JPH03260183A - Method for dyeing fiber - Google Patents

Abstract

PURPOSE:To dye fiber (especially silk or wool) to a red color with a bright color tone and excellent color fastness to light by regulating a dye bath containing anthocyanin to a strong acidic state. CONSTITUTION:Fiber such as silk or wool is dipped in a dye bath prepared by regulating pH of an aqueous solution containing anthocyanin (cyanidine-3- arabinoside) to >=2.5 with, e.g. hydrochloric acid and dyed to a red color with a bright color tone and high color fastness to light. A compound having sulfonic acid, e.g. dodecylbenzenesulfonic acid can be used together in the dye bath to improve the color fastness to light.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a dye method that uses anthocyanin as a dye and imparts high light fastness.

(Conventional technology) Silk dyeing using anthocyanin contained in red flowers is
It has been known since ancient times as ``flower dyeing,'' which is a type of vegetable dyeing.

However, even when silk cloth is dyed by dipping it in a red dyeing solution containing andocyanin, the color of the dyed cloth does not reflect the bright red color of the flowers, but has the disadvantage that the color ranges from purple to reddish-purple. The biggest drawback of such vegetable dyeing is that the light fastness of the dyed fabric is basically inferior.

(Problem to be solved by the invention) The present invention improves the dyeing method using andocyanin,
The purpose is to provide a dyeing method with excellent color hue and high light fastness.

(Means for Solving the Problems) That is, the present invention provides a method for dyeing fibers in a dye solution containing anthocyanins having a pH of 2.5 or less.

Conventional dyeing using anthocyanin is carried out in a weakly acidic region, specifically in a pH range of 4 to 7, from the viewpoint of ease of handling. In the present invention, by adjusting this pH range to a strongly acidic range, that is, pH 2.5 or less, the color color and light fastness are greatly improved.

The anthocyanin used in the present invention may be any andocyanin normally contained in flower petals or pericarp, but for dyeing and weaving applications in which vivid colors are to be obtained, andocyanin consisting of only one type of compound is desirable. It is known that anthocyanins collected from normal biological tissues are composed of multiple anthocyanin compounds, and for this purpose,
It is preferable to use cyanidin-3-arabinocyto, which is the only type of anthocyanin produced by Hanakirin cultured cells (see JP-A-57-14653).

The fibers used in the present invention may be of any type, but silk and wool, which are protein-derived animal fibers, give desirable results in terms of red dyeability, but synthetic fibers such as polyester and acrylic may also be used. .

The fibers used in the present invention are preferably sulfonic acid-modified fibers into which sulfonic acid groups have been introduced. Although sulfonated polyester or acrylic may be used, it is preferable to use silk or wool containing 7 amino groups in the fiber treated with a sulfonating agent in terms of red dyeability. Examples of the sulfonating agent include Sandspace S (manufactured by Sandoz Co., Ltd.) and butane sultone (manufactured by Fuji Photo Film Co., Ltd.). Sulfonation is usually carried out by dissolving or dispersing the above chemicals in water or alcohol, immersing the fibers to be treated in the dispersion at 40 to 80°C for 30 minutes to 2 hours, then taking them out and washing them with water.
The dye bath solution used in the present invention is obtained by drying a 0.01% (v/v) to 10% (w/v) aqueous solution of the above-mentioned anthocyanin with hydrochloric acid or the like to a pH of 2.5 or less, preferably pH 2. It is used with the following adjustments. pH
When the pH value is higher than 2.5, the dyeing property becomes purple instead of the red seen at pH 2.5 or lower, and the light fastness becomes poor.

The stronger the acidity, the better the results. Further, preferable results can be obtained by adding a compound having sulfonic acid to silk or wool. In addition to this, the red dyeability can also be improved by adding an electrolyte. As for the compound having sulfonic acid, when using arylsulfonic acid (for example, dodecylbenzenesulfone Ll, 5-naphthalenesulfonic acid, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid), red dyeing property, Favorable results can be obtained in both light resistance. The amount of the compound having sulfonic acid in the dye bath solution is 0.01% (w/v
) to 5% (,/V), favorable results are obtained in both red dyeability and light resistance.

The amount of electrolyte present is from 0.5% (W/V) to ]0% (v/V).
In v), favorable results in red stainability are obtained.

The dye bath is maintained at 80 to 95° C., and the cloth or thread of the fiber is immersed in the dye bath solution for 30 minutes to 2 hours to dye. Thereafter, the dyeing solution is removed by thorough washing with water, and the material is air-dried. The obtained dyed and woven fabric or dyed and woven thread is further
Mordant may be used with an aqueous solution containing various metal ions. Sulfonic acid-modified fibers can be dyed in a variety of ways compared to unmodified fibers. Examples of metal ions include copper ions, iron ions, chromium ions, aluminum ions, tin ions, etc., and the concentration thereof is 0.1 to 10% (v/v
) is within the range. Mordanting is usually carried out by immersion at 25° C. for 5 minutes to 1 hour.

