CN112521769B

CN112521769B - Safflower red pigment and preparation method and dyeing method thereof

Info

Publication number: CN112521769B
Application number: CN202011336184.0A
Authority: CN
Inventors: 杨建军
Original assignee: Tsinghua University
Current assignee: Tsinghua University
Priority date: 2020-11-25
Filing date: 2020-11-25
Publication date: 2021-11-30
Anticipated expiration: 2040-11-25
Also published as: CN112521769A

Abstract

The invention provides a safflower red pigment, a preparation method and a dyeing method thereof. The preparation method of the carthamus red pigment comprises the following steps: an extraction step: removing yellow pigment from Carthami flos, and dissolving the residual pigment in Carthami flos with alkaline solution to obtain crude product of safflower red pigment; a purification step: and adsorbing the crude red pigment by using cotton fibers under an acidic condition, and dissolving to obtain a safflower red liquid. The carthamus red pigment can be extracted from the carthamus tinctorius, and the preparation process of the carthamus tinctorius red pigment is green and pollution-free, and is beneficial to environmental protection and health. Furthermore, the carthamus red pigment is simple and convenient to operate, environment-friendly and harmless when being dyed; is especially suitable for dyeing wool fiber.

Description

Safflower red pigment and preparation method and dyeing method thereof

Technical Field

The invention relates to a safflower red pigment, a preparation method and a dyeing method thereof, belonging to the field of dyes.

Background

Carthami flos is an annual (spring sowing) or biennial (autumn sowing) Compositae herb, and its petal contains safflower yellow and safflower red. Carthamin (chemical name: Carthamine) also belongs to chalcone pigments in flavonoids compounds, and is used for preparing cosmetic rouge from old times. The safflower red pigment has styrene type structure, has mordant group on the benzene ring of the closed conjugated system, and can be directly dyed on cellulose fiber and protein fiber. However, the content of carthamus tinctorius red pigment is small (about 0.3% -0.6%), which is very rare.

Chemical dyes used in the printing and dyeing industry have serious influence on the natural environment and certain harm to the health of producers and users. Therefore, in recent years, green ecological dyeing techniques for dyeing by extracting pigments from natural plant materials have been developed rapidly. However, in the prior art documents, some processes related to the extraction, purification and hair dyeing of the safflower red pigment use toxic substances, and some processes only include safflower materials, but the processes cannot extract and obtain the safflower red pigment.

Citation 1 provides a method for obtaining a red pigment, which comprises the steps of adding water to a safflower raw material which is subjected to impurity removal, drying and sterilization in sequence, performing first solid-liquid separation and second solid-liquid separation, and combining liquids obtained after the two solid-liquid separations to obtain a safflower extract. Then adding ethanol with a certain concentration into the safflower extract for elution to obtain eluent. Adjusting the pH value of 2-5 with glacial acetic acid, adjusting the eluent to be neutral, and then concentrating to obtain the red pigment. However, since safflower yellow is soluble in water, safflower red is insoluble in water. Therefore, the safflower extract obtained by immersing safflower in water may be obtained as a safflower yellow liquid, not a safflower red liquid.

Citation 2 provides a process for producing an environment-friendly dyeing material, which comprises the steps of picking safflower with dew, mashing the safflower into mud, soaking the mud in hot water of 80-100 ℃ for 5-8 hours, and filtering. Heating the solid part at 100-120 ℃ for 50-80 min, adding glacial acetic acid, cellulose, bactericide and adhesive, and soaking for 5-8 h. Filtering to obtain the finished product. However, the carthamus red pigment is gradually decomposed at a temperature of 50 ℃ or higher, and the decomposition speed is higher as the temperature is higher, so that the red pigment in the obtained product may be already decomposed, and the dyeing effect is deteriorated.

Citation 3 provides a method for extracting carthamus tinctorius red pigment from safflower residue, and discloses a process flow of extraction, adsorption, analysis and refining of the carthamus tinctorius red pigment. Soaking the dry safflower residue material with safflower yellow in room temperature potassium carbonate solution with certain concentration, and filtering to obtain crude extract of safflower red. Adding microcrystalline cellulose, adjusting the pH value to 3-5 by using acetic acid, stirring for 30min, and standing for 2 h. Filtering to obtain microcrystalline cellulose with adsorbed safflower red. It was stirred in potassium carbonate solution for 15min and filtered. Adding citric acid into the filtrate to adjust the pH value of 3-5, and standing for 10-12 h at 5 ℃. Removing supernatant, and freeze drying the precipitate at-20 deg.C to obtain safflower red pigment. However, the technology is limited to the extraction of the carthamus tinctorius red pigment by industrial production.

