Preparation method and product of plant dye-collagen complex and application thereof

Abstract

The invention discloses a preparation method and product of a plant dye-collagen complex and its application, including pre-treating fresh pigskin to obtain pre-treated pigskin, enzymatically treating it with pepsin to obtain a collagen extract; preparing a plant dye solution with a mass concentration of 20 to 40 g / L, adding the collagen extract, stirring at room temperature, filtering, and collecting the precipitate; washing the obtained precipitate with deionized water, dissolving it in an acetic acid solution, and preparing a plant dye-collagen complex solution with a mass concentration of 20 to 40 g / L. The present invention utilizes the characteristic that collagen is easily precipitated under alkaline conditions and precipitates it on textiles. By pre-treating the metal ions of the textiles to the coordination effect between the collagen and the plant dye, and the film-forming property of the collagen, the plant dye-collagen complex is fixed on the textiles to achieve a good coloring effect on the textiles.

Description

Technical Field

[0001] The invention belongs to the field of textile technology, and particularly relates to a preparation method and product of a plant dye-collagen complex and application thereof. Background Art

[0002] Plant dyes have garnered increasing attention in recent years, with some domestic companies experimenting with using them for clothing and home textiles. However, due to the lack of strong bonding between plant dyes and textiles, the color fastness of plant dyes is significantly lower than that of synthetic dyes, limiting their widespread application.

[0003] Collagen is highly compatible with human skin. Its molecular chains contain numerous hydrophilic groups, such as hydroxyl and carboxyl groups, as well as natural moisturizing factors like glycine, which promote skin hydration. Textiles finished with collagen are widely favored by consumers for their skin-friendly, moisturizing, comfortable, and safe properties.

[0004] However, there are few reports on the use of collagen to improve the dyeing performance of plant dyes on textiles. Summary of the Invention

[0005] The purpose of this section is to summarize some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of this application to avoid obscuring the purpose of this section, the abstract and the title of the invention, and such simplifications or omissions should not be used to limit the scope of the present invention.

[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0007] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a plant dye-collagen complex.

[0008] In order to solve the above technical problems, the present invention provides the following technical solutions: a method for preparing a plant dye-collagen complex, comprising:

[0009] pre-treating fresh pigskin to obtain pre-treated pigskin;

[0010] The pretreated pig skin is subjected to enzymatic hydrolysis with pepsin to obtain collagen extract;

[0011] Prepare a plant dye solution with a mass concentration of 20-40 g / L, add the collagen extract, stir at room temperature, filter, and collect the precipitate;

[0012] The obtained precipitate is washed with deionized water and dissolved in acetic acid solution to prepare a plant dye-collagen complex solution with a mass concentration of 20-40 g / L. After stirring for 30-60 minutes, the insoluble matter is removed by filtration to obtain a plant dye-collagen complex product.

[0013] As a preferred embodiment of the preparation method of the present invention, the fresh pigskin is pretreated, comprising:

[0014] Wash fresh pigskin with 25-30℃ deionized water to remove surface stains, remove subcutaneous fat, cut into 5mm×5mm pieces, soak in 10% NaCl solution for 12-24h, and wash with deionized water 2-3 times;

[0015] Immerse the pigskin in a 5% by mass Na2CO3 solution, stir at room temperature for 1 to 2 hours, and wash with deionized water 2 to 3 times to obtain the pretreated pigskin.

[0016] As a preferred embodiment of the preparation method of the present invention, the preparation method of the collagen extract comprises:

[0017] The pretreated pigskin was dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:50-1:100 g / mL and enzymatically hydrolyzed at 25-35°C for 48-72 hours;

[0018] After the enzymatic hydrolysis, centrifuge at 4°C and 8000 rpm for 5-8 min, and collect the supernatant.

[0019] Add 1 mol / L sodium hydroxide solution to the supernatant and adjust the pH of the solution to 5.8-7.0. When collagen precipitate is observed, let it stand for 4-6 hours, filter it, and quickly wash the collagen precipitate with deionized water 3-4 times to obtain a collagen extract.

[0020] As a preferred embodiment of the preparation method of the present invention, the concentration of acetic acid in the acetic acid-pepsin mixed solution is 0.5-1.0 mol / L, the mass ratio of pepsin to pigskin is 1:10-1:40, and the enzyme activity is ≥1200 U / g.

