CN110041687A - A kind of preparation method of colour polyurethane and artificial leather - Google Patents

Abstract

The invention discloses a preparation method of colored polyurethane. The colored waterborne polyurethane emulsion is obtained by mixing a colored regenerated cellulose suspension and an aqueous polyurethane emulsion. The invention also discloses a preparation method of the colored artificial leather. The invention can obtain colorful water-based polyurethane with rich colors, and after the colorful water-based polyurethane is applied to the dyeing process of superfine fiber artificial leather, compared with the current processing method of polyurethane resin and color paste, the abrasion resistance of artificial leather can be improved Fastness, can greatly expand the use of artificial leather.

Description

A kind of preparation method of colored polyurethane and artificial leather

technical field

The invention belongs to the technical field of coating preparation and fiber dyeing, and in particular relates to a preparation method of colored polyurethane and a method for preparing colored artificial leather by utilizing the same.

Background technique

Solvent-based polyurethane is a widely used polymer material, which has the advantages of good wear resistance, water resistance and corrosion resistance. Therefore, the development of safe, non-toxic, green and environmentally friendly water-based polyurethane is the future development direction. Water-based polyurethane uses water as the dispersion medium. It has excellent wear resistance, flexibility, corrosion resistance, good chemical stability and comprehensive performance equivalent to solvent-based polyurethane. Therefore, it has been used in textiles, leather, coatings, wood, paper and other fields. widely used. At present, the colorization of waterborne polyurethane has attracted extensive attention of researchers. There are two preparation methods of colored water-based polyurethane: one is direct mixing method, that is, dyes or pigments are directly mixed with water-based polyurethane emulsion; the other is covalent bonding method, that is, dyes or pigments are combined with water-based polyurethane through covalent bonds. together. However, the direct mixing method has problems of low compatibility and fastness, and the covalent bonding method has the problem of complicated preparation process.

Cellulose is the most abundant renewable resource in nature. Regenerated cellulose can be prepared by dissolving and regenerating cellulose. It has the advantages of green environmental protection, good hydrophilicity, good dispersion stability and high reactivity, so it can be used as water-based cellulose. Use of fillers for polyurethane emulsions. Reactive dyes have good reactivity with cellulose, and regenerated cellulose with rich colors can be prepared by grafting reactive dyes onto regenerated cellulose.

SUMMARY OF THE INVENTION

In order to overcome the deficiencies of the prior art, the present invention provides a method for preparing colored waterborne polyurethane with rich colors, simple preparation process and easy industrialization, and a method for preparing colored artificial leather with excellent fastness.

The technical solution adopted by the present invention to solve the technical problem is: a method for preparing colored polyurethane, which prepares regenerated cellulose by phosphoric acid method, sodium hydroxide/urea method or ionic liquid method, comprising the following steps:

1) Take regenerated cellulose and configure it into a 0.1-5wt% regenerated cellulose suspension;

2) Add reactive dye, electrolyte and color-fixing alkali agent to the regenerated cellulose suspension in step 1) and mix evenly, wherein the consumption ratio of reactive dye, electrolyte, color-fixing alkali agent and regenerated cellulose is 0.01-30g/L : 20-150g/L: 5-60g/L: 0.1-30g/L, heat up to a color fixing temperature of 40-90°C at a speed of 1-3°C/min, and react to obtain a stock solution of colored regenerated cellulose suspension;

3) fully washing the stock solution obtained in step 2) with deionized water to remove unfixed reactive dyes to obtain a colored regenerated cellulose suspension;

4) get the colored regenerated cellulose suspension obtained in step 3) and the water-based polyurethane emulsion and stir for 1-2 hours at a rotating speed of 200-400rpm to obtain a uniform colored water-based polyurethane emulsion, wherein the consumption of the water-based polyurethane emulsion is 5-400g/ L, the dosage of color regenerated cellulose suspension is 0.1-20g/L.

Further, the color fixing reaction time in the step 2) is 30-120min.

Further, the reactive dyes in the step 2) are a chloro-s-triazine reactive dye, a dichloro-s-triazine reactive dye, a vinyl sulfone reactive dye, a vinyl sulfone active group and a chloro-s-triazine active group. One or more of the multi-reactive reactive dyes.