In addition, cited document 4 discloses a method of obtaining a carthamus tinctorius red pigment by extraction with a salting-out method, purification with acetic acid, diethyl ether and ethanol, and further purification with an organic reagent. The technology has the defects of solvent residue, long period and low extraction rate. The method for extracting safflower red disclosed in cited document 5 using borate or phosphate buffer at pH8 to 12 has a disadvantage of containing a large amount of impurities.

In the prior art, a specific dyeing method aiming at the carthamus red pigment of the wool fiber is not found in the prior art, but the dyeing process in the prior art is not suitable for the carthamus red pigment.

Citation 6 discloses a method for dyeing wool fabric with carthamin red pigment, which comprises dissolving carthamin red pigment in a mixed solution of carbon tetrachloride and phenol, adding surfactant sodium alkyl benzene sulfate, and subjecting to ultrasonic treatment to obtain a transparent solution. And (3) putting the wool fabric into the dyeing kettle, oscillating and heating the wool fabric to 30-60 ℃, and preserving heat and dyeing for 5-30 min. The fabric is washed in carbon tetrachloride and dried at 80 deg.c. The technology dyes the wool fabric at 30-60 ℃ and dries at 80 ℃, while the carthamus red pigment is gradually decomposed at the temperature of more than 50 ℃, and the decomposition speed is faster when the temperature is higher. The method has adverse effect on safflower red pigment. More seriously, the carbon tetrachloride and phenol used in this method are toxic and not suitable for dyeing.

Citation 7 discloses a method for dyeing mohair fibers with a natural plant extract, which provides a method for dyeing mohair fibers with a natural dye extract for a mohair raw material. However, the method only introduces the natural plant dye including the safflower, and the specific pigment extraction technology disclosed is a high-temperature decocting method, which is not suitable for the safflower. In the dyeing process of the embodiment, only gardenia, black tea and mugwort are taken as examples, and safflower is not involved.

Therefore, research on a preparation method of the carthamus tinctorius red pigment and a dyeing method of the carthamus tinctorius red pigment is a technical problem to be solved urgently.

Cited document 1: CN 201710839072.9

Cited document 2: CN201710543788.4

Cited document 3: CN201410338257.8

Cited document 4: CN102295839A

Cited document 5: CN102031014A

Cited document 6: CN201611089027.8

Cited document 7: CN201710150133.0

Disclosure of Invention

Problems to be solved by the invention

In view of the technical problems in the prior art, for example: the invention aims to provide a carthamus red pigment and a preparation method thereof, wherein the carthamus red pigment is extracted from natural plants, and the preparation process of the carthamus red pigment is green and pollution-free, is beneficial to environmental protection and is beneficial to health.

Furthermore, the invention also provides a dyeing method, and the dyeing process is safe, environment-friendly and easy to operate.

Means for solving the problems

The invention firstly provides a preparation method of carthamus red pigment, which comprises the following steps:

an extraction step: removing yellow pigment from Carthami flos, and dissolving the residual pigment in Carthami flos with alkaline solution to obtain crude product of safflower red pigment;

a purification step: and adsorbing the crude red pigment by using cotton fibers under an acidic condition, and dissolving to obtain a safflower red liquid.

The production method according to the present invention, wherein the extraction step includes: soaking the safflower with water to remove yellow pigment from the safflower.

The preparation method comprises the following steps of (1) preparing a basic substance, wherein the basic substance comprises one or the combination of more than two of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide and sodium hydroxide; preferably, the amount of the alkaline substance is 0.5-20% by mass of the total mass of the safflower.

The preparation method comprises the following steps of (1) preparing cotton fiber, wherein the cotton fiber comprises one or more of absorbent cotton, desized pure cotton white yarn and white cotton cloth; preferably, the amount of the cotton fiber is 5-50% by taking the total mass of the safflower as 100%.

The production method according to the present invention, wherein the purification step is performed under the acidic condition using an acidic substance; preferably, the acidic substance comprises one or a combination of more than two of citric acid, hydrochloric acid, acetic acid and sulfuric acid.

The preparation method comprises the step of adding 1-30% of the acidic substance by taking the total mass of the safflower as 100%.

The invention also provides a safflower red liquid which is prepared by the preparation method.

The invention also provides a dyeing method, which comprises the following steps:

and (3) dyeing: heating the carthamus red pigment liquid to below 50 ℃, adding an acidic substance to obtain a red pigment dye solution, immersing a sample to be dyed into the red pigment dye solution, heating to below 50 ℃ for dyeing, and obtaining a pre-dyed sample;

and (3) color fixation: placing the pre-dyed sample in a color fixing agent for color fixing to obtain a dyed sample;

wherein the carthamus red pigment is the carthamus red pigment according to claim 7.

