A modified sericin anti-ultraviolet coating and preparation method thereof

Abstract

The present invention belongs to the technical field of polymer material surface treatment, and discloses a modified sericin anti-ultraviolet coating and a preparation method thereof. The preparation method of the modified sericin anti-ultraviolet coating comprises the following steps: mixing sericin, water and a copper source to obtain a composite anti-ultraviolet finishing agent; mixing the composite anti-ultraviolet finishing agent with a curing agent to obtain a mixed liquid, and then curing it on the surface of a fabric to obtain a modified sericin anti-ultraviolet coating. The modified sericin anti-ultraviolet coating of the present invention has a dual interaction. On the one hand, sericin acts as a reducing agent for copper ions, reducing part of the copper source into copper nanoparticles of different valence states and attaching them to the coating on the surface of the fabric. These copper nanoparticles can reflect and refract part of the ultraviolet rays, thereby enhancing the ultraviolet protection performance; on the other hand, copper ions denature sericin, thereby increasing the content of amino acid residues with ultraviolet absorption ability.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer material surface treatment, and in particular to a modified sericin anti-ultraviolet coating and a preparation method thereof. Background Art

[0002] As the degree of ozone layer depletion continues to increase, the amount of ultraviolet rays reaching the ground will increase directly, and it is inevitable that textiles will be exposed to ultraviolet light. Long-term exposure to ultraviolet light will cause fabric fibers to age, reduce strength, shorten life, and even break. In addition, the increasing amount of ultraviolet rays passing through fabrics leads to a sharp increase in the risk of people suffering from diseases such as skin cancer. Applying an anti-ultraviolet coating on the surface of fabric fibers is the simplest and most effective way to improve their anti-ultraviolet performance.

[0003] Sericin is secreted by the silk glands of silkworms and wrapped in the surface of silk fibers. It is a natural macromolecular protein. Sericin is widely used in various fields due to its good water solubility, lower immunogenicity and antioxidant activity. The amino acid residues of sericin contain a large number of strong polar groups such as hydroxyl, carboxyl, and amino groups, so it has a strong ability to absorb ultraviolet light. However, most of the amino acid residues are wrapped inside the double helix structure of the protein and are difficult to be exposed to the surface to absorb ultraviolet light.

[0004] The solvents in the common anti-ultraviolet finishing agents are mostly toxic and complicated to post-process, and toxic gases may be released during the drying process. Therefore, how to provide a coating with low cost, non-toxic and environmentally friendly and excellent anti-ultraviolet effect has become an urgent problem to be solved. Summary of the invention

[0005] The object of the present invention is to provide a modified sericin anti-ultraviolet coating and a preparation method thereof, so as to solve the problems existing in the prior art.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a method for preparing a modified sericin anti-ultraviolet coating, comprising the following steps:

[0008] (1) mixing sericin, water and a copper source to obtain a composite anti-ultraviolet finishing agent;

[0009] (2) The composite anti-ultraviolet finishing agent is mixed with a curing agent to obtain a mixed solution, which is then cured on the surface of the fabric to obtain a modified sericin anti-ultraviolet coating.

[0010] Preferably, in the above method for preparing a modified sericin anti-ultraviolet coating, the copper source in step (1) is one or more of copper acetate, copper chloride, copper nitrate, copper sulfate, and copper-based MOF.

[0011] Preferably, in the above method for preparing a modified sericin anti-ultraviolet coating, the curing agent in step (2) is one or more of peroxidase, polyphenol oxidase, glutaraldehyde, and maleimide.

[0012] Preferably, in the above-mentioned method for preparing a modified sericin anti-ultraviolet coating, the mass volume ratio of sericin to water in step (1) is 1 g: 10-100 mL, the mass ratio of the copper source to sericin is 1: 10-300, and the mass ratio of the curing agent to sericin in step (2) is 1: 50-200.

[0013] Preferably, in the above method for preparing a modified sericin anti-ultraviolet coating, the specific process of mixing in step (1) is: first dissolving the sericin in water, and then mixing with the copper source.

[0014] Preferably, in the above method for preparing a modified sericin anti-ultraviolet coating, the conditions for mixing with the copper source are: temperature of 0 to 60° C. and time of 4 to 24 hours.

