Method for producing protein composite fiber

Abstract

To provide a manufacturing method for a protein composite fiber that is soft for skin care, has good moisture absorption and moisture harmonizing effect, and is rich in amino acids and proteins.SOLUTION: There is provided a manufacturing method for a protein composite fiber, which specifically includes: spinning; pre-treatment; surface treatment; modified mineral powder; loading; mixing; and cross-linking in a field of fibers. The method is configured in that: a pretreated nascent fiber is immersed in a protein composite solution to be in full contact with a modified extract mineral powder and a soluble protein to perform a crosslinking reaction; a structure of a dried fiber is more compact; an extract article and soluble protein are more stable in the fiber while a fiber strength is improved; and a loss rate is less than 1% after washing for 50 times. The protein composite fiber prepared by the present invention is skin-friendly and soft, has a good moisture absorption and moisture harmonizing effect, and is rich in amino acids and proteins, in which a content of the protein is about 12%. Moreover, in the present invention, a common fiber is used as a base material, thereby achieving natural antibacterial, anti-oxidation and deodorizing effects while endowing fibers such as viscose, acryl, polyester, nylon, Vinylon, and acryl with an advantage of a natural protein fiber on the basis of ensuring an excellent property of the base material itself, and thus a range of application becomes wider.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention belongs to the field of fiber spinning technology, and specifically relates to a method for producing protein composite fibers. [Background technology]

[0002] Natural protein fibers such as wool and silk contain a special scale structure made up of amino acids, which gives them excellent heat retention, moisture absorption, and elasticity, making them popular with many consumers. However, the supply of natural protein fibers is limited, and the modification of natural protein fibers has become one of the hot topics in the textile industry.

[0003] Protein-modified fibers include milk protein fiber, soy protein fiber, feather protein fiber, collagen fiber, saelaria protein fiber, and furikake keratin fiber. The proteins are based on polyvinyl alcohol, polyacrylonitrile, or viscose fiber. For example, patent application number "CN202110312949.5" titled "A kind of flexible filaggrin / polyvinyl alcohol composite fiber and its manufacturing method" involves blending a filaggrin aqueous solution with a polyvinyl alcohol aqueous solution and adjusting the blending ratio of filaggrin to polyvinyl alcohol to prepare a filaggrin-polyvinyl alcohol composite spinning solution with a relatively stable compatibility, and then using a dry spinning method to prepare a filaggrin / polyvinyl alcohol composite fiber. Patent application number "CN201310356755.0" titled "A kind of flexible filaggrin / polyvinyl alcohol composite fiber and its manufacturing method" involves blending a filaggrin aqueous solution with a polyvinyl alcohol aqueous solution and adjusting the blending ratio of filaggrin to polyvinyl alcohol to prepare a filaggrin-polyvinyl alcohol composite spinning solution with a relatively stable compatibility, and then using a dry spinning method to prepare a spinning technique to prepare a filaggrin / polyvinyl alcohol composite fiber. Patent application number "CN201310356755.0" titled "A kind of flexible filaggrin / polyvinyl alcohol composite fiber and its manufacturing method" involves blending a filaggrin aqueous solution with a polyvinyl alcohol aqueous solution and adjusting the blending ratio of filaggrin to polyvinyl alcohol to prepare a filaggrin-polyvinyl alcohol composite fiber. A homogeneous spinning solution of wool and cellulose is prepared, and protein-modified polyacrylonitrile fiber is prepared by dry-jet wet spinning technology using water as a coagulant. In patent application number "CN201210033741.0" titled "Production process of a kind of wool protein composite cement fiber", wool protein is dissolved in sodium hydroxide aqueous solution to obtain a wool protein solution, which is mixed with viscose spinning solution and spun to produce wool protein composite cement fiber. In patent application number "CN201210304021.3" titled "Production method of a kind of pupa protein cellulose composite adhesive filament", pupa protein powder is dissolved in sodium hydroxide aqueous solution, filtered, and then a protein modification assistant is added to obtain pupa protein spinning solution, which is mixed with viscose spinning solution and spun to produce pupa protein cellulose composite adhesive yarn filament.

[0004] Adding protein to fiber makes it more flexible and provides skin care effects, but protein is expensive, unstable, and highly susceptible to acid-base and high temperature sensitivities. It also has a single function and a narrow dosage range. Therefore, the development of protein composite fiber with unlimited and complete functions can meet the increasing consumption needs of customers. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Chinese patent application number CN202110312949.5 [Patent Document 2] Chinese patent application number CN201310356755.0 [Patent Document 3] Chinese patent application number CN201210033741.0 [Patent Document 4] Chinese patent application number CN201210304021.3 Summary of the Invention [Problem to be solved by the invention]

[0006] In order to solve the problems existing in the prior art, the present invention provides a method for producing protein composite fibers, and achieves the following objectives of the invention.

[0007] 1. Avoid the influence of protein powder addition on the mechanical properties of the fiber.

[0008] 2. Avoid the influence of protein powder on the spinnability of the fiber spinning solution, which increases the spinning difficulty and production costs.