According to the dyeing method, the temperature rise is 6-10 ℃ every 10 min.

The dyeing method according to the invention, wherein the fixing agent comprises an acidic solution.

ADVANTAGEOUS EFFECTS OF INVENTION

The carthamus red pigment can be extracted from the carthamus tinctorius, and the preparation process of the carthamus tinctorius red pigment is green and pollution-free, and is beneficial to environmental protection and health.

Furthermore, the carthamus red pigment is simple and convenient to operate, environment-friendly and harmless when being dyed; is especially suitable for dyeing wool fiber.

Drawings

Fig. 1 shows a flow chart of a method for preparing carthamus tinctorius red pigment according to an embodiment of the present invention.

Fig. 2 shows a flow chart of a dyeing method according to another embodiment of the present invention.

Detailed Description

Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.

Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.

All units used in the present invention are international standard units unless otherwise stated, and numerical values and numerical ranges appearing in the present invention should be understood to include errors allowed in industrial production.

As used herein, "water" includes any feasible water such as tap water, deionized water, distilled water, double distilled water, purified water, ion-exchanged water, and the like.

First aspect

The first aspect of the invention provides a preparation method of carthamus red pigment, which comprises the following steps:

The preparation method of the carthamus red pigment is green and pollution-free, is beneficial to environmental protection and is beneficial to health. The preparation method of the carthamus red pigment comprises the steps of removing carthamus yellow, extracting the carthamus red pigment, purifying the carthamus red pigment and the like. Specifically, the method comprises the following steps:

< removal of safflower yellow >

In order to obtain the safflower red pigment which has high content and high purity and is beneficial to dyeing, the invention removes the safflower yellow as clean as possible so as to ensure the purity of the safflower red pigment. Safflower yellow has good water solubility, while safflower red is insoluble in water. Therefore, the safflower yellow can be removed by dissolving it in water as much as possible before extracting the safflower red.

Specifically, the removal of safflower yellow comprises: soaking Carthami flos in water, squeezing the Carthami flos, and collecting yellow pigment liquid.

Specifically, the method for removing the safflower yellow comprises the following steps:

step 1) soaking safflower in water, extruding and standing, and collecting primary yellow pigment liquid;

step 2) soaking the extruded safflower obtained in the step 1) in water again, extruding the safflower again, and collecting secondary yellow pigment liquid;

and 3) washing the extruded safflower obtained in the step 2) with water, and continuously extruding to remove yellow pigment to the maximum extent.

Further, in order to remove safflower yellow as much as possible, in the step 1), the addition amount of water required by each 100g of safflower is 1-6L, preferably 3-5L, for example: 1.5L, 2L, 2.5L, 3L, 3.5L, 4L, 4.5L, 5.5L, etc.; the standing time is 0.5-5 h, preferably 1-3 h, for example: 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h and the like; in the step 2), the addition amount of water required by each 100g of safflower is 2-6L, preferably 3-5L, for example: 1.5L, 2L, 2.5L, 3L, 3.5L, 4L, 4.5L, 5.5L, etc.; the soaking time is 3-24 h, preferably 6-18 h, for example: 4h, 6h, 8h, 10h, 12h, 15h, 18h, 20h, 22h and the like.

The mode of extrusion is not particularly limited in the present invention, and the extrusion may be carried out with a tool, for example, cotton cloth, or the like, or may be carried out by rubbing with hands. The method for collecting the primary yellow pigment liquid and the secondary yellow pigment liquid is not particularly limited in the present invention, and any conventional method such as centrifugation and filtration may be used, and filtration is preferably used, and filtration using cotton cloth may be used to reduce the loss of safflower yellow during filtration.

Preferably, in the present invention, the removal of safflower yellow comprises the steps of:

1. soaking Carthami flos in water in a container, kneading with hand, and standing.

2. Filtering with cotton cloth, and collecting yellow pigment liquid.

3. And (4) putting the filtered safflower into a container, injecting water, and uniformly stirring and soaking.

4. Filtering, wrapping petals in cotton cloth, wringing to obtain juice, and collecting secondary yellow pigment liquid.

5. And mixing the obtained yellow pigment dye solutions obtained in two times, and storing the mixture (for dyeing yellow).

6. The petals are put into a cloth bag, are fully washed by water, and are continuously kneaded and extruded to remove yellow pigment to the maximum extent.

