阅读说明：本技术 一种多功能蛋白质纤维素纤维及其制备方法 (Multifunctional protein cellulose fiber and preparation method thereof ) 是由 郑文娟 许晓花 于 2020-04-26 设计创作，主要内容包括：本发明提供了一种多功能蛋白质纤维素纤维及其制备方法,所述多功能蛋白质纤维素纤维,含有2.0~4.0wt%的蛋白质,2.0～4.0wt%的抗菌物质以及4.0～8.0wt%的凉感物质,所述方法包括高粘度蛋白质溶液的制备、含蛋白质、抗菌物质的凉感物质分散液的制备、纺丝及后处理。所述高粘度蛋白质溶液的制备,将蛋白质按10.0%～25.0%的比例加入到尿素溶液中,在温度20~50℃下溶解2.5～4h,使得蛋白质完全溶解。本发明的多功能蛋白质纤维素纤维q<Sub>max</Sub>值≥0.22J/秒/cm<Sup>2</Sup>,对大肠杆菌的抑菌率≥75.6%,对金黄色葡萄球菌≥81.5%,吸湿速度快,快干性能好,工艺运行可靠简单。(The invention provides a multifunctional protein cellulose fiber and a preparation method thereof, wherein the multifunctional protein cellulose fiber contains 2.0-4.0 wt% of protein, 2.0-4.0 wt% of antibacterial substances and 4.0-8.0 wt% of cool substances, and the method comprises the steps of preparation of a high-viscosity protein solution, preparation of a cool substance dispersion liquid containing the protein and the antibacterial substances, spinning and post-treatment. The preparation of the high-viscosity protein solution comprises the steps of adding 10.0-25.0% of protein into a urea solution, and dissolving for 2.5-4 hours at the temperature of 20-50 ℃ to completely dissolve the protein. The multifunctional protein cellulose fiber q of the invention max The value is more than or equal to 0.22J/s/cm 2 The bacteriostasis rate to the escherichia coli is not less than75.6 percent of the total weight of the active carbon, more than or equal to 81.5 percent of the total weight of staphylococcus aureus, high moisture absorption speed, good quick-drying performance and reliable and simple process operation.)

1. A multifunctional protein cellulose fiber is characterized in that,

the multifunctional protein cellulose fiber, q_maxThe value is more than or equal to 0.22J/s/cm²The bacteriostasis rate to colibacillus is more than or equal to 75.6 percent, and the bacteriostasis rate to staphylococcus aureus is more than or equal to 81.5 percent.

2. A preparation method of multifunctional protein cellulose fiber is characterized in that,

the preparation method of the multifunctional protein cellulose fiber comprises the steps of preparation of a high-viscosity protein solution, preparation of a cool substance dispersion liquid containing protein and an antibacterial substance, preparation of a blended spinning stock solution, spinning and post-treatment.

3. The method for preparing multifunctional protein cellulose fiber according to claim 2,

the preparation method of the high-viscosity protein solution comprises the steps of adding protein into a urea solution according to the mass fraction of 10.0-25.0%, and dissolving for 2.5-4 hours at the temperature of 20-50 ℃ to completely dissolve the protein.

4. The method for preparing multifunctional protein cellulose fiber according to claim 2,

preparing the high-viscosity protein solution, wherein the protein is one of isolated soy protein, collagen or rice protein;

the viscosity of the prepared high-viscosity protein solution is 30-50 s.

5. The method for preparing multifunctional protein cellulose fiber according to claim 2,

the preparation of the cool substance dispersion liquid containing the protein and the antibacterial substance comprises the following steps that the weight ratio of the protein to the antibacterial substance to the cool substance in the cool substance dispersion liquid containing the protein and the antibacterial substance is 0.5-2: 1.5-2: 1-3.

6. The method for preparing multifunctional protein cellulose fiber according to claim 2,

the preparation method of the cool substance dispersion liquid containing the protein and the antibacterial substance comprises the steps of adding the antibacterial substance into a high-viscosity protein solution for dissolving, adding the cool substance, and fully stirring, dispersing, grinding and adsorbing to obtain the cool substance dispersion liquid containing the protein and the antibacterial substance.

7. The method for preparing multifunctional protein cellulose fiber according to claim 2,

the cool feeling substance is silicate substance with porous structure, and comprises one or more of jade, mica, talc, kaolinite, montmorillonite, zeolite, etc.;

the antibacterial substance is plant extract, including one or more of radix Isatidis extract, herba Menthae extract, and herba Pileae Scriptae extract.