In order to obtain even higher light fastness, the cloth or yarn dyed as described above may be steamed or immersed in a solution containing a polymeric substance. Image processing may also be used. The steaming process is carried out at 80 to 100°C for 30 minutes to 1 hour using a commercially available steamer. The polymer substance used in the dipping treatment may be any synthetic or natural polymer that is water-insoluble and has the property of adsorbing or intertwining with fibers. Examples of synthetic polymers include polystyrene resin, acrylic resin, polyester resin, epoxy resin,
Examples include polyamide resins and polyurethane resins, and examples of natural polymers include polysaccharides such as cellulose or derivatives thereof. Among these polymeric substances, it is preferable to use substances with highly UV-absorbing functional groups such as aromatic groups in their molecules, such as polystyrene and phthalate ester resins, to improve the light resistance of treated dyed and woven fabrics and dyed and woven yarns. Desirable from a gender perspective. The substances that dissolve these polymers are generally organic solvents, such as aromatic hydrocarbons such as toluene and benzene, aliphatic hydrocarbons such as hexasan and octane, ketones such as acetone, and ethyl acetate. Examples include esters such as esters, alcohols such as amyl alcohol, and mixed solvents thereof. Additionally, 0% of each of ultraviolet absorber and/or antioxidant was added to this solution.
A content of 1 to 10% is preferable because the light resistance of the resulting treated fabric or treatment system is improved. The immersion treatment is performed in a solution containing the polymeric substance at 10 to 30°C for 1 to 60 minutes, preferably 5 to 30 minutes.

The obtained dyed and woven fabric or dyed and woven thread is visually observed to confirm its dyeability, and furthermore, a light fastness test (J I 5-L-842) using a carbon arc lamp is conducted to confirm its light fastness.

(Effects of the Invention) By the method of the present invention, the dyeability of andocyanin on fibers was improved from the conventional purple to red, and the light fastness was also improved. Furthermore, by using various mordants in combination, more diverse dyeing properties can be achieved than in the past.

(Examples) The present invention will be explained in more detail by Examples, but the present invention is not limited to these Examples.

Example-1 0, 1 obtained by immersing dried Hanakirin cultured cells 209 in an acidic aqueous hydrochloric acid solution of pH 2 1.0OOjlQ and filtering it.
% cyanidin-3-arabinosyte aqueous solution 200x (2), 19% sodium chloride and 0.489% 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid were added, and the dye bath solution was adjusted to pH 2 with hydrochloric acid. 500RI2 glass beaker The dye bath solution was transferred to a container and kept at 95°C.A 5cm square piece of silk or wool cloth was immersed in the dye bath solution for 1 hour and dyed.The dyed fabric was taken out and immersed in running water to thoroughly remove the dye solution. After that, the fabric was air-dried to remove moisture.The red dyeability and light resistance of the obtained dyed and woven fabric were observed.The results are shown in Table 1.

Example 2) The same procedure as Example 1 was carried out except that 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid in Jt Example 1 was replaced with dodecylbenzenesulfonic acid, and the resulting dyed and woven fabric was dyed red. The properties and light resistance were observed. Table = 1
Shown below.

Example 3 The same procedure as Example 1 was carried out except that 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid in Example 1 was replaced with 1,5-naphthalenesulfonic acid, and the obtained dyed and woven fabric was Red stainability and light fastness were observed. Table 1 shows the results.
Shown below.

Example-4 0.1% obtained by immersing 20 g of dried Hanakirin cultured cells in 1,000 m6 of an acidic hydrochloric acid solution of pH 2 and filtering it.
Cyanidin-3-arabinosite aqueous solution 200 villages to 500
Transfer to a 112 glass beaker and adjust the pH to 2 with hydrochloric acid.
The temperature was kept at 95°C. 5cJIl in the dye bath solution! 1 g of sulfonated polyester cloth or sulfonated acrylic cloth was soaked for 1 hour and dyed.

The dyed fabric was taken out and soaked in running water to thoroughly remove the dyeing solution, and then air-dried to remove water. The red dyeability and light resistance of the obtained dyed and woven fabrics were observed. The results are shown in Table-2.

Comparative Example-1 Pi-(0
, 1% cyanidin-3-arabinosite aqueous solution 200jI
i2 was transferred to a 5001I2 glass beaker, the pH was adjusted to 4, a dye bath solution was prepared, and the temperature was kept at 95°C. 5cx in the dye bath
Four sides of silk or wool cloth were soaked and dyed for 1 hour. The dyed fabric was taken out and soaked in running water to thoroughly remove the dyeing solution, and then air-dried to remove water. The red dyeability and light resistance of the obtained dyed and woven fabrics were observed. The results are shown in Table-1.

