CN110080010B - Preparation method of colored cellulose fibers - Google Patents

Abstract

The invention relates to a colored cellulose fiber and a preparation method thereof. The preparation method comprises the following steps: extruding, coagulating, stretching and washing a cellulose fiber spinning solution through a spinneret to obtain washed silk, and the washing temperature is ≥90 ℃, and then use a dye aqueous solution with a temperature of 40 to 90 ℃ to treat the washed silk, and finally rinse and dry to obtain colored cellulose fibers. The rinsing temperature is 20 to 40 ℃, and the dye contains X, Y and Z groups in the One or more of X, Y and Z groups correspond to groups capable of forming covalent bonds with cellulose hydroxyl groups, groups capable of self-crosslinking reaction, and groups capable of forming hydrogen bonds with cellulose hydroxyl groups. The mass of the dye in the colored cellulose fibers is 0.1-5.0% of the mass of the cellulose fiber matrix, and the washing resistance is excellent. The method of the invention is simple and easy to implement, and the durability of the colored cellulose fibers is good.

Description

A kind of preparation method of colored cellulose fibers

technical field

The invention belongs to the technical field of colored fiber manufacturing, and relates to a colored cellulose fiber and a preparation method thereof.

Background technique

Cellulose fiber has the advantages of natural and renewable resources, comfortable wearing, non-toxic, hygienic, and degradable waste. Therefore, cellulose fiber has long been the mainstream raw material of textiles and is enduring. However, due to the limited output of natural cellulose fibers such as cotton and hemp, which cannot meet consumer demand, people often use natural cellulose materials such as cotton linters, wood, bamboo and straw as raw materials to prepare regenerated cellulose fibers, so as to achieve The purpose of effectively utilizing natural materials and increasing the supply of cellulose fibers. With the development of consumer demand, people not only increase the demand for cellulose fibers, but also require a variety of fiber products, colors and styles, so that they can meet the different needs of different groups of people. put forward higher requirements.

At present, there are several methods for preparing colored cellulose fibers: one is the dope addition method, that is, dyes are added to the spinning solution, and colored fibers are prepared by spinning. This method is a relatively common technical method for the production of colored regenerated cellulose fibers. The effect is remarkable, but there are also disadvantages: 1) The dye is easy to remain in the spinning equipment and the coagulation washing system, which affects the extrusion and forming of the fiber and the recycling of the solvent; 2) The degree of dispersion of the dye and the amount of addition of the dye affect the mechanical properties of the fiber, etc. It will have adverse effects; 3) The batch replacement in production is inflexible, and there are many transition silks, which increases the production cost; the second is the fiber or fabric post-treatment method, which is common to both natural fibers and regenerated fibers, and the advantage is that the batch can be large or small. , The production conversion is flexible and adaptable to many varieties, but the disadvantages are: 1) The general treatment method may cause the problem of poor durability; 2) When the fiber or fabric is dyed after finishing, it often affects the feel and softness of the fiber and fabric. 3) The fiber microstructure of the finished product is dense, the post-treatment mainly occurs on the fiber surface, the dyes that can be added are limited, which affects the dyeing effect, or needs to be swelled or activated to improve reactivity, and Subsequent reactions or processing solvents still need to be processed, which undoubtedly increases the process and processing costs.

Therefore, it is of great significance to study a colored cellulose fiber with good durability that does not affect the extrusion and forming of the fiber and its preparation method.

SUMMARY OF THE INVENTION

The purpose of the present invention is to overcome the above-mentioned problems in the prior art, and provide a colored cellulose fiber with good durability that does not affect the extrusion and forming of the fiber and a preparation method thereof.