[0021] As a preferred embodiment of the preparation method of the present invention, the plant dye is one of honeysuckle extract, green tea extract, wormwood extract, chestnut shell extract, madder extract, turmeric extract, sappanwood extract, gardenia fruit extract, pomegranate peel extract, loquat leaf extract, sophora japonica extract or cotinus coggygria extract.

[0022] As a preferred embodiment of the preparation method of the present invention, the concentration of the collagen extract in the plant dye solution is 5 to 10 g / L.

[0023] As a preferred embodiment of the preparation method of the present invention, the concentration of the acetic acid solution is 1 mol / L.

[0024] Another object of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a plant dye-collagen complex and to use the plant dye-collagen complex product in textile coloring.

[0025] As a preferred embodiment of the application of the present invention, the invention comprises:

[0026] Immerse the desized, scouring and bleached textiles in a metal salt solution with a bath ratio of 1:5 to 1:8, adjust the pH value of the solution to 4 to 5 with 0.5 mol / L acetic acid, and treat at 30 to 40°C for 30 to 60 minutes;

[0027] Then, deionized water is added to dilute the bath ratio to 1:30-1:40, the temperature is raised to 50-70°C, and the treatment is carried out for 30-60 minutes, followed by washing with deionized water for 3-5 times, dehydration and drying to obtain the pretreated textiles;

[0028] The pretreated textile is immersed in a plant dye-collagen complex solution. After adsorption at room temperature for 30 to 60 minutes, the textile is taken out and immersed in a 0.5% by mass Na2CO3 solution to deposit the plant dye-collagen complex on the surface of the textile.

[0029] After roller pressing and dehydration, the textiles were immersed in the plant dye-collagen complex solution again. After adsorption at room temperature for 30 to 60 minutes, the textiles were taken out and immersed in a 0.5% by mass Na2CO3 solution.

[0030] After repeating the operation 3 to 5 times, the product is rolled and dehydrated, immersed in a 25% glutaraldehyde solution with a concentration of 10 to 20 g / L for 6 to 12 hours, rolled and dehydrated, and vacuum dried at 30 to 40°C.

[0031] As a preferred embodiment of the application of the present invention, the fabric is cotton, linen, polyester or a blend of the two; the metal salt is one of ferrous sulfate, ferrous chloride, ferric sulfate, ferric chloride, zinc chloride, zinc acetate, zinc nitrate, aluminum chloride, aluminum sulfate, titanium sulfate or titanium chloride, and the concentration of the metal salt is 2 to 5 g / L.

[0032] Beneficial effects of the present invention:

[0033] The present invention utilizes for the first time the characteristics of collagen and plant dyes forming hydrogen bonds, van der Waals forces, and ionic bonds to prepare a plant dye-collagen complex; utilizing the characteristic of collagen being easily precipitated under alkaline conditions, it is precipitated on textiles, and through the coordination effect between the metal ions pretreated into the textiles and the collagen and plant dyes, as well as the film-forming property of collagen, the plant dye-collagen complex is fixed to the textiles, achieving a good coloring effect on the textiles. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort. Among them:

[0035] Figure 1 This is the infrared spectrum of collagen obtained in Example 2.

[0036] Figure 2 This is a photo of the fabric sample obtained in Example 2. DETAILED DESCRIPTION

[0037] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0038] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0039] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0040] The raw materials in the present invention are all common commercially available products.

[0041] Example 1

[0042] (1) Fresh pigskin was cleaned of surface stains with 25°C deionized water, subcutaneous fat was removed, and the skin was cut into 5 mm x 5 mm pieces. The pieces were soaked in a 10% NaCl solution for 12 h, washed twice with deionized water, immersed in a 5% Na2CO3 solution, stirred at room temperature for 1 h, washed twice with deionized water, and stored in a refrigerator for later use.

