Textile dye fixing agent and method of making same

Abstract

The application belongs to the field of pure cotton textile fixing, and particularly relates to a textile dye fixing agent and a preparation method thereof. The fixing agent comprises the following raw materials: 22-30 parts of nano polydimethyl diallyl ammonium chloride, 0.3-0.8 parts of acetic acid, 2-6 parts of ammonium sulfate, 0.2-1 parts of sodium chloride, 0.03-0.07 parts of methylene bis naphthalene sulfonic acid sodium and 5-15 parts of water. The preparation method is as follows: the nano polydimethyl diallyl ammonium chloride, the acetic acid, the ammonium sulfate, the sodium chloride, the methylene bis naphthalene sulfonic acid sodium and modified silicon dioxide are sequentially added in water, mixed and stirred for 2-4 hours, uniformly dissolved, filtered and discharged, the pH is controlled to be 7.5-8, and the textile dye fixing agent is obtained. The fixing agent provided by the application can improve the fixing ability of the dye under high temperature and also has antibacterial effect on the textile.

Description

Technical Field

[0001] This invention belongs to the field of color fixing of pure cotton textiles, specifically relating to a textile dye fixing agent and its preparation method. Background Technology

[0002] With economic growth and technological development, people have increasingly higher requirements for clothing. They not only want it to be aesthetically pleasing, but also safe and durable. They also need to choose safe color-fixing agents to make the clothes suitable for various scenarios such as washing machines, dryers, and special weather conditions. Dimethyl diallyl ammonium chloride is a highly water-soluble quaternary ammonium salt containing two unsaturated bonds. Its homopolymer, polydimethyl diallyl ammonium chloride, is a resin-type color-fixing agent. The cationic groups in the polymer can form lakes by ionic bonding with the anionic groups of dyes, thereby improving the binding force between dyes and color-fixing agents. In addition, its high efficiency and non-toxicity have made it a key area of ​​development both domestically and internationally in recent years.

[0003] Chinese invention patent application number 201110370967.5 discloses a micro-crosslinked polydimethyldiallylammonium chloride modified fixing agent and its synthesis method. In view of the shortcomings or weaknesses of the current PDMDAAC fixing agent, the crosslinking monomer triallylmethylammonium chloride is copolymerized with the monomer dimethyldiallylammonium chloride. By controlling the structural characteristics and relative molecular mass of the product, a micro-crosslinked copolymer modified PDMDAAC fixing agent with controlled relative molecular mass and structure and its synthesis method are obtained.

[0004] Chinese invention patent application number 20231139152 discloses a color-fixing agent for blended fabrics and its preparation method, as well as a dyeing and color-fixing method for blended fabrics. By adopting the mature DMDAAC route, it introduces siloxanes, acrylates or methacrylates containing unsaturated bonds to improve the hand feel of the fabric, thereby increasing the fabric's softness and improving its color fastness.

[0005] However, the color-fixing agents in the aforementioned patents can only enhance the color-fixing effect under normal conditions. The effect is not obvious under conditions such as washing machine friction, high-temperature drying, and extreme weather. At the same time, bacteria and other microorganisms are also very easy to grow in humid environments. Therefore, for underwear, the need for antibacterial properties and the need for color-fixing of dyes still exist. Otherwise, long-term use may pose health risks.

[0006] Therefore, the urgent technical problem to be solved is how to improve the color-fixing ability of dyes at higher temperatures and the antibacterial ability of clothing. Summary of the Invention

[0007] In view of the shortcomings of the prior art, the purpose of this invention is to provide a textile dye fixing agent and its preparation method, which improves the dye fixing ability and antibacterial properties.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] This application provides a textile dye fixing agent, which, by weight, comprises the following raw materials: 22-30 parts of nano-polydimethyldiallylammonium chloride, 0.3-0.8 parts of acetic acid, 2-6 parts of ammonium sulfate, 0.2-1 parts of sodium chloride, 0.03-0.07 parts of sodium methylene bis(naphthalene)sulfonate, and 5-15 parts of water.