8. The method for preparing multifunctional protein cellulose fiber according to claim 2,

the cool substance containing protein and antibacterial substance has a particle size D97 of 2.536 μm or less.

9. The method for preparing multifunctional protein cellulose fiber according to claim 2,

the preparation of the blended spinning solution comprises 8.0-16.0% of cool substance dispersion liquid containing protein and antibacterial substances in the content of alpha cellulose in the viscose.

10. The method for preparing multifunctional protein cellulose fiber according to claim 2,

the spinning and post-treatment are carried out, the blended spinning stock solution passes through a spinning device, a flat spinneret orifice is adopted to obtain a formed tow, and the obtained tow is subjected to a mild desulfurization process to obtain the protein cellulose fiber with multiple functions of antibiosis, cool feeling and the like;

the length-diameter ratio of the flat spinneret orifices is 4: 1-10: 1;

the desulfurization bath of the mild desulfurization process: na (Na)₂SO₃2.5-8.5 g/L, oil bath: 2.0-5.0 g/L, no bleaching, and drying temperature: drying for 40-60 min at 100-120 ℃;

the multifunctional protein cellulose fiber contains 2.0-4.0 wt% of protein, 2.0-4.0 wt% of antibacterial substance and 4.0-8.0 wt% of cool feeling substance.

Technical Field

The invention belongs to the chemical fiber technology in the technical field of textiles, and particularly relates to a multifunctional protein cellulose fiber and a preparation method thereof.

Background

Health and environmental protection are among the most interesting topics in today's society. In recent years, the textile industry has successively introduced many fibers and textiles thereof with health care and skin care functions, which are beneficial to human health and environmental protection. Because the regenerated cellulose fiber has the characteristics of good moisture absorption and air permeability and comfortable wearing, the functional modification of the cellulose fiber obtains an unprecedented development opportunity. On the basis, people develop protein modified cellulose fibers at a high-speed development stage, and certain results are obtained.

Chinese patents ZL02138823.7, 200410010327.3, 200710168521.8, 200910048098.7, etc. disclose soy protein modified cellulose fibers and a method for preparing the same; chinese patents ZL200610016426.1, ZL200910153053.6, ZL201110329457.3, ZL201220387021.4, 200910154855.9, etc. disclose silk modified cellulose fibers and methods of making the same; chinese patent ZL200710097723.8 discloses a method for producing protein viscose fiber from animal protein and plant fiber, which uses animal hair, skin, etc. as raw material to make protein liquid, extracts animal protein and plant fiber to co-spin. Chinese patent ZL200810163379.2 discloses a milk protein viscose and a preparation method thereof; chinese patent 201110170688.4 discloses a collagen/cellulose composite fiber and a preparation method thereof; chinese patent 200910172139.3 discloses a peanut protein cellulose blending composite fiber and a preparation method thereof; chinese patent ZL201110206559.6 discloses a chicken hair regenerated protein viscose fiber and a preparation method and application thereof; chinese patent 201010184697.4 discloses milk protein blending regenerated cellulose fiber and a preparation process thereof; chinese patents ZL200810302306.7 and ZL200710097723.8 disclose a method for manufacturing protein viscose fiber by using animal protein and plant fiber; chinese patent ZL201210033741.0 discloses a production process of wool protein composite viscose fiber; chinese patent ZL201210304512.8 discloses a preparation method of a pupa protein cellulose composite viscose staple fiber spinning solution; chinese patent 201110400581.4 discloses a regenerated animal micropowder protein cellulose fiber and a preparation method thereof.

In patent application No. CN201610040348.2, fibroin is dissolved in deionized water, added to the sodium hydroxide/urea solution prepared in the above steps, and stirred at constant temperature of 0 ℃ until fibroin is completely dissolved, so as to obtain a protein solution. The difference between the technology of the patent and the patent lies in that fibroin is dissolved in deionized water and then added into sodium hydroxide/urea solution for low-temperature dissolution. It is known that the addition of fibroin to a sodium hydroxide/urea solution after dissolution in deionized water has the following problems: proteins cannot be dissolved in deionized water unless the protein has a very low molecular weight; the sodium hydroxide solution damages the protein, so that the protein is degraded, and meanwhile, the viscosity of the protein solution is low; low temperature dissolution (0 ℃), long dissolution time, more energy consumption, inconsistent viscosity with the spinning solution, dilution of the spinning solution.