< extraction of safflower Red pigment >

The inventors of the present invention have found that the carthamin is originally present in safflower in the form of carthamin, and is easily soluble in an alkaline solution because it is a weakly acidic phenol group-containing compound. Therefore, the present invention uses a solution containing an alkaline substance to dissolve the remaining colorant of safflower to obtain a crude safflower carthamus colorant.

Preferably, in order to better realize the extraction, the alkaline substance comprises one or a combination of more than two of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide and sodium hydroxide; in the present invention, potassium carbonate is preferably used in the present invention because potassium carbonate has the best dyeing effect. Preferably, in order to obtain the carthamus red pigment better, the total amount of the alkaline substances can be 0.5-20%, preferably 4-16%, based on the total mass of the carthamus, for example: 1%, 3%, 5%, 7%, 9%, 11%, 13%, 15%, 17%, 19%, etc.

In addition, in order to obtain the carthamus red pigment to the maximum extent, the carthamus red pigment can be extracted by using an alkaline substance for many times. Preferably, the number of times of extraction is 2-4.

Specifically, in the extraction step, the safflower from which safflower yellow is to be removed is immersed in a solution containing an alkaline substance, thereby dissolving the remaining coloring matter of the safflower. The time for soaking is not particularly limited, and may be determined according to the color of the soaking water. Generally, the total time of soaking can be 2-6 h. The amount of water added during the soaking process is not particularly limited in the present invention, and may be added as needed, for example, the amount of water added per 100g of safflower is 0.5 to 7L.

Specifically, the extraction of safflower red pigment of the present invention mainly comprises the following steps:

1. the petals which are basically removed of the yellow pigment are placed in a container, and water is injected, wherein the addition amount of the water required by each 100g of the safflower is 0.5-4L, and 1-3L is preferred.

2. Dissolving alkaline substances by using water, pouring the alkaline substances into the container obtained in the step 1, fully stirring, soaking for 2-3 hours, and dissolving the red pigment, wherein the adding amount of the alkaline substances is 0.5-12%, preferably 1-10%, based on the total mass of the safflower as 100%.

3. Filtering with cotton cloth to obtain crude product of primary red pigment.

4. And then, placing the petals in a container, and injecting water, wherein the addition amount of the water required by each 100g of the safflower is 0.1-3L, and preferably 0.3-2L.

5. Dissolving potassium carbonate in water, pouring the potassium carbonate into the container obtained in the step 4, fully stirring, soaking for 2-3 hours, and further dissolving the red pigment, wherein the adding amount of the potassium carbonate is 0.5-8%, preferably 1-6%, based on the total mass of the safflower as 100%.

< purification of safflower Red pigment >

The inventors of the present invention found that the carthamus red pigment has affinity for cotton fibers, whereas the carthamus yellow pigment lacks dye affinity for cotton fibers. Therefore, the property of safflower yellow that lacks dyeing affinity for cotton fibers can be utilized to leave a small amount of residual yellow in the liquid and dye only the red pigment to cotton fibers. Specifically, the purification step of the present invention comprises adsorbing and dissolving the crude red pigment with cotton fiber under acidic conditions to obtain a liquid of safflower red.

In some specific embodiments, the cotton fibers comprise one or a combination of two or more of absorbent cotton, desized pure cotton white yarn, white cotton cloth; preferably, the amount of the cotton fiber is 5 to 50% based on 100% of the total mass of the safflower, for example: 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, etc.

In some specific embodiments, the purification step is conducted under the acidic conditions using an acidic material; preferably, the acidic substance comprises one or a combination of more than two of citric acid, hydrochloric acid, acetic acid and sulfuric acid. Further, in the present invention, the use of citric acid enables the dyeing effect to be more excellent. In order to obtain the carthamus tinctorius red pigment fully, the carthamus tinctorius red pigment can be purified by using an acidic substance for many times.

In some specific embodiments, the amount of the acidic substance is 1 to 30%, preferably 5 to 25%, based on 100% by mass of the total mass of the safflower, for example: 3%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 28%, etc.

In the process of purifying the safflower red, the crude safflower red is adsorbed and dissolved by using cotton fiber, and the safflower red can be dissolved by using a solution containing alkaline substances to obtain a safflower red liquid. The alkaline substance comprises one or the combination of more than two of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide and sodium hydroxide; in the present invention, potassium carbonate is preferably used in the present invention because potassium carbonate has the best dyeing effect. Preferably, the amount of the alkaline substance is 1 to 20%, preferably 3 to 16%, based on 100% of the total mass of the safflower, for example: 2%, 4%, 6%, 8%, 10%, 12%, 14%, 18%, etc.

