CN105821660B - A kind of modified silk fiber with high hygroscopicity and moisture retention and preparation method thereof - Google Patents

Abstract

The invention provides a modified silk fiber with high moisture absorption and moisture retention and a preparation method thereof, wherein the modified silk fiber with high moisture absorption and moisture retention is prepared by using fine-fiber silk fiber as a raw material, using low-molecular-weight chitosan, sodium alginate, corn starch and honeysuckle as a high moisture absorption and moisture retention finishing agent, sequentially dipping the high moisture absorption and moisture retention finishing agent and a silk fibroin solution, and then carrying out steam treatment, shaping, water washing and drying. The modified silk fiber prepared by the invention has high fibrillation degree and excellent moisture absorption and retention performance, and the practicability of the silk fiber is improved and the original properties of the silk are protected to the maximum extent through silk fibroin solidification and finishing.

Description

A kind of modified silk fiber with high hygroscopicity and moisture retention and preparation method thereof

Technical field:

The invention belongs to the technical field of textile materials, and in particular relates to a modified silk fiber with high hygroscopicity and moisture retention and a preparation method thereof.

Background technique:

With the gradual improvement of people's living standards, people have put forward higher requirements on the clothing fabric itself, not only to be durable and comfortable, but also to have antibacterial and antibacterial functions. As we all know, silk fiber has always been famous for its skin-friendly comfort and certain health benefits, but the hygroscopicity of silk fiber is not high, and the moisture regain is only 11%, which greatly limits the application of silk fiber in the field of moisture absorption.

Chinese patent CN 104213248A (disclosure date December 17, 2014) discloses a moisture-absorbing and breathable silk composite fiber and a preparation method thereof, first decocting frankincense, alba, and honeysuckle with water for 4-6 hours, filtering, and decocting the filtrate Add silk, camel hair, and milk protein fiber to soak for 10-13 hours, remove and dry, degrease, ultra-finely crush, and then evenly spray coconut oil essence; then add hot water to the tea polyphenols and stir until dissolved, add coral fleece , ramie fiber, PTT short fiber, plastic starch, sodium pyrophosphate ultrasonic treatment for 30-40 minutes; then weigh 1-butyl-3-methylimidazole dibutyl phosphate, 1-ethyl-3-methylimidazole Put diethyl ester into the reaction kettle and mix well, add the products of steps (1) and (2) and grind for 20-40 minutes, heat to 100-120°C, then add other remaining ingredients and stir for 50-70 minutes to obtain spinning Stock solution; finally, spinning, winding, bundling and stretching the obtained spinning stock solution. The silk composite fiber prepared by the method belongs to the regenerated silk composite fiber, which is obtained by fusion of silk and other functional raw materials through spinning. The regenerated silk composite fiber prepared by the method has low mechanical strength and low practicability. Chinese paper (“Preparation of HBP-HTC and Its Modification Research on Silk”, Zhang Desuo, master’s thesis of Soochow University) disclosed that after using hyperbranched compound HBP-HTC to impregnate silk, it was found that due to the large amount of HBP-HTC contained in The hydrophilic group is attached to the surface of the silk, which improves the hydrophilicity of the silk, and the silk is damaged to a certain extent during the high temperature treatment, which increases the gap in the fabric and enhances the capillary effect, so the water absorption of the silk fabric is slightly lower. enhanced. The silk fabric prepared by the method improves the water absorption of the silk fabric by adding hydrophilic groups on the surface of the silk fabric, and the enhanced water absorption performance is limited.

Invention content:

The technical problem to be solved by the present invention is to provide a modified silk fiber with high hygroscopicity and moisture retention and a preparation method thereof. Honeysuckle and honeysuckle are used as high moisture-absorbing and moisturizing finishing agents, which are prepared by impregnating the moisture-absorbing and moisturizing finishing agents and silk fibroin solution, and then steaming to shape, wash and dry. The modified silk fiber prepared by the invention has a high degree of fibrillation, and the inside and surface of the finely fibrillated silk contains a high moisture absorption and moisturizing finishing agent, so the modified silk fiber has good moisture absorption and moisture retention performance.