[0009] 3. Increasing the protein content in textiles can improve the cleaning effect of textiles, and the protein composite materials in textiles can give textiles more functionality. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention adopts the following technical solutions.

[0011] A method for producing a protein composite fiber, comprising the following steps:

[0012] S1, spinning Fiber spinning raw materials are wet spun or melt spun to obtain crude fibers with a fineness of 0.5-10 dtex.

[0013] Preferably, the fiber spinning raw material is one of viscose spinning solution, acrylic spinning solution, polyester, nylon, vinylon spinning solution, and polypropylene.

[0014] S2, preprocessing The crude fiber is hydrolyzed to obtain pretreated crude fiber.

[0015] S3, surface treatment The mineral powder was added to deionized water and ultrasonically dispersed for 2-5 minutes, then an epoxy silane coupling agent was added and stirred for 10-15 minutes, the pH was adjusted to 8-10, the temperature was raised to 60-70°C, and the reaction was carried out for 30-40 minutes to graft epoxy groups onto the surface of the mineral powder. After the reaction was completed, the mixture was centrifuged, filtered, washed, and then air-dried to obtain the surface-treated mineral powder.

[0016] Preferably, the mineral powder is one or more of zeolite, bakuhan stone, quartz stone, montmorillonite, sepiolite, and bentonite, and has a particle size of 1-2 μm.

[0017] Preferably, the mass ratio of the mineral powder to deionized water is 1:6-8.

[0018] Preferably, the epoxy silane coupling agent is one or more of 3-(2,3-glycidoxypropylmethyldimethoxysilane, 3-(2,3-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and the amount added is 25-35% of the mass of the mineral powder.

[0019] Preferably, the frequency of the ultrasonic dispersion is 20-30 kHz, and the stirring speed is 500-600 r / min.

[0020] Preferably, the speed of the centrifugation is 3000-4000 r / min, and the washing is carried out with absolute ethanol.

[0021] S4. Preparation of modified mineral powders The surface-treated mineral powder was added to deionized water and stirred for 15-30 minutes. A catalyst was added and the mixture was stirred for 1-2 minutes. After that, 1,2-propanediol and sodium hydroxide solution were added, and the mixture was heated to 50-60°C and stirred for 2-3 hours to react. Diethylenetriamine was then added and the mixture was stirred for 90-120 minutes. After the reaction was complete, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0022] Preferably, the mass ratio of the surface-treated mineral powder to deionized water is 1:4-6.

[0023] Preferably, the catalyst is one or more of BF3, SnCl4, and the amount of the catalyst added is 1-1.5% of the mass of the mineral powder after surface treatment.

[0024] Preferably, the amount of 1,2-propanediol added is 13-17% of the mass of the mineral powder after surface treatment; the concentration of the sodium hydroxide solution is 4-8 mol / L and the amount added is 30-40% of the mass of the mineral powder after surface treatment; and the amount of diethylenetriamine added is 18-24% of the mass of the mineral powder after surface treatment.

[0025] Preferably, the stirring speed is 500-600 r / min, the centrifugal speed is 3000-4000 r / min, the washing is carried out using an ethanol solution with a mass fraction of 85%-92%, the drying temperature is 50-60°C, and the drying time is 4-6 hours.

[0026] S5, load The plant extract is added to deionized water and stirred for 10-20 minutes to obtain a plant extract solution. The modified mineral powder is then added to the plant extract solution and stirred at 30-40°C for 30-50 minutes, and dried to obtain the modified mineral powder containing the plant extract.

[0027] Preferably, the plant extract comprises: Ta Extract of Staghorn Root, Extract of Malva Root, Aloe Extract, Rush Extract, Ginger Extract, Mint Extract, Camellia Extract, Lavender Extract, Green Leaf Extract of One or more of these have a particle size of 100-200 nm.

[0028] Preferably, the mass ratio of the plant extract to deionized water is 1:4-7.

[0029] Preferably, the amount of the modified mineral powder added is 15-18% of the mass of the plant extract.

[0030] Preferably, the stirring speed is 200-300 r / min, the drying temperature is 50-60° C., and the drying time is 4-6 h.

[0031] S6, mixed The denatured extract powder and soluble protein were added to deionized water and stirred for 10-20 min to obtain a protein complex solution.

[0032] Preferably, the mass ratio of the modified mineral powder with plant extract, the soluble protein fine powder and the deionized water is 20-30:13-18:100-110.

[0033] Preferably, the soluble protein is one or more of cassio protein, oat protein, milk protein, collagen, soy protein, silk protein, feather protein, quinoa protein, silkworm pupa protein, pearl protein, keratin, silk protein, corn protein, peanut protein, cheese protein, milk protein, corn bamboo protein, Poria cocos protein, aloe vera protein, phycocyanin, whey protein, peptide protein, pea protein, and wheat germ protein, and has a particle size of 2-4 μm.

[0034] Preferably, the stirring speed is 400-500 r / min.