In order to achieve the above object, the technical scheme adopted in the present invention is:

A method for preparing colored cellulose fibers. The cellulose fiber spinning solution is extruded, coagulated, stretched and washed with a spinneret to obtain washed filaments, and then the washed filaments are treated with an aqueous dye solution and then rinsed and washed with water. Drying to obtain colored cellulose fibers;

The temperature of washing is ≥90℃, and the temperature of the dye aqueous solution is 40～90℃. The temperature of the dyestuff aqueous solution is determined according to the reactivity of the dye. The reactivity is high. The dyeing temperature is about 40℃, and the reactivity is low. The dyeing temperature is 80-90°C, the rinsing temperature is 20-40°C, and the temperature of the dye aqueous solution is higher than the rinsing temperature during processing; , and then combined with the dye, shrinkage occurs again, and the dye is wrapped inside the fiber; the method of the invention has the advantages of the dope addition method and the post-finishing method, and at the same time effectively avoids the shortcomings of the two methods, and has great promotion value;

The dye contains more than one of X group, Y group and Z group, X group is a group capable of forming covalent bond with cellulose hydroxyl group, Y group is a group capable of self-crosslinking reaction, Z group The groups are groups capable of forming hydrogen bonds with cellulose hydroxyl groups.

As the preferred technical solution:

As mentioned above, the preparation method of colored cellulose fibers, the concentration of cellulose fibers spinning solution is 5-25wt%. The concentration will affect the phase separation during the spinning process. The concentration of the cellulose fiber spinning solution of the present invention can be adjusted appropriately, but it should not be too high. Or when there is a phase transition, only a loose and uneven structure is formed, which reduces the mechanical properties of the fiber; if the concentration is too high, it is equivalent to dry spinning to form a dense structure, which is not conducive to subsequent dyeing; cellulose fibers are regenerated Cellulose fibers or fibers of cellulose derivatives.

The preparation method of a kind of colored cellulose fibers as above, the cellulose fibers are viscose fibers, acetate fibers, Lyocell fibers, cupro fibers, regenerated cellulose fibers prepared with ionic liquid as solvent or with alkali. The solution is a solvent-prepared regenerated cellulose-based fiber. The colored cellulose fibers of the present invention include, but are not limited to, other regenerated cellulose fibers or cellulose derivative fibers that contain a microporous structure and can be combined with the above-mentioned dyes during the above-mentioned treatment process.

The above-mentioned preparation method of colored cellulose fibers, the termination condition of washing is: the water content of the washed silk is 40-70 wt%, and the water content of the washed silk of the present invention can be adjusted appropriately, but it should not be too high, and the water content If it is too low, the fiber has been dried, the number of internal micropores is reduced, and the diameter of the micropores is reduced, which is not conducive to subsequent dyeing, and is not conducive to the entry of dyes into the fiber; Water has a certain pressure difference with the outside world, which is also not conducive to the entry of dyes into the fiber; the crystallinity of the washed silk is less than 15%, the average diameter of the micropores is 10-200 nanometers, and the volume of the micropores accounts for 10% of the total volume of the washed silk. ~30%, the washed silk has low crystallinity and relatively loose microporous structure, which is conducive to the entry of dyes.

A kind of preparation method of colored cellulose fiber as mentioned above, X group is aldehyde group, cyano group, epoxy group, acid chloride group, acid anhydride or diisocyanate; Y group is siloxane; Z group is a sulfonic acid group or a sulfate group.

For the preparation method of a colored cellulose fiber as described above, the mass content of the dye in the dye aqueous solution is 2-10 wt%; due to the different structures of different dyes, the content of the dyes diffused into the fiber is different, and the selected concentration is different. For different dyes, the concentration used can be appropriately selected within the above range or adjusted outside the above range, but it should not be too high. The content should not be too low; and because for a certain amount of fiber, the amount of dye that can enter the interior is certain, and the mass content of the dye in the aqueous solution will cause waste, so the content should not be too high; also because the dye is easy to adhere to It is removed on the fiber surface and in the subsequent rinsing process, which will adversely affect the dyeing effect. Therefore, in order to ensure the final dyeing effect (the dye uptake rate can reach more than 80%), the lower mass content of the dye in the dye solution is controlled at 2%;

Dyes are more than one of direct dyes, reactive dyes and sulfur dyes. Here only some common dyes are listed. Others meet the requirements of "containing more than one of X group, Y group and Z group" and are soluble in water. Dyes are suitable for use in the present invention.