In order to solve the problems of the technologies described above, the technical solution of the present invention is:

A hygroscopic and moisture-retaining modified silk fiber, characterized in that the hygroscopic and moisture-retaining modified silk fiber is made from finely fibrillated silk fibers, which are soaked, steam-treated to shape, washed with water, and dried. , the interior and surface of the fibrillated silk fibers of the modified silk fiber with hygroscopicity and moisture retention contain a moisture absorption and moisture retention finishing agent, and the moisture absorption and moisture retention finishing agent comprises low molecular weight chitosan, sodium alginate, corn starch and honeysuckle.

As a preferred technical solution, the components in the moisture-absorbing and moisturizing finishing agent include, by weight, 5-15 parts of low molecular weight chitosan, 3-7 parts of sodium alginate, 2-8 parts of cornstarch, 1-5 parts of honeysuckle and 50-80 parts of deionized water.

The present invention also provides a method for preparing modified silk fibers with high hygroscopicity and moisture retention, which is characterized in that: comprising the following steps:

(1) After the silk is processed through degumming, it is added to the calcium chloride solution to swell, and then the swollen silk fiber is rubbed and combed to obtain finely fibrillated silk fiber;

(2) Add sodium alginate solution, cornstarch and honeysuckle extract to the chitosan solution with low molecular weight, stir until mixed evenly, and form a moisture-absorbing and moisturizing finishing agent;

(3) After the finely fibrillated silk fibers prepared in step (1) are dried at room temperature, they are immersed in the moisture-absorbing and moisturizing finishing agent prepared in step (2) to completely wet them, taken out and dried, and then immersed in an aqueous silk fibroin solution, Take it out, remove the excess solution on the surface, and finally use ethanol water vapor to fix the shape, wash and dry to obtain the modified silk fiber with high moisture absorption and moisturizing properties.

As a preference of the above technical solution, in the step (1), the concentration of the calcium chloride solution is 2-4%, the swelling temperature is 70-80°C, and the swelling time is 5-15min.

As a preference of the above technical solution, in the step (1), the degree of fibrillation of the fibrillated silk fibers is 20-35%.

As the preference of above-mentioned technical scheme, in described step (2), the degree of deacetylation of the chitosan of low molecular weight is 85-95%, the massfraction of chitosan in the chitosan solution of low molecular weight is not higher than 5% .

As a preference of the above technical solution, in the step (2), the mass fraction of sodium alginate in the sodium alginate solution is not higher than 3%.

As a preference of the above technical solution, in the step (3), the dipping temperature is 25-30° C., and the dipping time is not less than 10 minutes.

As a preference of the above technical solution, in the step (3), the drying and drying temperature is 60-70°C.

As a preference of the above technical solution, in the step (3), the volume ratio of ethanol to water vapor is 1:1, and the treatment time is 10-30min.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The present invention kneads and combs the swollen silk fiber to fibrillate the silk fiber, increases the amorphous region inside the silk protein macromolecule, loosens between the crystallized regions, and water molecules enter the amorphous region and the crystallized region , so that the distance between the silk fibroin molecular chains increases, the outer surface area of the fiber increases, and then the moisture absorption and moisturizing properties of the silk fiber are improved.

(2) the present invention adopts low molecular weight chitosan, sodium alginate, cornstarch and honeysuckle extract as raw material to prepare hygroscopicity moisturizing finishing agent, the hygroscopicity that contains cornstarch is strong in the finishing agent, and honeysuckle has antibacterial and antibacterial effect, It also contains low molecular weight chitosan and sodium alginate, which can form a certain complexation and cross-linking with the macromolecular chains in the silk fiber, and coat and fix the cornstarch and honeysuckle extract on the inside and surface of the silk fiber Forms a film to prevent the loss of cornstarch and honeysuckle extract during use and washing.