[0035] S7, cross-linked The crude fiber is immersed in a protein composite solution, heated to 130-150°C, and reacted for 10-30 minutes, after which it is washed with water, dried, and oiled to obtain a protein composite fiber.

[0036] Preferably, the drying temperature is 80-90°C, the drying time is 2-4 hours, and the oil used for the oiling is one of JL-DY, TK-1259, etc. [Effects of the Invention]

[0037] By adopting the above technical solution, the present invention has the following technical effects:

[0038] 1. The protein composite fiber produced by the present invention is soft to the touch, has good moisture absorption and retention properties, a smooth and even fiber surface, and is rich in amino acids and proteins, with a high protein content of about 12%. The present invention uses general-purpose fibers as the base material, and while maintaining the excellent properties of the base material itself, it imparts the advantages of natural protein fibers to fibers such as viscose, acrylic, polyester, nylon, vinylon, and acrylic, which has a wider consumer market and application range than pure natural protein fibers, especially in the field of medical spinning.

[0039] 2. The protein composite fiber prepared in the present invention has excellent antibacterial effect, whereby after 50 washes, the bacteriostatic rate against Staphylococcus aureus is greater than 98%, the bacteriostatic rate against Escherichia coli is greater than 97%, and the bacteriostatic rate against Candida is greater than 96% (measured in accordance with GB / T 20944.3-2008).

[0040] 3. The protein composite fiber prepared by the present invention has antioxidant effect, and the DPPH radical scavenging rate is more than 75% (determined according to T / CCTA 20102-2023). At the same time, the moisture absorption of the fiber is enhanced, thereby improving the antistatic effect.

[0041] 4. The protein composite fiber prepared in the present invention has excellent moisturizing effect. Taking aloe vera protein as an example, a fabric made of 30% protein composite fiber and 70% polyester absorbs moisture for 5 hours under conditions of 20°C and 80% RH. The moisture absorption rate is greater than 4% and the fiber has good deodorizing effect. The removal rates of ammonia, acetic acid, and isovaleric acid all reach 90% or more (measured in accordance with GB / T 33610.3-2019).

[0042] 5. In this invention, the surface of mineral powder is treated with grafted epoxy groups, and then reacted with polyhydric alcohol, sodium hydroxide, and diethylenetriamine to obtain grafted epoxy compound modified mineral powder. The modified mineral oil has grafted amino and epoxy groups, which provide good dispersibility and adsorption, and the loading rate of the modified mineral powder with plant extract is over 80%.

[0043] 6. After the crude fiber is hydrolyzed, the internal structure of the fiber is loosened and immersed in the protein complex liquid, which comes into full contact with the mineral powder and soluble protein of the modified extract. At 130-150°C, the epoxy groups in the mineral powder of the modified extract open and a crosslinking reaction occurs between the soluble protein and the fiber, forming a protein complex on the surface and inside of the fiber. After drying, the fiber structure is denser and the fiber strength is improved. The plant extract and soluble protein are more stable in the fiber, and the washout rate after 50 washes is less than 1%. In addition, there is no need to add other aldehyde-based crosslinking agents during the crosslinking process, and the fiber does not contain formaldehyde, heavy metals, or other substances harmful to the body, making it more environmentally friendly. DETAILED DESCRIPTION OF THE INVENTION

[0044] The present invention will now be further described with reference to specific examples.

[0045] Example 1 A method for producing a protein composite fiber, comprising the following steps:

[0046] S1, spinning After wet spinning the viscose spinning solution, a crude product fiber was obtained, and the fineness was 3.5 dtex.

[0047] S2, preprocessing The crude fiber was immersed in a sulfuric acid solution with a mass fraction of 0.5% and subjected to hydrolysis treatment at 70°C for 20 minutes to obtain a pretreated preliminary green fiber.

[0048] S3, surface treatment The mineral powder was added to deionized water and ultrasonically dispersed for 4 minutes. An epoxy silane coupling agent was added and stirred for 12 minutes. The pH was adjusted to 9, and the mixture was heated to 65°C and reacted for 35 minutes to graft epoxy groups onto the surface of the mineral powder. After the reaction was complete, the mixture was centrifuged, filtered, washed, and then air-dried to obtain the surface-treated mineral powder.

[0049] The mineral powder was bentonite, with a particle size of 1.2 μm and a specific surface area of ​​2.6 m / g.

[0050] The mass ratio of the mineral powder to deionized water is 1:7.

[0051] The epoxy silane coupling agent is 3-(2,3-glycidoxypropylmethyldimethoxysilane, and the amount added is 30% of the mass of the mineral powder.

[0052] The frequency of the ultrasonic dispersion is 25 kHz, and the stirring speed is 550 r / min.

[0053] The centrifugal speed is 3500 r / min, and the washing is carried out with absolute ethanol.

[0054] S4. Preparation of modified mineral powders The surface-treated mineral powder was added to deionized water and stirred for 20 minutes. A catalyst was added and the mixture was stirred for 2 minutes. 1,2-propanediol and sodium hydroxide solution were then added, and the mixture was heated to 57°C and stirred for 2.5 hours. Diethylenetriamine was then added and the mixture was stirred for 110 minutes. After the reaction was complete, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0055] The mass ratio of the surface-treated mineral powder to deionized water was 1:5.