[0043] (2) The pigskin treated in step (1) is dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:50 g / mL, wherein the concentration of acetic acid in the mixed solution is 0.5 mol / L, and the ratio of pepsin (enzyme activity ≥ 1200 U / g) to pigskin mass is 1:10, and the mixture is enzymatically hydrolyzed at 25° C. for 72 h, slowly stirred during the enzymatic hydrolysis process, and centrifuged at 8000 r / min for 5 min at about 4° C. after the enzymatic hydrolysis is completed, and the supernatant is collected; under stirring, 1 mol / L sodium hydroxide solution is slowly added to the supernatant, and the pH of the solution is adjusted to 5.8, and collagen precipitation can be observed. The mixture is allowed to stand for 4 h, filtered, and the collagen precipitate is quickly washed with deionized water 3 times to obtain a collagen extract;

[0044] (3) Prepare a honeysuckle extract solution with a mass concentration of 20 g / L. After it is completely dissolved, add the collagen extract obtained in step (2). The concentration of collagen in the honeysuckle extract solution is 5 g / L. Stir at room temperature for 30 minutes, filter, collect the precipitate, and wash it three times with deionized water. Dissolve the precipitate in 1 mol / L acetic acid solution to prepare a honeysuckle extract-collagen complex solution with a mass concentration of 20 g / L. After slowly stirring for 30 minutes, filter to remove insoluble matter, and set aside.

[0045] (4) Immerse the desized, scour, and bleached cotton fabric in a 2 g / L ferric sulfate solution with a bath ratio of 1:5, adjust the pH value of the solution to 4 with 0.5 mol / L acetic acid, and treat at 30°C for 60 min;

[0046] Then add deionized water to dilute to a bath ratio of 1:30, heat to 50 ° C, treat for 60 minutes, wash with deionized water three times, dehydrate and dry;

[0047] Immerse in the honeysuckle extract-collagen complex solution obtained in step (3), adsorb at room temperature for 30 minutes, take out the textile, immerse in a 0.5% by mass fraction Na2CO3 solution, and deposit the honeysuckle extract-collagen complex on the cloth surface. After roller pressing and dehydration, immerse in the honeysuckle extract-collagen complex solution again, adsorb at room temperature for 30 minutes, take out the textile, immerse in a 0.5% by mass fraction Na2CO3 solution, repeat this 3 times, roller press dehydration, immerse in a 10g / L 25% glutaraldehyde solution for 12 hours, roller press dehydration, and vacuum dry at 30°C.

[0048] Example 2

[0049] (1) Fresh pigskin was cleaned of surface stains with 30°C deionized water, subcutaneous fat was removed, and the skin was cut into 5 mm x 5 mm pieces. The pieces were soaked in a 10% NaCl solution for 24 h, and then washed three times with deionized water. The pieces were then immersed in a 5% Na2CO3 solution, stirred at room temperature for 2 h, and then washed three times with deionized water. The pieces were then refrigerated for later use.

[0050] (2) The pigskin treated in step (1) is dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:100 g / mL, wherein the concentration of acetic acid in the mixed solution is 1.0 mol / L, and the ratio of pepsin (enzyme activity ≥ 1200 U / g) to pigskin mass is 1:40, and the mixture is enzymatically hydrolyzed at 35° C. for 48 h, slowly stirred during the enzymatic hydrolysis process, and centrifuged at 8000 r / min for 8 min at about 4° C. after the enzymatic hydrolysis is completed, and the supernatant is collected; under stirring, 1 mol / L sodium hydroxide solution is slowly added to the supernatant, and the pH of the solution is adjusted to 7.0, and collagen precipitation can be observed. The mixture is allowed to stand for 6 h, filtered, and the collagen precipitate is quickly washed with deionized water 4 times to obtain a collagen extract;

[0051] (3) preparing a green tea extract solution with a mass concentration of 40 g / L, and after complete dissolution, adding the collagen extract obtained in step (2), wherein the concentration of collagen in the green tea extract solution is 10 g / L, stirring at room temperature for 60 min, filtering, collecting the precipitate, and washing it with deionized water four times, dissolving the precipitate in a 1 mol / L acetic acid solution to prepare a green tea extract-collagen complex solution with a mass concentration of 40 g / L, slowly stirring for 60 min, filtering to remove insoluble matter, and setting aside;