(3) Finally, the present invention solidifies the finishing agent on the surface and inside of the silk fiber by impregnating the silk fibroin aqueous solution and the ethanol aqueous solution and steaming treatment, further improves the washing resistance and serviceability of the silk fiber, and repairs the damage caused by fibrillation to the silk fiber. The damage to the high-quality performance of the fiber protects the original performance of the silk fiber to the greatest extent.

(4) The modified silk fiber prepared by the invention has excellent hygroscopicity, which can reach more than 25%, has good elasticity, and also has antibacterial and antibacterial effects.

Detailed ways:

The present invention will be described in detail below in conjunction with specific embodiments, where the exemplary embodiments and descriptions of the present invention are used to explain the present invention, but are not intended to limit the present invention.

Example 1:

(1) After the silk is degummed, it is added to a calcium chloride solution with a concentration of 2%, and it is swelled at 70°C for 5 minutes, and then the swollen silk fiber is kneaded and carded to obtain a fibrillation degree of 20%. of silk fibers.

(2) In parts by weight, add sodium alginate solution, cornstarch and honeysuckle extract to the chitosan solution with a low molecular weight of 85% deacetylation degree, stir until mixed evenly, and form a moisture-absorbing and moisturizing finishing agent, wherein low 5 parts of molecular weight chitosan, 3 parts of sodium alginate, 2 parts of corn starch, 1 part of honeysuckle and 50 parts of deionized water.

(3) After the finely fibrillated silk fibers prepared in step (1) are dried at room temperature, they are immersed in the moisture-absorbing and moisturizing finishing agent prepared in step (2) at 25° C. to completely wet them, taken out, dried at 60° C., and then Immerse in the silk fibroin aqueous solution for 15 minutes at 25°C, take it out, remove the excess solution on the surface, and finally use ethanol with a volume ratio of 1:1 to steam for 10 minutes to set the shape, wash with water, and dry at 60°C to obtain a modified product with high moisture absorption and moisture retention silk fiber.

Example 2:

(1) After the silk is degummed, it is added to a calcium chloride solution with a concentration of 4%, and it is swelled at 80°C for 15 minutes, and then the swollen silk fiber is rubbed and carded to obtain a fibrillation degree of 35%. of silk fibers.

(2) In parts by weight, add sodium alginate solution, cornstarch and honeysuckle extract to the chitosan solution with a low molecular weight of 95% deacetylation degree, stir until mixed evenly, and form a moisture-absorbing and moisturizing finishing agent, wherein low 15 parts of chitosan with molecular weight, 7 parts of sodium alginate, 8 parts of corn starch, 5 parts of honeysuckle and 80 parts of deionized water.

(3) After the finely fibrillated silk fibers prepared in step (1) are dried at room temperature, they are immersed in the moisture-absorbing and moisturizing finishing agent prepared in step (2) at 30° C. to completely wet them, taken out, dried at 70° C., and then Immerse in the silk fibroin aqueous solution for 20 minutes at 30°C, take it out, remove the excess solution on the surface, and finally use ethanol with a volume ratio of 1:1 for 30 minutes to set the shape, wash with water, and dry at 70°C to obtain a modified product with high moisture absorption and moisture retention silk fiber.

Example 3:

(1) After the silk is degummed, it is added to a calcium chloride solution with a concentration of 3%, and it is swelled at 75°C for 10 minutes, and then the swollen silk fiber is kneaded and carded to obtain a fibrillation degree of 25%. of silk fibers.

(2) In parts by weight, add sodium alginate solution, cornstarch and honeysuckle extract to the chitosan solution with a low molecular weight of 90% deacetylation degree, stir until mixed evenly, and form a moisture-absorbing and moisturizing finishing agent, wherein low 10 parts of chitosan with molecular weight, 5 parts of sodium alginate, 4 parts of corn starch, 2 parts of honeysuckle and 60 parts of deionized water.

(3) After the finely fibrillated silk fibers prepared in step (1) are dried at room temperature, they are immersed in the moisture-absorbing and moisturizing finishing agent prepared in step (2) at 27° C. to completely wet them, taken out, dried at 65° C., and then Immerse in the silk fibroin aqueous solution for 25 minutes at 26°C, take it out, remove the excess solution on the surface, and finally use ethanol with a volume ratio of 1:1 to steam for 15 minutes to set the shape, wash with water, and dry at 65°C to obtain a modified product with high moisture absorption and moisture retention silk fiber.

