A sized yarn, a greige cloth and a desizing method thereof

Abstract

The present invention belongs to the field of textile technology and relates to a sized yarn, a greige fabric and a desizing method thereof. The sized yarn comprises a yarn and a sizing film coated on the surface of the yarn. The yarn and the sizing film are connected by disulfide bonds. The sizing film is formed by direct cross-linking of proteins through disulfide bonds. The yarn is a yarn containing mercapto groups, and the protein is a protein subjected to mercapto group enrichment treatment. The greige fabric is woven from the sized yarn. The desizing method: Immerse the greige fabric in a desizing solution and wash it to break the covalent bonds connecting the yarn and the sizing film, thus completing the desizing of the greige fabric. Through the innovative design, preparation method and desizing method of the sized yarn, the present invention effectively solves the problems existing in the traditional sized yarn technology and improves the weaving efficiency, fabric quality and environmental protection performance.

Description

Technical Field

[0001] The invention belongs to the technical field of textiles and relates to a sizing yarn, a grey cloth and a desizing method thereof. Background Art

[0002] For a long time, fabrics have been the core demand in people's daily life and industrial production, and the continuous optimization and innovation of their production process is particularly important. Among the many preparation links in the modern weaving production process, the sizing process of the warp yarn plays a pivotal role and directly affects the production efficiency of the loom. The core purpose of the sizing process is to enhance the strength and wear resistance of the yarn and reduce the harmful hairiness on the yarn surface, thereby reducing the downtime caused by yarn breakage during the weaving process and improving the production efficiency of the loom.

[0003] However, traditional sizing materials and technologies have gradually shown their limitations in response to modern weaving needs. Natural sizing materials, such as starch sizing, are low-cost and widely available, but they have natural defects such as brittle film and poor adhesion, which make it difficult to meet the requirements of high-speed and high-quality weaving. Although the performance of starch sizing can be improved to a certain extent by physically adding sizing agents and chemically modifying the structure, problems such as insufficient adhesion and difficulty in desizing remain severe.

[0004] Synthetic sizing agents, such as polyvinyl alcohol (PVA) and acrylic sizing agents, have improved sizing performance, but their high price, non-biodegradable properties, and water waste and environmental pollution during the desizing process have seriously restricted their widespread application. Although compound sizing technology (such as patent application with publication number CN111335037A and patent with authorization announcement number CN101831805B) attempts to make up for the shortcomings of a single sizing agent by introducing multiple ingredients, the complex preparation process and numerous raw material types are also not conducive to large-scale preparation and industrial promotion.

[0005] In this context, protein sizing has gradually attracted the attention of the industry as an environmentally friendly and sustainable sizing material. Natural protein resources such as soy protein, keratin, and gelatin have been tried to be used in textile sizing due to their good biocompatibility and degradability. However, pure protein sizing has problems such as hard and brittle sizing film and easy to break and fall off, which seriously affects the quality of the fabric.

[0006] In order to improve this defect of protein slurry, the existing modification methods mainly focus on improving the performance of the slurry membrane itself, and try to improve the toughness and high temperature resistance of the slurry membrane through physical plasticization or chemical grafting. In the patent application with publication number CN118146463A, the thiol chemical click method is used to efficiently and controllably introduce polymer flexible branches of different structures on the protein molecular chain to prepare keratin-based slurry, which improves the toughness of the keratin slurry membrane; the patent with authorization announcement number CN107417939B self-assembles keratin with acid gelatin to increase the molecular weight of the protein to improve the toughness of the slurry membrane. However, these methods are often complicated to operate and costly, and do not fundamentally solve the problem of insufficient adhesion at the slurry interface. Therefore, how to balance high adhesion fastness and low desizing difficulty while maintaining the environmental advantages of protein slurry has become a hot spot and difficulty in current slurry technology research. Summary of the invention

[0007] The purpose of the invention is to solve the problems existing in the prior art and to provide a sized yarn, a grey cloth and a desizing method thereof.

[0008] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0009] A sized yarn A comprises a yarn and a size film coated on the surface of the yarn, wherein the yarn and the size film are connected via a disulfide bond, the size film is formed by direct cross-linking of proteins via disulfide bonds, the yarn is a thiol-containing yarn, the protein is a protein that has been thiol-enriched, the protein itself contains thiol groups, and the thiol-enriched treatment can further increase the number of thiol groups in the protein.

[0010] As the preferred technical solution:

[0011] As described above, the sized yarn A has a breaking strength of 7.62-16.17 MPa, an elongation at break of 41.3-101.11%, a breaking work of 0.95-5.27 J, a storage modulus of 239.275-736.4 MPa at 30°C, and a loss modulus of 82.042-119.014 MPa at 30°C; the sizing rate of the sized yarn is 15.1-20.93%, and the breaking strength of the roving is 15.13-22.3N.

[0012] As mentioned above, the sized yarn A, the yarn containing a mercapto group is a cellulose-based yarn that has been subjected to a mercapto treatment.

[0013] The sizing yarn A as described above, the preparation process of the thiol-containing yarn is as follows: Immerse the cellulose-based yarn in an L-cysteine solution, perform ultrasonic treatment at 20 - 30 °C for 5 - 10 min, then bake at 160 - 180 °C for 3 - 5 min. After washing away the excess L-cysteine with water, dry it in a vacuum oven to obtain the thiol-containing yarn. Among them, the concentration of the L-cysteine solution is 3 - 5 wt%, the mass ratio of the cellulose-based yarn to the L-cysteine solution is 1 - 1.2:100 - 200, and the ultrasonic power is 120 - 180 W.

[0014] The sizing yarn A as described above, the preparation process of the sizing yarn A is as follows: First, add 2-iminothiolane to the regenerated protein sizing agent, keep it warm at 25 - 30 °C for 30 - 50 min to obtain the sizing agent, then coat the sizing agent on the thiol-containing yarn by padding, and then react in hot air at 60 - 80 °C for 10 - 20 min to obtain the sizing yarn A. Among them, the concentration of the regenerated protein in the regenerated protein sizing agent is 6 wt%, the mass of 2-iminothiolane is 2 - 6% of the mass of the regenerated protein, the padding is two-bath two-roll padding, the sizing is single-roller type, the squeezing is upper and lower double-roller type, the squeezing pressure is 20 - 40 N, and the sizing yarn speed is 10 - 30 m / min.