The above-mentioned preparation method of colored cellulose fibers is treated by soaking or spraying, and the treatment time is 60 to 600 seconds. Due to the different structures of different dyes, the diffusion time into the fiber is different. Therefore, for different dyes, the treatment time can be appropriately selected within the above range or adjusted appropriately outside the above range, but it should not be too long. If the time is too short, the entry will not be comprehensive, resulting in poor dyeing effect and uneven dyeing; time If it is too long, the dyeing has reached equilibrium before this time, which is a waste of time; the rinsing time is 120 to 600 seconds.

The above-mentioned preparation method of colored cellulose fibers, the drying adopts the method of hot air drying, and the temperature of the hot air is 105-160 ° C. The drying temperature of the present invention can be adjusted appropriately, but it should not be too high. If the temperature is too low, the moisture content of the fiber cannot meet the specified requirements, and the reaction is not sufficient; if the temperature is too high, the fiber will have a large curl, and even a small part may be carbonized, decomposed and turned black, which will cause adverse effects on the fiber performance; Dry and dry until the moisture content of the fiber is less than 15wt%, and the moisture content of the fiber of the present invention is less than 15wt% to ensure that the fiber has been fully dried and densified to achieve the use effect of general cellulose fibers.

The present invention also provides colored cellulose fibers prepared by the above-mentioned preparation method of colored cellulose fibers, which are mainly composed of a cellulose fiber matrix and dyes dispersed in the cellulose fiber matrix; When it contains groups that can be combined with cellulose groups, on the one hand, the dye is fixed in the cellulose fiber matrix by the binding force between its own groups and the groups of the cellulose fiber matrix, and on the other hand, it is The entrapment of the micropores inside the cellulose fiber matrix is fixed in the cellulose fiber matrix; when the dye does not contain groups that can be combined with cellulose groups, it mainly passes through the micropores inside the cellulose fiber matrix. The embedding of the pores is fixed in the cellulose fiber matrix, and it also has excellent washing resistance.

As the preferred technical solution:

The above-mentioned colored cellulose fibers, the crystallinity of the colored cellulose fibers is more than 30%, containing micropores, the average diameter of the micropores is 5 to 50 nanometers, and the quality of the dye is 0.1 to 5.0 of the quality of the cellulose fiber matrix. % (Note: the dyeing depth is different, the dye content is different, when the dyeing is deep, the dye content is high, and vice versa); The adsorption is fast and can enter the interior of the fiber. After drying and densification, the dye reacts with the cellulose fiber, and a large amount of the dye can be fixed in the interior of the cellulose fiber matrix. The quality of the dye is equal to that of the cellulose fiber matrix. 0.1-5.0%, improve the durability of colored cellulose fibers.

The monofilament fineness of colored cellulose fibers is 0.5-5.0dtex, the breaking strength is 1.0-4.5cN/dtex, the breaking elongation is 5%-20%, the moisture regain is 5%-15%, and the color fastness to washing is It is equal to grade 5, and the color fastness to rubbing is equal to grade 5;

After the colored cellulose fibers are washed 50 times, the quality of the dye is 0.08-2.50% of the mass of the cellulose fiber matrix, the color fastness to washing is greater than or equal to 4, and the color fastness to rubbing is greater than or equal to 4; and the prior art In comparison, the colored cellulose fibers prepared by the invention have high washing fastness, good durability and good dyeing effect;

Colored cellulose fibers are filaments, staple fibers or tow, used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.

Invention Mechanism:

First, in the present invention, the cellulose fiber spinning solution is extruded, coagulated, stretched and washed to obtain washed filaments through a spinneret. The loose microporous structure, on the other hand, can speed up the diffusion rate and accelerate the washing, so that the coagulation bath and other solvents such as NMMO remaining in the washed silk can diffuse into the water, reducing the influence of the solvent on the dye, if the washing temperature is too low, It takes a long time to remove the solvent from the fiber, and the residual amount is large;

Next, in the present invention, the water-washed silk is treated with an aqueous dye solution at a temperature of 40-90° C. The water-washed silk maintains a microporous structure in the aqueous solution at a temperature of 40-90° C., and ensures that the dye has high solubility. Entering the inside of the washed silk, compared with the treatment at room temperature, it can shorten the treatment time of the dye solution, so that the dye can quickly enter the fiber and reach the diffusion equilibrium in a short time, and the next rinsing treatment can be carried out. If the temperature is too high, For dyes with good diffusivity, the dyes are easy to diffuse outwards, but the dye uptake rate will decrease;

