Multifunctional finishing liquid, its preparation method and application in silk products

Abstract

The present application relates to a kind of multifunctional finishing liquid and its preparation method and application in silk product, belong to textile technical field.The present application is first by tetramethylphosphonium chloride, polyhexamethylene biguanide and film-forming agent in water Crosslinking reaction, obtain colorless transparent, antibacterial, antifungal, flame-retardant multifunctional finishing liquid;Then by spraying, dry way is prepared antibacterial, antifungal, flame-retardant multifunctional silk product, and the safety protection is carried out to silk product.Tetramethylphosphonium chloride, polyhexamethylene biguanide are grafted on chitosan by covalent bond, and tetramethylphosphonium chloride, polyhexamethylene biguanide are fixed on silk product by the excellent film-forming property of chitosan, and the excess hydroxymethyl of tetramethylphosphonium chloride can occur crosslinking reaction with the amino group of silk product;Therefore, network multifunctional finishing agent can be fixed on silk product by film-forming effect and crosslinking effect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of textiles, and particularly relates to a multifunctional finishing liquid, a preparation method thereof and application of the multifunctional finishing liquid in silk products. BACKGROUND

[0002] Silk is a kind of textile with a long history and has been praised as the "Queen of Fibers" since ancient times. It has excellent properties such as softness, soft luster, moisture absorption, and breathability, and is comfortable to wear. Due to the properties of silk, silk products such as silk cultural relics are often very fragile after being unearthed and need special protection measures to prevent further damage from the modern environment. However, silk products are prone to bacterial growth and are easily moldy during exhibition, and the flame retardant performance of silk products is poor and is easily ignited. Protecting and inheriting silk culture is of great significance for promoting cultural exchange and economic development.

[0003] For special silk products such as silk cultural relics, it is not possible to perform safe protection treatment by impregnation, and it is necessary to perform protection 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 properties, and has high functional efficiency, and can achieve protection of silk cultural relics by simple spraying.

[0004] Currently, quaternary ammonium salt antibacterial agents are commonly used for antibacterial finishing of textiles, but the combination of quaternary ammonium salt antibacterial agents with fabrics is poor. Chinese invention patent CN109281166A discloses a protein fiber antibacterial finishing method based on enzymatic graft copolymerization. Tyrosine phenol-lyase is used to catalyze the conversion of serine in protein fiber macromolecules to tyrosine, and horseradish peroxidase is used to catalyze the graft copolymerization of tyrosine in protein fiber with vinyl-containing quaternary ammonium salt monomers for protein fiber antibacterial finishing. However, this method has a complex process and requires hydrolysis of protein fibers, which causes serious damage to protein fibers.

[0005] Reference (Zheng H F, Wang R Q, Wang Q, et al. Preparation and properties of antibacterial silk fabrics modified by oxidized chitosan [J]. Journal of Textile Research, 2020, 41(5): 121-128.) uses water-soluble oxidized chitosan to finish silk fabrics. The oxidized chitosan is grafted on the surface of silk fabrics by high-temperature and long-time treatment, which cannot be applied to the spraying protection of silk cultural relics, and the oxidized chitosan is a yellow substance which has a great influence on the color of silk cultural relics.

[0006] It is of great significance to develop a high-efficiency colorless and transparent antibacterial, mildew-proof and flame-retardant multifunctional finishing liquid, and then to prepare an antibacterial, mildew-proof and flame-retardant multifunctional silk product by spraying and drying, but there are great challenges. SUMMARY

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

[0008] To solve the above technical problem, the present application provides a multifunctional finishing liquid, a preparation method thereof and application thereof in silk products. First, a colorless and transparent multifunctional finishing liquid with antibacterial, mildew-proof and flame-retardant properties is prepared by using tetramethylphosphonium chloride, polyhexamethylene biguanide and a film-forming agent chitosan. Then, the multifunctional silk product with antibacterial, mildew-proof and flame-retardant properties is prepared by spraying and drying, so as to protect the silk product.

[0009] The first object of the present application is to provide a preparation method of a multifunctional finishing liquid, comprising the following steps: cross-linking reaction of tetramethylphosphonium chloride, polyhexamethylene biguanide and a film-forming agent in water to obtain the multifunctional finishing liquid.