In addition, absorbent cotton can be used for adsorbing the carthamus red pigment for multiple times in order to obtain the carthamus red pigment to the maximum extent. Preferably, the number of times of adsorption is 2 to 4.

Specifically, the purification of safflower red pigment of the present invention mainly comprises the following steps:

1. dissolving an acidic substance in water, pouring the red pigment dye solution into the red pigment dye solution, and uniformly stirring, wherein the adding amount of the acidic substance is 0.5-20%, preferably 4-16%, based on the total mass of the safflower.

2. And (2) putting cotton fibers into the pot, soaking the cotton fibers while stirring continuously to adsorb the dye red, wherein the soaking time is 5-30min, and the dosage of the cotton fibers is 5-50%, preferably 10-40% based on the total mass of the safflower.

3. The cotton fiber was taken out and sufficiently wrung.

4. Dissolving the acidic substance with water, pouring the solution into the red dye solution, and stirring uniformly.

5. And (3) continuously soaking the cotton fibers in the step (3) for 5-30min while continuously stirring, and further adsorbing the dyed red pigment, wherein the adding amount of the acidic substance is 0.5-10%, preferably 1-9%, based on the total mass of the safflower as 100%.

6. Dissolving alkaline substances in water, soaking the cotton fibers adsorbed with the red pigment in the water for 5-30 min. Continuously stirring the mixture during the period, and fully dissolving the red pigment from the absorbent cotton, wherein the dosage of the alkaline substance is 1-20 percent, preferably 3-16 percent, based on the total mass of the safflower.

7. And taking out the absorbent cotton and fully wringing.

8. Filtering with cotton cloth to obtain high-purity haematochrome liquid.

The first aspect of the present invention also provides a safflower red liquid which is prepared by the above-mentioned method for preparing safflower red of the present invention.

Second aspect of the invention

A second aspect of the present invention provides a dyeing method comprising the steps of:

wherein the carthamus red pigment is the carthamus red pigment according to the first aspect of the present invention.

The dyeing process of the invention is also safe, environment-friendly and easy to operate, and is particularly suitable for dyeing wool fibers.

< pretreatment >

In the present invention, a sample to be dyed needs to be pretreated. The pretreatment includes but is not limited to degreasing, impurity removal, bleaching and other procedures. After the sample to be dyed is degreased, decontaminated, bleached and the like, the sample is usually fully soaked by water added with neutral detergent before dyeing, and then washed and drained. When washing, the washing machine can be used for kneading or wringing so as to avoid felting.

The neutral detergent means a detergent having a pH in the range of 6 to 8 at a standard use concentration of 25 ℃. For example: conventional laundry detergents and the like.

The time for soaking is not particularly limited in the present invention, and may be a time generally used in the art, for example: 10-60 min, etc. The number of washing and the temperature of washing are not particularly limited in the present invention, but washing is generally carried out 2 to 4 times, and the temperature of washing may be 35 to 45 ℃.

Specifically, the pretreatment process comprises the following steps:

1. adding 6-10 mL of neutral detergent into 5-7L of water, and uniformly stirring to prepare a pretreatment solution, wherein the temperature of the water is 35-50 ℃.

2. Firstly, putting a sample to be dyed into a metal mesh basin, and then soaking the sample to be dyed into the pretreatment liquid for 20-30 min.

3. And taking the metal mesh basin and the sample to be dyed out of the pretreatment liquid, draining the liquid, and slightly rinsing the metal mesh basin in warm water at 35-50 ℃ for 2-4 times. The kneading or twisting can not be carried out during the kneading or twisting process, so as to avoid the felting phenomenon.

4. Suspending the sample to be dyed in a metal mesh basin, standing, and draining water.

< dyeing >

In the invention, the initial temperature for dyeing the sample to be dyed is 35-45 ℃. The highest temperature of the dye liquor is controlled below 50 ℃ to prevent the safflower red from decomposing at high temperature. The specific dyeing steps comprise: heating the safflower red dye liquid to below 50 ℃, adding an acidic substance to obtain a red dye liquid, immersing a sample to be dyed into the red dye liquid, heating to below 50 ℃ for dyeing, and obtaining a pre-dyed sample. In some specific embodiments, the heating is performed at a temperature of 6 ℃ to 10 ℃ per 10min, for example: 7 ℃, 8 ℃, 9 ℃ and the like.

Specifically, the acidic substance comprises one or more of citric acid, hydrochloric acid, acetic acid and sulfuric acid. Further, in the present invention, the use of citric acid enables the dyeing effect to be more excellent. Preferably, in the dyeing process, the adding amount of the acidic substance can be 5-20% based on the total mass of the safflower, for example: 2%, 4%, 6%, 8%, 10%, 12%, 14%, 18%, etc.

