written in the specification. same range.

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention, but not to limit the protection scope of the present invention. Improvements and adjustments made by those skilled in the art according to the present invention in practical applications still belong to the protection scope of the present invention.

Example 1

Add low-molecular-weight polyvinyl alcohol (4 parts), gallic acid (3 parts), deionized water (30 parts), and ammonium persulfate (0.2 parts) into the reaction kettle, stir well, heat up to 60°C, and stir for 1 h; 2-methacrylic acid (2 parts) was added dropwise, the dripping was completed within 30 min, then the temperature was raised to 85°C, and the reaction was stirred for 4 h; hydrogenated polydecene (2 parts) and deionized water (4 parts) were added, and the reaction was added after 1 h. Rutin (3 parts), and then stirred and reacted for 2 hours; after the reaction, the temperature of the reaction system was rapidly lowered to 20° C. with a cold water bath, and the pH value was adjusted to between 6-8 by adding sodium hydroxide solution to obtain a finishing agent.

Example 2

Pure cotton material (121.9 g/m ² ), the finishing agent of Example 1 was finished to pure cotton material by dipping method, and UPF value and antibacterial performance were tested.

The impregnation process is as follows:

Mix the finishing agent and water and stir evenly to prepare a finishing solution. The ratio of water to fabric is 50:1. After adding the fabric, finish at 60-90°C for 30-60 minutes, take out the fabric, and dry it to obtain the finished fabric.

Table 1 Effects of different dosages of finishing agents on UPF and antibacterial properties

It can be seen from Table 1 that the UPF value of pure cotton fabrics without finishing agents is very low and has no antibacterial properties. With the increase of the amount of finishing agent, the UPF value gradually increases. When the dosage is greater than 15mL/L, the UPF value is greater than 50, and the anti-ultraviolet performance is excellent. Therefore, the use of the finishing agent in the range of 2-15mL/L can make the cotton fabric obtain high anti-ultraviolet performance and antibacterial performance.

Example 3

Pure cotton (121.9 g/m ² ), the finishing agent of Example 1 was finished on the surface of pure cotton by padding method, and the UPF value and antibacterial performance were tested.

The padding method is as follows:

The finishing agent is added to the mangle tank, after adding water, the fabric enters the mangle tank, padding temperature: 25 ℃, nip rate: 90%-150%, after two dipping and two rolling, pre-bake at 100 ℃ for 2min, and then in Dry at 160°C for 4 min to obtain the finished fabric.

Table 2 Effects of different dosages of finishing agents on UPF and antibacterial properties

It can be seen from Table 2 that the UPF value of pure cotton fabrics is very low when no finishing agent is used, and there is no antibacterial property. With the increase of the amount of finishing agent, the UPF value gradually increases. When the amount of finishing agent is greater than 50mL/L, the UPF value is greater than 50, and the anti-ultraviolet performance is excellent. . Therefore, the dosage of the finishing agent is in the range of 20-80mL/L, which can enable the cotton fabric to obtain high anti-ultraviolet performance and antibacterial properties, and the dosage of the finishing agent does not need to be too much.

Example 4

Group A: Add low molecular weight polyvinyl alcohol (6 parts), gallic acid (3 parts), deionized water (30 parts), and ammonium persulfate (0.3 parts) into the reaction kettle, stir well, heat up to 60°C, and stir to react 1h; 2-methacrylic acid (3 parts) was added dropwise, the dripping was completed within 30min, then the temperature was raised to 85°C, and the reaction was stirred for 4h; hydrogenated polydecene (3 parts) and deionized water (40 parts) were added within 10min. After the reaction for 1 h, rutin (3 parts) was added, and the reaction was stirred for another 2 h. After the reaction was completed, the temperature of the reaction solution was rapidly lowered to 20°C in a cold water bath, and sodium hydroxide solution was added to adjust the pH between 6-8. Get a finisher. In this group, gallic acid: hydrogenated polydecene: rutin (molar ratio) = 1:1:1.

Group B: the preparation process of the finishing agent of this group is the same as that of the finishing agent of group A, the difference is that gallic acid: hydrogenated polydecene: rutin (molar ratio)=2:1:1.

Group C: The preparation process of the finishing agent of this group is the same as that of the finishing agent of Group A, the difference is that gallic acid: hydrogenated polydecene: rutin (molar ratio)=3:1:1.