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

[0011] In an embodiment of the present application, the mass ratio of tetramethylphosphonium chloride, polyhexamethylene biguanide and the film-forming agent is (5-8):(7-10):(0.3-0.5). The hydroxymethyl of tetramethylphosphonium chloride can cross-link with the amino group of the film-forming agent and the amino group / imino group of polyhexamethylene biguanide, so as to prepare a network multifunctional finishing agent. Increasing the amount of tetramethylphosphonium chloride can help to improve the functionality, but too high amount will lead to a decrease in the pH value of the multifunctional finishing liquid, which will affect the color performance and storage stability of the silk product, especially the silk cultural relics. Increasing the amount of polyhexamethylene biguanide can help to improve the functionality and the reaction degree of the hydroxymethyl of tetramethylphosphonium chloride. Increasing the amount of the film-forming agent can help to improve the functionality, but too high concentration will lead to too thick finishing liquid, which cannot be applied to the silk product by spraying.

[0012] In an embodiment of the present application, the concentration of the film-forming agent is 0.3g / L-0.5g / L, for example, it can be 0.3g / L, 0.4g / L, 0.5g / L, etc.

[0013] In an embodiment of the present application, the cross-linking reaction has a temperature of 75-85℃, for example, 75℃, 76℃, 77℃, 78℃, 79℃, 80℃, 81℃, 82℃, 83℃, 84℃, 85℃, etc., and a time of 60-90min, for example, 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. Both the increase of the reaction temperature and the extension of the reaction time can help to improve the reaction degree, but too high temperature and time will be a waste.

[0014] In an embodiment of the present application, the multifunctional finishing liquid has a pH of 6-7, which can reduce the adverse effect on the storage stability of silk products.

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

[0016] A third object of the present application is to provide a finishing method of multifunctional silk products, comprising the following steps: spraying the multifunctional finishing liquid on the surface of the silk products, and drying to obtain the multifunctional silk products.

[0017] In an embodiment of the present application, after spraying the multifunctional finishing liquid, the silk products have a liquid carrying rate of 30%-50%, for example, 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] A fourth object of the present application is to provide a multifunctional silk product finished by the method.

[0019] The technical solution of the present application has the following advantages compared with the prior art:

[0020] (1) The preparation method described in the application adopts chitosan as a film forming agent, grafts tetramethylphosphonium chloride and polyhexamethylene biguanide on chitosan through covalent bonds, fixes tetramethylphosphonium chloride and polyhexamethylene biguanide on silk products by virtue of the excellent film forming property of chitosan, and the excess hydroxymethyl of tetramethylphosphonium chloride can crosslink with the amino group of the silk products; therefore, the network-shaped multifunctional finishing agent can be fixed on the silk products through film forming and crosslinking.

[0021] (2) The preparation method described in the application has high efficiency through the synergistic effect of tetramethylphosphonium chloride, polyhexamethylene biguanide and chitosan; tetramethylphosphonium chloride has good flame retardant effect, and when it is applied by spraying, the amount is small, and it is difficult to effectively improve the flame retardant property of the silk products; tetramethylphosphonium chloride serves as an acid source, the nitrogen-containing group of polyhexamethylene biguanide chitosan serves as a gas source, and the sugar ring of chitosan serves as a carbon source, so that an intumescent flame retardant system is organically constructed, and the flame retardant efficiency is high. BRIEF DESCRIPTION OF DRAWINGS

[0022] In order to make the content of the application more easily understood, the application will be further described in detail below according to specific embodiments of the application and in conjunction with the drawings, in which:

[0023] Figure 1 The picture for testing the antibacterial properties of the silk products before and after finishing in Example 3 of the application. DETAILED DESCRIPTION

[0024] The application will be further described below in conjunction with the drawings and specific embodiments, so that those skilled in the art can better understand the application and implement it. Obviously, the described embodiments are only a part of the embodiments of the application, not all the embodiments. It should be understood that the specific embodiments are only used to explain the application, but the embodiments are not limited to the application.

[0025] In the application, unless otherwise specified, the technical and scientific terms used in the application are the same as the meanings commonly understood by the persons skilled in the art belonging to the technical field of the application.

[0026] In the application, unless otherwise specified, the term "and / or" used in the application includes any and all combinations of one or more related listed items.

[0027] In the application, unless otherwise specified, the experimental methods used in the embodiments of the application are conventional methods, and the materials, reagents, etc. used are commercially available, unless otherwise specified.