Finally, in the present invention, the treated water-washed silk is rinsed and dried to obtain colored cellulose fibers, and the rinsing temperature is 20-40° C. The rinsing at a lower temperature causes the micropores of the cellulose fibers to shrink and the degree of looseness of the fibers to decrease. Small, while removing the dyes adhering to the surface while retaining the dyes inside the fibers, the rinsing temperature is low, the internal dyes will not diffuse out quickly due to the difference in inner and outer concentrations, and the dyes inside the cellulose fibers will not be washed out, It can also save heating energy. If the temperature is too high, the unreacted part of the dye inside is easily washed out together, and the fiber is further crystallized and densified during the drying process, and the pores shrink, and the dye is embedded in the cellulose fiber base. In vivo, the durability of colored cellulose fibers is improved, especially the washing resistance. At the same time, because the dye contains more than one of the X group, the Y group and the Z group, it has a relationship with the cellulose fiber macromolecules. There is a strong interaction between them, which further improves the binding stability of the dye and the cellulose fiber matrix, and produces colored cellulose fibers with good durability.

The temperature used in the process of washing, dyeing, rinsing and the like of the fibers of the present invention shows a trend of gradual reduction. First, the washing temperature of 90° C. or more accelerates the diffusion speed of the solvent, so that the residual solvent in the primary fibers can be quickly washed out. , so that the solvent and dye will not interact in the subsequent process and affect the effect. At the same time, the washing temperature of greater than or equal to 90 ℃ also increases the pores inside the fiber, which is conducive to the entry of dyes. The temperature of the fiber surface can keep the microporous structure of the fiber surface in a loose state after washing, which accelerates the speed of dye molecules infiltrating into the fiber through the pores on the fiber surface, enabling the dye molecules to quickly enter the fiber and reach equilibrium in a short time. In this way, the dyeing time is shortened, and at this temperature, the dye will not react violently in water due to the high temperature, resulting in the reduction of the dye. Then, at the subsequent lower rinsing temperature, the pores in the fiber are shrunk, and the unreacted dye on the surface can be washed away without washing out the dye molecules in the fiber, so that enough and uniform dye can be maintained in the fiber. The cooperation of the temperature of the aqueous solution treatment and the rinsing significantly improves the durability and mechanical properties of the colored fibers.

In addition, the treatment temperature of the dye aqueous solution of the present application is 40 to 90 ° C, which can ensure that the dye has a high degree of dissolution in water and a fast dissolution rate, so that the dye is rapidly dissolved and diffused into the fiber at a faster rate. Dyeing at ℃ may make the color of the product obtained after dyeing light and dull, and the light fastness will also decrease.

beneficial effect

(1) The preparation method of a colored cellulose fiber of the present invention adopts washing silk for dyeing treatment to prepare durable colored cellulose fibers without adding dyes before spinning, does not affect extrusion and forming, and does not affect dyeing. It will affect the recovery and utilization of the coagulation washing solvent, and does not affect the existing spinning process. The method is flexible and suitable for both mass production and small batch and multi-variety production;

(2) The preparation method of a colored cellulose fiber of the present invention adopts washing silk for dyeing to prepare durable colored cellulose fibers, and uses the loose structure of the washing silk for processing, the dye diffusion is fast, and the production efficiency is high;

(3) In a method for preparing colored cellulose fibers of the present invention, low-temperature rinsing at a temperature of 20 to 40° C. and drying and densification are carried out, so that the dyes are firmly combined with the fibers and the washing fastness is improved;

(4) The preparation method of colored cellulose fibers of the present invention has good durability, remarkable dyeing effect, high washing fastness and good application prospect.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples 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 the present application.