[0056] The catalyst is BF3, and the amount added is 1.2% of the mass of the mineral powder after surface treatment.

[0057] The amount of 1,2-propanediol added was 15% of the mass of the mineral powder after surface treatment, the concentration of the sodium hydroxide solution was 6 mol / L and the amount added was 35% of the mass of the mineral powder after surface treatment, and the amount of diethylenetriamine added was 22% of the mass of the mineral powder after surface treatment.

[0058] The stirring speed is 550 r / min, the centrifugal speed is 3500 r / min, the washing is performed using an ethanol solution with a mass fraction of 90%, the drying temperature is 55° C., and the drying time is 5 hours.

[0059] S5, load The plant extract was added to deionized water and stirred for 15 minutes to obtain a plant extract solution. Modified mineral oil powder was then added to the plant extract solution and stirred at 35°C for 40 minutes, and then dried to obtain modified mineral powder with plant extract.

[0060] The plant extracts are in a mass ratio of 1:1:1:1 Ta The extracts are staghorn fern extract, moss purslane extract, aloe extract, and rush extract, and the particle size is 150 nm.

[0061] The mass ratio of the plant extract to deionized water is 1:5.

[0062] The amount of the modified mineral powder added is 16% of the mass of the plant extract.

[0063] The stirring speed is 250 r / min, the drying temperature is 55° C., and the drying time is 5 hours.

[0064] S6, mixed The denatured extract powder and soluble protein were added to deionized water and stirred for 15 minutes to obtain a protein complex solution.

[0065] The mass ratio of the modified mineral powder with plant extract, soluble protein fine powder and deionized water was 25:15:105.

[0066] The soluble protein is milk protein and has a particle size of 2 μm.

[0067] The stirring speed was 450 r / min.

[0068] S7, cross-linked The crude fiber is immersed in a protein composite solution, heated to 140°C and reacted for 20 minutes, then washed with water, dried and oiled to obtain a protein composite fiber.

[0069] The drying temperature was 85°C, the drying time was 3 hours, and the oil used for the oiling was JL-DY.

[0070] The protein composite fiber produced in Example 1 had a dry strength of 2.92 cN / dtex, a wet strength of 2.15 cN / dtex, a water permeability of 15.4%, a protein content of 12.6%, and after 50 washes, the bacteriostatic rates against Staphylococcus aureus were 98.8%, Escherichia coli were 97.5%, Candida was 96.7%, the DPPH radical scavenging rate was 79%, the ammonia gas removal rate was 98.7%, the acetic acid removal rate was 95.2%, and the isovaleric acid removal rate was 94.6%. The average plant extract and protein washout rate after 50 washes was 0.74%.

[0071] Example 2 A method for producing a protein composite fiber, comprising the following steps:

[0072] S1, spinning After wet spinning the viscose spinning solution, a crude product fiber was obtained, with a fineness of 2 dtex.

[0073] S2, preprocessing The crude fiber was immersed in a sulfuric acid solution with a mass fraction of 0.5% and subjected to hydrolysis treatment at 70°C for 20 minutes to obtain a pretreated preliminary green fiber.

[0074] S3, surface treatment The mineral powder was added to deionized water and ultrasonically dispersed for 2 minutes, then an epoxy silane coupling agent was added and stirred for 10 minutes, the pH was adjusted to 8, the temperature was raised to 60°C and the reaction was carried out for 30 minutes to graft epoxy groups onto the surface of the mineral powder, and after the reaction was completed, the mixture was centrifuged, filtered, washed and then air-dried to obtain the surface-treated mineral powder.

[0075] The mineral powder was bentonite, with a particle size of 1 μm and a specific surface area of ​​2.3 m / g.

[0076] The mass ratio of the mineral powder to deionized water is 1:6.

[0077] The epoxy silane coupling agent is 3-(2,3-glycidoxypropylmethyldiethoxysilane), and the amount added is 25% of the mass of the mineral powder.

[0078] The frequency of the ultrasonic dispersion was 20 kHz, and the stirring speed was 500 r / min.

[0079] The centrifugal speed is 3000 r / min, and the washing is carried out with absolute ethanol.

[0080] S4. Preparation of modified mineral powders The surface-treated mineral powder was added to deionized water and stirred for 15 minutes. A catalyst was added and the mixture was stirred for 1 minute. After that, 1,2-propanediol and sodium hydroxide solution were added, and the mixture was heated to 50°C and stirred for 2 hours to react. Diethylenetriamine was then added and the mixture was stirred for 90 minutes. After the reaction was complete, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0081] The mass ratio of the surface-treated mineral powder to deionized water was 1:4.

[0082] The catalyst is BF3, and the amount added is 1% of the mass of the mineral powder after surface treatment.