The application number CN201310415167.X discloses an ultra-soft cool fabric which is woven by cool nylon filaments or composite filaments of cool nylon filaments and other filaments, wherein nylon is melt-spun, and solution spinning and melt-spinning are two different spinning methods, and the methods are completely different, and the melt-spinning process can damage added functional substances such as cool substances, antibacterial substances and proteins, the dispersibility is also poor, and the functions of the added antibacterial substances, the cool feeling and the like cannot be achieved.

The above patent only makes a single modification of the cellulose fibers, i.e. only protein modification. Along with the improvement of the requirement of people on the comfort of fabrics, the multifunctional modified protein cellulose fiber is more and more valued.

The existing multifunctional protein cellulose fiber mainly has the following defects: (1) the content of protein is low, functional substances are damaged in the spinning process, and the skin-care, health-care, effective cooling and antibacterial functions cannot be realized at the same time; (2) the moisture absorption speed is slow, and the quick-drying performance is poor.

Disclosure of Invention

The invention provides a multifunctional protein cellulose fiber and a preparation method thereof for solving the technical problems of the existing liquid absorbing material, and the following aims are achieved:

(1) a multifunctional protein cellulose fiber contains higher protein, has the functions of skin care, health care, effective cooling and antibiosis, has the physical indexes of the product which can meet the requirements of first-class products of GB/T14463-2008 viscose staple fiber, and has excellent fiber wearability and good textile processing performance;

(2) the multifunctional protein cellulose fiber has high moisture absorption speed and good quick-drying performance;

(3) the preparation method of the multifunctional protein cellulose fiber has reliable and simple process operation.

In order to solve the technical problems, the following technical scheme is adopted:

a multifunctional protein cellulose fiber, q_maxThe value is more than or equal to 0.22J/s/cm²The bacteriostasis rate to colibacillus is more than or equal to 75.6 percent, and the bacteriostasis rate to staphylococcus aureus is more than or equal to 81.5 percent.

The following are the preferable technical scheme and the implementation mode of the technical scheme of the invention:

a multifunctional protein cellulose fiber contains 2.0-4.0 wt% of protein, 2.0-4.0 wt% of antibacterial substance and 4.0-8.0 wt% of cool feeling substance.

The invention also provides a preparation method of the multifunctional protein cellulose fiber, which comprises the steps of preparation of a high-viscosity protein solution, preparation of a cool substance dispersion liquid containing protein and an antibacterial substance, preparation of a blending spinning solution, spinning and post-treatment.

The preparation method of the high-viscosity protein solution comprises the steps of adding protein into a urea solution according to the mass fraction of 10.0-25.0%, and dissolving for 2.5-4 hours at the temperature of 20-50 ℃ to completely dissolve the protein.

Preparing the high-viscosity protein solution, wherein the protein is one of isolated soy protein, collagen or rice protein;

the viscosity of the prepared high-viscosity protein solution is 30-50 s (falling ball viscosity at 20 ℃).

The preparation of the cool substance dispersion liquid containing the protein and the antibacterial substance comprises the following steps that the weight ratio of the protein to the antibacterial substance to the cool substance in the cool substance dispersion liquid containing the protein and the antibacterial substance is 0.5-2: 1.5-2: 1-3.

The preparation method of the cool substance dispersion liquid containing the protein and the antibacterial substance comprises the steps of adding the antibacterial substance into a high-viscosity protein solution for dissolving, adding the cool substance, and fully stirring, dispersing, grinding and adsorbing to obtain the cool substance dispersion liquid containing the protein and the antibacterial substance.

The cool feeling substance is silicate substance with porous structure, and comprises one or more of jade, mica, talc, kaolinite, montmorillonite, zeolite, etc.;

the antibacterial substance is plant extract, including one or more of radix Isatidis extract, herba Menthae extract, and herba Pileae Scriptae extract.

The cool substance containing protein and antibacterial substance has a particle size D97 of 2.536 μm or less.