Example 1

A preparation method of colored cellulose fibers, the steps are as follows:

(1) the viscose fiber spinning solution with a degree of polymerization of 500 and a concentration of 20wt% is extruded through a spinneret, coagulated, stretched and washed at 95°C to obtain a washed silk, and the water content of the washed silk is 60wt%;

(2) The water washing silk was soaked for 200 seconds at a temperature of 80°C with an aqueous solution with a mass content of 1.5 wt % of direct scarlet 4BE, and then rinsed for 35 seconds at a temperature of 30°C and dried with hot air. The colored cellulose fibers were prepared by drying at a temperature of 130° C. until the moisture content of the fibers was 10 wt %.

The crystallinity of the finally prepared colored cellulose fibers is 40%, the micropores are contained, the average diameter of the micropores is 20 nanometers, and the mass of the direct dye is 2.0% of the mass of the cellulose fiber matrix.

The monofilament fineness of colored cellulose fibers is 2.5dtex, the breaking strength is 2.5cN/dtex, the elongation at break is 15%, and the moisture regain is 10%. After 50 times of washing, the quality of the direct dye is the quality of the cellulose fiber matrix. 1.6%, the color fastness to washing is 4-5, and the color fastness to rubbing is 4-5;

Colored cellulose fibers are filaments that can be used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.

Comparative Example 1

A preparation method of colored cellulose fibers is basically the same as Example 1, except that the temperature of washing in step (1) is 88 ° C, and the crystallinity of the obtained colored cellulose fibers is 38%, containing micro Pores, the average diameter of micropores is 18 nm, the mass of direct scarlet 4BE is 1.7% of the mass of the cellulose fiber matrix, the monofilament fineness is 2.4dtex, the breaking strength is 2.4cN/dtex, the elongation at break is 17%, and the moisture regain After washing 50 times, the quality of direct red 4BE is 0.09% of the mass of the cellulose fiber matrix, the color fastness to washing is 3, and the color fastness to rubbing is 3.

Comparative Example 2

A preparation method of colored cellulose fibers is basically the same as that in Example 1, except that the temperature of the soaking treatment in step (2) is 35° C., and the obtained colored cellulose fibers have a crystallinity of 39%, and contain Micropores, the average diameter of micropores is 19 nanometers, the mass of direct scarlet 4BE is 1.6% of the mass of the cellulose fiber matrix, the monofilament fineness is 2.5dtex, the breaking strength is 2.5cN/dtex, the elongation at break is 18%, and the moisture regain The ratio was 9%. After washing 50 times, the quality of direct red 4BE was 0.1% of the mass of the cellulose fiber matrix. The color fastness to washing was grade 3, and the color fastness to rubbing was grade 3.

Comparative Example 3

A preparation method of colored cellulose fibers is basically the same as that in Example 1, except that the temperature of rinsing in step (2) is 46° C., the crystallinity of the obtained colored cellulose fibers is 36%, and the Pores, the average diameter of micropores is 17 nm, the mass of direct scarlet 4BE is 1.5% of the mass of the cellulose fiber matrix, the monofilament fineness is 2.3dtex, the breaking strength is 2.4cN/dtex, the elongation at break is 16%, and the moisture regain After 50 washings, the mass of the direct red 4BE is 0.11% of the mass of the cellulose fiber matrix, the color fastness to washing is grade 3, and the color fastness to rubbing is grade 3.

To sum up, by comparing Comparative Examples 1 to 3 with Example 1, it can be seen that during water washing, the higher washing temperature accelerates the diffusion rate of the solvent, which can quickly wash out the solvent remaining in the spun fibers, thereby preventing In the subsequent process, the solvent and the dye will interact, which will affect the effect. At the same time, the higher temperature will also increase the pores inside the fiber, which is conducive to the entry of the dye. During dyeing, the secondary temperature can make the microporous structure on the fiber surface. The loose state after washing has been maintained, which accelerated the speed of dye molecules infiltrating into the fiber through the pores on the fiber surface, enabling the dye molecules to quickly enter the fiber and reach equilibrium in a short period of time, thereby shortening the dyeing time. At the same time, at this temperature Under high temperature, the dye will not react violently in water to reduce the dye; during rinsing, at a lower rinsing temperature, the pores inside the fiber will shrink, and the unreacted dye on the surface will be washed away without causing the dye molecules inside the fiber. After washing, sufficient and uniform dyes are kept inside the fibers. It is precisely because of the interaction of rinsing, water washing and the treatment temperature of the aqueous dye solution that the durability and dyeing performance of the colored cellulose fibers prepared by the present invention are fully improved.