Further, the electrolyte in the step 2) is sodium chloride, Yuanming powder or sodium sulfate.

Further, the color-fixing alkali agent in the step 2) is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium dihydrogen phosphate, and sodium silicate.

Further, the water-based polyurethane emulsion in the step 3) is an anionic or cationic water-based polyurethane emulsion.

The present invention also discloses a method for preparing colored artificial leather, comprising the following steps: taking a needle-punched or spunlace non-woven fabric whose single-fiber cross-section is sea-island type or split type and whose single-fiber fineness is 0.001-5dtex, in claim 1 The colored water-based polyurethane emulsion obtained in any one of -6 is subjected to an impregnation process, a weight reduction process, and a sanding process to obtain a colored artificial leather.

Preferably, the impregnation process includes a first impregnation process and a second impregnation process. The impregnation liquid of the first impregnation process contains 17-25 wt.% of water-soluble polyester, the amount of the liquid is 50-200 wt.%, and the drying temperature is 100-150 DEG C; the immersion solution of the second impregnation process contains 10-30 wt.% of colored water-based polyurethane, the drying temperature is 100-150 DEG C, and the weight gain of the water-based resin is 20-30 wt.%.

Preferably, the reduction process includes alkali reduction and solvent reduction.

The technical problem to be solved by the present invention is to provide a method for preparing a colored water-based polyurethane emulsion, a method for preparing superfine fiber artificial leather by using the colored polyurethane, and a superfine fiber artificial leather prepared by the method. In this method, the colored regenerated cellulose suspension is mixed with the water-based polyurethane emulsion to obtain the colorful water-based polyurethane with rich colors. After the colored water-based polyurethane is applied to the dyeing process of the superfine fiber artificial leather, compared with the current polyurethane resin, the color is added. The treatment method of pulp can improve the abrasion fastness of artificial leather, and can greatly expand the use of artificial leather.

The invention prepares a colored water-based polyurethane emulsion, the prepared colored water-based polyurethane is rich in color and excellent in fastness, and can well meet the industrial requirements for various colors and excellent fastness of the water-based polyurethane. The color water-based polyurethane emulsion obtained by the invention can be used as a raw material for color water-based paints, water-based paints, water-based inks, etc., which expands the application range of the water-based polyurethane and has great development prospects.

The present invention proposes to mix water-based polyurethane emulsion with colored regenerated cellulose to prepare colored water-based polyurethane. Because colored regenerated cellulose has good hydrophilic ability and dispersion stability, it can be uniformly dispersed in the aqueous polyurethane emulsion; colored regenerated cellulose is A nano-scale macromolecular reticulated cellulose, which can be embedded in the color water-based polyurethane, so the color water-based polyurethane can obtain excellent color fastness. The method is simple in process and easy to industrialize, and the prepared colored water-based polyurethane coating has good application prospects in the fields of leather, textiles, furniture, paper and the like.

In the present invention, the above-mentioned colored water-based polyurethane is used to impregnate the superfine fiber artificial leather. After the treatment, the colored water-based polyurethane forms a colored coating layer on the fiber surface, which is rich in color and excellent in fastness. Compared with the common superfine fiber artificial leather pigment type, the treatment process of the invention improves the dry-wet rubbing and washing fastness and the light fastness of the water-based superfiber, and has a better technical prospect.

The beneficial effects of the invention are as follows: 1) the preparation method is simple, and the industrial production is easy; 2) the colorful water-based polyurethane with rich colors can be obtained by using dyes of different colors, and the adaptability is wide; 3) the color fastness after dyeing is better; 4) It can be used as the raw material of color water-based paint, water-based paint, water-based ink, etc., and has a wide range of applications; 5) The coloring of colored artificial leather is uniform and has good color fastness.

Description of drawings

Fig. 1 is the physical picture of the color water-based polyurethane emulsion prepared in embodiment one, two and three of the present invention.

FIG. 2 is a physical diagram of the colored water-based polyurethane films prepared in Examples 1, 2, and 3 of the present invention.

