Preparation method and application of a machine-washable real silk finishing agent

Abstract

The present solution provides a preparation method and application of a machine-washable real silk finishing agent. Epoxy-terminated block polyether silicone oil and hexamethylenediamine are mixed, and after adding a solvent with the same mass as the epoxy-terminated block polyether silicone oil and hexamethylenediamine, the mixture is heated and reacted for a period of time to obtain a first mixed solution dissolving the first compound. The first mixed solution is slowly added to the cyanuric fluoride solution, and after adjusting the pH of the reaction system to 4 - 6, it is stirred for 2 - 8 h to obtain a second mixed solution. The temperature of the reaction system is lowered to 30 - 50 °C, and a para-ester solution including para-ester is slowly added to the second mixed solution. After adjusting the pH to 3 - 7, it is stirred for 2 - 8 h to prepare the machine-washable real silk finishing agent. The machine-washable real silk finishing agent contains two fluorine active groups and vinyl sulfone active groups respectively, achieving the machine-washable effect of real silk.

Description

Technical Field

[0001] The present invention relates to the technical field of real silk, and particularly relates to a preparation method and application of a machine-washable real silk finishing agent. Background Art

[0002] Real silk has a soft luster and a skin-friendly and soft texture. It is a high-grade textile fabric and is deeply favored by consumers. During the cleaning and maintenance of real silk, it is convenient to hand-wash some small real silk products such as silk scarves and underwear. However, for large real silk products such as home textile products, if they can only be hand-washed, it will not only be time-consuming and laborious, but also easily cause incomplete overall cleaning, which greatly reduces consumers' desire to purchase. However, during the machine-washing process of real silk, fibroin will be damaged due to fibrillation caused by the mutual friction between fabrics, between fabrics and water flow, and between fabrics and the cylinder wall, thereby affecting the properties such as the color, luster, and surface morphology of the silk surface, resulting in phenomena such as fading, graying, and wrinkling. Real silk without special treatment is not suitable for machine washing, which greatly limits the application of real silk in large real silk fields such as home textiles.

[0003] At present, the research on the machine-washability of real silk mainly starts from two aspects:

[0004] On the one hand, by improving the washing machine program or washing method to adapt to the cleaning conditions of real silk fabrics, but it cannot solve the problem at the root; for example, some studies have proposed using ultrasonic waves to replace traditional washing machines to wash real silk fabrics. This method can obtain better cleaning effects and a durable ironing appearance, and at the same time can reduce the degree of surface damage of the fabric. However, compared with traditional washing machines, ultrasonic washing has a greater impact on the color of the fabric, and there is currently no ultrasonic equipment specifically for household washing. There are also studies that analyze the action laws of different influencing factors by changing washing parameters to explore the influence of drum washing parameters on the gloss of real silk fabrics. It provides reference suggestions for household washing and home appliance manufacturers in the care of real silk fabrics. The improvement of the washing machine program can reduce the damage or color change problems caused during the washing of real silk fabrics, but at the same time, the cleaning effect of the fabric is also correspondingly reduced, and the machine-washing performance of real silk cannot be solved at the root.

[0005] On the other hand, silk fabrics are treated with anti-dust finishing. This method has low equipment requirements and good feasibility, but the difficulty lies in how to achieve better anti-dust effect and keep the color and gloss of silk unchanged as much as possible. At present, the anti-ash damage finishing agent is mainly a chemical cross-linking agent, such as cyanuric chloride and its derivatives, glutaraldehyde and its derivatives, polycarboxylic acids and epoxy compounds. Among them, cyanuric chloride is the main raw material for synthetic silk wool reactive dyes. Its active groups can be combined with amino or hydroxyl groups on silk in the form of covalent cross-linking, which can play a good fixation role and prevent the silk fibers from fibrillating during machine washing, such as breakage and slippage, thereby playing an anti-ash damage effect; for example, patents with publication numbers CN113463386A and CN117188150A both mention the use of cyanuric chloride derivatives as anti-ash damage finishing agents for silk, but they lack the preparation method of the cyanuric chloride derivatives, and may have the disadvantages of high chemical activity, low solubility in water, and easy hydrolysis; although the patent with publication number CN115897233A mentions the synthesis method of cyanuric chloride cross-linking agents, it has few active groups and cannot play a good cross-linking effect on silk. Although these cross-linking agents can have a certain anti-wrinkle and anti-dust effect on silk, the anti-dust effect is not obvious, and the feel and gloss of silk are reduced after finishing. On the other hand, although a double-active group finishing agent can be synthesized using cyanuric chloride and vinyl sulfone, the reaction of vinyl sulfone starts at 60°C, while the reaction temperature of monochlorotriazine is above 90°C. The difference in reaction activity makes the final reaction rate of the mixed double-active group dye low. Summary of the invention

[0006] The object of the present invention is to provide a preparation method and application of a machine-washable silk finishing agent, which contains two fluorine-active groups and vinyl sulfone-active groups, respectively, can react with silk at a high rate at 60°C, and can form a machine-washable silk finishing liquid with a synergistic effect on silk in combination with a bridging agent, thereby achieving a machine-washable effect of silk.