Comparative Example 4

A preparation method of colored cellulose fibers is basically the same as that in Example 1, except that in step (2), the fibers are directly dried without rinsing after soaking, and the obtained colored cellulose fibers have a crystallinity of 38%, containing micropores, the average diameter of the micropores is 18 nanometers, the mass of the direct scarlet 4BE is 1.4% of the mass of the cellulose fiber matrix, the monofilament fineness is 2.5dtex, the breaking strength is 2.5cN/dtex, and the breaking elongation is 16%, the moisture regain is 10%, after 50 washings, the quality of direct bright red 4BE is 0.1% of the mass of the cellulose fiber matrix, the color fastness to washing is grade 3, and the color fastness to rubbing is grade 3. Comparing Comparative Example 4 with Example 1, it can be seen that due to the addition of a rinsing step, at a lower rinsing temperature, the pores inside the fiber are shrunk, and the dye molecules inside the fiber will not be washed out, so that the interior of the fiber is kept. Sufficient and uniform dyestuffs can fully improve the durability and dyeing properties of the colored cellulose fibers prepared by the present invention.

Example 2

A preparation method of colored cellulose fibers, the steps are as follows:

(1) the Lyocell fiber spinning solution with a degree of polymerization of 200 and a concentration of 5wt% is extruded through a spinneret, coagulated, stretched and washed with water at 90°C to obtain a washed silk, and the water content of the washed silk is 40wt%;

(2) Using an aqueous solution with a mass content of reactive red A-2BF of 0.5 wt % at a temperature of 40° C., soaking the washed silk for 5 seconds, then rinsing at a temperature of 20° C. for 10 seconds and drying with hot air. The colored cellulose fibers were prepared by drying the fibers at a temperature of 105° C. until the moisture content of the fibers was 10 wt %.

The crystallinity of the finally prepared colored cellulose fibers is 35%, and the micropores have an average diameter of 5 nanometers. The mass of the reactive dye is 0.1% of the mass of the cellulose fiber matrix.

The monofilament fineness of colored cellulose fibers is 2.6dtex, the breaking strength is 4.5cN/dtex, the elongation at break is 20%, and the moisture regain is 5%. After 50 times of washing, the quality of reactive dyes is the quality of the cellulose fiber matrix. 0.08% of , the color fastness to washing is grade 4, and the color fastness to rubbing is grade 4;

Colored cellulose fibers are short filaments that can be used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.

Example 3

A preparation method of colored cellulose fibers, the steps are as follows:

(1) The acetate fiber spinning solution with a degree of polymerization of 300, a degree of esterification of 2.35, and a concentration of 25 wt% is extruded through a spinneret, coagulated, stretched, and washed with water at 95°C to obtain washed silk. The water content is 70wt%;

(2) The water-soluble black BR with the mass content of 3wt% is used to soak the washed silk for 300 seconds at a temperature of 90°C, then rinse it for 60 seconds at a temperature of 40°C and dry it with hot air. The colored cellulose fibers were prepared by drying at a temperature of 160° C. until the moisture content of the fibers was 12 wt %.

The crystallinity of the finally prepared colored cellulose fibers is 55%, and the micropores have an average diameter of 50 nanometers. The mass of the sulfur dye is 5.0% of the mass of the cellulose fiber matrix.

The monofilament fineness of the colored cellulose fibers is 4.0dtex, the breaking strength is 1.0cN/dtex, the elongation at break is 5%, and the moisture regain is 7%. After 50 times of washing, the quality of the sulfur dye is the quality of the cellulose fiber matrix. 2.5%, the color fastness to washing is level 5, and the color fastness to rubbing is level 5;

Colored cellulose fibers are tow, which can be used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.