[0015] The present invention also provides a greige fabric A woven from the sizing yarn A described in any one of the above.

[0016] The present invention also provides a desizing method for the greige fabric A as described above. Immerse the greige fabric A in a desizing solution containing a reducing agent for washing to perform the reduction reaction of the disulfide bond, thereby completing the desizing of the greige fabric A. Among them, the mass ratio of the greige fabric A to the desizing solution containing the reducing agent is 1:10 - 15; the pH value of the desizing solution containing the reducing agent is 7 - 9, the concentration of the reducing agent therein is 10 - 20 g / L, the reducing agent is L-cysteine; the washing temperature is 20 - 50 °C, and the time is 1 - 10 min; stirring is accompanied during washing; the desizing rate of the greige fabric A is 95.78 - 99.43%.

[0017] The present invention also provides a sizing yarn B, including a yarn and a sizing film coated on the surface of the yarn. The yarn and the sizing film are connected by an imine bond. The yarn is an aldehyde group-containing yarn, and the sizing film is formed by crosslinking protein with protein using dialdehyde starch through an imine bond. The protein itself contains amino groups, the dialdehyde starch contains aldehyde groups, and an imine bond is formed between the protein and the dialdehyde starch.

[0018] As a preferred technical solution:

[0019] For the sized yarn B as described above, the breaking strength of the sizing film is 7.62 - 8.33 MPa, the elongation at break is 92.02 - 113.85%, the work of rupture is 5.27 - 6.19 J, the storage modulus at 30°C is 736.4 - 950 MPa, and the loss modulus at 30°C is 119.014 - 150.79 MPa; the sizing rate of the sized yarn is 11.75 - 20.93%, and the breaking strength of the roving is 15.28 - 125.09 N.

[0020] For the sized yarn B as described above, the yarn containing aldehyde groups is a cellulosic yarn that has undergone aldehyde group treatment, or a polyester yarn that has been hydroxylated and then oxidized in sequence.

[0021] For the sized yarn B as described above, the preparation process of the yarn containing aldehyde groups is as follows: Add the cellulosic yarn to a sodium periodate solution, treat it at 50 - 60°C for 3 - 6 min, take it out, wash it with water, and dry it to obtain the yarn containing aldehyde groups. Among them, the concentration of the sodium periodate solution is 0.3 - 0.6 wt%, and the mass ratio of the cellulosic yarn to the sodium periodate solution is 1:100;

[0022] Alternatively, the preparation process of the yarn containing aldehyde groups is as follows: Add the polyester yarn to a sodium hydroxide solution, treat it at 60 - 70°C for 10 - 20 min, take it out, wash it with water, and dry it to obtain a yarn containing hydroxyl groups. Then, add the yarn containing hydroxyl groups to a sodium periodate solution, treat it at 50 - 65°C for 20 - 30 min, take it out, wash it with water, and dry it to obtain the yarn containing aldehyde groups. Among them, the concentration of the sodium hydroxide solution is 15 - 20 wt%, the mass ratio of the polyester yarn to the sodium hydroxide solution is 1:200 - 220, the concentration of the sodium periodate solution is 1 wt%, and the mass ratio of the yarn containing hydroxyl groups to the sodium periodate solution is 1:100 - 120.

[0023] For the sized yarn B as described above, the preparation process of the sized yarn B is as follows: First, add dialdehyde starch to the regenerated protein sizing solution and adjust the pH value to 8.13 - 9.5, keep it warm at 70 - 80°C for 30 - 40 min to obtain the sizing agent. Then, coat the sizing agent on the yarn containing aldehyde groups by padding, and then react in hot air at 60 - 80°C for 8 - 20 min to obtain the sized yarn B. Among them, the concentration of the regenerated protein in the regenerated protein sizing solution is 6 wt%, the mass of the dialdehyde starch is 5 - 20% of the mass of the regenerated protein, the padding is two - dip two - nip, the sizing is single - roller type, the squeezing is upper - lower double - roller type, the squeezing pressure is 20 - 40 N, and the sizing yarn speed is 20 - 30 m / min.

[0024] The present invention also provides a greige cloth B woven from the sized yarn B described in any one of the above.

[0025] The present invention also provides a desizing method for a greige fabric B as described above. The greige fabric B is immersed in an acidic desizing solution for washing, so as to break the imine bonds through acid response, and thus the desizing of the greige fabric B is completed. Among them, the mass ratio of the greige fabric B to the acidic desizing solution is 1 - 1.2:20 - 30; the pH value of the acidic desizing solution is 2 - 5; the washing temperature is 20 - 60 °C, and the time is 5 - 20 min; stirring is accompanied during washing; the desizing rate of the greige fabric B is 88.17 - 97.53%.

[0026] Beneficial effects:

[0027] (1) Through the dynamic covalent bonds formed between the yarn and the sizing film, the present invention significantly enhances the adhesion between the yarn and the sizing film. At the same time, by using a sizing film formed by directly cross-linking proteins with each other through dynamic covalent bonds (or a sizing film formed by cross-linking proteins with each other using a cross-linking agent through dynamic covalent bonds), the mechanical properties of the sizing film are improved, so that the sized yarn is not easily broken and shed during the weaving process, reducing weaving defects and improving the quality of the fabric.

[0028] (2) The method for preparing the sized yarn of the present invention is relatively simple, without the need for complex physical plasticization or chemical grafting processes, reducing production costs. At the same time, by using renewable resources such as agricultural and poultry waste as the protein source, not only the effective utilization of resources is realized, but also environmental pollution is reduced.

[0029] (3) The desizing method of the present invention not only has a high desizing rate, but also reduces water resource waste and environmental pollution, meeting the requirements of sustainable development.