The preparation of the blended spinning solution comprises that the cool substance dispersion liquid containing protein and antibacterial substances accounts for 8.0-16.0% of the content of alpha cellulose in the viscose;

the spinning and post-treatment are carried out, the blended spinning stock solution passes through a spinning device, a flat spinneret orifice is adopted to obtain a formed tow, and the obtained tow is subjected to a mild desulfurization process to obtain the protein cellulose fiber with multiple functions of antibiosis, cool feeling and the like;

the length-diameter ratio of the flat spinneret orifices is 4: 1-10: 1;

the desulfurization bath of the mild desulfurization process: na (Na)₂SO₃2.5-8.5 g/L, oil bath: 2.0-5.0 g/L, no bleaching, and drying temperature: drying for 40-60 min at 100-120 ℃;

the multifunctional protein cellulose fiber contains 2.0-4.0 wt% of protein, 2.0-4.0 wt% of antibacterial substance and 4.0-8.0 wt% of cool feeling substance.

The first technical problem to be solved by the invention is to provide a multifunctional protein cellulose fiber. The fiber contains 2.0-4.0 wt% of protein, 2.0-4.0 wt% of antibacterial substance and 4.0-8.0 wt% of cooling substance.

The cellulose fiber has the skin care and health care functions by utilizing the protein, can generate cool cooling touch feeling to achieve the effective cooling function by utilizing the cool feeling substance to contact with the human body, and simultaneously has the antibacterial function by combining the antibacterial substance, so that the prepared cellulose fiber has the multifunctionality. Subsequent toThe protein cellulose fiber with a multifunctional flat structure is prepared by changing the shape of a spinneret to enable the fiber to form a flat structure in the forming process. The fiber q_maxThe value was 0.21J/sec/cm²The antibacterial rate to escherichia coli is more than or equal to 75.6%, the antibacterial rate to staphylococcus aureus is more than or equal to 81.5%, the protein content is high, the physical index of the product can meet the requirements of first-class products of GB/T14463-2008 viscose staple fiber, and the fiber wearability is excellent and the textile processing performance is good.

The invention aims to solve another technical problem of providing a preparation method of the multifunctional protein cellulose fiber, which has reliable and simple process operation.

In order to solve the technical problems, the technical solution of the invention is as follows: the multifunctional protein cellulose fiber is prepared by taking cellulose pulp, protein liquid, antibacterial substances, cool substances and the like as main raw materials, fully adsorbing the protein solution and the antibacterial substances by the cool substances, dispersing and grinding to prepare the cool substance dispersion liquid containing the protein and the antibacterial substances. The prepared cool substance dispersion liquid containing the protein and the antibacterial substance is added into the viscose stock solution by using injection equipment before spinning, and then the subsequent bleaching is not carried out by using the existing production equipment, changing the specification of a spinning nozzle, using a flat spinning hole, and using a mild desulfurization process and a drying process, so that the decomposition and loss of effective components are reduced, and the functionality and the structure of the fiber are ensured.

The invention discloses a preparation method of multifunctional protein cellulose fiber, which comprises the following steps:

(1) preparation of high viscosity protein solutions

Under the stirring state, adding the protein into the urea solution according to the mass fraction of 10.0-25.0%, and dissolving for 2.5-4 h at the temperature of 20-50 ℃ to completely dissolve the protein, thereby preparing the high-viscosity protein solution with the viscosity of 30-50 s (the falling ball viscosity at 20 ℃).

Preferably, the protein is one of isolated soy protein, collagen or rice protein.

(2) Preparation of cool feeling substance dispersion liquid containing protein and antibacterial substance

Firstly, adding the antibacterial substance into the high-viscosity protein solution for dissolving, adding the cool substance into the solution according to a certain proportion, and fully stirring, dispersing, adsorbing and grinding to obtain the cool substance dispersion liquid containing the protein and the antibacterial substance.

Preferably, the cooling substance is a silicate substance with a porous structure, and comprises one or more of jade, mica, talc, kaolinite, montmorillonite, zeolite and the like.

The porous silicate is used as the cool substance, so that the cool effect can be achieved, the protein and the antibacterial substance can be fully adsorbed, the subsequent loss in the spinning process and the application process is reduced, and the durability of the function is improved.

Preferably, the antibacterial substance is a plant extract, including one or a combination of several of radix isatidis extract, mint extract, sarcandra glabra extract and the like.