[0083] The amount of 1,2-propanediol added was 13% of the mass of the mineral powder after surface treatment, the concentration of the sodium hydroxide solution was 4 mol / L and the amount added was 30% of the mass of the mineral powder after surface treatment, and the amount of diethylenetriamine added was 18% of the mass of the mineral powder after surface treatment.

[0084] The stirring speed is 500 r / min, the centrifugal speed is 3000 r / min, the washing is performed using an ethanol solution with a mass fraction of 85%, the drying temperature is 50° C., and the drying time is 4 hours.

[0085] S5, load The plant extract was added to deionized water and stirred for 10 minutes to obtain a plant extract solution. Modified mineral oil powder was then added to the plant extract solution and stirred at 30°C for 30 minutes, then dried to obtain modified mineral powder with plant extract, with a loading rate of 82%.

[0086] The plant extracts are ginger extract, mint extract, camellia extract, and hallelujah extract in a mass ratio of 1:1:1:1, and have a particle size of 200 nm.

[0087] The mass ratio of the plant extract to deionized water is 1:7.

[0088] The amount of the modified mineral powder added is 15% of the mass of the plant extract.

[0089] The stirring speed is 200 r / min, the drying temperature is 50° C., and the drying time is 4 hours.

[0090] S6, mixed The denatured extract powder and soluble protein were added to deionized water and stirred for 10 minutes to obtain a protein complex solution.

[0091] The mass ratio of the modified mineral powder with plant extract, soluble protein fine powder and deionized water was 20:13:100.

[0092] The soluble protein is collagen and has a particle size of 4 μm.

[0093] The stirring speed was 400 r / min.

[0094] S7, cross-linked The crude fiber is immersed in the protein composite solution, heated to 130°C and reacted for 10 minutes, then washed with water, dried and oiled to obtain the protein composite fiber.

[0095] The drying temperature was 80°C, the drying time was 2 hours, and the oil used for the oiling was JL-DY.

[0096] The protein composite fiber prepared in Example 2 had a dry strength of 2.83 cN / dtex, a wet strength of 2.04 cN / dtex, a water permeability of 14.8%, a protein content of 12.2%, and after 50 washes, the bacteriostatic rate against Staphylococcus aureus was 98.3%, the bacteriostatic rate against Escherichia coli was 97%, the bacteriostatic rate against Candida albicans was 96.2%, the DPPH radical scavenging rate was 75%, the ammonia gas removal rate was 97.9%, the acetic acid removal rate was 94.5%, and the isovaleric acid removal rate was 94%. After 50 washes, the plant extract and protein washout rate was an average of 0.89%.

[0097] Example 3 A method for producing a protein composite fiber, comprising the following steps:

[0098] S1, spinning After wet spinning the viscose spinning solution, an initial fiber was obtained, and the fineness was 5 dtex.

[0099] S2, preprocessing The crude fiber was immersed in a sulfuric acid solution with a mass fraction of 0.5% and subjected to hydrolysis treatment at 70°C for 20 minutes to obtain a pretreated preliminary green fiber.

[0100] S3, surface treatment The mineral powder was added to deionized water and ultrasonically dispersed for 5 minutes, then an epoxy silane coupling agent was added and stirred for 15 minutes, the pH was adjusted to 10, the temperature was raised to 70°C and the reaction was carried out for 40 minutes to graft epoxy groups onto the surface of the mineral powder. After the reaction was completed, the mixture was centrifuged, filtered, washed and then air-dried to obtain the surface-treated mineral powder.

[0101] The mineral powder is bentonite, with a particle size of 2 μm and a specific surface area of ​​3 m / g.

[0102] The mass ratio of the mineral powder to deionized water is 1:8.

[0103] The epoxy silane coupling agent is 3-(2,3-glycidoxypropylmethyldimethoxysilane, and the amount added is 35% of the mass of the powder.

[0104] The ultrasonic dispersion frequency was 30 kHz, and the stirring speed was 600 r / min.

[0105] The centrifugal speed is 4000 r / min, and the washing is carried out with absolute ethanol.

[0106] S4. Preparation of modified mineral powders The surface-treated mineral powder was added to deionized water and stirred for 30 minutes. A catalyst was added and the mixture was stirred for 2 minutes. Then, 1,2-propanediol and sodium hydroxide solution were added, the temperature was raised to 60°C, and the mixture was allowed to react for 3 hours while stirring. Diethylenetriamine was then added and the mixture was stirred for 120 minutes. After the reaction was complete, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0107] The mass ratio of the surface-treated mineral powder to deionized water was 1:6.

[0108] The catalyst is SnCl4, and the amount added is 1.5% of the mass of the mineral powder after surface treatment.

[0109] The amount of 1,2-propanediol added was 17% of the mass of the mineral powder after surface treatment, the concentration of the sodium hydroxide solution was 8 mol / L and the amount added was 40% of the mass of the mineral powder after surface treatment, and the amount of diethylenetriamine added was 24% of the mass of the mineral powder after surface treatment.

[0110] The stirring speed is 600 r / min, the centrifugal speed is 4000 r / min, the washing is performed using an ethanol solution with a mass fraction of 92%, the drying temperature is 60° C., and the drying time is 6 hours.