Figure 3 shows the soaking properties of the colored water-based polyurethane films prepared in Examples 1, 2, and 3 of the present invention.

FIG. 4 is the finished product of the red superfine fiber artificial leather according to the fifth embodiment of the present invention.

Fig. 5 is the finished product of blue superfine fiber artificial leather according to the sixth embodiment of the present invention.

Detailed ways

In order to enable those skilled in the art to better understand the solutions of the present invention, the technical solutions in the embodiments of the present invention will be described clearly and completely below with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only These are some embodiments of the present invention, but not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

1) Prepare a regenerated cellulose suspension with a concentration of 0.5 wt% by phosphoric acid method;

2) Mix 0.1 g of reactive red 194 dye, 45 g of the regenerated cellulose suspension prepared in step 1), 3 g of sodium chloride, 1.2 g of sodium carbonate and an appropriate amount of water in a total of 50 mL of mixture, and heat up at a rate of 2 °C/min. To the fixing temperature of 70 ℃, after dyeing for 90 minutes, the original solution of the colored regenerated cellulose suspension was obtained;

3) Use deionized water, fully wash the stock solution by filtration or centrifugation, remove the unfixed reactive dye, and then obtain the final red regenerated cellulose suspension;

4) Take 10g of the red regenerated cellulose suspension obtained in step 3), and mix it with 30g of anionic aqueous polyurethane emulsion and an appropriate amount of water in a total of 50mL of mixture, wherein the concentration of the red regenerated cellulose suspension is 1wt%, and the water-based polyurethane The concentration of the emulsion was 37 wt %, and the mixture was mechanically stirred at a speed of 200 rpm for 1 hour to obtain a uniformly dispersed red aqueous polyurethane emulsion.

The red aqueous polyurethane emulsion obtained under the above preparation method was spread on a glass plate, and dried at room temperature for 48 hours to obtain a red aqueous polyurethane film. The color parameters (K/S value, L, a, b, C, h) of the films and the soaking properties of the films in water were tested. After testing, it was found that the K/S value of the red water-based polyurethane film was 12.01, and the red water-based polyurethane film was immersed in water at room temperature for 30 days without fading, indicating that the prepared red film had excellent immersion fastness.

The physical diagram of the red water-based polyurethane emulsion prepared in this implementation is shown in Figure 1, the physical diagram of the prepared red water-based polyurethane film is shown in Figure 2, and the immersion performance of the red water-based polyurethane film in water is shown in Figure 3. The red water-based polyurethane film is shown in Figure 3. The color parameters of the water-based polyurethane film are shown in Table 1.

Embodiment 2

1) Prepare a regenerated cellulose suspension with a concentration of 1 wt% by the sodium hydroxide/urea method;

2) Mix 0.1 g of reactive yellow 145 dye, 60 g of the regenerated cellulose suspension prepared in step 1), 3 g of sodium chloride, 1.2 g of sodium carbonate and an appropriate amount of water in a total of 70 mL of mixture, and heat up at a rate of 3 °C/min. To the fixing temperature of 80℃, after dyeing for 60min, the original solution of colored regenerated cellulose suspension was obtained;

3) Use deionized water, fully wash the stock solution by filtration or centrifugation, and remove the unfixed reactive dyes to obtain the final yellow regenerated cellulose suspension;

4) Take 10g of the yellow regenerated cellulose suspension obtained in step 3), and mix it with a total of 50 mL of 20g anionic aqueous polyurethane emulsion and an appropriate amount of water, wherein the concentration of the yellow regenerated cellulose suspension is 2wt%, and the aqueous polyurethane The concentration of the emulsion was 37 wt %, and the mixture was mechanically stirred at a rotational speed of 350 rpm for 2 hours to obtain a uniformly dispersed yellow aqueous polyurethane emulsion.

The yellow aqueous polyurethane emulsion obtained by the above preparation method was spread on a glass plate and dried at room temperature for 48 hours to obtain a yellow aqueous polyurethane film. The color parameters (K/S value, L, a, b, C, h) of the films and the soaking properties of the films in water were tested. After testing, it was found that the K/S value of the yellow water-based polyurethane film was 11.98, and the yellow water-based polyurethane film was immersed in water at room temperature for 30 days without fading, indicating that the prepared yellow film had excellent immersion fastness.