[0015] Preferably, in the above-mentioned method for preparing a modified sericin anti-ultraviolet coating, the curing method in step (2) is: placing the fabric in the mixed liquid, immersing, pre-baking and drying to obtain the modified sericin anti-ultraviolet coating.

[0016] Preferably, in the above-mentioned method for preparing a modified sericin anti-UV coating, the immersion time is 4 to 8 hours; the pre-baking time is 2 to 10 minutes, and the pre-baking temperature is 40 to 80°C; the drying temperature is 20 to 30°C, and the drying time is 8 to 14 hours.

[0017] The present invention also provides a modified sericin anti-ultraviolet coating prepared by the preparation method of the modified sericin anti-ultraviolet coating.

[0018] Principles involved in the present invention:

[0019] The present invention provides a modified sericin anti-ultraviolet coating, wherein sericin, a byproduct produced during the degumming process of silk, is selected as the base of the anti-ultraviolet coating, and the sericin is modified by utilizing the property that copper metal ions can destroy the secondary structure of the protein to enhance the ultraviolet light absorption capacity. Deionized water is selected as the solvent of the anti-ultraviolet coating, which is pollution-free and non-toxic. The reduction effect of sericin can also reduce the copper metal ions into nanoparticles and deposit on the surface of the fabric to shield part of the ultraviolet light.

[0020] Copper ions, as typical heavy metal ions, can denature proteins (denaturation is equivalent to a change in the conformation of proteins, and chelates are produced by the interaction between amino groups on the surface of proteins and copper ions), destroying the double helix structure of proteins and exposing their amino acid residues to the surface. On the one hand, the UV protection of the finishing agent is enhanced, and on the other hand, more amino acid residues also make the cross-linking reaction of proteins more intense, and the binding force with fabrics is stronger.

[0021] A large number of amino groups on sericin will react with copper ions to form chelates, and then, under the action of a crosslinking agent, an anti-ultraviolet coating based on sericin is formed. Since sericin has strong ultraviolet absorption in the low-wavelength band of the ultraviolet region, and copper nanoparticles can also absorb ultraviolet rays of about 300nm, the prepared composite anti-ultraviolet coating can effectively improve the anti-ultraviolet performance of the fabric.

[0022] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The present invention makes full use of sericin extracted from sericin waste liquid and uses it as the base of the anti-ultraviolet coating. The coating has the advantages of excellent anti-ultraviolet performance, good biocompatibility, and non-toxic solvents.

[0024] (2) The modified sericin anti-ultraviolet coating of the present invention has a dual interaction. On the one hand, sericin acts as a reducing agent for copper ions, reducing part of the copper source into copper nanoparticles of different valence states and attaching them to the coating on the surface of the fabric. These copper nanoparticles can reflect and refract part of the ultraviolet rays, thereby enhancing the ultraviolet protection performance. On the other hand, copper ions denature sericin, thereby increasing the content of amino acid residues with ultraviolet absorption ability.

[0025] (3) The modified sericin anti-ultraviolet coating prepared by the present invention significantly enhances the ultraviolet protection performance of fabric fibers, improves the light aging resistance of the fabric, and prolongs its service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required to be used in the description of the embodiments or the prior art are briefly introduced below.

[0027] Figure 1 is the X-ray photoelectron spectrum of the composite anti-ultraviolet finishing agent in Example 1;

[0028] Figure 2 is the X-ray photoelectron spectrum of the composite anti-ultraviolet finishing agent in Example 5;

[0029] Figure 3This is a scanning electron microscope image of the modified sericin anti-ultraviolet coating in Example 2. DETAILED DESCRIPTION

[0030] The present invention provides a method for preparing a modified sericin anti-ultraviolet coating, comprising the following steps:

[0031] (1) mixing sericin, water and a copper source to obtain a composite anti-ultraviolet finishing agent;

[0032] (2) The composite anti-ultraviolet finishing agent is mixed with a curing agent to obtain a mixed solution, which is then cured on the surface of the fabric to obtain a modified sericin anti-ultraviolet coating.

[0033] In the present invention, the copper source in step (1) is preferably one or more of copper acetate, copper chloride, copper nitrate, copper sulfate, and copper-based MOF, further preferably one or more of copper acetate, copper chloride, and copper-based MOF, more preferably one or both of copper acetate and copper-based MOF.