[0010] Fixing agents are effective in improving the dye fastness of textiles and are favored by many because of their simple process and wide applicability. However, as the application scenarios for clothing are constantly changing, washing machines and dryers may expose clothes to high temperatures and friction, which can affect the fastness of the dye. This application uses nano-polydimethyldiallyl ammonium chloride as the main component of the dye fixing agent, which not only improves the adsorption of the fixing agent on the dye, but also enhances the antibacterial effect. It is speculated that the reason is that polydimethyldiallyl ammonium chloride itself can adsorb a small number of negatively charged bacteria by relying on positive charge. However, under conditions such as high temperature, its adsorption on the dye surface is not strong enough. Therefore, its antibacterial and color-fixing effects cannot reach the ideal effect. The nano-polydimethyldiallyl ammonium chloride synthesized by the applicant through micellar copolymerization has a nanostructure and has a higher specific surface area and a higher positive charge density than ordinary polydimethyldiallyl ammonium chloride. It is sufficient to maintain a strong adsorption under high temperature and friction conditions, significantly improving the color-fixing effect. At the same time, the adsorption of negatively charged microorganisms is also improved compared with the use of commercially available polydimethyldiallyl ammonium chloride, further improving the antibacterial effect under high temperature conditions, making the textiles more widely used.

[0011] In some embodiments, the textile dye fixing agent further includes 0.8-1.2 parts by weight of modified silica.

[0012] Silica can bring beneficial effects such as whitening, antibacterial and waterproofing in textile printing and dyeing, and has a wide range of application prospects. In the past, silica was usually added directly to the sizing agent to change the properties of textiles. The applicant found that adding modified silica to the fixing agent can also produce good results, which can improve the thermal stability of textile dyeing agents and thus improve the fixing effect at high temperature.

[0013] In some embodiments, the preparation method of the nano-polydimethyldiallylammonium chloride is as follows:

[0014] I. Place the dimethylamine ethanol solution in a reaction vessel, slowly add allyl chloride dropwise, and after 20-30 min, add sodium hydroxide. Reflux the reaction for 4-8 h, centrifuge and filter to obtain dimethyl diallyl ammonium chloride filtrate.

[0015] II. The dimethyl diallyl ammonium chloride filtrate obtained in step I is pre-emulsified under stirring at 600-750 r / min. After 15-20 min, the temperature is raised to 70-80℃ and maintained. Then, the initiator APPH is added to the reaction system, the heating is stopped, and the reaction is stirred at 250-300 r / min for 1.5-2.5 h under inert gas protection to obtain nano-polydimethyl diallyl ammonium chloride.

[0016] In some embodiments, the molar ratio of dimethylamine to allyl chloride in the dimethylamine ethanol solution is 1:(1.1-1.3).

[0017] The applicant improved the yield of dimethyl diallyl ammonium chloride during the preparation process by adjusting the ratio of dimethylamine and allyl chloride, thereby saving the overall cost of raw materials for textile dye fixing agents.

[0018] In some embodiments, the method for preparing the modified silica is as follows:

[0019] S1. Add silane coupling agent KH550 and silica to anhydrous ethanol, stir, and react at 40-50℃ for 5-6 hours. After the reaction is completed, centrifuge, wash, and dry to obtain amino-modified silica.

[0020] S2. Add allyl succinic anhydride and a condensing agent to N,N-dimethylformamide, stir at room temperature for 70-100 min, then add a catalytic activator and the amino-modified silica obtained in step S1, react at room temperature for 25-26 h, centrifuge, wash 2-3 times, and dry to obtain the modified silica.

[0021] The applicant modified silica and added it to textile fixatives. While achieving the whitening, antibacterial, and waterproof effects of silica itself, the modified silica also formed hydrogen bonds with textile fibers, making the fixative more tightly bonded to the fabric and improving wet rubbing fastness, thus significantly improving the fixation effect of the textile. On the other hand, the applicant also unexpectedly discovered that the fixation time of the fixative was extended. It is speculated that the possible reason is that the modified silica structure contains double bonds with strong reducing properties, which can be preferentially oxidized, thereby preventing the fixative from being oxidized, extending the fixation time, and improving the fastness of the fixative.

[0022] In some embodiments, the mass ratio of the silane coupling agent KH550 to silicon dioxide is 1:(20-30).

[0023] Preferably, the mass ratio of silane coupling agent KH550 to silica is 1:25.

[0024] In some embodiments, the mass ratio of the allyl succinic anhydride to the condensing agent is 1:(1-4).

[0025] In some embodiments, the condensing agent is dicyclohexylcarbodiimide.

[0026] In some embodiments, the catalytic activator is 4-pyrrolidinylpyridine.

[0027] Another aspect of this application provides a method for preparing a textile dye fixing agent, the specific steps of which are as follows: nano-polydimethyldiallylammonium chloride, acetic acid, ammonium sulfate, sodium chloride, sodium methylene bis(naphthalene)sulfonate and modified silica are added sequentially to water, mixed and stirred for 2-4 hours, uniformly dissolved, filtered and discharged, and the pH is controlled at 7.5-8 to obtain the textile dye fixing agent.