Example 4:

(1) After the silk is degummed, it is added to a calcium chloride solution with a concentration of 2%, and it is swelled at 80°C for 5 minutes, and then the swollen silk fiber is rubbed and carded to obtain a fibrillation degree of 35%. of silk fibers.

(2) In parts by weight, add sodium alginate solution, cornstarch and honeysuckle extract to the chitosan solution with a low molecular weight of 85% deacetylation degree, stir until mixed evenly, and form a moisture-absorbing and moisturizing finishing agent, wherein low 15 parts of chitosan with molecular weight, 3 parts of sodium alginate, 8 parts of corn starch, 5 parts of honeysuckle and 50 parts of deionized water.

(3) After the finely fibrillated silk fibers prepared in step (1) are dried at room temperature, they are immersed in the moisture-absorbing and moisturizing finishing agent prepared in step (2) at 30° C. to completely wet them, taken out, dried at 60° C., and then Immerse in silk fibroin aqueous solution at 30°C for 25 minutes, take it out, remove excess solution on the surface, and finally use ethanol with a volume ratio of 1:1 to steam for 25 minutes to set the shape, wash with water, and dry at 70°C to obtain a modified product with high moisture absorption and moisture retention silk fiber.

Example 5:

(1) After the silk is degummed, it is added to a calcium chloride solution with a concentration of 3%, and it is swelled at 75°C for 15 minutes, and then the swollen silk fiber is rubbed and carded to obtain a fibrillation degree of 25%. of silk fibers.

(2) In parts by weight, add sodium alginate solution, cornstarch and honeysuckle extract to the chitosan solution with a low molecular weight of 90% deacetylation degree, stir until mixed evenly, and form a moisture-absorbing and moisturizing finishing agent, wherein low 5 parts of chitosan with molecular weight, 5 parts of sodium alginate, 5 parts of corn starch, 5 parts of honeysuckle and 65 parts of deionized water.

(3) After the finely fibrillated silk fibers prepared in step (1) are dried at room temperature, they are immersed in the moisture-absorbing and moisturizing finishing agent prepared in step (2) at 30° C. to completely wet them, taken out, dried at 60° C., and then Immerse in the silk fibroin aqueous solution for 10 minutes at 25°C, take it out, remove the excess solution on the surface, and finally use ethanol with a volume ratio of 1:1 to steam for 30 minutes to set the shape, wash with water, and dry at 60°C to obtain a modified product with high moisture absorption and moisture retention silk fiber.

Embodiment 6:

(1) After the silk is degummed, it is added to a calcium chloride solution with a concentration of 4%, and it is swelled at 70°C for 15 minutes, and then the swollen silk fiber is rubbed and carded to obtain a fibrillation degree of 30%. of silk fibers.

(2) In parts by weight, add sodium alginate solution, cornstarch and honeysuckle extract to the chitosan solution with a low molecular weight of 90% deacetylation degree, stir until mixed evenly, and form a moisture-absorbing and moisturizing finishing agent, wherein low 10 parts of chitosan with molecular weight, 6 parts of sodium alginate, 6 parts of corn starch, 4 parts of honeysuckle and 70 parts of deionized water.

(3) After the finely fibrillated silk fibers prepared in step (1) are dried at room temperature, they are immersed in the moisture-absorbing and moisturizing finishing agent prepared in step (2) at 27° C. to completely wet them, taken out, dried at 65° C., and then Immerse in the silk fibroin aqueous solution for 15 minutes at 25°C, take it out, remove the excess solution on the surface, and finally use ethanol with a volume ratio of 1:1 to steam for 15 minutes to set the shape, wash with water, and dry at 70°C to obtain a modified product with high moisture absorption and moisture retention silk fiber.