[0030] (4) The present invention performs thiol-rich or dialdehyde starch cross-linking modification on the protein sizing agent. After cross-linking and forming a film on the yarn surface, a smoother, continuous and uniform surface structure is formed. This structure is beneficial to enhancing the mechanical properties and wear resistance of the sized yarn, while reducing the surface roughness of the sized yarn and improving the overall quality of the fabric. Description of the drawings

[0031] Figure 1 It is the SEM diagram of the surface and cross-section of the sized yarn; among them, (a) - (c) are the surfaces, (d) - (f) are the cross-sections, (a) and (d) correspond to Example A1, (b) and (e) correspond to Example A2, and (c) and (f) correspond to Example A3;

[0032] Figure 2 It is the X-ray photoelectron spectroscopy deconvolution analysis diagram of sulfur elements in the sizing film of the sized yarn; among them, (a) corresponds to Example A1, (b) corresponds to Example A2, and (c) corresponds to Example A3;

[0033] Figure 3 It is the X-ray photoelectron spectroscopy deconvolution analysis diagram of carbon elements in the sizing film of the sized yarn of Example B5. Detailed implementation manners

[0034] The present invention will be further described below in conjunction with specific implementation manners. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0035] The following are the test methods for relevant performance indicators in each embodiment:

[0036] Breaking strength, elongation at break, and work of rupture of the serosa: Tested according to the standard of GB / T 1040.1-2018.

[0037] Storage modulus and loss modulus at 30°C: Tested using a DMA-Q800 (TA, US) dynamic thermomechanical analyzer (using the DMA multi-frequency strain mode); wherein, the temperature range is 30-150°C, the frequency is 1 Hz, and the heating rate is 5°C / min.

[0038] Breaking strength of roving: Tested according to the standard of FZ / T 15001-2008.

[0039] Strength: Tested according to the standard of GB / T 3916-2013.

[0040] Number of harmful hairiness: Tested according to the standard of FZ / T 01086-2020.

[0041] The calculation methods of the sizing rate and desizing rate are as follows:

[0042] The sizing rate is calculated according to the following formula:

[0043] ;

[0044] In the formula, is the original mass of the yarn containing mercapto groups / yarn containing aldehyde groups, is the mass of the yarn containing mercapto groups / yarn containing aldehyde groups after sizing;

[0045] The desizing rate is calculated according to the following formula:

[0046] ;

[0047] In the formula, is the original mass of the grey fabric woven from the yarn containing mercapto groups / yarn containing aldehyde groups, is the mass of the grey fabric after sizing, is the mass of the grey fabric after desizing.

[0048] Example A1

[0049] A desizing method for grey fabric, the specific steps are as follows:

[0050] (1)Preparation of raw materials;

[0051] Cellulosic yarn: cotton yarn, the manufacturer is Changzhou Liwan Textile Co., Ltd., the fully cotton ring-spun high-quality yarn series, with a fineness of 32S;

[0052] L-cysteine solution: the solvent is water, and the concentration is 3wt%;

[0053] Regenerated protein sizing slurry: composed of regenerated protein, glycerol and water, the concentration of regenerated protein is 6wt%, and the concentration of glycerol is 1.2wt%; the regenerated protein is feather keratin extracted from duck feathers using L-cysteine, urea, water and sodium hydroxide. During the extraction process, the addition amount of L-cysteine is 10wt% of the added mass of duck feathers, the addition amount of urea is 480.48wt% of the added mass of duck feathers, the addition amount of water is 1000wt% of the added mass of duck feathers, and the addition amount of sodium hydroxide is 6.89wt% of the added mass of duck feathers;

[0054] 2-iminothiolane;

[0055] Desizing slurry containing L-cysteine: composed of L-cysteine, sodium hydroxide and deionized water, the pH value is in the range of [7, 9], the concentration of L-cysteine is 10g / L, and the concentration of sodium hydroxide is 0.192g / L;

[0056] (2)Preparation of sized yarn;

[0057] (2.1)Immerse the cellulosic yarn in the L-cysteine solution, under 20°C, ultrasonically treat it at a power of 120W for 10min, then bake it at 160°C for 5min, wash off the excess L-cysteine with water, and then dry it to obtain a mercapto-containing yarn with a strength of 13.86cN / tex and 74 harmful hairiness roots per 5 meters; among them, the mass ratio of the cellulosic yarn to the L-cysteine solution is 1:100;

[0058] (2.2)First add 2-iminothiolane to the regenerated protein sizing slurry, keep it warm at 25°C for 30min to obtain a sizing agent, then adopt the padding method of two-dip two-roll (the dipping is single-roller type, and the rolling is upper and lower double-roller type), and control the squeezing pressure to be 20N and the sizing yarn speed to be 10m / min, coat the sizing agent on the mercapto-containing yarn, and then react in hot air at 60°C for 20min to obtain a sized yarn (SEM as shown in Figure 1 figures (a) and (d) below); among them, the mass of 2-iminothiolane is 5% of the mass of the regenerated protein;

[0059] The obtained sized yarn consists of a mercapto-group-containing yarn and a sizing film coated on the surface of the mercapto-group-containing yarn (the X-ray photoelectron spectroscopy deconvolution analysis of sulfur elements in the sizing film is as shown in (a) of Figure 2 ; in order to ensure the accuracy of the spectrum, a set of parallel experiments are required to separately prepare the sizing film, that is, in step (2.2), the mercapto-group-containing yarn is replaced with a polytetrafluoroethylene substrate, and after preparation, the substrate is removed to obtain the sizing film). The breaking strength of the sizing film is 16.17 MPa, the elongation at break is 83.6%, the work of fracture is 1.82 J, the storage modulus at 30 °C is 300.679 MPa, and the loss modulus at 30 °C is 110.814 MPa; the sizing rate of the sized yarn is 16%, and the breaking strength of the roving is 20.23 N; the strength increase rate of the sized yarn relative to the mercapto-group-containing yarn is 20.82%, and the reduction rate of the number of harmful hairiness is 94.42%;

[0060] (3) Prepare the grey fabric;

[0061] Weave the sized yarn to obtain the grey fabric;

[0062] (4) Desize the grey fabric;

[0063] Immerse the grey fabric in a desizing solution containing L-cysteine and wash it at 20 °C for 10 min to complete the desizing of the grey fabric; among them, the mass ratio of the grey fabric to the desizing solution containing L-cysteine is 1:15.