[0028] The preparation method is simple to operate, the process is easy to control, the loss is small, and the raw material cost is saved.

[0029] Beneficial effects:

[0030] 1. The color-fixing agent of the present invention enables the dye to maintain good color-fixing ability at high temperatures, further enhancing the antibacterial effect of textiles in special environments;

[0031] 2. The nano-polydimethyldiallylammonium chloride of the present invention has a huge specific surface area and charge characteristics, which can significantly enhance the adsorption effect, making the fixing agent more tightly adsorbed on the fiber and improving the adsorption strength. At the same time, since the key to the antibacterial effect of cationic polymers lies in the effective adsorption of negatively charged microorganisms, the enhancement of adsorption can also significantly improve the antibacterial effect.

[0032] 3. The modified silica of this invention possesses excellent tensile mechanical properties and thermal stability, which can prevent the dye from becoming unstable during washing and drying due to stretching or excessive temperature. Simultaneously, the carboxyl groups can form hydrogen bonds with the hydroxyl groups in cotton fibers, and the acetic acid in the system can also catalyze esterification to a certain extent, further strengthening the bond between the fixing agent and the fabric, improving wet rubbing fastness. Furthermore, the highly reducing double bonds in the modified silica can be preferentially oxidized, thus preventing the fixing agent from being oxidized, extending the fixing time, and improving the fastness of the fixing agent. Detailed Implementation

[0033] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0034] A textile dye fixing agent was prepared according to the proportions of the components specified in the following examples. The components of the textile dye fixing agent were prepared by mixing according to the methods described in the examples and comparative examples. The polydimethyldiallyl ammonium chloride was purchased from Wuhan Jixin Yibang Biotechnology Co., Ltd.

[0035] Preparation Example 1

[0036] Nano-sized polydimethyldiallylammonium chloride A was prepared according to the following method:

[0037] I. Place 50 ml of dimethylamine ethanol solution (30 wt%) in a reaction vessel, slowly add 110 ml of allyl chloride, and after 25 min, add 42 g of sodium hydroxide. Reflux at 70 °C for 6 h, centrifuge and filter to obtain dimethyl diallyl ammonium chloride filtrate.

[0038] II. The dimethyl diallyl ammonium chloride filtrate obtained in step I was pre-emulsified under stirring at 650 r / min. After 15 min, the temperature was raised to 75 °C and maintained. Then, 0.75 g of initiator APPH was added to the reaction system, heating was stopped, and the reaction was stirred at 250 r / min for 2 h under nitrogen protection to obtain nano-polydimethyl diallyl ammonium chloride A.

[0039] Preparation Example 2

[0040] Nano-sized polydimethyldiallylammonium chloride B was prepared according to the following method:

[0041] I. Place 50 ml of dimethylamine ethanol solution (30 wt%) in a reaction vessel, slowly add 200 ml of allyl chloride, and after 25 min, add 42 g of sodium hydroxide. Reflux at 70 °C for 6 h, centrifuge and filter to obtain dimethyl diallyl ammonium chloride filtrate.

[0042] II. The dimethyl diallyl ammonium chloride filtrate obtained in step I was pre-emulsified under stirring at 650 r / min. After 15 min, the temperature was raised to 75 °C and maintained. Then, 0.75 g of initiator APPH was added to the reaction system, heating was stopped, and the reaction was stirred at 250 r / min for 2 h under nitrogen protection to obtain nano-polydimethyl diallyl ammonium chloride B.

[0043] Preparation Example 3

[0044] Modified silica A is prepared according to the following method:

[0045] S1. Add 0.2g of silane coupling agent KH550 and 5g of silica to anhydrous ethanol, stir, and react at 45℃ for 5h. After the reaction is completed, centrifuge, wash, and dry to obtain amino-modified silica.

[0046] S2. Add 15 ml of allyl succinic anhydride and 20 g of dicyclohexylcarbodiimide to N,N-dimethylformamide, stir at 24 °C for 80 min, then add 0.3 g of 4-pyrrolidinylpyridine and 4 g of amino-modified silica prepared in step S1, react at room temperature for 24 h, centrifuge, wash twice, and dry to obtain modified silica A.

[0047] Preparation Example 4

[0048] Modified silica B is prepared according to the following method:

[0049] S1. Add 0.2g of silane coupling agent KH550 and 2.5g of silica to anhydrous ethanol, stir, and react at 45℃ for 5h. After the reaction is completed, centrifuge, wash, and dry to obtain amino-modified silica.