Particularly, when dyeing is carried out, the sample to be dyed can be properly turned over, so that the coloring is more uniform. And stopping heating when the temperature reaches 50 ℃, and naturally cooling to 35-45 ℃ to finish dyeing.

Further, after dyeing is finished, the sample can be placed in a device capable of leaking water or is gently dehydrated by a dehydrator, and then rinsed for 2-4 times in warm water at 35-50 ℃ and drained to obtain a final mordant sample.

Specifically, the dyeing comprises the following steps:

1. heating the purified safflower red liquid to below 50 deg.C in a container.

2. And (3) dissolving the acid substance by using water, pouring the acid substance into the container in the step (1), and uniformly stirring to obtain the red pigment dye solution.

3. Immersing the sample to be dyed into the red pigment dye solution, slightly stirring, covering and heating with slow fire (the temperature is increased to 6-10 ℃ every 10 min). During the period, the sample to be dyed is slightly turned over for 1-3 times, so that the color of the sample to be dyed is uniform.

4. And (3) turning off the fire when the temperature is 45-50 ℃, covering the cover, and naturally cooling to 35-45 ℃.

5. Putting the sample to be dyed into a water-leaking device of a metal mesh basin, rinsing the sample in warm water at the temperature of about 35-50 ℃ for 2-4 times, and draining (or softly dewatering for 0.1-2 min by using a dewatering machine).

< fixation >

The inventor finds that the carthamus tinctorius red pigment has weak acidity, and the dyed wool fibers are soaked in acid liquor, so that the red pigment can be further precipitated and fixed, and the color fastness is effectively improved. Specifically, a pre-dyed sample may be placed in a fixing agent for fixation to obtain a final dyed sample. In some specific embodiments, the fixing agent comprises an acidic solution.

The acid solution is not particularly limited, and vinegar and the like are usually used. The time for soaking is not particularly limited, and may be set as required, for example: 15-30min, and the like.

Further, after dyeing is finished, the sample can be placed in a device capable of leaking water or is gently dehydrated by a dehydrator, and then rinsed for 2-4 times in warm water at 35-45 ℃ and drained, so that a final mordant dyeing sample is obtained.

Specifically, the fixation comprises the following steps:

1. and dissolving or diluting the acidic substance with water to prepare an acidic solution which is used as a color fixing agent.

2. And putting the sample to be dyed into a metal mesh basin and soaking the sample to be dyed into the color fixing agent for 15-30 min.

3. Rinsing the sample to be dyed and the metal mesh basin in warm water at 30-50 ℃ for 2-4 times, and draining (or performing soft dehydration for 0.1-2 min by using a dehydrator).

4. And (5) ventilating and drying in the shade to obtain a final dyed sample.

Preferably, when vinegar is used as the acidic substance to prepare the color fixing agent, 40mL of vinegar may be added to 5 to 10L of warm water at 35 to 50 ℃ and uniformly stirred to prepare a color fixing solution.

Examples

Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Example 1

Example 1 and application example 1 the following weight of starting materials were used: 50g of sheep wool, 200g of dry safflower, 40g of potassium carbonate, 60g of citric acid and 40mL of vinegar.

Removing safflower yellow

1. Soaking Carthami flos in 8L water, kneading with hand, and standing for 2 hr.

2. Filtering with cotton cloth, and collecting yellow pigment liquid.

3. Putting the safflower into a container again, injecting 8L of water, stirring uniformly and soaking for about 12 hours.

Secondly, extracting the carthamus red pigment

1. The petals, from which the yellow pigment was substantially removed, were placed in a container and 3L of water was injected.

2. Dissolving 16g (8% of the weight of the safflower) of potassium carbonate in 400mL of water, pouring the potassium carbonate into the container in the step 1, fully stirring, and soaking for 3 hours to dissolve the red pigment.

3. Filtering with cotton cloth to obtain crude product of primary red pigment.

4. The petals were then placed in a container and 1.5L of water was injected.

5. Dissolving 8g (4% of safflower weight) of potassium carbonate in 200mL of water, pouring the solution into the container in the step 4, fully stirring, and soaking for 3h to further dissolve the red pigment.

6. Filtering with cotton cloth to obtain crude product of secondary safflower red.

7. Mixing the primary red pigment crude product and the secondary red pigment crude product.

Thirdly, purifying the safflower red pigment

1. Dissolving 24g of citric acid (12% of the weight of safflower) in 400mL of water, pouring the solution into the crude red pigment, and stirring uniformly.

2. Continuously adding 40g of absorbent cotton, soaking for 15min while continuously stirring, and adsorbing the dye red pigment.