[0064] The desizing rate of the final grey fabric is 95.78%.

[0065] Example A2

[0066] A method for desizing grey fabric, the specific steps are as follows:

[0067] (1) Preparation of raw materials;

[0068] Cellulosic yarn: viscose yarn, the manufacturer is Hangzhou Huichuang Textile Co., Ltd., the rayon ring-spun series, and the fineness is 32S;

[0069] L-cysteine solution: the solvent is water and the concentration is 4 wt%;

[0070] Regenerated protein sizing solution: It consists of regenerated protein, glycerol and water. The concentration of regenerated protein is 6 wt%, and the concentration of glycerol is 1.2 wt%; the regenerated protein is feather keratin extracted from duck feathers using L-cysteine, urea, water and sodium hydroxide. During the extraction process, the addition amount of L-cysteine is 10 wt% of the added mass of duck feathers, the addition amount of urea is 480.48 wt% of the added mass of duck feathers, the addition amount of water is 1000 wt% of the added mass of duck feathers, and the addition amount of sodium hydroxide is 6.89 wt% of the added mass of duck feathers;

[0071] 2-Iminothiolane;

[0072] Desizing agent containing L-cysteine: It consists of L-cysteine, sodium hydroxide and deionized water, with the pH value in the range of [7, 9], the concentration of L-cysteine being 15 g / L, and the concentration of sodium hydroxide being 0.200 g / L;

[0073] (2) Prepare sized yarns;

[0074] (2.1) Immerse the cellulose-based yarns in the L-cysteine solution, ultrasonically treat them at a power of 160 W for 10 min at 25 °C, then bake them at 170 °C for 4 min, wash away the excess L-cysteine with water, and then dry them to obtain mercapto-containing yarns with a strength of 15.05 cN / tex and 38 harmful hairiness roots per 5 m; among them, the mass ratio of the cellulose-based yarns to the L-cysteine solution is 1:150;

[0075] (2.2) First, add 2-iminothiolane to the regenerated protein sizing agent, keep it at 30 °C for 40 min to obtain the sizing agent, then adopt the padding method of two-dip two-roll (the dipping is single-roller type, and the rolling is upper and lower double-roller type), and control the squeezing pressure to be 40 N and the sizing yarn speed to be 20 m / min, coat the sizing agent on the mercapto-containing yarns, and then react in hot air at 70 °C for 10 min to obtain sized yarns (SEM as shown in (b), (e) in Figure 1 ); among them, the mass of 2-iminothiolane is 6% of the mass of the regenerated protein;

[0076] The obtained sized yarns are composed of mercapto-containing yarns and a sizing film coated on the surface of the mercapto-containing yarns (the X-ray photoelectron spectroscopy deconvolution analysis of sulfur elements in the sizing film is as shown in (b) in Figure 2 ); in order to ensure the accuracy of the spectrum, a set of parallel experiments are needed to prepare the sizing film separately, that is, in step (2.2), replace the mercapto-containing yarns with a polytetrafluoroethylene substrate, and remove the substrate after preparation to obtain the sizing film), the breaking strength of the sizing film is 11.79 MPa, the breaking elongation rate is 80.35%, the breaking work is 1.38 J, the storage modulus at 30 °C is 251.160 MPa, and the loss modulus at 30 °C is 92.233 MPa; the sizing rate of the sized yarns is 15.1%, and the breaking strength of the roving is 17.73 N; the strength improvement rate of the sized yarns relative to the mercapto-containing yarns is 20.16%, and the reduction rate of the harmful hairiness roots is 85.74%;

[0077] (3) Prepare grey cloth;

[0078] Weave the sized yarns to obtain grey cloth;

[0079] (4) Desize the grey cloth;

[0080] The grey fabric is immersed in a desizing solution containing L-cysteine and washed at 35°C for 5 min to complete the desizing of the grey fabric; wherein, the mass ratio of the grey fabric to the desizing solution containing L-cysteine is 1:15.

[0081] The desizing rate of the final grey fabric is 99.43%.

[0082] Example A3

[0083] A desizing method for grey fabric, the specific steps are as follows:

[0084] (1) Preparation of raw materials;

[0085] Cellulosic yarn: cotton yarn, the manufacturer is Changzhou Liwan Textile Co., Ltd., the fully cotton ring-spun high-quality yarn series, and the fineness is 21S;

[0086] L-cysteine solution: the solvent is water and the concentration is 5 wt%;

[0087] Regenerated protein sizing solution: composed of regenerated protein, glycerol and water, the concentration of regenerated protein is 6 wt%, and the concentration of glycerol is 1.2 wt%; the regenerated protein is feather keratin extracted from duck feathers using L-cysteine, urea, water and sodium hydroxide. During the extraction process, the addition amount of L-cysteine is 10 wt% of the added mass of duck feathers, the addition amount of urea is 480.48 wt% of the added mass of duck feathers, the addition amount of water is 1000 wt% of the added mass of duck feathers, and the addition amount of sodium hydroxide is 6.89 wt% of the added mass of duck feathers;

[0088] 2-iminothiolane;

[0089] Desizing solution containing L-cysteine: composed of L-cysteine, sodium hydroxide and deionized water, the pH value is in the range of [7, 9], the concentration of L-cysteine is 20 g / L, and the concentration of sodium hydroxide is 0.210 g / L;

[0090] (2) Preparation of sized yarn;

[0091] (2.1) Immerse the cellulosic yarn in the L-cysteine solution, ultrasonically treat it at 30°C with a power of 180 W for 5 min, then bake it at 180°C for 3 min, wash off the excess L-cysteine with water, and then dry it to obtain a mercapto-containing yarn with a strength of 27.92 cN / tex and 25 harmful hairiness roots per 5 meters; wherein, the mass ratio of the cellulosic yarn to the L-cysteine solution is 1.2:200;