Example 4

A preparation method of colored cellulose fibers, the steps are as follows:

(1) the copper ammonia fiber spinning solution with a degree of polymerization of 400 and a concentration of 10wt% is extruded through a spinneret, coagulated, stretched and washed at 98°C to obtain a washed silk, and the water content of the washed silk is 50wt%;

(2) The water-soluble vulcanized light yellow GC mass content is 1.5wt% aqueous solution at the temperature of 70 ℃, after 60 seconds of soaking treatment on the washed silk, rinsed at 25 ℃ for 20 seconds and dried with hot air The colored cellulose fibers were prepared by drying the fibers at a temperature of 110° C. to a moisture content of 12 wt %.

The crystallinity of the finally prepared colored cellulose fibers is 38%, and the micropores have an average diameter of 10 nanometers. The mass of the sulfur dye is 0.8% of the mass of the cellulose fiber matrix.

The monofilament fineness of colored cellulose fibers is 0.5dtex, the breaking strength is 4.0cN/dtex, the elongation at break is 15%, and the moisture regain is 12%. After 50 times of washing, the quality of the sulfur dye is the quality of the cellulose fiber matrix. 0.3%, the color fastness to washing is grade 4, and the color fastness to rubbing is grade 4;

Colored cellulose fibers are filaments that can be used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.

Example 5

A preparation method of colored cellulose fibers, the steps are as follows:

(1) The spinning solution of cellulose fibers with a degree of polymerization of 800 and a concentration of 15 wt% (regenerated cellulose fibers prepared with ionic liquid 1-butyl-3-methylimidazolium chloride as a solvent) through a spinneret Extruded, coagulated, stretched and washed with water at 95°C to obtain washed silk, and the water content of the washed silk was 55wt%;

(2) After the water-washed silk was sprayed for 100 seconds at a temperature of 80°C with an aqueous solution with a mass content of 2 wt % of a dye (a mixture of reactive yellow 4RFN and a water-soluble sulfurized light yellow GC mass ratio of 1:1) The colored cellulose fibers were prepared by rinsing at a temperature of 30° C. for 40 seconds and drying at a temperature of 10° C. by means of hot air drying until the moisture content of the fibers was 12 wt %.

The finally obtained colored cellulose fibers have a crystallinity of 40%, contain micropores, the average diameter of the micropores is 20 nanometers, and the mass of the dye is 2.0% of the mass of the cellulose fiber matrix.

The monofilament fineness of colored cellulose fibers is 3.0dtex, the breaking strength is 3.5cN/dtex, the breaking elongation is 20%, and the moisture regain is 10%. 1.5%, the color fastness to washing is 4-5, and the color fastness to rubbing is 4-5;

Colored cellulose fibers are tow, which can be used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.

Example 6

A preparation method of colored cellulose fibers, the steps are as follows:

(1) The spinning solution of cellulose fibers with a degree of polymerization of 600 and a concentration of 18wt% (regenerated cellulose fibers prepared with urethane/NaOH system as a solvent) is extruded, coagulated, and stretched through a spinneret and washing with water at 95°C to obtain washed silk, and the water content of the washed silk is 60wt%;

(2) The water-washed silk was washed with water at a temperature of 75° C. for 200 hrs with an aqueous solution with a mass content of 2 wt % of dyes (a mixture of reactive yellow 4RFN, direct yellow R and water-soluble sulfurized light yellow GC mass ratio of 1:1:1). After the second spray treatment, the colored cellulose fibers were obtained by rinsing for 30 seconds at a temperature of 25° C. and drying at a temperature of 140° C. by means of hot air drying until the moisture content of the fibers was 12 wt %.

The crystallinity of the finally prepared colored cellulose fibers is 40%, and the micropores have an average diameter of 40 nanometers. The mass of the dye is 2.2% of the mass of the cellulose fiber matrix.

The monofilament fineness of colored cellulose fibers is 2.5dtex, the breaking strength is 3.5cN/dtex, the elongation at break is 18%, and the moisture regain is 15%. 1.8%, the color fastness to washing is 5, and the color fastness to rubbing is 5;

Colored cellulose fibers are tow, which can be used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.