[0007] To achieve the above objectives, the present technical solution provides a method for preparing a machine washable silk finishing agent, comprising the following steps:

[0008] S1: mixing the terminal epoxy block polyether silicone oil and hexamethylenediamine in a molar ratio of 1:(2-2.1), adding a solvent having the same mass as the terminal epoxy block polyether silicone oil and the hexamethylenediamine, and heating to react for a period of time to obtain a first mixed solution in which the first compound is dissolved;

[0009] S2: Add cyanuric fluoride to a solvent and keep the temperature of the reaction system at 0 - 5 °C to obtain a cyanuric fluoride solution. Slowly add the first mixed solution to the cyanuric fluoride solution. After adjusting the pH of the reaction system to 4 - 6, stir for 2 - 8 h to obtain a second mixed solution that dissolves the second compound, where the molar ratio of cyanuric fluoride to the first compound is (2 - 2.1):1.

[0010] S3: Lower the temperature of the reaction system to 30 - 50 °C. Slowly add a para - ester solution containing para - ester to the second mixed solution. After adjusting the pH to 3 - 7, stir for 2 - 8 h to prepare a machine - washable real silk finishing agent, where the molar ratio of the second compound to para - ester is 1:(2 - 2.1).

[0011] The structural formula of the machine - washable real silk finishing agent synthesized in this scheme is:

[0012] , and the specific reaction equation for the preparation method of this machine - washable real silk finishing agent is as Figure 1 shown.

[0013] In step S1, the epoxy group in the terminal - epoxy - block polyether silicone oil undergoes a ring - opening reaction with the amino group in hexamethylenediamine. The epoxy group has high reactivity and can undergo a nucleophilic addition reaction with the amino group, thereby connecting hexamethylenediamine to the terminal - epoxy - block polyether silicone oil molecule to form the first compound. In step S2, the fluorine atoms in cyanuric fluoride have high activity and can undergo a substitution reaction with the first compound in the first mixed solution. By controlling the pH and temperature of the reaction system, cyanuric fluoride and the first compound react in a certain ratio and manner to form the second mixed solution. In step S3, the active groups in para - ester react with the components in the second mixture solution to further introduce vinyl sulfone active groups, and finally a machine - washable real silk finishing agent containing two fluorine - active and vinyl sulfone - active groups is prepared. Through the design of steps S1 to S3 in this scheme, different chemical groups are gradually introduced into the molecular structure, and finally a machine - washable real silk finishing agent with specific active groups and properties is obtained.

[0014] Specifically, in step S1, the solvent is one or more of water, acetone, or isopropyl alcohol. The role of this solvent is to provide a uniform reaction environment so that the reactants can fully contact.

[0015] In some embodiments, after adding a solvent with the same mass as the terminal - epoxy - block polyether silicone oil and hexamethylenediamine, heat up to 70 - 100 °C and react for 3 - 7 h. Heating up can accelerate the reaction rate and enable the reaction to be completed within a reasonable time. After the reaction is completed, a first mixed solution that dissolves the first compound is obtained.

[0016] In step S2, the solvent for dissolving cyanuric fluoride is one or more of water, acetone, or isopropyl alcohol. Additionally, the low-temperature condition is set in this solution to control the reaction activity of cyanuric fluoride and avoid unnecessary side reactions.

[0017] In some embodiments, the first mixed solution is slowly added to the cyanuric fluoride solution, and the pH of the reaction system is adjusted to 4 - 6 with an acid-binding agent and then stirred for 2 - 8 h to obtain a second mixed solution, where the acid-binding agent is one or more of sodium hydroxide, sodium carbonate, or sodium bicarbonate. Slowly adding the first mixed solution can make the reaction more stable and avoid overly intense local reactions. Adjusting the pH is to create an acid-base environment suitable for the reaction and promote the substitution reaction.