The physical diagram of the yellow water-based polyurethane emulsion prepared in this implementation is shown in Figure 1, the physical diagram of the prepared yellow water-based polyurethane film is shown in Figure 2, the soaking performance of the yellow water-based polyurethane film in water is shown in Figure 3, and the yellow water-based polyurethane film is shown in Figure 3. The color parameters of the water-based polyurethane film are shown in Table 1.

Embodiment 3

1) Prepare a regenerated cellulose suspension with a concentration of 1.5 wt% by ionic liquid method;

2) Mix 0.1 g of reactive blue 19 dye, 75 g of the regenerated cellulose suspension prepared in step 1), 3 g of sodium chloride, 1.2 g of sodium carbonate and an appropriate amount of water in a total of 80 mL of mixture, and heat up at a rate of 1 °C/min. To the fixing temperature of 50℃, after dyeing for 120min, the original solution of colored regenerated cellulose suspension was obtained;

3) Use deionized water to fully wash the stock solution by filtration or centrifugation to remove the unfixed reactive dyes to obtain the final blue regenerated cellulose suspension;

4) Take 10 g of the blue regenerated cellulose suspension obtained in step 3), and mix it with a total of 50 mL of a mixture of 10 g of anionic aqueous polyurethane emulsion and an appropriate amount of water, wherein the concentration of the blue regenerated cellulose suspension is 3wt%, The concentration of the aqueous polyurethane emulsion was 37 wt %, and mechanical stirring was performed at a speed of 400 rpm for 1.5 hours to obtain a uniformly dispersed blue aqueous polyurethane emulsion.

The blue water-based polyurethane emulsion obtained by the above preparation method was spread on a glass plate, and dried at room temperature for 48 hours to obtain a blue water-based polyurethane film. The color parameters (K/S value, L, a, b, C, h) of the films and the soaking properties of the films in water were tested. After testing, it was found that the K/S value of the blue water-based polyurethane film was 11.79, and the blue water-based polyurethane film was immersed in water at room temperature for 30 days without fading, indicating that the prepared blue film had excellent immersion fastness.

The physical map of the blue water-based polyurethane emulsion prepared in this implementation is shown in Figure 1, the physical map of the prepared blue water-based polyurethane film is shown in Figure 2, and the immersion performance of the blue water-based polyurethane film in water is shown in Figure 3 The color parameters of the blue water-based polyurethane film are shown in Table 1.

Table 1 Color parameters of red, yellow and blue waterborne polyurethane films

It can be seen from Table 1 that the prepared colored water-based polyurethane film has a higher K/S value, so its color is darker and has different lightness (L), saturation (C), hue (h), so The prepared water-based polyurethane has colorful colors and has broad application prospects in production and life.

Embodiment 4

Polyester microfiber, using fiber size 2D, 37 islands and islands, sea component is polyester, island component is polyester, length is 51mm, sea/island ratio is 30/70. The above-mentioned fibers are laid out and needle punched to prepare grey cloth. The apparent density of the grey cloth is 300g/m ² , and the apparent density of the grey cloth after thermal shrinkage is 350g/m ² . After increasing the apparent density, water-based polyurethane resin impregnation treatment is performed.

The impregnation treatment is divided into two impregnations. The first immersion process is a water-soluble polyester containing 20 wt.%, the amount of liquid is 100%, and the drying temperature is 130 ° C; the second immersion process is an embodiment containing 30 wt.%. 2, the drying temperature is 130° C., and the amount of liquid carried is controlled so that the weight gain of the water-based polyurethane of the grey fabric is 25 wt.%. After that, the water-soluble polyester of the first impregnation process was removed by a warm water washing process, and an aqueous NaOH solution was used for fiber opening treatment. The concentration of the NaOH aqueous solution during the fiber opening treatment was 10 g/L, the temperature of the fiber opening treatment was 130 ° C, and the treatment time was 40 minutes, the liquor ratio is 1:20, the fiber-opened base fabric is sanded, and the sanding treatment uses a #400 sander roll, and the sanding treatment is carried out in forward and reverse directions. The ratio of forward and reverse rolling is 1: 1. The finished microfiber artificial leather is obtained after the above-mentioned treatment.