[0092] (2.2) First, add 2-iminothiolane to the regenerated protein slurry and keep it at 30 °C for 50 min to obtain the sizing agent. Then, adopt the dip-rolling method of two-dip two-roll (the dipping is single-roller type and the rolling is upper and lower double-roller type), and control the squeezing pressure to be 40 N and the sizing speed to be 30 m / min. Coat the sizing agent on the mercapto-containing yarn, and then react in hot air at 80 °C for 10 min to obtain the sized yarn (SEM is as shown in Figure 1 in (c) and (f)); among them, the mass of 2-iminothiolane is 2% of the mass of the regenerated protein;

[0093] The obtained sized yarn is composed of the mercapto-containing yarn and the sizing film coated on the surface of the mercapto-containing yarn (the deconvolution analysis of the X-ray photoelectron spectrum of sulfur element in the sizing film is as shown in Figure 2 in (c); in order to ensure the accuracy of the spectrum, a set of parallel experiments are needed to prepare the sizing film separately, that is, in step (2.2), replace the mercapto-containing yarn with a polytetrafluoroethylene substrate, and remove the substrate after preparation to obtain the sizing film). The breaking strength of the sizing film is 8.65 MPa, the breaking elongation rate is 41.3%, the breaking work is 0.95 J, the storage modulus at 30 °C is 239.275 MPa, and the loss modulus at 30 °C is 82.042 MPa; the sizing rate of the sized yarn is 15.5%, and the breaking strength of the roving is 15.13 N; the strength improvement rate of the sized yarn relative to the mercapto-containing yarn is 11.86%, and the reduction rate of the number of harmful hairiness is 81.18%;

[0094] (3) Prepare the grey fabric;

[0095] Weave the sized yarn to obtain the grey fabric;

[0096] (4) Desize the grey fabric;

[0097] Immerse the grey fabric in the desizing solution containing L-cysteine and wash it at 50 °C for 1 min to complete the desizing of the grey fabric; among them, the mass ratio of the grey fabric to the desizing solution containing L-cysteine is 1:10.

[0098] The desizing rate of the final grey fabric is 99.23%.

[0099] Example B1

[0100] A method for desizing grey fabric, the specific steps are as follows:

[0101] (1) Preparation of raw materials;

[0102] Cellulosic yarn: cotton yarn, the manufacturer is Changzhou Liwan Textile Co., Ltd., the fully cotton ring-spun high-quality yarn series, and the fineness is 32S;

[0103] Sodium periodate solution: the solvent is water and the concentration is 0.3 wt%;

[0104] Regenerated protein sizing liquor: It consists of regenerated protein (soybean isolate protein, manufactured by Shandong Yuwang Biotechnology Co., Ltd., model SD-200), water and glycerol. The concentration of the regenerated protein is 6 wt%, and the concentration of glycerol is 1.2 wt%.

[0105] Dialdehyde starch: CAS No. is 9047-50-1;

[0106] Acidic desizing liquor: Hydrochloric acid aqueous solution, pH value is 5.0;

[0107] (2) Prepare sized yarn;

[0108] (2.1) Add cellulose-based yarn into sodium periodate solution, treat it at 60 °C for 3 min, take it out, wash with water and dry to obtain aldehyde-group-containing yarn with a strength of 13.71 cN / tex and 72 harmful hairiness roots per 5 meters. Among them, the mass ratio of the cellulose-based yarn to the sodium periodate solution is 1:100;

[0109] (2.2) First, add dialdehyde starch into the regenerated protein sizing liquor, adjust the pH value to 8.13, keep it warm at 70 °C for 30 min to obtain a sizing agent. Then, adopt a dip-roll (single-roller type for dipping and double-roller type for squeezing) dipping and rolling method, control the squeezing pressure at 20 N and the sizing yarn speed at 20 m / min, coat the sizing agent on the aldehyde-group-containing yarn, and then react in hot air at 80 °C for 20 min to obtain sized yarn. Among them, the mass of dialdehyde starch is 5% of the mass of the regenerated protein;

[0110] The obtained sized yarn consists of aldehyde-group-containing yarn and a sizing film coated on the surface of the aldehyde-group-containing yarn. The breaking strength of the sizing film is 7.62 MPa, the breaking elongation rate is 101.11%, the breaking work is 5.27 J, the storage modulus at 30 °C is 736.4 MPa, and the loss modulus at 30 °C is 119.014 MPa; the sizing rate of the sized yarn is 20.93%, and the breaking strength of the roving is 22.3 N; the strength improvement rate of the sized yarn relative to the aldehyde-group-containing yarn is 26.86%, and the reduction rate of the number of harmful hairiness roots is 99.3%;

[0111] (3) Prepare grey fabric;

[0112] Weave the sized yarn to obtain grey fabric;

[0113] (4) Desize the grey fabric;

[0114] Immerse the grey fabric in the acidic desizing liquor, wash it at 20 °C (accompanied by stirring) for 20 min, and the desizing of the grey fabric is completed. Among them, the mass ratio of the grey fabric to the acidic desizing liquor is 1:30.

[0115] The desizing rate of the final grey fabric is 89.47%.

[0116] Example B2

[0117] A desizing method for grey fabric, the specific steps are as follows:

[0118] (1) Preparation of raw materials;

[0119] Cellulosic yarn: Viscose yarn, the manufacturer is Hangzhou Huichuang Textile Co., Ltd., the rayon ring spinning series, and the fineness is 32S;

[0120] Sodium periodate solution: The solvent is water, and the concentration is 0.4wt%;

[0121] Regenerated protein sizing agent: It is composed of soy protein isolate (the manufacturer is Shandong Yuwang Biotechnology Co., Ltd., model SD-200), water and glycerol. The concentration of soy protein isolate is 6wt%, and the concentration of glycerol is 1.2wt%;

[0122] Dialdehyde starch: The CAS number is 9047-50-1;

[0123] Acidic desizing agent: Hydrochloric acid aqueous solution, pH value is 4.0;

[0124] (2) Preparation of sized yarn;

[0125] (2.1) Add the cellulosic yarn into the sodium periodate solution, treat it at 50°C for 3 min, take it out, wash it with water, and dry it to obtain an aldehyde group-containing yarn with a strength of 14.97 cN / tex and 36 harmful hairiness roots per 5 meters; among them, the mass ratio of the cellulosic yarn to the sodium periodate solution is 1:100;