[0050] S2. Add 15 ml of allyl succinic anhydride and 20 g of dicyclohexylcarbodiimide to N,N-dimethylformamide, stir at 24 °C for 80 min, then add 0.3 g of 4-pyrrolidinylpyridine and 4 g of amino-modified silica prepared in step S1, react at room temperature for 24 h, centrifuge, wash twice, and dry to obtain modified silica B.

[0051] Example 1

[0052] This embodiment provides a textile dye fixing agent, comprising the following raw materials: 25 parts of nano-polydimethyldiallylammonium chloride A, 0.5 parts of acetic acid, 4 parts of ammonium sulfate, 0.8 parts of sodium chloride, 0.05 parts of sodium methylene bis(naphthalene)sulfonate, 1 part of modified silica A, and 10 parts of water.

[0053] The preparation method of the textile dye fixing agent in this embodiment is as follows: Nano-polydimethyldiallylammonium chloride A, acetic acid, ammonium sulfate, sodium chloride, sodium methylene bisnaphthalene sulfonate and modified silica A are added sequentially to water, mixed and stirred for 3 hours, uniformly dissolved, filtered and discharged, and the pH is controlled at 7.8 to obtain the textile dye fixing agent.

[0054] Example 2

[0055] This embodiment provides a textile dye fixing agent, comprising the following raw materials: 22 parts of nano-polydimethyldiallylammonium chloride A, 0.3 parts of acetic acid, 2 parts of ammonium sulfate, 0.2 parts of sodium chloride, 0.03 parts of sodium methylene bis(naphthalene)sulfonate, 0.8 parts of modified silica A, and 5 parts of water.

[0056] The preparation method of the textile dye fixing agent in this embodiment is as follows: Nano-polydimethyldiallylammonium chloride A, acetic acid, ammonium sulfate, sodium chloride, sodium methylene bis(naphthalene)sulfonate and modified silica A are added sequentially to water, mixed and stirred for 2 hours, uniformly dissolved, filtered and discharged, and the pH is controlled at 7.5 to obtain the textile dye fixing agent.

[0057] Example 3

[0058] This embodiment provides a textile dye fixing agent, comprising the following raw materials: 30 parts of nano-polydimethyldiallylammonium chloride A, 0.8 parts of acetic acid, 6 parts of ammonium sulfate, 1 part of sodium chloride, 0.07 parts of sodium methylene bis(naphthalene)sulfonate and modified silica A, and 15 parts of water.

[0059] The preparation method of the textile dye fixing agent in this embodiment is as follows: Nano-polydimethyldiallylammonium chloride A, acetic acid, ammonium sulfate, sodium chloride, sodium methylene bis(naphthalene)sulfonate and modified silica A are added sequentially to water, mixed and stirred for 4 hours, uniformly dissolved, filtered and discharged, and the pH is controlled at 8 to obtain the textile dye fixing agent.

[0060] Example 4

[0061] A textile dye fixing agent and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that modified silica A is replaced by an equal amount of modified silica B.

[0062] Example 5

[0063] A textile dye fixing agent and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that nano-polydimethyldiallylammonium chloride A is replaced by an equal amount of nano-polydimethyldiallylammonium chloride B.

[0064] Example 6

[0065] A textile dye fixing agent and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that the raw materials do not include modified silica A.

[0066] Comparative Example 1

[0067] A textile dye fixing agent and its preparation method are disclosed. The specific implementation method is the same as that in Example 1, except that nano-polydimethyldiallyl ammonium chloride A is replaced by an equal amount of polydimethyldiallyl ammonium chloride.

[0068] Performance testing:

[0069] (1) Wet rubbing fastness at 180℃: The test shall be conducted in accordance with the wet rubbing test method in GB / T 42223-2022, using the gray scale for evaluating staining, with 1 being the worst and 5 being the best.

[0070] (2) Antibacterial performance evaluation: Escherichia coli and Staphylococcus aureus were selected according to GB / T20944.1-2007 and tested using the agar plate diffusion method. The specific calculation formula is as follows:

[0071] Antibacterial rate % = (BA) / B × 100%,

[0072] B = viable bacterial concentration of the control sample after 24 hours

[0073] A = the concentration of viable bacteria in the antibacterial product after 24 hours.

[0074] The textile dye fixing agents prepared in each embodiment and comparative example were tested according to the above method, and the test results are shown in Table 1.