[0034] In the present invention, the curing agent in step (2) is preferably one or more of peroxidase, polyphenol oxidase, glutaraldehyde, and maleimide, more preferably one or more of peroxidase, glutaraldehyde, and maleimide, and more preferably one or both of peroxidase and glutaraldehyde.

[0035] In the present invention, the mass volume ratio of sericin to water in step (1) is preferably 1 g: 10-100 mL, more preferably 1 g: 15-95 mL, and more preferably 1 g: 25-80 mL; the mass ratio of the copper source to sericin is preferably 1: 10-300, more preferably 1: 20-250, and more preferably 1: 30-160; the mass ratio of the curing agent to sericin in step (2) is preferably 1: 50-200, more preferably 1: 60-180, and more preferably 1: 80-150.

[0036] In the present invention, the specific process of mixing in step (1) is as follows: firstly dissolving the sericin in water, and then mixing it with the copper source.

[0037] In the present invention, the conditions for mixing with the copper source are: the temperature is preferably 0-60°C, more preferably 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60°C, more preferably 20, 25, 30 or 35°C; the time is preferably 4-24h, more preferably 4, 8, 10, 12, 15, 18, 20 or 24h, more preferably 12, 15 or 18h.

[0038] In the present invention, the curing method in step (2) is: placing the fabric in the mixed liquid, immersing, pre-baking and drying to obtain the modified sericin anti-ultraviolet coating; before placing the fabric in the mixed liquid, the method also includes: washing the fabric in anhydrous ethanol for 5 minutes and drying it in a vacuum oven at 60°C for 10 minutes.

[0039] In the present invention, the impregnation time is preferably 4 to 8 hours, more preferably 4, 5, 6, 7 or 8 hours, more preferably 6 or 7 hours; the pre-baking time is preferably 2 to 10 minutes, more preferably 2, 4, 5, 6, 8 or 10 minutes, more preferably 5, 6 or 8 minutes, the pre-baking temperature is preferably 40 to 80°C, more preferably 40, 45, 50, 55, 60, 65, 70, 75 or 80°C, more preferably 60, 65 or 70°C; the drying temperature is preferably 20 to 30°C, more preferably 20, 22, 24, 25, 28 or 30°C, more preferably 24 or 25°C, the drying time is preferably 8 to 14 hours, more preferably 8, 9, 10, 11, 12, 13 or 14 hours, more preferably 10, 11 or 12 hours.

[0040] In the present invention, the ratio of sericin in step (1) to fabric in step (2) is preferably 2-7 g: 8-15 cm 3 , more preferably 2.5 to 6 g: 9 to 13 cm 3 , more preferably 4-5g: 10-12cm 3 .

[0041] The present invention also provides a modified sericin anti-ultraviolet coating prepared by the preparation method of the modified sericin anti-ultraviolet coating.

[0042] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] Example 1

[0044] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0045] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.025 g of copper acetate monohydrate at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0046] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0047] (3) 10cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0048] Example 2

[0049] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0050] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.05 g of copper acetate monohydrate at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0051] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0052] (3) 10cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0053] Example 3

[0054] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0055] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.075 g of copper acetate monohydrate at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0056] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0057] (3) 10cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0058] Example 4

[0059] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0060] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.1 g of copper acetate monohydrate at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0061] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0062] (3) 10cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0063] Example 5

[0064] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0065] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.025 g of copper-based MOF-[Cu2(bptc)(bpy)2] at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0066] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0067] (3) 10cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0068] Example 6

[0069] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0070] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.05 g of copper-based MOF-[Cu2(bptc)(bpy)2] at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0071] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0072] (3) 10cm 3The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0073] Example 7

[0074] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0075] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.075 g of copper-based MOF-[Cu2(bptc)(bpy)2] at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0076] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0077] (3) 10cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0078] Example 8

[0079] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0080] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.1 g of copper-based MOF-[Cu2(bptc)(bpy)2] at 35°C, and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0081] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0082] (3) 10cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0083] [Cu2(bptc)(bpy)2] described in Examples 5 to 8 was prepared according to Patent 202310098811.9, and the specific preparation method is as follows:

[0084] (1) Dissolve 1.0 g of cupric acetate monohydrate, 0.39 g of 4,4'-bipyridine, and 0.90 g of 3,3',4,4'-tetracarboxylic acid benzophenone in 70 mL of deionized water and mix well;

[0085] (2) the mixed solution was reacted in a hydrothermal reactor at 140° C. for 60 hours and then the precipitate was taken out;

[0086] (3) The product was washed four times with deionized water by centrifugation and then dried in vacuum at 80 °C for 12 h to obtain [Cu2(bptc)(bpy)2].