Group D: the preparation process of the finishing agent of this group is the same as that of the finishing agent of group A, the difference is that gallic acid: hydrogenated polydecene: rutin (molar ratio) = 3:5:5.

Pure cotton (121.9g/m ² ), the above-mentioned finishing agents of Group A, Group B, Group C, and Group D were finished to the surface of pure cotton by the same dipping process as in Example 2, and the UPF value and antibacterial value were tested. performance, and the amount of finishing agent is 8mL/L.

Table 3 Effects of different raw material ratios on the performance of finishing agents

It can be seen from Table 3 that in groups A, B and C, when the amount of gallic acid is large, the amount of hydrogenated polydecene and rutin remains unchanged, and the antibacterial performance of the finishing agent is little improved at this time, and the UPF value Not much to improve. However, in group D, after increasing the dosage and ratio of hydrogenated polydecene and rutin, the UPF value and bacteriostatic properties were significantly improved. It shows that the interaction between gallic acid, hydrogenated polydecene and rutin can significantly affect the UV protection and antibacterial properties of finishing products. When gallic acid: hydrogenated polydecene: rutin (molar ratio) = 3: 5: 5, the finishing agent product can obtain excellent anti-ultraviolet performance and also have significant antibacterial performance.

Example 5:

After treating the pure cotton (121.9 g/m ² ) with the finishing agent prepared in Example 1 through the same dipping process as in Example 2, the treated pure cotton was shaken in a water bath at a bath ratio of 50:1 and a temperature of 60°C. Washing in the pot for 30min is 1 time, and the anti-ultraviolet effect and antibacterial effect of the fabric after different times of washing are tested.

Table 4 Anti-ultraviolet effect and antibacterial effect of fabrics after different times of washing

It can be seen from Table 4 that the pure cotton treated in this example still has excellent anti-ultraviolet and antibacterial effects after 50 times of washing, indicating that its durability is good.

Comparative Example 1:

This comparative example provides a finishing agent, which is similar to the finishing agent of Example 1, except that no hydrogenated polydecene is added during synthesis. The finishing agent synthesized in this comparative example was finished to pure cotton (121.9 g/m ² ) by the impregnation method of Example 2, and the UPF value and antibacterial performance were tested.

Table 5 Effects of finishing agents on UPF value and antibacterial properties

As can be seen from Table 5, compared with the effect of the finishing agent in Example 2, the finishing agent of this comparative example adopts the same process, and the UPF value is obviously lower than that of the product with hydrogenated polydecene added, but the effect of the antibacterial performance is not large, indicating that the hydrogenation The addition of polydecene can significantly improve the anti-ultraviolet performance of the finishing product, and has little effect on the antibacterial performance.

Comparative Example 2:

This comparative example provides a finishing agent, which is similar to the finishing agent of Example 1, except that no hydrogenated polydecene and rutin are added during synthesis. The finishing agent synthesized in this comparative example was finished to pure cotton (121.9 g/m ² ) by the impregnation method of Example 2, and the UPF value and antibacterial performance were tested.

Table 6 Effects of finishing agents on UPF value and antibacterial properties

It can be seen from Table 6 that compared with Example 2, the UPF value is significantly lower than the UPF value of the finishing agent of Example 2, and the antibacterial performance is also greatly reduced, which shows that the addition of rutin and hydrogenated polydecene can prevent the finishing agent product. The improvement of UV performance and antibacterial performance has a significant impact. Compared with Comparative Example 1, after adding rutin, the UPF value and antibacterial performance were improved, indicating that the addition of rutin can enhance the anti-ultraviolet performance and antibacterial performance of the product.

Comparative Example 3:

This comparative example provides a finishing agent, which is similar to the finishing agent of Example 1, except that no hydrogenated polydecene, rutin and gallic acid are added during synthesis. The finishing agent synthesized in this comparative example was finished to pure cotton (121.9 g/m ² ) by the impregnation method of Example 2, and the UPF value and antibacterial performance were tested.

Table 7 Effects of finishing agents on UPF value and antibacterial properties

As can be seen from Table 7, the addition of hydrogenated polydecene, rutin and gallic acid was not used during the synthesis, and the UPF value of the obtained finishing agent changed little after use, and basically had no UV protection effect and did not have bacteriostatic properties. Compared with Comparative Example 2, it shows that gallic acid has anti-ultraviolet and antibacterial effects, but the effect is limited. Compared with the comparative example 1, it shows that the product of the polymerization of gallic acid and rutin in the comparative example 1 has certain anti-ultraviolet and antibacterial effects. Compared with Example 2, it shows that the polymerized product of hydrogenated polydecene, rutin and gallic acid can significantly improve the anti-ultraviolet performance and antibacterial performance.