Comparative Example-2 Hydrochloric acid acidic aqueous solution with pH 4! ,000rff, immerse 20g of dried Hanakirin cultured cells and filter it.0.1
% cyanidin-3-arabinocyte aqueous solution 200 ml to 50
The mixture was transferred to a glass beaker, the pH was adjusted to 4, a dye bath solution was prepared, and the temperature was kept at 95°C. A 5 cm square piece of sulfonated polyester cloth or sulfonated acrylic cloth was immersed in the dye bath solution for 1 hour and dyed. The dyed fabric was taken out and soaked in running water to thoroughly remove the dyeing solution, and then air-dried to remove water.

The red dyeability and light resistance of the obtained dyed and woven fabrics were observed. The results are shown in Table-2.

Table-1 1) Visual judgment. 2) J l5-L-8042 standard.

2) JI 5-L-8042 standard.

1) Visual judgment.

Reference Example 1 A solution in which 312.5 g of sand space was dissolved in 10011Q water and a solution in which 14 g of potassium carbonate was dissolved in 10031 (!) were mixed and kept at 80°C. Silk cloth,
Alternatively, the wool cloth was soaked for 30 minutes. The cloth was taken out, washed under running water, and the treatment solution was thoroughly removed. Example 7 1 g of basic copper acetate was dissolved in 100 m+2 of ion-exchanged water, and the andocyanine-dyed silk cloth obtained in Example 1 was added to the 25° C. solution. Alternatively, the wool cloth was soaked for 1 hour. The dyed fabric was taken out and soaked in running water to remove the dyeing solution sufficiently, and then air-dried to remove water.

The dyeability and light fastness were observed. The results are shown in Table-3.

1) Visual judgment 2) J I 5-L-8042 Example 8 0.1% cyanidin-3-arabinosyte aqueous solution 100011Q obtained by immersing 20 g of dried Hanakirin cultured cells in 11000 mL of acidic aqueous solution of pH 2 hydrochloric acid and filtering it. To,
The dye bath was adjusted to pH 2 with hydrochloric acid by adding 19 mg of sodium chloride. After drying at 10,100 O, it was air-dried.

Reference Example 2 5 g of butane sultone was dispersed in 100 IR, and the solution kept at 80°C was treated in the same manner as in Reference Example 1.

Example 5 Drying in an acidic aqueous solution of hydrochloric acid of pH 2 1000112] 0, 1 obtained by immersing 20 g of Nakirin cultured cells and filtering.
% cyanidin 3-arabinosite aqueous solution 200z (in l,
1 g of sodium chloride was added and the pH of the dye bath was adjusted to 2 with hydrochloric acid. 500m (transfer the dye bath solution to a glass beaker,
The temperature was kept at 95°C. A 5 cm square piece of silk or wool fabric produced in Reference Example 1 was immersed in the dye bath solution for 1 hour and dyed.

The dyed fabric was taken out and soaked in running water to remove the dyeing solution sufficiently, and then air-dried to remove water. The dyeability and light fastness were observed.

The results are shown in Table-3.

Example 6 The same process as in Example 5 was carried out except that the silk cloth or wool cloth in Example 1 was changed to that prepared in Reference Example 2. Display the results -
Shown in 3.

The dye bath solution was transferred to a speaker and kept at 95°C.

Add 5 sheets of 5 cz square silk cloth or wool to the dye bath solution.
Dipped and dyed for a while. The dyed fabric was taken out and soaked in running water to thoroughly remove the dyeing solution, and then air-dried to remove water. Iron acetate, copper acetate, stannous chloride, chromium alum, 19 each
Each of 100 rice grains was dissolved in ion-exchanged water, and two pieces of the obtained anthocyanin-dyed silk cloth or wool filling were immersed in each solution at 25° C. for 1 hour. The dyed cloth was taken out and soaked in running water to thoroughly remove the mordant, and then air-dried to remove moisture. Furthermore, the obtained dyed fabric and dyed mordanted fabric were heated at 100°C for 6
After steaming for 0 minutes, the mixture was cooled and air-dried to remove moisture. The dyeability and light fastness were observed. The results are shown in Table 4.

Example 9 Silk cloth or wool cloth dyed and mordanted in the same manner as in Example 7,
in a toluene solution containing 5% polystyrene at 25°C.
After soaking for a minute, it was taken out and air-dried. The dyeability and light fastness were observed. The results are shown in Table 4.

Claims (1)

[Claims] 1. A method of dyeing fibers in a dye solution containing anthocyanins with a pH of 2.5 or less.