3. And taking out the absorbent cotton and fully wringing.

4. 12g of citric acid (6% of the weight of safflower) was dissolved in 200mL of water. Pouring it into red dye liquor, and stirring uniformly.

5. And (4) putting the absorbent cotton in the step (3) again, continuously soaking for 15min, continuously stirring during the soaking, and further adsorbing the dyed red pigment.

6. Dissolving 16g potassium carbonate in 4L water, soaking in the absorbent cotton for 15min while stirring, and dissolving red pigment from the absorbent cotton.

7. And taking out the absorbent cotton and fully wringing.

8. Filtering with cotton cloth to obtain high-purity carthamus red pigment liquid.

Application example 1

First, pretreatment

1. 8mL of laundry detergent is added into a container containing 6L of warm water at 40 ℃, and the laundry detergent is uniformly stirred to prepare a pretreatment liquid.

2. Firstly, sheep wool is put into a metal mesh basin, and then the sheep wool and the metal mesh basin are immersed into pretreatment liquid for 30 min.

3. And taking the metal mesh basin and the sheep wool out of the pretreatment liquid, draining the liquid, and slightly rinsing in warm water at 40 ℃ for 2-3 times. The kneading or twisting can not be carried out during the kneading or twisting process, so as to avoid the felting phenomenon.

4. The sheep wool is suspended and kept stand in a metal mesh basin, and the water is drained.

Secondly, dyeing

1. The purified safflower red liquid of example 1 was warmed to about 40 c in a container.

2. Dissolving 24g of citric acid in 400mL of water, pouring the solution into the container in the step 1, and uniformly stirring to obtain the red pigment dye solution.

3. Immersing sheep wool in red dye solution, slightly stirring, covering, heating with slow fire (10min at 6 deg.C, slightly turning sheep wool for 2 times to obtain uniform color.

4. When the temperature is close to 50 ℃, the fire is turned off, and the cover is covered to naturally cool to about 40 ℃.

5. Placing sheep wool into a metal mesh basin capable of leaking water, rinsing in warm water at about 40 deg.C for 3 times, and draining.

Third, color fixing

1. Adding 40mL of edible vinegar into 8L of warm water at about 40 ℃, and uniformly stirring to prepare the color fixing agent.

2. Placing sheep wool into a metal mesh basin, and soaking in the color fixing solution for 15 min.

3. Sheep wool was rinsed 3 times with a metal mesh basin in warm water at about 40 ℃ and then drained.

4. Ventilating and drying in the shade.

Example 2

Example 2 and application example 2 the following raw materials by weight were used: 50g of mohair, 200g of dry safflower, 40g of potassium carbonate, 60g of citric acid and 40mL of table vinegar.

Removing safflower yellow

1. Soaking Carthami flos in 7.5L water, kneading with hand, and standing for 2.5 hr.

2. Filtering with cotton cloth, and collecting yellow pigment liquid.

3. Putting Carthami flos into container, adding 8.5L water, stirring, and soaking overnight.

Secondly, extracting the carthamus red pigment

1. The petals, after substantially removing the yellow pigment, were placed in a container and 2.5L of water was injected.

2. Dissolving 14g (7% of the weight of the safflower) of potassium carbonate in 400mL of water, pouring the potassium carbonate into the container in the step 1, fully stirring, and soaking for 2.5h to dissolve the red pigment.

3. Filtering with cotton cloth to obtain crude product of primary red pigment.

4. The petals were then placed in a container and 2L of water was injected.

5. Dissolving 10g (5% of safflower weight) of potassium carbonate in 200mL of water, pouring into the container in the step 4, stirring thoroughly, soaking for 3h, and further dissolving the red pigment.

6. Filtering with cotton cloth to obtain secondary red pigment dye solution.

Thirdly, purifying the safflower red pigment

1. Dissolving 22g of citric acid (11% of the weight of the safflower) in 380mL of water, pouring the citric acid into the crude red pigment, and stirring uniformly.

2. Continuously adding 40g of absorbent cotton, soaking for 18min while continuously stirring, and adsorbing the dye red pigment.

3. And taking out the absorbent cotton and fully wringing.

4. Then 180mL of water was added to dissolve 14g of citric acid (7% of the weight of safflower). Pouring it into red dye liquor, and stirring uniformly.

5. And (4) putting the absorbent cotton in the step (3) again and continuing to soak for 18 min. During the process, the mixture is continuously stirred to further adsorb the dyed red pigment.

6. Dissolving 16g potassium carbonate in 4L water, soaking in the absorbent cotton, and soaking for 12 min. Stirring is carried out continuously during the process, and the red pigment is fully dissolved from the absorbent cotton.

