Multifunctional finishing liquid as well as preparation method and application thereof in silk products

Abstract

The invention relates to multifunctional finishing liquid as well as a preparation method and application thereof in silk products, and belongs to the technical field of textiles. The preparation method comprises the following steps: firstly, carrying out cross-linking reaction on tetrakis (hydroxymethyl) phosphonium chloride, polyhexamethylene biguanide and a film-forming agent in water to obtain colorless, transparent, antibacterial, mildew-proof and flame-retardant multifunctional finishing liquid; then the antibacterial, mildew-proof and flame-retardant multifunctional silk product is prepared in a spraying and airing mode, and safety protection is conducted on the silk product. Tetrakis (hydroxymethyl) phosphonium chloride and polyhexamethylene biguanide are grafted on chitosan through covalent bonds, tetrakis (hydroxymethyl) phosphonium chloride and polyhexamethylene biguanide are fixed on the silk product by means of excellent film-forming property of chitosan, and redundant hydroxymethyl of tetrakis (hydroxymethyl) phosphonium chloride can be subjected to cross-linking reaction with amino groups of the silk product; therefore, the network-shaped multifunctional finishing agent can be fixed on the silk product through a film-forming effect and a cross-linking effect.

Description

Technical Field

[0001] The invention belongs to the technical field of textiles, and in particular relates to a multifunctional finishing liquid and a preparation method thereof and application thereof in silk products. Background Art

[0002] Silk is a textile with a long history. It has been known as the "Queen of Fibers" since ancient times. It has excellent properties such as soft touch, soft luster, moisture absorption and breathability, and comfortable wearing. Silk products such as silk cultural relics are often very fragile after being unearthed due to the characteristics of their materials, and special protection measures are required to prevent further damage to them in the modern environment. However, silk products are prone to breeding bacteria and are prone to mold during exhibition. In addition, silk products have poor flame retardant properties and are easily ignited. Protecting and inheriting silk culture is of great significance to promoting cultural exchanges and economic development.

[0003] For special silk products such as silk cultural relics, it is impossible to carry out safety protection treatment by immersion method, and they need to be carried out by spraying and natural drying. Therefore, it is of great significance to develop a multifunctional finishing liquid that integrates antibacterial, mildew-proof and flame-retardant functions and has high functional efficiency. The protection of silk cultural relics can be achieved by simple spraying.

[0004] At present, quaternary ammonium salt antimicrobial agents are commonly used in the antimicrobial finishing of textiles, but the binding performance of quaternary ammonium salt antimicrobial agents and fabrics is poor. Chinese invention patent CN109281166A discloses a protein fiber antimicrobial finishing method based on enzymatic graft copolymerization, which uses tyrosine phenol lyase to catalyze the conversion of serine in protein fiber macromolecules into tyrosine, and then uses horseradish peroxidase to catalyze the graft copolymerization of tyrosine in protein fiber and vinyl-containing quaternary ammonium salt monomers to perform protein fiber antimicrobial finishing. However, this method has a complicated process, requires the protein fiber to be hydrolyzed, and causes serious damage to the protein fiber.

[0005] References (Zheng Hongfei, Wang Ruiqi, Wang Qing, et al. Preparation and properties of oxidized chitosan modified antibacterial silk fabrics [J]. Journal of Textile Research, 2020, 41(5): 121-128.) Silk fabrics are finished with water-soluble oxidized chitosan, and the oxidized chitosan is grafted on the surface of silk fabrics through high temperature and long-term treatment. It cannot be used for spray protection of silk cultural relics, and oxidized chitosan is a yellow substance, which has a great impact on the color of silk cultural relics.

[0006] It is of great significance to develop a highly efficient, colorless, transparent, antibacterial, mildew-proof and flame-retardant multifunctional finishing liquid, and then produce antibacterial, mildew-proof and flame-retardant multifunctional silk products by spraying and drying, but there are great challenges. Summary of the invention

[0007] To this end, the technical problem to be solved by the present invention is to overcome the problem in the prior art that special silk products such as silk cultural relics cannot be treated for safety protection by the immersion method, so they need to be treated by spraying and natural drying, so the antibacterial, mildew-proof and flame-retardant efficiency of the multifunctional finishing liquid is required to be high.

[0008] In order to solve the above technical problems, the present invention provides a multifunctional finishing liquid and a preparation method thereof and application in silk products. Firstly, tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and film-forming agent chitosan are used to prepare a colorless, transparent, antibacterial, mildew-proof and flame-retardant multifunctional finishing liquid; then, antibacterial, mildew-proof and flame-retardant multifunctional silk products are prepared by spraying and drying, thereby providing safety protection for the silk products.