Preferably, the weight ratio of the protein to the antibacterial substance to the cooling substance in the cooling substance dispersion liquid containing the protein and the antibacterial substance is 1.0: 1.0: 2.0.

preferably, the particle size of the cool feeling substance containing the protein and the antibacterial substance is required to be D97 not more than 2.536 μm.

(3) Preparation of blended spinning dope

Cellulose pulp is used as a raw material, a viscose stock solution is prepared through a subsequent known viscose preparation process, and the prepared cool substance dispersion liquid containing protein and antibacterial substances is added into the viscose stock solution according to the effective component calculation to prepare a blended spinning stock solution.

Preferably, the proportion of the cool substance dispersion liquid containing the protein and the antibacterial substance added to the viscose accounts for 8.0-16.0% of the content of the alpha cellulose in the viscose.

(4) Spinning and after-treatment

And (3) passing the blended spinning stock solution through a spinning device, changing the shape of a spinneret orifice, and drafting the nascent tows through an adjusted coagulating bath by utilizing a flat spinneret orifice to obtain formed tows. The obtained tows are subjected to refining baths such as cutting, mild desulfurization process, oil bath, water washing and the like, and are dried, so that the protein cellulose fiber with the functions of antibiosis, cool feeling and the like is obtained.

The invention adopts the mode of changing the shape of the spinneret orifice, combines the flat spinneret orifice with the adjusted coagulating bath (the components of the coagulating bath are adjusted), endows the fiber with a primary flat structure shape through the flat spinneret orifice, does not add zinc sulfate in the coagulating bath, only contains sulfuric acid and sodium sulfate, not only can reduce the environmental pollution, but also can accelerate the forming, and keeps the flat structure of the fiber, simultaneously, because the forming speed is accelerated, the forming difference inside and outside the nascent fiber is larger, and a bent hollow structure is formed in the stretching process, thereby preparing the multifunctional protein cellulose fiber with different section characteristics, not only keeping the flat shape of the flat cellulose fiber, but also endowing the cellulose fiber with the bent hollow structure.

Preferably, the aspect ratio of the selected flat spinneret orifice is 4:1 to 10: 1.

Preferably, the coagulating bath comprises 100-120 g/L of sulfuric acid and 280-300 g/L of sodium sulfate.

Preferably, the desulfurization bath: na (Na)₂SO₃2.5-8.5 g/L, oil bath: 2.0-5.0 g/L, no bleaching, and drying temperature: drying for 40-60 min at 100-120 ℃.

The invention has the beneficial effects that:

1) compared with the conventional viscose fiber, the multifunctional protein cellulose fiber provided by the invention has the composite multifunctional properties of skin care, cool feeling and temperature reduction, antibiosis and the like, and is lasting in functionality. The multifunctional protein cellulose fiber prepared by the invention utilizes protein to endow cellulose fiber with skin care function; the cool feeling substance can generate cool temperature-reducing touch feeling when contacting with human body to achieve the function of effective temperature reduction, q is_maxThe value is more than or equal to 0.22J/s/cm²(ii) a Meanwhile, the antibacterial function is endowed by combining with antibacterial substances, the inhibition rate of the antibacterial agent on staphylococcus aureus is more than or equal to 92.8 percent, the inhibition rate on escherichia coli is more than or equal to 88.5 percent, the inhibition rate on candida albicans is more than or equal to 92.3 percent, and the physical index of the product can reach GB/T14463 + 2008 viscose staple fiber, etc., excellent fiber wearability and good textile processing performance, and meets the requirements of people. Meanwhile, the prepared composite multifunctional fiber has more lasting functionality by utilizing the adsorption and protection effects of the porous structure of the cool substance, and the loss rate can be reduced by 55 percent compared with the method of directly adding plant extract and protein.

2) Compared with the conventional viscose fiber, the multifunctional protein cellulose fiber has a flat structure in cross section, the fiber surface of the structure is in a hollow groove shape, and the formed capillary action discharges moisture and sweat on the surface of the skin out of the body through the actions of wicking, diffusion, transmission and the like, so that the wearability is better. Compared with the conventional viscose fiber, the moisture absorption performance (speed) is faster by 3-5 s, and the quick drying performance (after 60 min) is faster by 5.6% -10.2%.

3) The preparation method of the multifunctional protein cellulose fiber is simple, wide in raw material source, less in equipment investment, capable of being realized on the existing production line and easy to realize industrialization.

The present invention will be described in detail with reference to examples.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.