[0052] (4) The desized, scouring and bleached polyester fabric was immersed in a 5g / L ferrous chloride solution with a bath ratio of 1:8, and the pH value of the solution was adjusted to 5 with 0.5mol / L acetic acid, and treated at 40°C for 30min; then deionized water was added to dilute the solution to a bath ratio of 1:40, and the temperature was raised to 70°C. After the treatment for 30min, the fabric was washed with deionized water for 5 times, dehydrated and dried; and immersed in the green tea extract-collagen complex solution obtained in step (3), and adsorbed at room temperature for 60min. The textile was taken out and immersed in a 0.5% mass fraction Na2CO3 solution. The green tea extract-collagen complex was deposited on the surface of the fabric. After roller pressing and dehydration, it was immersed in the green tea extract-collagen complex solution again. After adsorption at room temperature for 60 minutes, the textile was taken out and immersed in a 0.5% mass fraction Na2CO3 solution. After repeating this 5 times, it was roller pressed and dehydrated, immersed in a 20g / L 25% glutaraldehyde solution for 6 hours, roller pressed and dehydrated, and vacuum dried at 40°C.

[0053] The infrared spectrum of collagen obtained in this example is shown in Figure 1 ; The fabric sample photos obtained in this embodiment 2 are shown in Figure 2 .

[0054] Example 3

[0055] (1) Fresh pigskin was cleaned of surface stains with 28°C deionized water, subcutaneous fat was removed, and the skin was cut into 5 mm x 5 mm pieces. The pieces were soaked in a 10% NaCl solution for 18 h, washed twice with deionized water, immersed in a 5% Na2CO3 solution, stirred at room temperature for 1.5 h, washed twice with deionized water, and stored in a refrigerator for later use.

[0056] (2) The pigskin treated in step (1) is dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:80 g / mL, wherein the concentration of acetic acid in the mixed solution is 0.8 mol / L, and the ratio of pepsin (enzyme activity ≥ 1200 U / g) to pigskin mass is 1:30, and the mixture is enzymatically hydrolyzed at 30° C. for 54 h, slowly stirred during the enzymatic hydrolysis process, and centrifuged at 8000 r / min for 6 min at about 4° C. after the enzymatic hydrolysis is completed, and the supernatant is collected; under stirring, 1 mol / L sodium hydroxide solution is slowly added to the supernatant, and the pH of the solution is adjusted to 6.0, and collagen precipitation can be observed. The mixture is allowed to stand for 5 h, filtered, and the collagen precipitate is quickly washed with deionized water 3 times to obtain a collagen extract;

[0057] (3) Prepare a 25 g / L wormwood leaf extract solution, and after it is completely dissolved, add the collagen extract obtained in step (2), the concentration of collagen in the wormwood leaf extract solution is 8 g / L, stir at room temperature for 40 minutes, filter, collect the precipitate, and wash it three times with deionized water. Dissolve the precipitate in 1 mol / L acetic acid solution to prepare a 30 g / L wormwood leaf extract-collagen complex solution, slowly stir for 40 minutes, filter to remove insoluble matter, and set aside;

[0058] (4) Immerse the desized, scouring and bleached linen fabric in a 3g / L zinc acetate solution with a bath ratio of 1:6, adjust the pH value of the solution to 4.2 with 0.5mol / L acetic acid, and treat at 35°C for 40min; then add deionized water to dilute to a bath ratio of 1:35, heat to 60°C, treat for 40min, wash with deionized water 4 times, dehydrate and dry; immerse in the wormwood extract-collagen complex solution obtained in step (3), adsorb at room temperature for 40min, The textile is taken out and immersed in a 0.5% mass fraction Na2CO3 solution. The wormwood extract-collagen complex is deposited on the cloth surface. After roller pressing and dehydration, it is immersed in the wormwood extract-collagen complex solution again. After adsorption at room temperature for 40 minutes, the textile is taken out and immersed in a 0.5% mass fraction Na2CO3 solution. After repeating this 4 times, it is roller pressed and dehydrated, immersed in a 15g / L 25% glutaraldehyde solution for 8 hours, roller pressed and dehydrated, and vacuum dried at 35°C.

[0059] Example 4

[0060] (1) Fresh pigskin was cleaned of surface stains with 26°C deionized water, subcutaneous fat was removed, and the skin was cut into 5 mm x 5 mm pieces. The pieces were soaked in a 10% NaCl solution for 20 h, washed three times with deionized water, immersed in a 5% Na2CO3 solution, stirred at room temperature for 75 min, washed twice with deionized water, and stored in a refrigerator for later use.