[0028] Example 1

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

[0030] S1, crosslinking reaction of tetramethylphosphonium chloride, polyhexamethylene biguanide and chitosan in water at 80℃ for 75min, adjusting pH to about 6.5, to obtain a multifunctional finishing liquid; wherein the amount of tetramethylphosphonium chloride is 6.5g / L, the amount of polyhexamethylene biguanide is 8.5g / L, and the amount of chitosan is 0.4g / L;

[0031] S2, the multifunctional finishing liquid is loaded into a pneumatic spray gun, and the multifunctional finishing liquid is uniformly sprayed on the surface of the silk product, so that the liquid carrying rate of the silk product is 40%, and the multifunctional silk product is obtained after air drying.

[0032] Example 2

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

[0034] S1, crosslinking reaction of tetramethylphosphonium chloride, polyhexamethylene biguanide and chitosan in water at 75℃ for 90min, adjusting pH to about 6, to obtain a multifunctional finishing liquid; wherein the amount of tetramethylphosphonium chloride is 5g / L, the amount of polyhexamethylene biguanide is 7g / L, and the amount of chitosan is 0.3g / L;

[0035] S2, the multifunctional finishing liquid is loaded into a pneumatic spray gun, and the multifunctional finishing liquid is uniformly sprayed on the surface of the silk product, so that the liquid carrying rate of the silk product is 30%, and the multifunctional silk product is obtained after air drying.

[0036] Example 3

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

[0038] S1, crosslinking reaction of tetramethylphosphonium chloride, polyhexamethylene biguanide and chitosan in water at 85℃ for 60min, adjusting pH to about 7, to obtain a multifunctional finishing liquid; wherein the amount of tetramethylphosphonium chloride is 8g / L, the amount of polyhexamethylene biguanide is 10g / L, and the amount of chitosan is 0.5g / L;

[0039] S2, the multifunctional finishing liquid is loaded into a pneumatic spray gun, and the multifunctional finishing liquid is uniformly sprayed on the surface of the silk product, so that the liquid carrying rate of the silk product is 50%, and the multifunctional silk product is obtained after air drying.

[0040] Comparative Example 1

[0041] The same as Example 1, except that tetramethylphosphonium chloride is replaced by phosphoric acid.

[0042] Comparative Example 2

[0043] The same as Example 1 except that no tetramethylphosphonium chloride was added.

[0044] Comparative Example 3

[0045] The same as Example 1 except that polyhexamethylene biguanide was replaced by polyethyleneimine.

[0046] Comparative Example 4

[0047] The same as Example 1 except that no polyhexamethylene biguanide was added.

[0048] Comparative Example 5

[0049] The same as Example 1 except that chitosan was replaced by polyethyleneimine.

[0050] Comparative Example 6

[0051] The same as Example 1 except that no chitosan was added.

[0052] Test Example 1

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

[0054] The antibacterial rate of the silk product was determined according to the standard of GB / T 20944.3-2008 “Evaluation of Antibacterial Properties of Textiles Part 3: Oscillation Method”;

[0055] The mildew-proof property of the silk product was determined according to the standard of GB / T 24346-2009 “Evaluation of Mildew-Proof Properties of Textiles”;

[0056] The flame-retardant property of the silk product was determined according to the standard of GB / T 5455-2014 “Determination of Vertical Burning Length, Afterglow and Afterflame Time of Textiles”;

[0057] Figure 1 The antibacterial property test pictures of the silk product before and after finishing in Example 1 are shown in the following table:

[0058] The relevant properties of the unfinishing silk product and the finishing silk product determined finally are shown in Table 1:

[0059] Table 1

[0060] Specimen Escherichia coli inhibition rate (%) Staphylococcus aureus inhibition rate (%) Mildew-proof grade Char length (cm) Unfinished silk product 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 multifunctional silk product of the embodiment has an antibacterial rate of 95.1%-99.9% against E. coli and S. aureus, a mildew-proof grade of less than 1, and a char length of less than 12.1 cm, indicating that the multifunctional silk product has excellent antibacterial performance, mildew-proof performance, and flame-retardant performance.