[0111] S5, load The plant extract was added to deionized water and stirred for 20 minutes to obtain a plant extract solution. Modified mineral oil powder was then added to the plant extract solution, and the mixture was stirred at 40°C for 50 minutes and dried to obtain a modified mineral powder containing the plant extract.

[0112] The plant extracts are mixed in a mass ratio of 1:1:1 in be Ta Rockfish Sanshichisou extract, aloe extract, green leaf extract in The particle size was 100 nm.

[0113] The mass ratio of the plant extract to deionized water is 1:4.

[0114] The amount of the modified mineral powder added is 18% of the mass of the plant extract.

[0115] The stirring speed is 300 r / min, the drying temperature is 60° C., and the drying time is 6 hours.

[0116] S6, mixed The denatured extract powder and soluble protein were added to deionized water and stirred for 20 minutes to obtain a protein complex solution.

[0117] The mass ratio of the modified mineral powder with plant extract, soluble protein fine powder and deionized water was 30:18:110.

[0118] The soluble protein is soy protein and the particle size is 3 μm.

[0119] The stirring speed was 500 r / min.

[0120] S7, cross-linked The crude fiber is immersed in a protein composite solution, heated to 150°C, and reacted for 30 minutes. After that, the fiber is washed with water, dried, and oiled to obtain a protein composite fiber.

[0121] The drying temperature was 90°C, the drying time was 4 hours, and the oil used for the oiling was JL-DY.

[0122] The protein composite fiber prepared in Example 3 had a dry strength of 2.89 cN / dtex, a wet strength of 2.11 cN / dtex, a water permeability of 16%, a protein content of 13.4%, and after 50 washes, the bacteriostatic rate against Staphylococcus aureus was 99.3%, the bacteriostatic rate against Escherichia coli was 98.2%, the bacteriostatic rate against Candida albicans was 97.1%, the DPPH radical scavenging rate was 82%, the ammonia removal rate was 99.2%, the acetic acid removal rate was 95.6%, and the isovaleric acid removal rate was 94.9%. After 50 washes, the plant extract and protein washout rate was an average of 0.77%.

[0123] Example 4 A method for producing a protein composite fiber, comprising the following steps:

[0124] S1, spinning After melt spinning the polyester chips, an initial fiber was obtained, and the fineness was 3.5 dtex.

[0125] S2, preprocessing The crude fiber was immersed in a 2% by mass sodium hydroxide solution and hydrolyzed at 80°C for 20 minutes to obtain a pretreated pre-green fiber.

[0126] S3, surface treatment The mineral powder was added to deionized water and ultrasonically dispersed for 4 minutes. An epoxy silane coupling agent was added and stirred for 12 minutes. The pH was adjusted to 9, and the mixture was heated to 65°C and reacted for 35 minutes to graft epoxy groups onto the surface of the mineral powder. After the reaction was complete, the mixture was centrifuged, filtered, washed, and then air-dried to obtain the surface-treated mineral powder.

[0127] The mineral powder was bentonite, with a particle size of 1.2 μm and a specific surface area of ​​2.6 m / g.

[0128] The mass ratio of the mineral powder to deionized water is 1:7.

[0129] The epoxy silane coupling agent is 3-(2,3-glycidoxypropylmethyldimethoxysilane, and the amount added is 30% of the mass of the mineral powder.

[0130] The frequency of the ultrasonic dispersion is 25 kHz, and the stirring speed is 550 r / min.

[0131] The centrifugal speed is 3500 r / min, and the washing is carried out with absolute ethanol.

[0132] S4. Preparation of modified mineral powders The surface-treated mineral powder was added to deionized water and stirred for 20 minutes. A catalyst was added and the mixture was stirred for 2 minutes. 1,2-propanediol and sodium hydroxide solution were then added, and the mixture was heated to 57°C and stirred for 2.5 hours. Diethylenetriamine was then added and the mixture was stirred for 110 minutes. After the reaction was complete, the mixture was cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder.

[0133] The mass ratio of the surface-treated mineral powder to deionized water was 1:5.

[0134] The catalyst is BF3, and the amount added is 1.2% of the mass of the mineral powder after surface treatment.

[0135] The amount of 1,2-propanediol added was 15% of the mass of the mineral powder after surface treatment, the concentration of the sodium hydroxide solution was 6 mol / L and the amount added was 35% of the mass of the mineral powder after surface treatment, and the amount of diethylenetriamine added was 22% of the mass of the mineral powder after surface treatment.

[0136] The stirring speed is 550 r / min, the centrifugal speed is 3500 r / min, the washing is performed using an ethanol solution with a mass fraction of 90%, the drying temperature is 55° C., and the drying time is 5 hours.

[0137] S5, load The plant extract was added to deionized water and stirred for 15 minutes to obtain a plant extract solution. Modified mineral oil powder was then added to the plant extract solution and stirred at 35°C for 40 minutes, and then dried to obtain modified mineral powder containing the plant extract.