[0009] The first object of the present invention is to provide a method for preparing a multifunctional finishing liquid, comprising the following steps: tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and a film-forming agent are subjected to a cross-linking reaction in water to obtain the multifunctional finishing liquid.

[0010] In one embodiment of the present invention, the film-forming agent is chitosan.

[0011] In one embodiment of the present invention, the mass ratio of tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and film-forming agent is (5-8):(7-10):(0.3-0.5). The hydroxymethyl group of tetrakis(hydroxymethyl)phosphonium chloride can undergo cross-linking reaction with the amino group of the film-forming agent and the amino / imino group of polyhexamethylene biguanide, thereby preparing a network-like multifunctional finishing agent. An increase in the amount of tetrakis(hydroxymethyl)phosphonium chloride helps to improve functionality, but too high a concentration will lead to a decrease in the pH value of the multifunctional finishing liquid, which will affect the color performance and storage stability of silk products, especially silk cultural relics; an increase in the amount of polyhexamethylene biguanide helps to improve functionality and helps to increase the degree of reaction of the hydroxymethyl group of tetrakis(hydroxymethyl)phosphonium chloride; an increase in the amount of film-forming agent helps to improve functionality, but too high a concentration will cause the finishing liquid to be too viscous and cannot be applied to silk products by spraying.

[0012] In one embodiment of the present invention, the concentration of the film-forming agent is 0.3 g / L-0.5 g / L, for example, 0.3 g / L, 0.4 g / L, 0.5 g / L, etc.

[0013] In one embodiment of the present invention, the temperature of the cross-linking reaction is 75°C-85°C, for example, it can be 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, etc.; the time is 60min-90min, for example, it can be 60min, 61min, 62min, 63min, 64min, 65min, 66min, 67min, 68min, 69min, 70min, 71min, 72min, 73min, 74min, 75min, 76min, 77min, 78min, 79min, 80min, 81min, 82min, 83min, 84min, 85min, 86min, 87min, 88min, 89min, 90min, etc.; increasing the reaction temperature and extending the time are helpful to improve the degree of reaction, but too high a temperature will cause waste.

[0014] In one embodiment of the present invention, the pH of the multifunctional finishing liquid is 6-7, which can reduce the adverse effects on the storage stability of silk products.

[0015] The second object of the present invention is to provide a multifunctional finishing liquid prepared by the method.

[0016] The third object of the present invention is to provide a method for finishing a multifunctional silk product, comprising the following steps: spraying the multifunctional finishing liquid on the surface of the silk product, and obtaining the multifunctional silk product by drying.

[0017] In one embodiment of the present invention, after spraying the multifunctional finishing liquid, the liquid carrying rate of the silk product is 30%-50%, for example, it can be 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, etc.

[0018] The fourth object of the present invention is to provide a multifunctional silk product finished by the method.

[0019] The technical solution of the present invention has the following advantages over the prior art:

[0020] (1) The preparation method of the present invention uses chitosan as a film-forming agent, and grafts tetrakis(hydroxymethyl)phosphonium chloride and polyhexamethylene biguanide onto chitosan through covalent bonds. The tetrakis(hydroxymethyl)phosphonium chloride and polyhexamethylene biguanide are fixed on the silk product by means of the excellent film-forming property of chitosan, and the excess hydroxymethyl groups of tetrakis(hydroxymethyl)phosphonium chloride can undergo cross-linking reaction with the amino groups of the silk product; therefore, the network-like multifunctional finishing agent can be fixed on the silk product through film-forming and cross-linking effects.

[0021] (2) The preparation method of the present invention has an antibacterial and antifungal effect through the synergistic effect of tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and chitosan, and has high efficiency; tetrakis(hydroxymethyl)phosphonium chloride has a good flame retardant effect, but the amount used is small when it is applied by spraying alone, and it is difficult to effectively improve the flame retardant properties of silk products; tetrakis(hydroxymethyl)phosphonium chloride acts as an acid source, the nitrogen-containing groups of polyhexamethylene biguanide chitosan act as a gas source, and the sugar rings of chitosan act as a carbon source, so as to organically construct an intumescent flame retardant system with high flame retardant efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:

[0023] Figure 1 These are pictures of the antibacterial performance test of the silk products before and after finishing in Example 3 of the present invention. DETAILED DESCRIPTION

[0024] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. It should be understood that the specific embodiments are only used to explain the present invention, but the embodiments are not intended to limit the present invention.

[0025] In the present invention, unless otherwise explained, technical and scientific terms used in the present invention have the same meanings as commonly understood by those skilled in the art to which the present invention belongs.

[0026] In the present invention, unless otherwise stated, the term "and / or" used in the present invention includes any and all combinations of one or more of the associated listed items.