[0075] Table 1 Performance Test Results

[0076] Example 1 5 99.7％ 99.6％ Example 2 4.5 99.4％ 99.3％ Example 3 4.5 99.3％ 99.4％ Example 4 4.5 99.7％ 99.5％ Example 5 4 98.6％ 98.5％ Example 6 3.5 99.6％ 99.5％ Comparative Example 1 3.5 93.5％ 93.9％

[0077] As can be seen from the table above, the textile dye fixing agents provided in Examples 1-3 of the present invention have strong fixing ability, which significantly enhances the wet rubbing fastness of the dye at high temperature and improves the antibacterial effect of the textile.

[0078] In Example 4, modified silica B was used instead of modified silica A, which resulted in a slight decrease in the wet rubbing fastness and antibacterial effect of the textile at high temperature.

[0079] In Example 5, nano-polydimethyldiallylammonium chloride B was used instead of nano-polydimethyldiallylammonium chloride A. It was found that the antibacterial performance decreased slightly, and the wet friction fastness under high temperature conditions was weakened to some extent.

[0080] In Example 6, no silica was added, and it was found that the wet rubbing fastness of the textile at high temperature decreased significantly, indicating that the modified silica of the present invention has a significant effect on improving fastness.

[0081] Comparative Example 1 used commercially available polydimethyldiallyl ammonium chloride, which significantly reduced the antibacterial properties of the textile and also resulted in poor wet rubbing fastness at high temperatures. The nano-modified polydimethyldiallyl ammonium chloride showed significantly better antibacterial effects.

[0082] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A textile dye fixing agent, characterized in that, The color-fixing agent comprises, by weight, the following raw materials: 22-30 parts of nano-polydimethyldiallylammonium chloride, 0.3-0.8 parts of acetic acid, 2-6 parts of ammonium sulfate, 0.2-1 parts of sodium chloride, 0.03-0.07 parts of sodium methylene bis(naphthalene)sulfonate and 5-15 parts of water.

2. The textile dye fixing agent as described in claim 1, characterized in that, The textile dye fixing agent also includes 0.8-1.2 parts by weight of modified silica.

3. A textile dye fixing agent as described in claim 1, characterized in that, The specific preparation method of the nano-polydimethyldiallylammonium chloride is as follows: I. Place the dimethylamine ethanol solution in a reaction vessel, slowly add allyl chloride dropwise, and after 20-30 min, add sodium hydroxide. Reflux the reaction for 4-8 h, centrifuge and filter to obtain dimethyl diallyl ammonium chloride filtrate. II. The dimethyl diallyl ammonium chloride filtrate obtained in step I is pre-emulsified under stirring at 600-750 r / min. After 15-20 min, the temperature is raised to 70-80℃ and maintained. Then, the initiator APPH is added to the reaction system, the heating is stopped, and the reaction is stirred at 250-300 r / min for 1.5-2.5 h under inert gas protection to obtain nano-polydimethyl diallyl ammonium chloride.

4. A textile dye fixing agent as described in claim 3, characterized in that, The molar ratio of dimethylamine to allyl chloride in the dimethylamine ethanol solution is 1:(1.1-1.3).

5. A textile dye fixing agent as described in claim 2, characterized in that, The specific method for preparing the modified silica is as follows: S1. Add silane coupling agent KH550 and silica to anhydrous ethanol, stir, and react at 40-50℃ for 5-6 hours. After the reaction is completed, centrifuge, wash, and dry to obtain amino-modified silica. S2. Add allyl succinic anhydride and a condensing agent to N,N-dimethylformamide, stir at room temperature for 70-100 min, then add a catalytic activator and the amino-modified silica obtained in step S1, react at room temperature for 25-26 h, centrifuge, wash 2-3 times, and dry to obtain the modified silica.

6. A textile dye fixing agent as described in claim 5, characterized in that, The mass ratio of the silane coupling agent KH550 to silicon dioxide is 1:(20-30).

7. A textile dye fixing agent as described in claim 5, characterized in that, The mass ratio of the allyl succinic anhydride to the condensing agent is 1:(1-4).

8. A textile dye fixing agent as described in claim 5, characterized in that, The condensing agent is dicyclohexylcarbodiimide.

9. A textile dye fixing agent as described in claim 5, characterized in that, The catalytic activator is 4-pyrrolidinylpyridine.

10. A method for preparing a textile dye fixing agent as described in any one of claims 2-9, characterized in that, The specific steps are as follows: Add nano-polydimethyldiallylammonium chloride, acetic acid, ammonium sulfate, sodium chloride, sodium methylene bis(naphthalene)sulfonate and modified silica to water in sequence, mix and stir for 2-4 hours, filter and discharge the material evenly, control the pH to 7.5-8, and obtain textile dye fixing agent.