[0018] In step S3, the pH is adjusted to 3 - 7 with an acid-binding agent and then stirred for 2 - 8 h, where the acid-binding agent is one or more of sodium hydroxide, sodium carbonate, or sodium bicarbonate, to prepare a machine-washable real silk finishing agent. Adjusting the pH is to meet the acid-base conditions for the para-ester reaction, and stirring enables the reaction to proceed fully, ultimately preparing a machine-washable real silk finishing agent.

[0019] In a second aspect, this solution provides an application method for a machine-washable real silk finishing agent, including the following steps:

[0020] The machine-washable real silk finishing agent prepared in the first aspect and a bridging agent are added to water and stirred evenly to obtain a finishing solution. The real silk to be treated is added to the finishing solution, where the mass ratio of the real silk to the finishing solution is 1:(5 - 30). The temperature is slowly raised to 40 - 60 °C, and then the pH value is adjusted to 6 - 10. The temperature is further raised to 60 - 90 °C and reacted for 20 - 40 min. The real silk is washed and dried to obtain machine-washable real silk.

[0021] In some embodiments, the temperature is raised to 40 - 60 °C at a rate of 1 - 2 °C / min. Within this temperature range, the thermal motion of molecules gradually intensifies. For the molecules of the machine-washable real silk finishing agent and the bridging agent in the finishing solution, an appropriate temperature enables them to diffuse more freely in water, thus better contacting the real silk fibers. The real silk fibers also expand to a certain extent at this temperature, increasing the gaps between the fibers, which is conducive to the finishing agent molecules entering the interior of the fibers and laying the foundation for subsequent reactions. If the temperature is raised too high at the beginning, the finishing agent and the bridging agent may quickly react with the surface of the real silk, but this reaction may be uneven and may cause excessive reaction on the surface of the real silk while the interior is not fully treated. The temperature of 40 - 60 °C can initiate the reaction more gently and ensure the uniformity of the reaction.

[0022] When the temperature rises to 60 - 90 °C, the reaction rate between the fluorine - active and vinyl sulfone - active groups in the machine - washable silk finishing agent and the protein molecules in the silk will increase significantly. The increase in temperature provides sufficient energy for the reactant molecules to overcome the activation - energy barrier of the reaction, thereby promoting the formation of covalent bonds, enabling the finishing agent and the bridging agent to bind more firmly to the silk fibers, improving the properties of the silk, and achieving the effect of machine - washability.

[0023] In some embodiments, the bridging agent is glycerol triglycidyl ether. The addition of the tricyclic epoxy compound in the bridging agent glycerol triglycidyl ether can further strengthen the cross - linking of the silk, play a synergistic role with the machine - washable finishing agent, and better prevent the silk from being damaged by greying during machine washing.

[0024] In some embodiments, the dosage of the machine - washable finishing agent in the finishing solution is 2 - 10% of the mass of the silk, and the dosage of the bridging agent glycerol triglycidyl ether is 0.1 - 5% of the mass of the silk.

[0025] In some embodiments, the silk includes degummed white silk, natural colored silk without degumming treatment, and dyed silk.

[0026] Furthermore, the dyed silk includes silk dyed with reactive dyes, acid dyes, and natural dyes.

[0027] Compared with the prior art, the present technical solution has the following characteristics and beneficial effects:

[0028] The machine - washable silk finishing agent synthesized in the present invention contains two fluorine - active and vinyl sulfone - active groups respectively, which can have a relatively high reaction rate with silk at 60 °C. A small amount can achieve good cross - linking with silk. In addition, the extra active groups can react with the amino and hydroxyl groups on some dyes to form a highly diversified cross - linking system, making the dyes and fibers adhere more tightly together, preventing fibrillation of the silk fibers during washing and friction, and at the same time preventing the dyes from falling off the fibers. Further, the present invention introduces the soft - property - containing terminal - epoxy - block polyether silicone oil into the structure of the machine - washable silk finishing agent, which reduces the friction between the silk and the machine and among the silk fibers during machine washing. Finally, through the triple effects of preventing fibrillation of the silk, preventing dye shedding, and reducing silk friction, the machine - washability of the silk is achieved.

[0029] In addition, the present invention mixes the synthesized machine - washable silk finishing agent and the bridging agent glycerol triglycidyl ether into the finishing solution for simultaneous use on silk. The addition of the tricyclic epoxy compound in the bridging agent glycerol triglycidyl ether can further strengthen the cross - linking of the silk, play a synergistic role with the machine - washable silk finishing agent, and better prevent the silk from being damaged by greying during machine washing. Brief Description of the Drawings

[0030] Figure 1 It is the specific reaction equation for the preparation method of the machine-washable real silk finishing agent of this solution. Detailed Embodiments

[0031] The specific embodiment schemes listed in the present invention are only for clearly showing the technical solutions and implementation processes of the invention, and do not constitute a limitation on the implementation manners of the present invention. The actual applications and implementation manners of the present invention are not limited to the above content. Without departing from the core technical idea of the present invention, any equivalent replacement, improvement, change or other implementation manners based on the disclosed content of the present invention should be covered within the protection scope of the present invention.