[0061] (2) The pigskin treated in step (1) is dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:60 g / mL, wherein the concentration of acetic acid in the mixed solution is 0.6 mol / L, and the ratio of pepsin (enzyme activity ≥ 1200 U / g) to pigskin mass is 1:20, and the mixture is enzymatically hydrolyzed at 28° C. for 60 h, slowly stirred during the enzymatic hydrolysis process, and centrifuged at 8000 r / min for 7 min at about 4° C. after the enzymatic hydrolysis is completed, and the supernatant is collected; under stirring, 1 mol / L sodium hydroxide solution is slowly added to the supernatant, and the pH of the solution is adjusted to 6.5, and collagen precipitation can be observed. The mixture is allowed to stand for 4.5 h, filtered, and the collagen precipitate is quickly washed with deionized water 4 times to obtain a collagen extract;

[0062] (3) A chestnut shell extract solution with a mass concentration of 30 g / L was prepared. After complete dissolution, the collagen extract obtained in step (2) was added. The concentration of collagen in the chestnut shell extract solution was 6 g / L. The solution was stirred at room temperature for 50 min, filtered, and the precipitate was collected. After washing with deionized water 4 times, the precipitate was dissolved in 1 mol / L acetic acid solution to prepare a chestnut shell extract-collagen complex solution with a mass concentration of 25 g / L. The solution was slowly stirred for 50 min, filtered to remove insoluble matter, and set aside.

[0063] (4) Immerse the desized, scouring and bleached cotton / polyester blended fabric in a 4g / L aluminum sulfate solution with a bath ratio of 1:7, adjust the pH value of the solution to 4.8 with 0.5mol / L acetic acid, and treat at 38°C for 50min; then add deionized water to dilute to a bath ratio of 1:38, heat to 55°C, treat for 50min, wash with deionized water 5 times, dehydrate and dry; immerse in the chestnut shell extract-collagen complex solution obtained in step (3), adsorb at room temperature for 50min, take out the textile, immerse in a 0.5% by mass Na2CO3 solution, and deposit the chestnut shell extract-collagen complex on the fabric surface. After roller pressing and dehydration, immerse in the chestnut shell extract-collagen complex solution again, adsorb at room temperature for 50min, take out the textile, immerse in a 0.5% by mass Na2CO3 solution, repeat this 5 times, and then roller press and dehydrate the textile. Add 25% glutaraldehyde solution for 10 hours, roll to dehydrate, and dry in vacuum at 38°C.

[0064] Comparative Example 1

[0065] (1) Fresh pigskin was cleaned of surface stains with 25°C deionized water, subcutaneous fat was removed, and the skin was cut into 5 mm x 5 mm pieces. The pieces were soaked in a 10% NaCl solution for 12 h, washed twice with deionized water, immersed in a 5% Na2CO3 solution, stirred at room temperature for 1 h, washed twice with deionized water, and stored in a refrigerator for later use.

[0066] (2) The pigskin treated in step (1) is dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:50 g / mL, wherein the concentration of acetic acid in the mixed solution is 0.5 mol / L, and the ratio of pepsin (enzyme activity ≥ 1200 U / g) to pigskin mass is 1:10, and the mixture is enzymatically hydrolyzed at 25° C. for 72 h, slowly stirred during the enzymatic hydrolysis process, and centrifuged at 8000 r / min for 5 min at about 4° C. after the enzymatic hydrolysis is completed, and the supernatant is collected; under stirring, 1 mol / L sodium hydroxide solution is slowly added to the supernatant, and the pH of the solution is adjusted to 5.8, and collagen precipitation can be observed. The mixture is allowed to stand for 4 h, filtered, and the collagen precipitate is quickly washed with deionized water 3 times to obtain a collagen extract;

[0067] (3) Immerse the desized, scouring and bleached cotton fabric in a 2g / L ferric sulfate solution with a bath ratio of 1:5, adjust the pH value of the solution to 4 with 0.5mol / L acetic acid, and treat at 30°C for 60min; then add deionized water to dilute to a bath ratio of 1:30, heat to 50°C, treat for 60min, wash with deionized water 3 times, dehydrate and dry; immerse in a 5g / L collagen solution obtained in step (2), adsorb at room temperature for 30min, and then The fabric is taken out and immersed in a 0.5% mass fraction Na2CO3 solution. Collagen is deposited on the fabric surface. After roller pressing and dehydration, it is immersed in the collagen solution again. After adsorption at room temperature for 30 minutes, the textile is taken out and immersed in a 0.5% mass fraction Na2CO3 solution. After repeating this three times, roller pressing and dehydration are performed, and then immersed in a 20g / L mass concentration of honeysuckle extract solution. After immersion at room temperature for 30 minutes, the fabric is taken out and immersed in a 10g / L concentration of 25% glutaraldehyde solution for 12 hours, roller pressing and dehydration, and vacuum drying at 30°C.