[0027] In the present invention, unless otherwise stated, the experimental methods used in the embodiments of the present invention are conventional methods unless otherwise stated, and the materials, reagents, etc. used are all commercially available unless otherwise stated.

[0028] Example 1

[0029] The multifunctional finishing liquid of this embodiment and its application in silk products specifically include the following steps:

[0030] S1. Tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and chitosan are placed in water, cross-linked for 75 minutes at 80°C, and the pH is adjusted to about 6.5 to obtain a multifunctional finishing liquid; wherein the amount of tetrakis(hydroxymethyl)phosphonium chloride is 6.5 g / L, the amount of polyhexamethylene biguanide is 8.5 g / L, and the amount of chitosan is 0.4 g / L;

[0031] S2. Load the multifunctional finishing liquid into a pneumatic spray gun, and spray the multifunctional finishing liquid evenly on the surface of the silk product, so that the liquid carrying rate of the silk product is 40%, and obtain the multifunctional silk product after drying.

[0032] Example 2

[0033] The multifunctional finishing liquid of this embodiment and its application in silk products specifically include the following steps:

[0034] S1. Tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and chitosan are placed in water for cross-linking reaction at 75°C for 90 minutes, and the pH is adjusted to about 6 to obtain a multifunctional finishing liquid; wherein the amount of tetrakis(hydroxymethyl)phosphonium chloride is 5 g / L, the amount of polyhexamethylene biguanide is 7 g / L, and the amount of chitosan is 0.3 g / L;

[0035] S2. Load the multifunctional finishing liquid into a pneumatic spray gun, and spray the multifunctional finishing liquid evenly on the surface of the silk product, so that the liquid carrying rate of the silk product is 30%, and obtain the multifunctional silk product after drying.

[0036] Example 3

[0037] The multifunctional finishing liquid of this embodiment and its application in silk products specifically include the following steps:

[0038] S1. Tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and chitosan are placed in water for cross-linking reaction at 85°C for 60 minutes, and the pH is adjusted to about 7 to obtain a multifunctional finishing liquid; wherein the amount of tetrakis(hydroxymethyl)phosphonium chloride is 8 g / L, the amount of polyhexamethylene biguanide is 10 g / L, and the amount of chitosan is 0.5 g / L;

[0039] S2. Load the multifunctional finishing liquid into a pneumatic spray gun, and spray the multifunctional finishing liquid evenly on the surface of the silk product, so that the liquid carrying rate of the silk product is 50%, and obtain the multifunctional silk product after drying.

[0040] Comparative Example 1

[0041] The method is basically the same as Example 1, except that tetrakis hydroxymethyl phosphonium chloride is replaced with phosphoric acid.

[0042] Comparative Example 2

[0043] The method is basically the same as Example 1, except that no tetrakis(hydroxymethyl)phosphonium chloride is added.

[0044] Comparative Example 3

[0045] The method is basically the same as Example 1, except that polyhexamethylene biguanide is replaced by polyethyleneimine.

[0046] Comparative Example 4

[0047] The method is basically the same as Example 1, except that no polyhexamethylene biguanide is added.

[0048] Comparative Example 5

[0049] The method is basically the same as Example 1, except that chitosan is replaced by polyethyleneimine.

[0050] Comparative Example 6

[0051] The method is basically the same as Example 1, except that chitosan is not added.

[0052] Test Example 1

[0053] The flame retardant properties and other properties of the unfinished silk products, the multifunctional silk products (finished silk products) prepared in Examples 1-3 and Comparative Examples 1-6 were tested:

[0054] Antibacterial rate of silk products: Determined according to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method";

[0055] Anti-mildew performance of silk products: measured in accordance with the standard GB / T 24346-2009 "Evaluation of Anti-mildew Performance of Textiles";

[0056] Flame retardant properties of silk products: Determined according to GB / T 5455-2014 "Determination of vertical damage length, smoldering and afterflaming time of textile combustion performance";

[0057] Figure 1 The antibacterial performance test pictures of the silk products before and after finishing in Example 1;

[0058] Table 1 shows the relevant properties of the unfinished silk products and finished silk products finally measured:

[0059] Table 1

[0060] Sample Escherichia coli inhibition rate (%) Staphylococcus aureus inhibition rate (%) Mildew resistance level Charcoal length (cm) Unfinished silk products 22.1 19.8 5 30 Example 1 98.1 98.6 0 11.4 Example 2 95.3 95.1 1 12.1 Example 3 99.9 99.9 0 11.0 Comparative Example 1 68.4 69.2 3 15.9 Comparative Example 2 67.2 68.3 3 30 Comparative Example 3 59.3 60.2 4 13.5 Comparative Example 4 58.9 59.6 4 20.5 Comparative Example 5 81.6 83.2 4 14.2 Comparative Example 6 75.3 78.1 4 23.3

[0061] from Figure 1As can be seen from Table 1, the antibacterial rate of the multifunctional silk product in the embodiment against Escherichia coli and Staphylococcus aureus is 95.1%-99.9%, the mildew resistance level is less than level 1, and the charcoal length is less than 12.1 cm, indicating that the multifunctional silk product has excellent antibacterial, mildew resistance and flame retardant properties.