Comparative Example 4:

The commercially available finishing functional agent was finished to pure cotton (121.9 g/m ² ) by the impregnation method of Example 2, and the UPF value and antibacterial performance were tested.

Table 8 Effects of finishing agents on UPF value and antibacterial properties

It can be seen from Table 8 that the UPF value of cotton fabrics treated with commercially available anti-ultraviolet finishing agents can generally reach more than 40, and there is no bacteriostatic effect. Commercially available antibacterial agents have no anti-ultraviolet performance, have little effect on the UPF value, have a bacteriostatic performance greater than 90%, and have a single function.

testing method:

Antibacterial property (bacteriostatic rate): GB 20944.3-2008-T "Evaluation of Antibacterial Properties of Textiles Part 3: Oscillation Method" test.

UV protection UPF value of textiles: Determined according to GB/T 18830-2009 "Evaluation of UV Protection Properties of Textiles".

The above disclosures are merely preferred embodiments of the present invention. The preferred embodiments do not exhaust all the details, nor do they limit the invention to only the described embodiments. Obviously, many modifications and variations are possible in light of the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can make good use of the present invention. The present invention is to be limited only by the claims and their full scope and equivalents.

Under the teaching of the present invention and the above-mentioned embodiments, those skilled in the art can easily foresee that each raw material or its equivalent replacement, each processing method or its equivalent replacement listed or exemplified in the present invention can realize the present invention, As well as the upper and lower limit values and interval values of parameters of each raw material and processing method, the present invention can be realized, and the embodiments are not listed one by one here.

Claims (10)

1. a UV protective finishing agent, is characterized in that, described finishing agent is in parts by weight: gallic acid (3-9 parts), low molecular polyvinyl alcohol (4-8 parts), 2-methacrylic acid ( 2-6 parts), hydrogenated polydecene (2-5 parts), rutin (3-5 parts), catalyst (0.1-1 part), deionized water (70-90 parts). 2 . The ultraviolet protective finishing agent according to claim 1 , wherein the molar ratio of gallic acid: hydrogenated polydecene: rutin is 1-5: 1-5: 1-5. 3 . 3 . The UV protective finishing agent according to claim 1 , wherein the catalyst is selected from at least one of ammonium persulfate and dibenzoyl peroxide. 4 . 4 . The UV protective finishing agent according to claim 1 , wherein the molar ratio of gallic acid: hydrogenated polydecene: rutin is 3:5:5. 5 . 5. a preparation method of a UV protective finishing agent, is characterized in that, comprises steps: (1) low molecular polyvinyl alcohol, gallic acid, deionized water, catalyst are added in reaction vessel, fully stirred; (2) add 2-methyl alcohol base acrylic acid, heat up and stir the reaction; (3) add a mixture of hydrogenated polydecene and deionized water, and add rutin after at least 1 hour of reaction; (4) after the reaction is completed, the temperature of the reaction solution is quickly lowered to below 20°C in a cold water bath , and adjust the pH value between 6-8 to get the finishing agent. 6. The preparation method of ultraviolet protective finishing agent according to claim 5, is characterized in that, in step (1), reaction temperature is 50-70 ℃, and reaction time is 0.5-2h; The reaction is carried out at 90° C. for 3-5 hours; in step (3), the rutin is added and the reaction is stirred for 1-3 hours. 7 . The preparation method of an ultraviolet protective finishing agent according to claim 5 , wherein the molar ratio of gallic acid: hydrogenated polydecene: rutin is 1-5: 1-5: 1-5. 8 . 8. an application of the ultraviolet protective finishing agent as described in any one of claims 1-4 or the finishing agent prepared by the method described in any one of claims 5-7, wherein the finishing agent adopts dipping method or Padding to the surface of the fabric. 9 . The application of the UV protective finishing agent according to claim 8 , wherein, in the dipping process, the consumption of the finishing agent is 5mL/L-30mL/L. 10 . 10. The application of the ultraviolet protective finishing agent according to claim 8 or 9, wherein the fabric is a fabric made of cotton, hemp, real silk, wool or regenerated fibers.