[0068] Comparative Example 2

[0069] (1) Fresh pigskin was cleaned of surface stains with 25°C deionized water, subcutaneous fat was removed, and the skin was cut into 5 mm x 5 mm pieces. The pieces were soaked in a 10% NaCl solution for 12 h, washed twice with deionized water, immersed in a 5% Na2CO3 solution, stirred at room temperature for 1 h, washed twice with deionized water, and stored in a refrigerator for later use.

[0070] (2) The pigskin treated in step (1) is dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:50 g / mL, wherein the concentration of acetic acid in the mixed solution is 0.5 mol / L, and the ratio of pepsin (enzyme activity ≥ 1200 U / g) to pigskin mass is 1:10, and the mixture is enzymatically hydrolyzed at 25° C. for 72 h, slowly stirred during the enzymatic hydrolysis process, and centrifuged at 8000 r / min for 5 min at about 4° C. after the enzymatic hydrolysis is completed, and the supernatant is collected; under stirring, 1 mol / L sodium hydroxide solution is slowly added to the supernatant, and the pH of the solution is adjusted to 5.8, and collagen precipitation can be observed. The mixture is allowed to stand for 4 h, filtered, and the collagen precipitate is quickly washed with deionized water 3 times to obtain a collagen extract;

[0071] (3) Prepare a honeysuckle extract solution with a mass concentration of 15 g / L. After it is completely dissolved, add the collagen extract obtained in step (2). The concentration of collagen in the honeysuckle extract solution is 5 g / L. Stir at room temperature for 30 minutes, filter, collect the precipitate, and wash it three times with deionized water. Dissolve the precipitate in 1 mol / L acetic acid solution to prepare a honeysuckle extract-collagen complex solution with a mass concentration of 20 g / L. After slowly stirring for 30 minutes, filter to remove insoluble matter, and set aside.

[0072] (4) Immerse the desized, scouring and bleached cotton fabric in a 2g / L ferric sulfate solution with a bath ratio of 1:5, adjust the pH value of the solution to 4 with 0.5mol / L acetic acid, and treat at 30°C for 60min; then add deionized water to dilute to a bath ratio of 1:30, heat to 50°C, treat for 60min, wash with deionized water 3 times, dehydrate and dry; immerse in the honeysuckle extract-collagen complex solution obtained in step (3), adsorb at room temperature for 30min, and then The textile was taken out and immersed in a 0.5% by mass fraction Na2CO3 solution. The honeysuckle extract-collagen complex was deposited on the cloth surface. After roller pressing and dehydration, it was immersed in the honeysuckle extract-collagen complex solution again. After adsorption at room temperature for 30 minutes, the textile was taken out and immersed in a 0.5% by mass fraction Na2CO3 solution. This was repeated 3 times, and then roller pressing and dehydration were performed. The textile was immersed in a 10g / L 25% glutaraldehyde solution for 12 hours, roller pressing and dehydration were performed, and vacuum drying was performed at 30°C.

[0073] Comparative Example 3

[0074] (1) Fresh pigskin was cleaned of surface stains with 25°C deionized water, subcutaneous fat was removed, and the skin was cut into 5 mm x 5 mm pieces. The pieces were soaked in a 10% NaCl solution for 12 h, washed twice with deionized water, immersed in a 5% Na2CO3 solution, stirred at room temperature for 1 h, washed twice with deionized water, and stored in a refrigerator for later use.