[0032] The specific embodiment schemes presented above are for facilitating the understanding of the technical solutions and innovation points of the present invention. It should be clear that the implementation of the present invention is not limited to the above content. Any other implementation manners obtained through reasonable adjustment, optimization, expansion, etc. based on the principle of the present invention fall within the patent protection scope of the present invention.

[0033] Example 1

[0034] Add 21.6 g of terminal epoxy block polyether silicone oil and 2.32 g of hexamethylenediamine to a reaction kettle, and add a mixed solution of acetone and water with the same mass as the terminal epoxy block polyether silicone oil and hexamethylenediamine. Then heat up to 80 °C and react for 5 h to obtain a first mixed solution containing a first compound; further, dissolve 2.7 g of cyanuric fluoride in acetone, keep the system temperature at 0 - 5 °C, slowly add cyanuric fluoride to the reaction kettle, then adjust the pH to 5 with sodium carbonate, and stir the reaction mixture for 6 h; then lower the system temperature to 40 °C, slowly add 5.62 g of dissolved para-ester, then adjust the pH to 5 with sodium carbonate, and stir the reaction mixture for 6 h to prepare the machine-washable finishing agent.

[0035] Weigh 0.5 g of the machine-washable finishing agent and 0.2 g of the cross-linking agent glycerol triglycidyl ether at room temperature, add them to water and stir evenly to obtain a finishing solution. Then add 10 g of the real silk to be treated, and then heat the finishing solution to 50 °C at a rate of 1 - 2 °C / min, add sodium carbonate to adjust the pH value to 8, then heat up to 70 °C, react for 30 min, and finally wash and dry the real silk to obtain machine-washable real silk.

[0036] Blank Example

[0037] The original real silk fabric to be finished that has been dyed with a red reactive dye.

[0038] Comparative Example 1

[0039] Other steps are the same as those in Example 1, and the only difference is that no crosslinking agent glycerol triglycidyl ether is added.

[0040] Comparative Example 2

[0041] Other steps are the same as those in Example 1, and the only difference is that no terminal epoxy block polyether silicone oil is added to the reaction system.

[0042] Comparative Example 3

[0043] Other steps are the same as those in Example 1, and the only difference is that no para-ester is added to the reaction system.

[0044] Comparative Example 4

[0045] Other steps are the same as those in Example 1, and the only difference is that no cyanuric fluoride and para-ester are added to the reaction system.

[0046] Test Example:

[0047] The real silk of the blank example, Example 1, and Comparative Examples 1 to 4 was washed with reference to the national standard GB / T 3921-2008 "Textiles - Tests for colour fastness - Colour fastness to soaping": the soap solution was 5 g / L, the bath ratio was 1:50, the washing temperature was 40 °C, and the washing time for one time was 30 min. The real silk was washed 10 times, dried, and ironed for subsequent tests.

[0048] Color index test: During the machine washing process, the color and luster of the real silk will be affected due to friction and the use of detergent. Therefore, the degree of grey damage of the real silk is evaluated through the color indexes before and after washing. The color indexes were used to measure the K / S value of the real silk with a colorimetric and color matching instrument Datacolor 800; the change in the glossiness of the real silk was measured with a YG524 fabric glossiness tester in accordance with FZ / T 01097-2006 "Test method for fabric glossiness"; the visual evaluation of grey damage was carried out by selecting the D65 international standard light source in a standard light source color matching lamp box and placing the sample under the light. There were 10 evaluators in total, with normal vision and color vision. Through the initial visual evaluation experiment training, it was ensured that all evaluators had the same cognition of the sample glossiness. During the experiment, the evaluators carried out the evaluation in a room with appropriate temperature and humidity and no ambient light interference. The eyes were above the sample, and the position distance was kept consistent, and the evaluation was carried out multiple times under the same conditions at different time periods. The test data are shown in Table 1 below.