[0126] (2.2) First add dialdehyde starch to the regenerated protein sizing agent, adjust the pH value to 9.26, keep it warm at 80°C for 40 min to obtain a sizing agent, then adopt the dip-rolling method of two-dip two-roll (the dipping is single-roller type, and the rolling is upper and lower double-roller type), and control the squeezing pressure to be 40 N and the sizing yarn speed to be 30 m / min, coat the sizing agent on the aldehyde group-containing yarn, and then react in hot air at 60°C for 15 min to obtain a sized yarn; among them, the mass of dialdehyde starch is 10% of the mass of the regenerated protein;

[0127] The obtained sized yarn is composed of an aldehyde group-containing yarn and a sizing film coated on the surface of the aldehyde group-containing yarn. The breaking strength of the sizing film is 8.12 MPa, the breaking elongation rate is 113.85%, the breaking work is 5.86 J, the storage modulus at 30°C is 812.3 MPa, and the loss modulus at 30°C is 141.54 MPa; the sizing rate of the sized yarn is 15.32%, and the breaking strength of the roving is 23.766 N; the strength improvement rate of the sized yarn relative to the aldehyde group-containing yarn is 31.64%, and the reduction rate of the harmful hairiness roots is 94.35%;

[0128] (3) Prepare the grey fabric;

[0129] Weave the sized yarn to obtain the grey fabric;

[0130] (4) Desize the grey fabric;

[0131] Immerse the grey fabric in the acidic desizing solution, wash it at 40 °C (with stirring) for 15 min to complete the desizing of the grey fabric; wherein, the mass ratio of the grey fabric to the acidic desizing solution is 1:20.

[0132] The desizing rate of the final grey fabric is 88.17%.

[0133] Example B3

[0134] A method for desizing grey fabric, the specific steps are as follows:

[0135] (1) Preparation of raw materials;

[0136] Cellulosic yarn: cotton yarn, the manufacturer is Changzhou Liwan Textile Co., Ltd., the fully cotton ring-spun high-quality yarn series, and the fineness is 21S;

[0137] Sodium periodate solution: the solvent is water, and the concentration is 0.6 wt%;

[0138] Regenerated protein sizing solution: composed of soy protein isolate (the manufacturer is Shandong Yuwang Biotechnology Co., Ltd., model SD-200), water and glycerol, the concentration of soy protein isolate is 6 wt%, and the concentration of glycerol is 1.2 wt%;

[0139] Dialdehyde starch: CAS number is 9047-50-1;

[0140] Acidic desizing solution: hydrochloric acid aqueous solution, pH value is 3.0;

[0141] (2) Prepare the sized yarn;

[0142] (2.1) Add the cellulosic yarn to the sodium periodate solution, treat it at 50 °C for 6 min, take it out, wash it with water, and dry it to obtain an aldehyde group-containing yarn with a strength of 27.64 cN / tex and 23 harmful hairiness roots per 5 meters; wherein, the mass ratio of the cellulosic yarn to the sodium periodate solution is 1:100;

[0143] (2.2) First, add dialdehyde starch to the regenerated protein sizing agent slurry, adjust the pH value to 9.5, and keep it warm at 80 °C for 40 min to obtain the sizing agent. Then, adopt the padding method of two-dip and two-roll (the dipping is a single-roller type, and the rolling is an upper and lower double-roller type), control the squeezing pressure to be 40 N, and the sizing speed to be 30 m / min. Coat the sizing agent on the aldehyde group-containing yarn, and then react in hot air at 60 °C for 15 min to obtain the sized yarn. Among them, the mass of dialdehyde starch is 20% of the mass of the regenerated protein.

[0144] The obtained sized yarn is composed of the aldehyde group-containing yarn and the sizing film coated on the surface of the aldehyde group-containing yarn. The breaking strength of the sizing film is 8.33 MPa, the breaking elongation rate is 92.02%, the breaking work is 6.10 J, the storage modulus at 30 °C is 950 MPa, and the loss modulus at 30 °C is 150.79 MPa. The sizing rate of the sized yarn is 16.52%, and the breaking strength of the roving is 15.28 N. The strength improvement rate of the sized yarn relative to the aldehyde group-containing yarn is 26.6%, and the reduction rate of the number of harmful hairiness is 97.31%.

[0145] (3) Prepare the grey fabric;

[0146] Weave the sized yarn to obtain the grey fabric;

[0147] (4) Desize the grey fabric;

[0148] Immerse the grey fabric in the acidic desizing agent solution and wash it at 60 °C (accompanied by stirring) for 5 min to complete the desizing of the grey fabric. Among them, the mass ratio of the grey fabric to the acidic desizing agent solution is 1:10.

[0149] The desizing rate of the final grey fabric is 92.5%.

[0150] Example B4

[0151] A method for desizing grey fabric, the specific steps are as follows:

[0152] (1) Preparation of raw materials;

[0153] Polyester yarn: Polyester yarn, the manufacturer is Hangzhou Huichuang Textile Co., Ltd., the polyester ring spinning series, and the fineness is 40S;

[0154] Sodium hydroxide solution: The solvent is water, and the concentration is 15 wt%;

[0155] Sodium periodate solution: The solvent is water, and the concentration is 1 wt%;

[0156] Regenerated protein sizing agent slurry: It is composed of soy protein isolate (the manufacturer is Shandong Yuwang Biotechnology Co., Ltd., model SD-200), water and glycerol. The concentration of soy protein isolate is 6 wt%, and the concentration of glycerol is 1.2 wt%;

[0157] Dialdehyde starch: CAS No. is 9047-50-1;

[0158] Acidic desizing liquor: Hydrochloric acid aqueous solution with a pH value of 5.0;

[0159] (2) Prepare sized yarn;

[0160] (2.1) Add polyester yarn into sodium hydroxide solution, treat at 60 °C for 20 min, take out, wash with water, dry, to obtain hydroxyl-containing yarn. Then add the hydroxyl-containing yarn into sodium periodate solution, treat at 50 °C for 30 min, take out, wash with water, dry, to obtain aldehyde group-containing yarn with a strength of 30.83 cN / tex and 28 harmful hairiness roots per 5 m; among them, the mass ratio of polyester yarn to sodium hydroxide solution is 1:200, and the mass ratio of hydroxyl-containing yarn to sodium periodate solution is 1:100;