[0075] (2) The pigskin treated in step (1) is dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:50 g / mL, wherein the concentration of acetic acid in the mixed solution is 0.5 mol / L, and the ratio of pepsin (enzyme activity ≥ 1200 U / g) to pigskin mass is 1:10, and the mixture is enzymatically hydrolyzed at 25° C. for 72 h, slowly stirred during the enzymatic hydrolysis process, and centrifuged at 8000 r / min for 5 min at about 4° C. after the enzymatic hydrolysis is completed, and the supernatant is collected; under stirring, 1 mol / L sodium hydroxide solution is slowly added to the supernatant, and the pH of the solution is adjusted to 5.8, and collagen precipitation can be observed. The mixture is allowed to stand for 4 h, filtered, and the collagen precipitate is quickly washed with deionized water 3 times to obtain a collagen extract;

[0076] (3) Prepare a honeysuckle extract solution with a mass concentration of 20 g / L, and after it is completely dissolved, add the collagen extract obtained in step (2), the concentration of collagen in the honeysuckle extract solution is 4 g / L, stir at room temperature for 30 minutes, filter, collect the precipitate, and wash it with deionized water three times, dissolve the precipitate in 1 mol / L acetic acid solution, prepare a honeysuckle extract-collagen complex solution with a mass concentration of 20 g / L, slowly stir for 30 minutes, filter to remove insoluble matter, and set aside;

[0077] (4) Immerse the desized, scouring and bleached cotton fabric in a 2g / L ferric sulfate solution with a bath ratio of 1:5, adjust the pH value of the solution to 4 with 0.5mol / L acetic acid, and treat at 30°C for 60min; then add deionized water to dilute to a bath ratio of 1:30, heat to 50°C, treat for 60min, wash with deionized water 3 times, dehydrate and dry; immerse in the honeysuckle extract-collagen complex solution obtained in step (3), adsorb at room temperature for 30min, and then The textile was taken out and immersed in a 0.5% by mass fraction Na2CO3 solution. The honeysuckle extract-collagen complex was deposited on the cloth surface. After roller pressing and dehydration, it was immersed in the honeysuckle extract-collagen complex solution again. After adsorption at room temperature for 30 minutes, the textile was taken out and immersed in a 0.5% by mass fraction Na2CO3 solution. This was repeated 3 times, and then roller pressing and dehydration were performed. The textile was immersed in a 10g / L 25% glutaraldehyde solution for 12 hours, roller pressing and dehydration were performed, and vacuum drying was performed at 30°C.

[0078] Color parameter test: Fold the dyed fabric in half and use a datacolor colorimeter to measure the K / S value of the dyed fabric under the test conditions of D65 light source and 10° observation angle. Select different positions for each sample and test 4 times, and take the average value.

[0079] Color fastness test: Color fastness to rubbing is determined according to the method specified in GB / T 3920-2008; Color fastness to washing is determined according to the method specified in GB / T 3921-2008.

[0080] The test results are as follows:

[0081] Table 1 Color fastness of dyed fabrics

[0082]

[0083] As can be seen from the table above, the products obtained in Examples 1-4 have deep colors and excellent color fastness. In Comparative Example 1, the fabric was first treated with collagen before dyeing. The collagen formed a film on the fabric surface, hindering the dye's penetration into the fibers. As a result, the color only appeared on the fiber surface, and the resulting fabric was lighter in color. In the rubbing fastness test, the surface collagen film may have been worn away, resulting in poor wet rubbing fastness.

[0084] In Comparative Example 2, in the honeysuckle extract-collagen complex, the amount of honeysuckle extract was small, and the resulting fabric was light in color.

[0085] In Comparative Example 3, in the honeysuckle extract-collagen complex, the amount of collagen is small and the honeysuckle extract may be excessive. After coloring the fabric, it is easy to cause a lot of floating color, resulting in poor color fastness of the dyed fabric.

[0086] The present invention uses enzymes to degrade fresh pig skin, and the triple helix structure of collagen fibers is not destroyed. When external conditions such as the pH and salt concentration of the solution change, collagen can precipitate from the solution to form a collagen film on the surface of the textile. After cross-linking treatment, a leather-like effect can be formed.

[0087] The present invention utilizes the characteristics of collagen and plant dyes forming hydrogen bonds, van der Waals forces, and ionic bonds to prepare a plant dye-collagen complex; utilizes the characteristic of collagen being easily precipitated under alkaline conditions to precipitate it on textiles; and through the coordination effect between metal ions pretreated into the textiles and the collagen and plant dyes, as well as the film-forming property of collagen, the plant dye-collagen complex is fixed to the textiles, thereby achieving a good coloring effect on the textiles.