[0049] Table 1 K / S value, glossiness, and visual grey damage of real silk before and after washing

[0050] 。

[0051] As can be seen from Table 1, for the blank example without anti-greying finish and Comparative Example 4 finished with a finishing agent without any active groups, after 10 washes, the color change was obvious, the glossiness decreased significantly, and a large amount of greying occurred; for Comparative Example 1 without adding the cross-linking agent glycerol triglycidyl ether, Comparative Example 2 without adding the terminal epoxy block polyether silicone oil to the reaction system, and Comparative Example 3 finished with a single fluorine-containing active group finishing agent, after 10 washes, there were slight color changes, the glossiness decreased, and a small amount of greying occurred; while for Example 1 of the present invention, after 10 washes, there was no obvious color change, the change in glossiness was very small, and no obvious greying occurred. Therefore, the preparation and application method of a machine-washable real silk finishing agent involved in the present invention can effectively protect real silk during the machine washing process of real silk, prevent greying of real silk, and the real silk produced by the present invention can be used for machine washing without affecting the wearing performance of real silk.

[0052] The above embodiments only represent several implementation manners of the present application, and the description thereof is relatively specific and detailed, but it should not be construed as a limitation to the scope of the present application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several deformations and improvements can still be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the appended claims.

Claims

1. A preparation method of a machine-washable real silk finishing agent, characterized in that, It includes the following steps: S1: Mix the terminal epoxy block polyether silicone oil and hexamethylenediamine according to a molar ratio of 1:(2 - 2.1), add a solvent with the same mass as the terminal epoxy block polyether silicone oil and hexamethylenediamine, and then raise the temperature for a certain period of time to obtain a first mixed solution dissolving the first compound; S2: Add cyanuric fluoride to the solvent and keep the temperature of the reaction system at 0 - 5 °C to obtain a cyanuric fluoride solution. Slowly add the first mixed solution to the cyanuric fluoride solution, adjust the pH of the reaction system to 4 - 6, and then stir for 2 - 8 h to obtain a second mixed solution dissolving the second compound, where the molar ratio of cyanuric fluoride to the first compound is (2 - 2.1):1; S3: Lower the temperature of the reaction system to 30 - 50 °C, slowly add a para - ester solution including para - ester to the second mixed solution, adjust the pH to 3 - 7, and then stir for 2 - 8 h to prepare a machine - washable real silk finishing agent, where the molar ratio of the second compound to the para - ester is 1:(2 - 2.1).

2. The preparation method of the machine-washable real silk finishing agent according to claim 1, characterized in that, The structural formula of the synthesized machine - washable real silk finishing agent is: 。 3. The preparation method of the machine-washable real silk finishing agent according to claim 1, characterized in that, In steps S1 and S2, the solvent is one or more of water, acetone, or isopropanol.

4. The preparation method of the machine-washable real silk finishing agent according to claim 1, characterized in that The acid - binding agent is one or more of sodium hydroxide, sodium carbonate, or sodium bicarbonate.

5. The preparation method of the machine-washable real silk finishing agent according to claim 1, wherein In step S1, after adding a solvent with the same mass as the terminal epoxy block polyether silicone oil and hexamethylenediamine, raise the temperature to 70 - 100 °C and react for 3 - 7 h.

6. A method for applying a finishing agent for machine-washable real silk, characterized in that, It includes the following steps: Add the machine - washable real silk finishing agent prepared by the preparation method of the machine - washable real silk finishing agent according to any one of claims 1 to 5 and a cross - linking agent into water, stir evenly to obtain a finishing solution, add the real silk to be treated into the finishing solution, where the mass ratio of the real silk to the finishing solution is 1:(5 - 30), slowly raise the temperature to 40 - 60 °C, then adjust the pH value to 6 - 10, continue to raise the temperature to 60 - 90 °C and react for 20 - 40 min, and then wash and dry the real silk to obtain machine - washable real silk.

7. The application method of the machine-washable real silk finishing agent according to claim 6, characterized in that, Raise the temperature to 40 - 60 °C at a rate of 1 - 2 °C / min.

8. The application method of the machine-washable real silk finishing agent according to claim 6, characterized in that, The cross - linking agent is glycerol triglycidyl ether.

9. The application method of the machine-washable real silk finishing agent according to claim 6, characterized in that, The dosage of the machine - washable finishing agent in the finishing solution is 2 - 10% of the mass of the real silk, and the dosage of the cross - linking agent glycerol triglycidyl ether is 0.1 - 5% of the mass of the real silk.

10. The application method of the machine-washable real silk finishing agent according to claim 6, characterized in that, The real silk includes degummed white real silk, natural colored real silk without degumming treatment, and dyed real silk, where the dyed real silk includes real silk dyed with reactive dyes, acid dyes, and natural dyes.

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