[0161] (2.2) First add dialdehyde starch into the regenerated protein sizing slurry, and adjust the pH value to 8.26, keep warm at 70 °C for 40 min to obtain a sizing agent. Then adopt the padding method of two-dip two-roll (single roller for dipping slurry and upper and lower double rollers for squeezing slurry), and control the squeezing pressure to be 20 N and the sizing yarn speed to be 30 m / min, coat the sizing agent on the aldehyde group-containing yarn, and then react in hot air at 80 °C for 8 min to obtain sized yarn; among them, the mass of dialdehyde starch is 5% of the mass of regenerated protein;

[0162] The obtained sized yarn is composed of aldehyde group-containing yarn and a sizing film coated on the surface of the aldehyde group-containing yarn. The breaking strength of the sizing film is 7.62 MPa, the breaking elongation rate is 101.11%, the breaking work is 5.27 J, the storage modulus at 30 °C is 736.4 MPa, and the loss modulus at 30 °C is 119.014 MPa; the sizing rate of the sized yarn is 13.44%, and the breaking strength of the roving is 114.6 N; the strength improvement rate of the sized yarn relative to the aldehyde group-containing yarn is 13.63%, and the reduction rate of the number of harmful hairiness roots is 94.95%;

[0163] (3) Prepare grey fabric;

[0164] Weave the sized yarn to obtain grey fabric;

[0165] (4) Desize the grey fabric;

[0166] Immerse the grey fabric in the acidic desizing liquor, wash at 50 °C (accompanied by stirring) for 10 min, and the desizing of the grey fabric is completed; among them, the mass ratio of the grey fabric to the acidic desizing liquor is 1:10.

[0167] The desizing rate of the final grey fabric is 95.42%.

[0168] Example B5

[0169] A desizing method for grey fabric, the specific steps are as follows:

[0170] (1)Preparation of raw materials;

[0171] Polyester yarn: Polyester yarn, the manufacturer is Hangzhou Huichuang Textile Co., Ltd., the polyester ring spinning series, and the fineness is 40S;

[0172] Sodium hydroxide solution: The solvent is water, and the concentration is 15wt%;

[0173] Sodium periodate solution: The solvent is water, and the concentration is 1wt%;

[0174] Regenerated protein sizing agent: It is composed of soy protein isolate (the manufacturer is Shandong Yuwang Biotechnology Co., Ltd., model SD-200), water and glycerol. The concentration of soy protein isolate is 6wt%, and the concentration of glycerol is 1.2wt%;

[0175] Dialdehyde starch: The CAS number is 9047-50-1;

[0176] Acidic desizing agent: Hydrochloric acid aqueous solution, pH value is 4.0;

[0177] (2)Preparation of sized yarn;

[0178] (2.1)Add the polyester yarn into the sodium hydroxide solution, treat it at 60°C for 20 min, take it out, wash it with water, and dry it. After obtaining the hydroxyl-containing yarn, add the hydroxyl-containing yarn into the sodium periodate solution, treat it at 60°C for 20 min, take it out, wash it with water, and dry it to obtain an aldehyde group-containing yarn with a strength of 33.83 cN / tex and 28 harmful hairiness roots per 5 m; among them, the mass ratio of the polyester yarn to the sodium hydroxide solution is 1:200, and the mass ratio of the hydroxyl-containing yarn to the sodium periodate solution is 1.2:120;

[0179] (2.2)First, add dialdehyde starch to the regenerated protein sizing agent and adjust the pH value to 9, keep it warm at 70°C for 40 min to obtain a sizing agent. Then, adopt the dip-rolling method of two-dip two-roll (the dipping is single-roller type, and the squeezing is upper and lower double-roller type), and control the squeezing pressure to be 40 N and the sizing speed to be 20 m / min. Coat the sizing agent on the aldehyde group-containing yarn, and then react in hot air at 70°C for 12 min to obtain a sized yarn; among them, the mass of dialdehyde starch is 10% of the mass of the regenerated protein;

[0180] The obtained sized yarn consists of an aldehyde group-containing yarn and a sizing film coated on the surface of the aldehyde group-containing yarn (the X-ray photoelectron spectroscopy deconvolution analysis of carbon elements in the sizing film is as Figure 3As shown in the figure; to ensure the accuracy of the atlas, a set of parallel experiments are required to separately prepare the sericin film. That is, in step (2.2), the mercapto-containing yarn is replaced with a polytetrafluoroethylene substrate, and the substrate is removed after preparation to obtain the sericin film. The breaking strength of the sericin film is 8.12 MPa, the elongation at break is 113.85%, the work of rupture is 6.19 J, the storage modulus at 30 °C is 812.3 MPa, and the loss modulus at 30 °C is 141.540 MPa; the sizing rate of the sized yarn is 12.2%, and the breaking strength of the roving is 125.09 N; the strength increase rate of the sized yarn relative to the aldehyde group-containing yarn is 16.1%, and the reduction rate of the number of harmful hairiness is 98.75%.

[0181] (3) Prepare the grey fabric;

[0182] Weave the sized yarn to obtain the grey fabric;

[0183] (4) Desize the grey fabric;

[0184] Immerse the grey fabric in the acidic desizing solution and wash it at 20 °C (with stirring) for 20 min to complete the desizing of the grey fabric; among them, the mass ratio of the grey fabric to the acidic desizing solution is 1:20.

[0185] The desizing rate of the final grey fabric is 94.31%.