[0087] Example 9

[0088] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0089] (1) Weigh 3 g of sericin powder, dissolve it in 80 mL of deionized water, add 0.024 g of cupric chloride dihydrate at 40° C., and stir for 6 h to obtain a composite anti-ultraviolet finishing agent;

[0090] (2) adding 0.03 g of peroxidase to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0091] (3) 7cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 5 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0092] Example 10

[0093] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0094] (1) Weigh 6 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.08 g of copper nitrate trihydrate at 50° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0095] (2) adding 0.08 g of polyphenol oxidase to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0096] (3) 12cm 3The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0097] Embodiment 11

[0098] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0099] (1) Weigh 8 g of sericin powder, dissolve it in 120 mL of deionized water, add 0.09 g of copper acetate monohydrate at 25° C., and stir for 15 h to obtain a composite anti-ultraviolet finishing agent;

[0100] (2) adding 0.05 g of maleimide to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0101] (3) 15cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 56 fiber cloth. The treated nylon 56 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0102] Example 12

[0103] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0104] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.025 g of copper acetate monohydrate at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0105] (2) adding 0.05 g of maleimide to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0106] (3) 10cm 3 The nylon 6 fiber cloth was washed in anhydrous ethanol for 5 minutes, dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 6 fiber cloth, and the treated nylon 6 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0107] Embodiment 13

[0108] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0109] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.05 g of copper nitrate trihydrate at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0110] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0111] (3) 10cm 3 The nylon 6 fiber cloth was washed in anhydrous ethanol for 5 minutes, dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 6 fiber cloth, and the treated nylon 6 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0112] Embodiment 14

[0113] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0114] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.075 g of copper nitrate trihydrate at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0115] (2) adding 0.05 g of maleimide to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0116] (3) 10cm 3 The nylon 66 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 66 fiber cloth. The treated nylon 66 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0117] Embodiment 15

[0118] A method for preparing a modified sericin anti-ultraviolet coating comprises the following steps:

[0119] (1) Weigh 5 g of sericin powder, dissolve it in 100 mL of deionized water, add 0.1 g of copper acetate monohydrate at 35° C., and stir for 8 h to obtain a composite anti-ultraviolet finishing agent;

[0120] (2) adding 0.05 g of glutaraldehyde to the composite anti-ultraviolet finishing agent to obtain a mixed solution;

[0121] (3) 10cm 3The nylon 66 fiber cloth was washed in anhydrous ethanol for 5 minutes and dried in a vacuum oven at 60°C for 10 minutes to obtain the treated nylon 66 fiber cloth. The treated nylon 66 fiber cloth was immersed in the mixed solution for 6 hours, roll-dried, pre-baked at 60°C for 5 minutes, and then dried at room temperature for 12 hours to obtain a modified sericin anti-ultraviolet coating.

[0122] Comparative Example

[0123] 10cm 3 The nylon 56 fiber cloth was washed in anhydrous ethanol for 5 min and dried in a vacuum oven at 60°C for 10 min.

[0124] Figure 1 , 2 They are respectively the X-ray photoelectron spectra of the composite anti-ultraviolet finishing agent in Example 1 and Example 5. Figure 1 , 2 It can be seen that regardless of the type of copper source added, the characteristic peaks of copper ions and reduced copper can be observed in the XPS spectrum of the composite anti-UV finishing agent, indicating that there is an interaction between sericin and copper ions.

[0125] Figure 3 is a scanning electron microscope image of the modified sericin anti-ultraviolet coating in Example 2. Figure 3 It can be seen that the anti-ultraviolet finishing agent based on sericin can be cured on the surface of nylon 56 fiber cloth under the action of cross-linking agent glutaraldehyde.

[0126] The ultraviolet protection factor (UPF) represents the ultraviolet protection ability of a sample. The higher the UPF value, the better the ultraviolet shielding performance of the material. The ultraviolet protection factor results of the modified sericin anti-ultraviolet coating based on nylon 56 fiber cloth prepared in Examples 1 to 8 are shown in Table 1.