[0138] The plant extracts are in a mass ratio of 1:1:1:1 Ta The extracts are staghorn fern extract, moss purslane extract, aloe extract, and rush extract, and the particle size is 150 nm.

[0139] The mass ratio of the plant extract to deionized water is 1:5.

[0140] The amount of the modified mineral powder added is 16% of the mass of the plant extract.

[0141] The stirring speed is 250 r / min, the drying temperature is 55° C., and the drying time is 5 hours.

[0142] S6, mixed The denatured extract powder and soluble protein were added to deionized water and stirred for 15 minutes to obtain a protein complex solution.

[0143] The mass ratio of the modified mineral powder with plant extract, soluble protein fine powder and deionized water was 25:15:105.

[0144] The soluble protein is milk protein and has a particle size of 2 μm.

[0145] The stirring speed was 450 r / min.

[0146] S7, cross-linked The crude fiber is immersed in a protein composite solution, heated to 140°C and reacted for 20 minutes, then washed with water, dried and oiled to obtain a protein composite fiber.

[0147] The drying temperature was 85°C, the drying time was 3 hours, and the oil used for the oiling was TK-1259.

[0148] The protein composite fiber prepared in Example 4 had a breaking strength of 4.83 cN / dtex, a water permeability of 3.8%, a protein content of 12.3%, and after 50 water washes, had a bacteriostatic rate of 98.6% against Staphylococcus aureus, a bacteriostatic rate of 97.4% against Escherichia coli, a bacteriostatic rate of 96.8% against Candida, a DPPH radical scavenging rate of 78%, ammonia gas removal rate of 98.5%, acetic acid removal rate of 95%, and isovaleric acid removal rate of 94.3%, and the average loss rate of plant extracts and proteins after 50 water washes was 0.85%.

[0149] Comparative Example 1 Representative Example 1 was selected, and the S2 pretreatment step was omitted, while the other aspects were the same as Example 1, and this was designated as Comparative Example 1.

[0150] The protein composite fiber prepared in Comparative Example 1 had a dry strength of 2.6 cN / dtex, a wet strength of 1.82 cN / dtex, a water permeability of 14.1%, a protein content of 8.8%, and after 50 washes, the bacteriostatic rates against Staphylococcus aureus were 93.5%, against Escherichia coli 92.3%, and against Candida albicans 92.5%, the DPPH radical scavenging rate was 73%, the ammonia gas removal rate was 91.7%, the acetic acid removal rate was 90%, and the isovaleric acid removal rate was 90%, and the plant extract and protein washout rate after 50 washes was 2.52% on average.

[0151] Comparative Example 2 Representative Example 4 was selected, and the S2 pretreatment step was omitted, while the other aspects were the same as Example 1, and designated as Comparative Example 2.

[0152] The protein composite fiber prepared in Comparative Example 2 had a breaking strength of 3.94 cN / dtex, a water permeability of 1.8%, a protein content of 8.2%, and after 50 washes, the antibacterial rates against Staphylococcus aureus were 92.2%, Escherichia coli were 91.7%, and Candida were 92%, the DPPH radical scavenging rate was 71%, the ammonia gas removal rate was 91.1%, the acetic acid removal rate was 90.3%, and the isovaleric acid removal rate was 90%, and the plant extract and protein washout rate after 50 washes was 2.97% on average.

[0153] Comparative Example 3 Selected representative Example 1, in which the modified mineral powder was removed, and unmodified bentonite was used as the direct mineral powder, the temperature in S7 was 50°C, and the other conditions were the same as those in Example 1; as Comparative Example 3, the loading rate of unmodified mineral oil to plant extract was 67%.

[0154] The protein composite fiber prepared in Comparative Example 3 had a dry strength of 2.02 cN / dtex, a wet strength of 0.98 cN / dtex, a water permeability of 13.9%, a protein content of 7.5%, and after 50 washes, the bacteriostatic rates against Staphylococcus aureus were 81.7%, against Escherichia coli, and against Candida albicans were 81.4%, the DPPH radical scavenging rate was 60%, the ammonia gas removal rate was 85.5%, the acetic acid removal rate was 83.2%, and the isovaleric acid removal rate was 82.8%, and the plant extract and protein washout rate after 50 washes was an average of 46%.

[0155] Comparative Example 4 Selected representative Example 4, in which the modified mineral powder was removed and unmodified bentonite was used as the direct mineral powder, the temperature in S7 was 50°C, and the other conditions were the same as those in Example 4; as Comparative Example 4, the loading rate of unmodified mineral oil to plant extract was 67%.

[0156] The protein composite fiber prepared in Comparative Example 4 had a breaking strength of 3.14 cN / dtex, a water permeability of 1.7%, a protein content of 6.9%, and after 50 washes, the antibacterial rates against Staphylococcus aureus were 80.6%, against Escherichia coli, and Candida, respectively, were 79.4%, 78.8%, DPPH radical scavenging rates were 58%, ammonia gas removal rates were 83.7%, acetic acid removal rates were 82.9%, and isovaleric acid removal rates were 82.4%, and the average loss rate of plant extracts and proteins after 50 washes was 49%.