[0186] Example B6

[0187] A method for desizing grey fabric, the specific steps are as follows:

[0188] (1) Preparation of raw materials;

[0189] Polyester yarn: polyester yarn, the manufacturer is Hangzhou Huichuang Textile Co., Ltd., polyester ring spinning series, fineness is 40S;

[0190] Sodium hydroxide solution: the solvent is water, and the concentration is 20 wt%;

[0191] Sodium periodate solution: the solvent is water, and the concentration is 1 wt%;

[0192] Regenerated protein sizing solution: composed of soy protein isolate (the manufacturer is Shandong Yuwang Biotechnology Co., Ltd., model SD-200), water and glycerol, the concentration of soy protein isolate is 6 wt%, and the concentration of glycerol is 1.2 wt%;

[0193] Dialdehyde starch: CAS number is 9047-50-1;

[0194] Acidic desizing solution: hydrochloric acid aqueous solution, pH value is 2.0;

[0195] (2) Prepare the sized yarn;

[0196] (2.1) Add the polyester yarn into the sodium hydroxide solution, treat it at 70 °C for 10 min, take it out, wash it with water, dry it, and obtain the yarn containing hydroxyl groups. Then add the yarn containing hydroxyl groups into the sodium periodate solution, treat it at 65 °C for 20 min, take it out, wash it with water, dry it, and obtain the yarn containing aldehyde groups with a strength of 34.74 cN / tex and 31 harmful hairiness roots per 5 m. Among them, the mass ratio of the polyester yarn to the sodium hydroxide solution is 1:220, and the mass ratio of the yarn containing hydroxyl groups to the sodium periodate solution is 1:120;

[0197] (2.2) First, add dialdehyde starch to the regenerated protein slurry and adjust the pH value to 9. Keep it warm at 80 °C for 30 min to obtain the sizing agent. Then adopt the dipping and rolling method of two-dip two-roll (the dipping is a single-roller type, and the rolling is an upper and lower double-roller type), and control the squeezing pressure to be 40 N and the sizing speed to be 20 m / min. Coat the sizing agent on the yarn containing aldehyde groups, and then react in hot air at 60 °C for 12 min to obtain the sized yarn. Among them, the mass of dialdehyde starch is 20% of the mass of the regenerated protein;

[0198] The obtained sized yarn is composed of the yarn containing aldehyde groups and the sizing film coated on the surface of the yarn containing aldehyde groups. The breaking strength of the sizing film is 8.33 MPa, the breaking elongation rate is 92.02%, the breaking work is 6.12 J, the storage modulus at 30 °C is 950 MPa, and the loss modulus at 30 °C is 141.029 MPa. The sizing rate of the sized yarn is 11.75%, and the breaking strength of the roving is 118.57 N. The strength improvement rate of the sized yarn relative to the yarn containing aldehyde groups is 11.62%, and the reduction rate of the number of harmful hairiness roots is 98.75%;

[0199] (3) Prepare the grey fabric;

[0200] Weave the sized yarn to obtain the grey fabric;

[0201] (4) Desize the grey fabric;

[0202] Immerse the grey fabric into the acidic desizing solution and wash it at 40 °C (accompanied by stirring) for 15 min to complete the desizing of the grey fabric. Among them, the mass ratio of the grey fabric to the acidic desizing solution is 1.2:20.

[0203] The desizing rate of the final grey fabric is 97.53%.

Claims

1. A sized yarn, comprising a yarn and a sizing film coated on the surface of the yarn, characterized in that, The yarn and the sizing film are connected by disulfide bonds. The sizing film is formed by directly cross-linking proteins with each other through disulfide bonds. The yarn is a yarn containing mercapto groups, and the protein is a protein that has been subjected to mercapto group enrichment treatment. The preparation process of the sized yarn is as follows: First, 2-iminothiolane is added to the regenerated protein sizing solution, and the mixture is kept warm at 25 - 30 °C for 30 - 50 min to obtain the sizing agent. Then, the sizing agent is coated on the yarn containing mercapto groups by padding, and then reacted in hot air at 60 - 80 °C for 10 - 20 min to obtain the sized yarn. The regenerated protein is feather keratin, and the yarn containing mercapto groups is a cellulose-based yarn that has been subjected to mercapto group treatment.

2. The sized yarn according to claim 1, characterized in that, The breaking strength of the sizing film is 7.62 - 16.17 MPa, the elongation at break is 41.3 - 101.11%, the work of rupture is 0.95 - 5.27 J, the storage modulus at 30 °C is 239.275 - 736.4 MPa, and the loss modulus at 30 °C is 82.042 - 119.014 MPa; the sizing percentage of the sized yarn is 15.1 - 20.93%, and the breaking strength of the roving is 15.13 - 22.3 N.

3. The size yarn according to claim 1, wherein The preparation process of the yarn containing mercapto groups is as follows: The cellulose-based yarn is immersed in an L-cysteine solution, ultrasonically treated at 20 - 30 °C for 5 - 10 min, then baked at 160 - 180 °C for 3 - 5 min, washed with water to remove the excess L-cysteine, and then dried to obtain the yarn containing mercapto groups. Among them, the concentration of the L-cysteine solution is 3 - 5 wt%, the mass ratio of the cellulose-based yarn to the L-cysteine solution is 1 - 1.2:100 - 200, and the ultrasonic power is 120 - 180 W.

4. The sized yarn according to claim 1, wherein, During the preparation process of the sized yarn, the concentration of the regenerated protein in the regenerated protein sizing solution is 6 wt%, the mass of 2-iminothiolane is 2 - 6% of the mass of the regenerated protein, the padding is two-bath two-roll padding, the sizing is single-roller type, the squeezing is upper and lower double-roller type, the squeezing pressure is 20 - 40 N, and the sizing speed is 10 - 30 m / min.

5. A grey fabric, characterized in that, It is woven from a sized yarn according to any one of claims 1 to 4.

6. The desizing method of a grey fabric according to claim 5, characterized in that, The greige fabric is immersed in a desizing solution containing a reducing agent for washing to carry out the reduction reaction of disulfide bonds, thereby completing the desizing of the greige fabric. Among them, the mass ratio of the greige fabric to the desizing solution containing the reducing agent is 1:10 - 15; the pH value of the desizing solution containing the reducing agent is 7 - 9, the concentration of the reducing agent therein is 10 - 20 g / L, and the reducing agent is L-cysteine; the washing temperature is 20 - 50 °C, and the time is 1 - 10 min; the desizing rate of the greige fabric is 95.78 - 99.43%.

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