7. And taking out the absorbent cotton and fully wringing.

Application example 2

First, pretreatment

1. 7.5mL of laundry detergent was added to a container containing 5.5L of warm water at 40 ℃ and stirred uniformly to prepare a pretreatment liquid.

2. The mohair is firstly put into a metal mesh basin and then is soaked in the pretreatment liquid for 35 min.

3. Taking out the metal mesh basin and the mohair from the pretreatment liquid, draining the liquid, and gently rinsing in warm water at 40 ℃ for 4 times. The kneading or twisting can not be carried out during the kneading or twisting process, so as to avoid the felting phenomenon.

4. Suspending the mohair in a metal mesh basin, standing, and draining water.

Secondly, dyeing

1. The purified safflower red liquid of example 2 was warmed to about 40 c in a vessel.

2. Dissolving 24g of citric acid in 380mL of water, pouring the solution into the container in the step 1, and uniformly stirring to obtain the red pigment dye solution.

3. Immersing the mohair into the red pigment dye solution, slightly stirring, covering, and heating with slow fire (10min for 6 ℃). During the period, the mohair was gently tumbled 3 times to make the color uniform.

5. Putting the mohair into a water-leaking device of a metal mesh basin, rinsing in warm water at about 40 deg.C for 4 times, and dewatering gently with a dewatering machine for 0.5 min.

Third, color fixing

1. Adding 38mL of edible vinegar into 7.5L of warm water at about 40 ℃, and uniformly stirring to prepare a color fixing solution.

2. Putting the mohair into a metal mesh basin, and soaking in the color fixing solution for 20 min.

3. The mohair was rinsed 4 times with a metal mesh pan in warm water at about 40 c, followed by soft dehydration for 0.5min using a dehydrator.

4. Ventilating and drying in the shade.

Performance testing

1. Colour fastness to rubbing

The dyeings of application example 1 and application example 2 were tested for crockfastness using a Y571D crockfastness tester (Wenzhou Square instruments Co., Ltd.) according to GB/T5712-1997, the results of which are shown in Table 1 below:

TABLE 1

	Dry friction	Wet friction
			Application example 1	4 stage	Grade 3
Application example 2	4 stage	Grade 3

2. Color fastness to washing

The dyed articles of application example 1 and application example 2 were tested for color fastness to washing with water using an SW-12B launder-ometer (Wenzhou Square-round instruments Co., Ltd.) with reference to GB/T3921.1-5, and the test results were as follows:

TABLE 2

	Washing with water
		Application example 1	Grade 3-4
Application example 2	Grade 3-4

As can be seen from tables 1 and 2, the dyed products dyed by the dyeing method have excellent rubbing color fastness and washing color fastness, bright and appropriate color, obvious advantages of the dyeing method, simple and convenient operation, no organic solvent residue, environmental protection and no harm.

The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for dyeing wool fibers, comprising the steps of:

and (3) dyeing: heating the carthamus red pigment liquid to below 50 ℃, adding an acidic substance to obtain a red pigment dye solution, immersing a sample to be dyed into the red pigment dye solution, wherein the initial temperature of the sample to be dyed is 35-45 ℃, heating to below 50 ℃ for dyeing, and heating to 6-10 ℃ every 10min to obtain a pre-dyed sample;

the preparation method of the carthamus red pigment comprises the following steps:

2. The method for dyeing wool fibers according to claim 1, wherein said extraction step comprises: soaking the safflower with water to remove yellow pigment from the safflower.

3. The method of dyeing wool fibers according to claim 1 or 2, wherein the basic substance comprises one or a combination of two or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, potassium hydroxide, and sodium hydroxide; wherein the amount of the alkaline substance is 0.5-20% by total mass of the safflower.

4. The method for dyeing wool fiber according to claim 1 or 2, wherein the cotton fiber comprises one or a combination of two or more of absorbent cotton, desized pure cotton white yarn, and white cotton cloth; wherein the usage amount of the cotton fiber is 5-50% based on the total mass of the safflower as 100%.

5. The method of dyeing wool fibers according to claim 1 or 2, wherein the purification step is carried out under the acidic condition using an acidic substance; wherein, the acidic substance comprises one or the combination of more than two of citric acid, hydrochloric acid, acetic acid and sulfuric acid.

6. The method for dyeing wool fibers according to claim 5, wherein the amount of the acidic substance is 1 to 30% based on 100% by mass of the total mass of the safflower.

7. The method of dyeing wool fibers according to claim 1 or 2 wherein the fixing agent comprises an acidic solution.