The obtained yellow superfine fiber artificial leather is tested, and the results show that its dry rubbing fastness is 4-5, wet rubbing fastness is 4-5, and its soaping fastness is 4-5.

Embodiment 5

Nylon microfiber, using fiber denier 2D, 16 islands fixed island, sea component is polyester, island component is nylon, length is 51mm, sea/island ratio is 20/80. The above-mentioned fibers are laid out and needle punched to prepare grey cloth. The apparent density of the grey cloth is 400g/m ² . The apparent density of the grey cloth after thermal shrinkage is 480g/m ² . After increasing the apparent density, water-based polyurethane resin impregnation treatment is performed.

The impregnation treatment is divided into two impregnations. The first immersion process is an example containing 20wt.% of water-soluble polyester, the amount of liquid is 50%, and the drying temperature is 120°C; the second immersion process is an example containing 30wt.% 1 red water-based polyurethane, the drying temperature is 120 ° C, and the amount of liquid is controlled to make the weight gain of the gray fabric water-based polyurethane at 20wt.%. After that, the water-soluble polyester of the first impregnation process was removed by a warm water washing process, and an aqueous NaOH solution was used for fiber opening treatment. The concentration of the NaOH aqueous solution during the fiber opening treatment was 10g/L, the temperature of the fiber opening treatment was 130 degrees, and the treatment time was 40 minutes, the liquor ratio is 1:20, the fiber-opened base fabric enters the sanding treatment, and the sanding treatment uses a #400 sander roll, and the sanding treatment is carried out in forward and reverse directions. The ratio of forward and reverse rolls is 1: 1. After the above treatment, the finished microfiber artificial leather is obtained, as shown in FIG. 4 .

The obtained red superfine fiber artificial leather is tested, and the results show that its dry rubbing fastness is 4-5, wet rubbing fastness is 4-5, and its soaping fastness is 4-5.

Embodiment 6

Nylon microfiber, using fiber fineness 6D, indefinite island, sea component is PE, island component is nylon, sea/island ratio is 45:55, length is 51mm. The above-mentioned fibers are laid net and needle punched to prepare grey fabric. The apparent density of the grey cloth was 350 g/m ² , and the apparent density of the grey cloth after thermal shrinkage was 370 g/m ² . After increasing the apparent density, the water-based polyurethane grease is impregnated.

The impregnation treatment is divided into two impregnations. The first immersion solution is a water-soluble polyester containing 20 wt.%, the amount of liquid is 150%, and the drying temperature is 140 ° C; Blue water-based polyurethane, the drying temperature is 140°C, and the amount of liquid carried is controlled so that the weight gain of the water-based polyurethane of the grey fabric is 30wt.%. After that, the water-soluble polyester impregnated for the first time was removed by a warm water washing process, and toluene (100%) was used for fiber opening treatment. The temperature during fiber opening treatment was room temperature and the time was 20 minutes. After the fiber-opening treatment, the base fabric is subjected to sanding treatment. The sanding treatment uses a #400 sander roll, and the sanding treatment is carried out in forward and reverse directions. The ratio of forward and reverse rolls is 1:1. After the above treatment, the finished superfine fiber artificial leather is obtained, as shown in FIG. 5 .

The obtained blue microfiber artificial leather was tested, and the results showed that its dry rubbing fastness was grade 4, the wet rubbing fastness was grade 4, and the soaping fastness was grade 4-5.

Comparative Example 1

Polyester microfiber, using fiber denier 2D, 37 islands fixed island, the sea component is modified polyester, the island component is polyester, the length is 51mm, and the sea/island ratio is 30/70. The above-mentioned fibers are laid net and needle punched to prepare grey fabric. The apparent density of the grey fabric is 300 g/m ² , and the apparent density of the grey fabric after thermal shrinkage is 350 g/m ² . After increasing the apparent density, the water-based polyurethane grease is impregnated.