[0062] As can be seen from Comparative Example 1 and Comparative Example 2, when the phosphorus tetrahydroxymethyl chloride is not added, the antibacterial performance and the mildew-proof performance of the finished silk product are reduced, and the flame-retardant performance is lost, because the acid source is lacking in the flame-retardant system, and the intumescent flame-retardant system cannot be formed, and the phosphorus tetrahydroxymethyl chloride is a good antibacterial and mildew-proof agent.

[0063] As can be seen from Comparative Example 1 and Comparative Example 2, when the phosphorus tetrahydroxymethyl chloride is not added, the antibacterial performance and the mildew-proof performance of the finished silk product are reduced, and the flame-retardant performance is lost, because the acid source is lacking in the flame-retardant system, and the intumescent flame-retardant system cannot be formed, and the phosphorus tetrahydroxymethyl chloride is a good antibacterial and mildew-proof agent.

[0064] As can be seen from Comparative Example 1 and Comparative Example 3, when the polyhexamethylene biguanide is replaced by polyethylene imine, the antibacterial performance, the mildew-proof performance, and the flame-retardant performance of the finished silk product are reduced, because the antibacterial and mildew-proof performance of the polyethylene imine is poor, and the polyethylene imine has many branched chains, and precipitates are easily formed after the reaction with the phosphorus tetrahydroxymethyl chloride, resulting in poor flame-retardant efficiency.

[0065] As can be seen from Comparative Example 1 and Comparative Example 4, when the polyhexamethylene biguanide is not added, the antibacterial performance, the mildew-proof performance, and the flame-retardant performance of the finished silk product are reduced, because the gas source is lacking in the flame-retardant system, and the intumescent flame-retardant system cannot be formed, and the polyhexamethylene biguanide is a good antibacterial and mildew-proof agent.

[0066] As can be seen from Comparative Example 1 and Comparative Example 5, when the chitosan is replaced by polyethylene imine, the antibacterial performance, the mildew-proof performance, and the flame-retardant performance of the finished silk product are reduced, because the antibacterial and mildew-proof performance of the polyethylene imine is poor, and the polyethylene imine has many branched chains, and precipitates are easily formed after the reaction with the phosphorus tetrahydroxymethyl chloride, and the film-forming property of the polyethylene imine is also poor, resulting in poor flame-retardant efficiency.

[0067] As can be seen from Comparative Example 1 and Comparative Example 6, when the chitosan is not added, the antibacterial performance, the mildew-proof performance, and the flame-retardant performance of the finished silk product are reduced, because the chitosan itself has certain antibacterial and mildew-proof performance, and can act as a gas source and a carbon source, further improving the flame-retardant efficiency of the intumescent system, in addition, the chitosan has good film-forming performance, and helps the finishing agent to be further attached to the surface of the silk product.

[0068] Obviously, the above embodiments are merely example for clearly illustrating, and are not limitation to the embodiments. For ordinary skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, all the embodiments need not and can not be exhausted. The obvious changes or variations derived therefrom are still within the scope of the present invention.

Claims

1. A method for preparing a multifunctional finishing liquid, characterized by, The method comprises the following steps: The cross-linking reaction of tetramethyl phosphonium chloride, polyhexamethylene biguanide and film forming agent in water obtains the multifunctional finishing liquid. The film forming agent is chitosan; the mass ratio of tetramethyl phosphonium chloride, polyhexamethylene biguanide and film forming agent is (5-8):(7-10):(0.3-0.5); the concentration of the film forming agent is 0.3g / L-0.5g / L.

2. The method for preparing a multifunctional finishing liquid according to claim 1, characterized in that, The temperature of the cross-linking reaction is 75-85℃, and the time is 60-90min.

3. The method of claim 1, wherein the multi-functional finishing liquid is prepared by adding 0.1 to 5 parts by weight of the polyurethane resin to 100 parts by weight of the solvent. The pH of the multifunctional finishing liquid is 6-7. 4.A multifunctional finishing liquid prepared by the method in any one of claims 1-3.

5. A finishing method of a multifunctional silk product, characterized by, The method comprises the following steps: Spraying the multifunctional finishing liquid in claim 4 on the surface of silk products, and drying to obtain the multifunctional silk products.

6. The method of claim 5, wherein, After spraying the multifunctional finishing liquid, the liquid carrying rate of the silk products is 30%-50%. 7.A multifunctional silk product finished by the method in claim 5 or 6.

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