[0088] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. Application of a plant dye-collagen complex product in textile coloring, characterized in that: include, Immerse the desized, scour and bleached textiles in a metal salt solution with a bath ratio of 1:5-1:

8. Use 0.5 mol / L acetic acid to adjust the pH value of the solution to 4-5. Treat at 30-40°C for 30-60 minutes. Then, deionized water was added to dilute the mixture to a bath ratio of 1:30-1:40, the temperature was raised to 50-70°C, and the mixture was treated for 30-60 minutes, followed by washing with deionized water for 3-5 times, dehydration, and drying to obtain the pretreated textiles. The pretreated textiles were immersed in a plant dye-collagen complex solution. After adsorption at room temperature for 30 to 60 minutes, the textiles were taken out and immersed in a 0.5% mass fraction Na2CO3 solution. The plant dye-collagen complex was deposited on the fabric surface. After roller pressing and dehydration, the textiles were immersed in the plant dye-collagen complex solution again. After adsorption at room temperature for 30-60 minutes, the textiles were taken out and immersed in a 0.5% Na2CO3 solution. After repeating the operation 3-5 times, the product was rolled and dehydrated, immersed in a 25% glutaraldehyde solution with a concentration of 10-20 g / L for 6-12 hours, rolled and dehydrated, and vacuum dried at 30-40°C. The method for preparing the plant dye-collagen complex solution comprises: pre-treating fresh pigskin to obtain pre-treated pigskin; The pretreated pig skin is subjected to enzymatic hydrolysis with pepsin to obtain collagen extract; A plant dye solution with a mass concentration of 20-40 g / L is prepared, and a collagen extract is added. The mixture is stirred at room temperature, filtered, and the precipitate is collected, wherein the plant dye is one of honeysuckle extract, green tea extract, wormwood extract, chestnut shell extract, madder extract, turmeric extract, sappanwood extract, gardenia fruit extract, pomegranate peel extract, loquat leaf extract, sophora japonica extract, or cotinus coggygria extract, and the concentration of the collagen extract in the plant dye solution is 5-10 g / L; The obtained precipitate is washed with deionized water and then dissolved in an acetic acid solution to prepare a plant dye-collagen complex solution with a mass concentration of 20-40 g / L. After stirring for 30-60 minutes, the insoluble matter is removed by filtration to obtain a plant dye-collagen complex product, wherein the concentration of the acetic acid solution is 1 mol / L.

2. The use according to claim 1, characterized in that: The fresh pigskin pretreatment comprises: Fresh pigskin was washed with 25-30℃ deionized water to remove surface stains, subcutaneous fat was removed, and the skin was cut into 5mm×5mm pieces. The pieces were soaked in 10% NaCl solution for 12-24h and then washed with deionized water 2-3 times. Immerse in a 5% by mass Na2CO3 solution, stir at room temperature for 1 to 2 hours, and wash with deionized water 2 to 3 times to obtain the pretreated pigskin.

3. The use according to claim 1 or 2, characterized in that: The preparation method of the collagen extract comprises: The pretreated pigskin was dispersed in an acetic acid-pepsin mixed solution at a solid-liquid ratio of 1:50-1:100 g / mL and enzymatically hydrolyzed at 25-35°C for 48-72 h. After the enzymatic hydrolysis, centrifuge at 4°C and 8000 rpm for 5-8 minutes and collect the supernatant. Add 1 mol / L sodium hydroxide solution to the supernatant and adjust the pH of the solution to 5.8-7.

0. When collagen precipitate is observed, let it stand for 4-6 hours, filter it, and quickly wash the collagen precipitate with deionized water 3-4 times to obtain the collagen extract.

4. The use according to claim 3, characterized in that: The concentration of acetic acid in the acetic acid-pepsin mixed solution is 0.5-1.0 mol / L, the mass ratio of pepsin to pigskin is 1:10-1:40, and the enzyme activity is ≥1200 U / g.

5. The use according to claim 1, characterized in that: The textile is cotton, linen, polyester fabric or a blend of the two; the metal salt is one of ferrous sulfate, ferrous chloride, ferric sulfate, ferric chloride, zinc chloride, zinc acetate, zinc nitrate, aluminum chloride, aluminum sulfate, titanium sulfate or titanium chloride, and the concentration of the metal salt is 2-5 g / L.

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