The impregnation treatment is divided into two impregnations. The first immersion is a water-soluble polyester containing 20 wt.%, the amount of liquid is 50%, and the drying temperature is 120 ° C; the second immersion is RG8170 (Weifang Ruiguang) containing 5 wt.%. Chemical Industry, CI Red 170) water-based polyurethane solution, the drying temperature is 120 ° C, and the amount of liquid is controlled to make the weight gain of the water-based polyurethane for grey fabrics at 20wt.%. After that, the water-soluble polyester impregnated for the first time is removed by a warm water washing process, and the fiber-opening treatment is carried out with an aqueous NaOH solution. The concentration of the NaOH aqueous solution during the fiber-opening treatment is 10g/L, the temperature of the fiber-opening treatment is 130 degrees, and the treatment time is 40 minutes. , the liquor ratio is 1:20. After the fiber-opening treatment, the base fabric is subjected to sanding treatment. The sanding treatment uses a #400 sander roll, and the sanding treatment is carried out in forward and reverse directions. The ratio of forward and reverse rolls is 1:1. The finished superfine fiber artificial leather is obtained after the above-mentioned treatment.

Comparative Example 2

Nylon microfiber, using fiber fineness 2D, 16 islands fixed island, the sea component is modified polyester, the island component is nylon, the length is 51mm, and the sea/island ratio is 20/80. The above-mentioned fibers are laid net and needle punched to prepare grey fabric. The apparent density of the grey cloth is 400 g/m ² , and the apparent density of the grey cloth after thermal shrinkage is 480 g/m ² . After increasing the apparent density, the water-based polyurethane grease is impregnated.

The impregnation treatment is divided into two impregnations. The first immersion solution is a water-soluble polyester containing 20wt.%, the amount of liquid is 100%, and the drying temperature is 130 ° C; the second immersion solution is RG8201 (Weifang Ruiguang) containing 3wt.%. Chemical Industry, CIYellow 1) Water-based polyurethane, drying temperature is 130 ° C, and the amount of liquid is controlled so that the weight gain of water-based polyurethane for grey fabric is 25wt.%. After that, the water-soluble polyester impregnated for the first time is removed by a warm water washing process, and the fiber-opening treatment is carried out with an aqueous NaOH solution. The concentration of the NaOH aqueous solution during the fiber-opening treatment is 10g/L, the temperature of the fiber-opening treatment is 130 degrees, and the treatment time is 40 minutes. , the liquor ratio is 1:20. After the fiber-opening treatment, the base fabric is subjected to sanding treatment. The sanding treatment uses a #400 sander roll, and the sanding treatment is carried out in forward and reverse directions. The ratio of forward and reverse rolls is 1:1. The finished superfine fiber artificial leather is obtained after the above-mentioned treatment.

Comparative Example Three

Nylon microfiber, using fiber fineness 6D, indefinite island, sea component is PE, island component is nylon, sea/island ratio is 45:55, length is 51mm. The above-mentioned fibers are laid net and needle punched to prepare grey fabric. The apparent density of the grey cloth was 350 g/m ² , and the apparent density of the grey cloth after thermal shrinkage was 370 g/m ² . After increasing the apparent density, the water-based polyurethane grease is impregnated.

The impregnation treatment is divided into two impregnations. The first immersion solution is a water-soluble polyester containing 20wt.%, the amount of liquid is 150%, and the drying temperature is 140°C; the second immersion solution is RG RG8301 Weifang Ruiguang containing 3wt.% Chemical industry, CIBlue15:0) water-based polyurethane, drying temperature is 140 ° C, and the amount of liquid is controlled so that the weight gain of the water-based polyurethane of grey fabric is 30wt.%. Then, the water-soluble polyester impregnated for the first time was removed by a warm water washing process, and toluene (100%) was used for fiber opening treatment. The temperature during fiber opening treatment was room temperature, and the treatment time was 20 minutes. After the fiber-opening treatment, the base fabric is subjected to sanding treatment. The sanding treatment uses a #400 sander roll, and the sanding treatment is carried out in forward and reverse directions. The ratio of forward and reverse rolls is 1:1. The finished superfine fiber artificial leather is obtained after the above-mentioned treatment.