Example 7

A preparation method of colored cellulose fibers, the steps are as follows:

(1) the viscose fiber spinning solution with a degree of polymerization of 500 and a concentration of 22wt% is extruded through a spinneret, coagulated, stretched and washed with water at 98°C to obtain a washed silk, and the water content of the washed silk is 60wt%;

(2) use the aqueous solution that the mass content of direct scarlet 4BE is 2.8 wt% again at the temperature of 85 DEG C to carry out the spray treatment for 250 seconds to the washed silk, rinse at 35 DEG C for 50 seconds and use hot air drying The colored cellulose fibers were prepared by drying at a temperature of 150° C. until the moisture content of the fibers was 12 wt %.

The crystallinity of the finally prepared colored cellulose fibers is 45%, and the micropores have an average diameter of 40 nanometers. The mass of the dye is 2.7% of the mass of the cellulose fiber matrix.

The monofilament fineness of colored cellulose fibers is 2.5dtex, the breaking strength is 4.0cN/dtex, the breaking elongation is 19%, and the moisture regain is 15%. 2.2%, the color fastness to washing is level 5, and the color fastness to rubbing is level 5;

Colored cellulose fibers are tow, which can be used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.

Claims (8)

1. a preparation method of colored cellulose fibers, is characterized in that: the cellulose fibers spinning solution is extruded, coagulated, stretched and washed to make water-washed silk through a spinneret, and the water-washed silk is then washed with an aqueous dye solution. After treatment, rinsing and drying are carried out to obtain colored cellulose fibers; The concentration of the cellulose fiber spinning solution is 5-25 wt%; The temperature of washing is greater than or equal to 90°C, the temperature of the dye aqueous solution during processing is a°C, the temperature of rinsing is b°C, a>b, a is 40-90, and b is 20-40; The termination condition of washing is as follows: the water content of the washed silk is 40-70wt%; The dye contains more than one of X group, Y group and Z group, X group is aldehyde group, cyano group, epoxy group, acid chloride group, acid anhydride or diisocyanate; Y group is siloxane ; Z group is a sulfonic acid group or a sulfate group. 2 . The method for preparing colored cellulose fibers according to claim 1 , wherein the cellulose fibers are regenerated cellulose fibers or cellulose derivative fibers. 3 . 3 . The method for preparing a colored cellulose fiber according to claim 2 , wherein the cellulose fiber is viscose fiber, acetate fiber, Lyocell fiber or cupro fiber. 4 . 4. the preparation method of a kind of colored cellulose fibers according to claim 1, is characterized in that, the mass content of dyestuff in the aqueous dye solution is 2～10wt%; The dyestuff is a kind of direct dyestuff, reactive dyestuff and sulfur dyestuff above. 5 . The preparation method of colored cellulose fibers according to claim 1 , wherein the treatment adopts the method of soaking or spraying, and the treatment time is 60-600 seconds; the rinsing time is 120-600 seconds. 6 . . 6. the preparation method of a kind of colored cellulose fiber according to claim 1, is characterized in that, drying adopts the mode of hot air drying, and the temperature of hot air is 105～160 ℃, and is dried to the moisture content of fiber≤ 15wt%. 7. The colored cellulose fibers prepared by the method for preparing colored cellulose fibers according to any one of claims 1 to 6, characterized in that: they are mainly composed of a cellulose fiber matrix and dispersed in cellulose fibers. Dye composition within a fiber-like matrix. 8 . The colored cellulose fibers according to claim 7 , wherein the colored cellulose fibers have a crystallinity of >30%, contain micropores, the average diameter of the micropores is 5 to 50 nanometers, and the quality of the dye is fiber 0.1-5.0% of the mass of the plain fiber matrix; The monofilament fineness of colored cellulose fibers is 0.5-5.0dtex, the breaking strength is 1.0-4.5cN/dtex, the breaking elongation is 5%-20%, the moisture regain is 5%-15%, and the color fastness to washing is It is equal to grade 5, and the color fastness to rubbing is equal to grade 5; After the colored cellulose fibers are washed 50 times, the quality of the dye is 0.08-2.50% of the mass of the cellulose fiber matrix, the color fastness to washing is greater than or equal to level 4, and the color fastness to rubbing is greater than or equal to level 4; Colored cellulose fibers are filaments, staple fibers or tow, used in knitted fabrics, woven fabrics, non-woven fabrics or mixed with other fibers.