After testing, the results of the water absorption of the modified silk fibers with high moisture absorption and moisturizing properties prepared in Examples 1-6 and the unmodified silk fibers of the prior art and the silk fabrics modified by the hyperbranch compound HBP-HTC are as follows :

It can be seen from the above table that the modified silk fiber with high hygroscopicity and moisture retention property prepared by the present invention greatly improves the moisture absorption and moisture retention performance, and expands the application field of the silk fiber.

The above-mentioned embodiments only illustrate the principles and effects of the present invention, but are not intended to limit the present invention. Anyone skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those skilled in the art without departing from the spirit and technical ideas disclosed in the present invention should still be covered by the claims of the present invention.

Claims (9)

1. a kind of modified silk fiber of highly hygroscopic moisture retention, it is characterised in that the modified silk of the highly hygroscopic moisture retention is fine Dimension is using the silk fiber of fibrillating as raw material, is made through dipping, steam treatment sizing, washing, drying steps, the height The inside and surface of the silk fiber of the fibrillating of the modified silk fiber of moisture absorbability and moisture retentivity are contained highly hygroscopic moisture retention and are arranged Agent, chitosan, sodium alginate, cornstarch and the honeysuckle of low molecular weight are included in the highly hygroscopic wet keeping finishing agent；

Wherein, the preparation method of the modified silk fiber of the highly hygroscopic moisture retention, comprises the following steps：

(1) by silk after degumming process, add in calcium chloride solution and be swollen, then by the silk fiber of swelling through rubbing and combing Reason obtains the silk fiber of fibrillating；

(2) sodium alginate soln, cornstarch and Flos Lonicerae extractive solution will be added in the chitosan solution of low molecular weight, stirring is extremely It is uniformly mixed, forms highly hygroscopic wet keeping finishing agent；

(3) the silk fiber room temperature for the fibrillating for preparing step (1) is impregnated in step after drying

(2) complete wetting in the highly hygroscopic wet keeping finishing agent prepared, takes out drying, then is impregnated in silk fibroin water solution, takes Go out, remove the solution of excess surface, finally handled and shaped with alcohol steam, washing and drying obtains the modification of highly hygroscopic moisture retention Silk fiber.

2. the modified silk fiber of a kind of highly hygroscopic moisture retention according to claim 1, it is characterised in that described highly hygroscopic Component in wet keeping finishing agent, by weight, including：3-7 parts of 5-15 parts of chitosan, sodium alginate, the corn of low molecular weight form sediment 50-80 parts of 2-8 parts of powder, 1-5 parts of honeysuckle and deionized water.

A kind of 3. modified silk fiber of highly hygroscopic moisture retention according to claim 1, it is characterised in that：The step (1) in, the concentration of calcium chloride solution is 2-4%, and the temperature of swelling is 70-80 DEG C, and the time of swelling is 5-15min.

A kind of 4. modified silk fiber of highly hygroscopic moisture retention according to claim 1, it is characterised in that：The step (1) in, the original fiber degree of the silk fiber of fibrillating is 20-35%.

A kind of 5. modified silk fiber of highly hygroscopic moisture retention according to claim 1, it is characterised in that：The step (2) in, the deacetylation of the chitosan of low molecular weight is 85-95%, the quality of chitosan in the chitosan solution of low molecular weight Fraction is not higher than 5%.

A kind of 6. modified silk fiber of highly hygroscopic moisture retention according to claim 1, it is characterised in that：The step (2) in, the mass fraction of sodium alginate is not higher than 3% in sodium alginate soln.

A kind of 7. modified silk fiber of highly hygroscopic moisture retention according to claim 1, it is characterised in that：The step (3) in, the temperature of dipping is 25-30 DEG C, and the time of dipping is not less than 10min.

A kind of 8. modified silk fiber of highly hygroscopic moisture retention according to claim 1, it is characterised in that：The step (3) in, drying and dry temperature are 60-70 DEG C.

A kind of 9. modified silk fiber of highly hygroscopic moisture retention according to claim 1, it is characterised in that：The step (3) in, the volume ratio of alcohol steam is 1:1, processing time 10-30min.