In terms of the color fastness tests of the above-mentioned embodiments three, four, five and comparative examples one, two and three, the textiles are rubbed according to the test method of GB/T3920-2008 "Color fastness to rubbing of textiles". Color fastness to be tested

Table 2 Color fastness of colored artificial leather

It can be seen from Table 2 that the colored artificial leather prepared by the colored water-based polyurethane obtained by the present invention has significantly increased dry rubbing fastness and wet rubbing fastness under the premise of ensuring soaping fastness, and has excellent performance.

To sum up the comparison between the above examples and the comparative examples, the colored water-based polyurethane ultra-fine fiber artificial leather of the present invention has better dry and wet rubbing fastness than the ordinary color paste polyurethane ultra-fine fiber artificial leather. The artificial leather produced by pulp dyeing technology has a great improvement.

The above-mentioned specific embodiments are used to explain the present invention, rather than limit the present invention. Any modification and change made to the present invention within the spirit of the present invention and the protection scope of the claims all fall into the protection scope of the present invention.

Claims (9)

1. a preparation method of colored polyurethane, prepares regenerated cellulose by phosphoric acid method, sodium hydroxide/urea method or ionic liquid method, it is characterized in that comprising the following steps: 1) Take regenerated cellulose and configure it into a 0.1-5wt% regenerated cellulose suspension; 2) Add reactive dye, electrolyte and color-fixing alkali agent to the regenerated cellulose suspension in step 1) and mix evenly, wherein the consumption ratio of reactive dye, electrolyte, color-fixing alkali agent and regenerated cellulose is 0.01-30g/L : 20-150g/L: 5-60g/L: 0.1-30g/L, heat up to a color fixing temperature of 40-90°C at a speed of 1-3°C/min, and react to obtain a stock solution of colored regenerated cellulose suspension; 3) fully washing the stock solution obtained in step 2) with deionized water to remove unfixed reactive dyes to obtain a colored regenerated cellulose suspension; 4) get the colored regenerated cellulose suspension obtained in step 3) and the water-based polyurethane emulsion and stir for 1-2 hours at a rotating speed of 200-400rpm to obtain a uniform colored water-based polyurethane emulsion, wherein the consumption of the water-based polyurethane emulsion is 5-400g/ L, the dosage of color regenerated cellulose suspension is 0.1-20g/L. 2. preparation method according to claim 1 is characterized in that: in the described step 2), the color-fixing reaction time is 30-120min. 3. preparation method according to claim 1 is characterized in that: the reactive dyes in described step 2) are monochloro-s-triazine-type reactive dyes, dichloro-s-triazine-type reactive dyes, vinylsulfone-type reactive dyes, One or more of the multi-reactive reactive dyes of vinylsulfone reactive group and monochloro-s-triazine reactive group. 4. preparation method according to claim 1 is characterized in that: the electrolyte in described step 2) is sodium chloride, Yuanming powder or sodium sulfate. 5. preparation method according to claim 1 is characterized in that: the color-fixing alkali agent in described step 2) is sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium dihydrogen phosphate, silicic acid One or more types of sodium. 6 . The preparation method according to claim 1 , wherein the water-based polyurethane emulsion in the step 3) is an anionic or cationic water-based polyurethane emulsion. 7 . 7. a preparation method of colored artificial leather, is characterized in that comprising the following steps: getting single fiber section is sea island type or split type, and single fiber fineness is the needle punching or spunlace nonwoven fabric of 0.001-5dtex, in claim 1 The colored water-based polyurethane emulsion obtained in any one of -6 is subjected to an impregnation process, a weight reduction process, and a sanding process to obtain a colored artificial leather. 8 . The preparation method according to claim 7 , wherein the impregnation process comprises a first impregnation process and a second impregnation process, and the dipping solution of the first impregnation process contains 17-25wt.% of water-soluble polyester, 9 . The amount of liquid carried is 50-200wt.%, and the drying temperature is 100-150 ℃; the immersion liquid of the second impregnation process contains 10-30 wt.% of colored water-based polyurethane, the drying temperature is 100-150 ℃, and the weight gain of the water-based resin is 20 -30wt.%. 9 . The preparation method according to claim 7 , wherein the reduction process comprises alkali reduction and solvent reduction. 10 .