[0062] By comparing Example 1 and Comparative Example 1, it can be seen that the antibacterial, mildew-proof and flame-retardant properties of the finished silk products are reduced after tetrakis(hydroxymethyl)phosphonium chloride is replaced with phosphoric acid. This is because phosphoric acid is mainly combined with cationic polyhexamethylene biguanide and chitosan through ionic bonds, resulting in precipitation, poor application performance, and thus affecting the functionality of the finished silk products.

[0063] By comparing Example 1 and Comparative Example 2, it can be seen that when tetrakis(hydroxymethyl)phosphonium chloride is not added, the antibacterial and antifungal properties of the finished silk products are reduced, and the flame retardant properties are lost. This is because the flame retardant system lacks an acid source and cannot form an intumescent flame retardant system, and tetrakis(hydroxymethyl)phosphonium chloride is a good antibacterial and antifungal agent.

[0064] By comparing Example 1 and Comparative Example 3, it can be seen that after replacing polyhexamethylene biguanide with polyethylene imine, the antibacterial, mildew-proof and flame-retardant properties of the finished silk products are reduced. This is because polyethylene imine has poor antibacterial and mildew-proof properties, and polyethylene imine has many side chains, which easily form precipitates after reacting with tetrakis(hydroxymethyl)phosphonium chloride, resulting in poor flame retardant efficiency.

[0065] By comparing Example 1 and Comparative Example 4, it can be seen that when polyhexamethylene biguanide is not added, the antibacterial, antifungal and flame retardant properties of the finished silk products are reduced. This is because the flame retardant system lacks a gas source and cannot form an expanding flame retardant system, and polyhexamethylene biguanide is a good antibacterial and antifungal agent.

[0066] By comparing Example 1 and Comparative Example 5, it can be seen that when chitosan is replaced with polyethyleneimine, the antibacterial, mildew-proof and flame-retardant properties of the finished silk products are reduced. This is because polyethyleneimine has poor antibacterial and mildew-proof properties, and polyethyleneimine has many side chains, which easily form precipitates after reacting with tetrakis(hydroxymethyl)phosphonium chloride, and its film-forming properties are also poor, resulting in poor flame retardant efficiency.

[0067] By comparing Example 1 and Comparative Example 6, it can be seen that when chitosan is not added, the antibacterial, antifungal and flame retardant properties of the finished silk products are reduced. This is because chitosan itself has certain antibacterial and antifungal properties, and can act as a gas source and carbon source to further improve the flame retardant efficiency of the expansion system. In addition, chitosan has good film-forming properties, which helps to further attach the finishing agent to the surface of the silk product.

[0068] Obviously, the above embodiments are merely examples for clear explanation and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from these are still within the protection scope of the invention.

Claims

1. A method for preparing a multifunctional finishing liquid, characterized in that: The following steps are involved: Tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and a film-forming agent are cross-linked in water to obtain the multifunctional finishing liquid.

2. The method for preparing the multifunctional finishing liquid according to claim 1, characterized in that: The film-forming agent is chitosan.

3. The method for preparing the multifunctional finishing liquid according to claim 1, characterized in that: The mass ratio of the tetrakis(hydroxymethyl)phosphonium chloride, polyhexamethylene biguanide and film-forming agent is (5-8):(7-10):(0.3-0.5).

4. The method for preparing the multifunctional finishing liquid according to claim 1, characterized in that: The concentration of the film-forming agent is 0.3 g / L-0.5 g / L.

5. The method for preparing the multifunctional finishing liquid according to claim 1, characterized in that: The cross-linking reaction is carried out at a temperature of 75°C-85°C and for a time of 60min-90min.

6. The method for preparing the multifunctional finishing liquid according to claim 1, characterized in that: The pH of the multifunctional finishing liquid is 6-7.

7. A multifunctional finishing liquid prepared by the method according to any one of claims 1 to 6.

8. A method for finishing a multifunctional silk product, characterized in that: The following steps are involved: The multifunctional silk product is obtained by spraying the multifunctional finishing liquid as claimed in claim 7 on the surface of the silk product and drying it.

9. The method according to claim 8, characterized in that After spraying the multifunctional finishing liquid, the liquid carrying rate of the silk products is 30%-50%.

10. A multifunctional silk product finished by the method according to claim 8 or 9.

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