[0157] In Comparative Examples 1 and 2, no pretreatment process was performed, and the internal structure of the fibers was dense, so the subsequent crosslinking reaction often occurred on the fiber surface, resulting in a relatively reduced fiber strength and functional durability.In Comparative Examples 3 and 4, the mineral powder was not modified, so there was no crosslinking reaction between the fiber and the protein, and the three were bonded by physical action, resulting in severe washout in water and a tendency for the unmodified powder to aggregate, causing uneven distribution in the fibers, resulting in fine protrusions on the fiber surface, and a reduction in fiber strength.

[0158] Unless otherwise specified, all of the ratios and percentages in the present invention are mass ratios and mass percentages, respectively, and all of the raw materials are commercially available.

[0159] Finally, it should be noted that the above are only preferred embodiments 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 above embodiments, those skilled in the art may still modify the technical solutions described in the above embodiments or equivalently replace some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention shall all be included in the protection scope of the present invention.

Claims

1. A method for producing a protein composite fiber, comprising a spinning step, a pretreatment step, a surface treatment step, a modified mineral powder preparation step, a loading step, a mixing step, and a crosslinking step, In the pretreatment step, the crude raw fiber is hydrolyzed to obtain a pretreated crude raw fiber; In the surface treatment process, the mineral powder is added to deionized water and ultrasonically dispersed for 2-5 minutes, an epoxy silane coupling agent is added and stirred for 10-15 minutes, the pH is adjusted to 8-10, the temperature is raised to 60-70°C, and the mixture is reacted for 30-40 minutes. Epoxy groups are grafted onto the surface of the mineral powder, and after the reaction is completed, the resulting mixture is centrifuged, filtered, washed, and then air-dried to obtain a surface-treated mineral powder; In the preparation process of the modified mineral powder, the surface-treated mineral powder is added to deionized water and stirred for 15-30 minutes, a catalyst is added and stirred for 1-2 minutes, then 1,2-propanediol and sodium hydroxide solution are added, the temperature is raised to 50-60°C and stirred for 2-3 hours to react, diethylenetriamine is added and reacted for 90-120 minutes while stirring, after the reaction is completed, it is cooled to room temperature, centrifuged, filtered, washed, and dried to obtain the modified mineral powder, In the loading step, the plant extract is added to deionized water and stirred for 10-20 minutes to obtain a plant extract solution, and then the modified mineral powder is added to the plant extract solution and stirred at 30-40°C for 30-50 minutes, and then dried to obtain a modified mineral powder containing the plant extract. In the mixing step, the denatured extract powder and the soluble protein are added to deionized water and stirred for 10-20 minutes to obtain a protein complex solution; In the crosslinking step, the pretreated crude fiber is immersed in a protein composite solution, heated to 130-150°C, and reacted for 10-30 minutes, followed by washing with water, drying, and oiling to obtain a protein composite fiber. The mass ratio of the modified mineral powder with plant extract, the soluble protein fine powder, and the deionized water is 20-30:13-18:100-110; A method for producing a protein composite fiber.

2. The mineral powder is one or more of zeolite, bakuhan stone, quartz stone, montmorillonite, sepiolite, and bentonite; The particles of the mineral powder are 1-2 μm, The epoxy silane coupling agent is one or more of 3-(2,3-glycidoxypropylmethyldimethoxysilane, 3-(2,3-glycidoxypropylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, The amount of the epoxy silane coupling agent added is 25-35% of the mass of the mineral powder; The method for producing a protein composite fiber according to claim 1,

3. The catalyst is BF ３ , SnCl ４ and the amount of the catalyst added is 1-1.5% of the mass of the mineral powder after surface treatment; The amount of 1,2-propanediol added is 13-17% of the mass of the mineral powder after surface treatment; The concentration of the sodium hydroxide solution is 4-8 mol / L, and the amount of the sodium hydroxide solution added is 30-40% of the mass of the mineral powder after surface treatment; The amount of diethylenetriamine added is 18-24% of the mass of the mineral powder after surface treatment. The method for producing a protein composite fiber according to claim 1,

4. the plant extract is one or more of an extract of Takasago Sanshichisou, an extract of Malva japonica, an extract of aloe vera, an extract of rush grass, an extract of ginger, an extract of mint, an extract of camellia japonica, an extract of evergreen herb, and an extract of Mitaka Daisy, and the particle size of the crushed plant is 100-200 nm; The amount of the modified mineral powder added is 15-18% of the mass of the plant extract. The method for producing a protein composite fiber according to claim 1,

5. the soluble protein is one or more of oat protein, milk protein, collagen, soy protein, silk fibroin, feather protein, quinoa protein, silkworm protein, pearl protein, keratin, silk protein, corn protein, peanut protein, cheese protein, milk protein, Poria cocos protein, aloe vera protein, phycocyanin, whey protein, peptide protein, pea protein, wheat germ protein, and has a particle size of 2-4 μm; The method for producing a protein composite fiber according to claim 1 .