[0127]

[0128] Where E(λ) is the solar spectral radiance, ε(λ) is the relative erythema action spectrum value, T(λ) is the ultraviolet spectral transmittance at the wavelength of λ, and Δλ is the wavelength interval of the measured value.

[0129] From the results of the comparative example and Examples 1 to 8 in Table 1, it can be seen that the modified sericin anti-ultraviolet coatings based on nylon 56 fiber cloth obtained in Examples 1 to 4 and Examples 5 to 8 can enhance the ultraviolet protection performance of nylon cloth under different copper source addition mass conditions, indicating that the modified sericin anti-ultraviolet coating of the present invention is an effective anti-ultraviolet coating. In addition, under the same copper source addition mass condition, due to the presence of benzophenone structure in the organic framework, the UPF values ​​of Examples 5 to 8 are much higher than those of Examples 1 to 4.

[0130] The modified sericin anti-ultraviolet coatings based on nylon 56 fiber cloth prepared in Examples 1 to 8 and the nylon 56 fiber cloth of the comparative example were subjected to an ultraviolet light accelerated aging performance test, with 24 hours as a cycle, and each cycle included 8 hours of spraying, 8 hours of high temperature drying, and a full cycle of xenon lamp ultraviolet irradiation; the modified sericin anti-ultraviolet coatings based on nylon 56 fiber cloth prepared in Examples 1 to 8 and the nylon 56 fiber cloth of the comparative example were subjected to thermogravimetric analysis and single fiber strength test after accelerated aging for 72 hours, and the results are shown in Table 1.

[0131] From the results of the comparative example and Examples 1 to 8 in Table 1, it can be seen that the nylon 56 fiber fabrics based on sericin anti-ultraviolet coatings obtained in Examples 1 to 4 and Examples 5 to 8, under the condition of different copper source addition masses, the thermal decomposition temperature and single filament tensile strength of the nylon 56 fiber fabrics coated with the modified sericin anti-ultraviolet coatings are stronger than those of the untreated nylon 56 fiber fabrics, that is, the modified sericin anti-ultraviolet coatings in Examples 1 to 8 can improve the ultraviolet aging resistance of the nylon 56 fiber fabrics.

[0132] Table 1 Performance test results of Examples 1 to 8 and Comparative Examples

[0133]

[0134] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a modified sericin anti-ultraviolet coating, characterized in that: The following steps are involved: (1) Mixing sericin, water and a copper source to obtain a composite anti-ultraviolet finishing agent; (2) mixing the composite anti-ultraviolet finishing agent with the curing agent to obtain a mixed solution, and then curing the mixed solution on the surface of the fabric to obtain a modified sericin anti-ultraviolet coating; In step (1), the copper source is one or more of copper acetate, copper chloride, copper nitrate, copper sulfate, and copper-based MOF; In step (2), the curing agent is one or more of peroxidase, polyphenol oxidase, glutaraldehyde, and maleimide; In step (1), the mass volume ratio of sericin to water is 1 g: 10-100 mL, the mass ratio of the copper source to sericin is 1: 10-300, and the mass ratio of the curing agent to sericin in step (2) is 1: 50-200; The specific process of mixing in step (1) is as follows: firstly dissolving the sericin in water, and then mixing it with the copper source; The mixing conditions with the copper source are: temperature of 0-60°C and time of 4-24h; Copper ions can denature proteins, destroy their double helix structure, expose their amino acid residues to the surface, and enhance the UV protection performance of the finishing agent. More amino acid residues also make the cross-linking reaction of proteins more intense and the bonding with fabrics stronger.

2. The method for preparing the modified sericin anti-ultraviolet coating according to claim 1, characterized in that: The curing method in step (2) is: placing the fabric in the mixed liquid, dipping, pre-baking and drying to obtain the modified sericin anti-ultraviolet coating.

3. The method for preparing the modified sericin anti-ultraviolet coating according to claim 2, characterized in that: The dipping time is 4 to 8 hours; the pre-baking time is 2 to 10 minutes, and the pre-baking temperature is 40 to 80° C.; the drying temperature is 20 to 30° C., and the drying time is 8 to 14 hours.

4. The modified sericin anti-ultraviolet coating prepared by the method for preparing the modified sericin anti-ultraviolet coating according to any one of claims 1 to 3.

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