JPH0116957B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel dyeing process using sulfur dyes or sulfur vat dyes.

Conventional dyeing methods using sulfur dyes or sulfur vat dyes include, for example, a butt steam method and a butt steam method. All of these methods involve dyeing in steam, but they have many problems, such as long processing steps, large amounts of steam, and high fuel costs. Particularly in the steamer, due to high humidity, it is unavoidable that sulfur dyes or sulfur vat dyes fixed on the textile material are transferred to the rollers, so the rollers must be washed frequently even when the dyeing machine is in operation. By necessity, long hours are required to dye large quantities of textile material.

The present inventors previously discovered that at least one -
₁ SM (M ₁ is hydrogen atom or alkali metal atom)
It has been discovered that an organic mercapto compound having a mercapto group and/or an organic sulfur compound capable of producing a mercapto group under heating conditions can be an excellent reducing agent for sulfur dyes or sulfur vat dyes, and has already filed an application (Japanese Patent Laid-Open No. 55-142777). (No. 158386, Japanese Patent Publication No. 158386). The present inventors have conducted further research on dyeing methods using sulfur dyes or sulfur vat dyes that use the above-mentioned organic mercapto compounds and/or organic sulfur compounds as reducing agents, and have found that an alkaline dye solution containing the reducing agent and urea. It has been discovered that good dyeing can be achieved in a short period of time by a simple operation of immersing a fiber material in water, drying the fiber material, subjecting it to dry heat treatment if necessary, and further oxidation treatment.
The present invention was completed based on this knowledge.

That is, the present invention provides at least one -SM ₁ in the molecule.
After immersing the textile material in an alkaline dye solution containing an organic mercapto compound having a group (M ₁ is a hydrogen atom or an alkali metal atom) and/or an organic sulfur compound capable of forming a mercapto group under heating conditions and urea. , a dyeing method using a sulfur dye or a sulfur vat dye characterized by drying the fiber material and further performing an oxidation treatment, and a dyeing method with at least one _-SM group in the molecule (M ₁ is a hydrogen atom or an alkali After immersing the fiber material in an alkaline dye solution containing urea and an organic mercapto compound having metal atoms) and/or an organic sulfur compound capable of forming mercapto groups under heating conditions, the fiber material is dried, and then The present invention relates to a dyeing method using a sulfur dye or a sulfur vat dye, which is characterized by dry heat treatment and further oxidation treatment.

According to the method of the present invention, good dyeing can be obtained in a very short time with simple operations and short steps, and since no steam is required, the fuel cost and amount of water required for dyeing can be significantly reduced. In addition, it is not necessary to wash the rollers, and the dyeing machine can be operated for a long time, which is extremely advantageous industrially.

Organic mercapto compounds having at least one -SM ₁ group (M ₁ is a hydrogen atom or an alkali metal atom) used in the present invention and/or organic sulfur compounds capable of producing a mercapto group under heating conditions (hereinafter referred to as these) A wide variety of known organic mercapto acids can be used (collectively referred to as "organic mercapto compounds"), such as mercapto organic acids such as thioglycolic acid and β-mercaptopropionic acid, their sodium salts, potassium salts, mercaptoethanol, and monothioglycerol. , mercapto alcohol such as 1,3-dithioglycerol or its sodium salt, potassium salt, dithiodiglycolic acid, β,
dithioorganic acids such as β'-dithiodipropionic acid or their sodium salts, potassium salts, di- or polythioalcohols such as dithioethanol, bis(3-hydroxy-n-propyl) disulfide, trithiodiethanol, dithiodiglycerol,
Isothiocyanates such as 4-sulfobenzene isothiocyanate and 4-sulfo-1,3-phenylene diisothiocyanate, or their sodium and potassium salts, S-(2-sulfoethyl)thiuronium, S-(4-sulfophenyl)thiuronium , sulfothiuronium such as S-(4-sulfobenzyl)thiuronium, or its sodium salt, potassium salt, xanthogen compound of an organic acid such as methylxanthogenacetic acid, ethylxanthogenethanesulfonic acid, or its sodium salt, potassium salt, acetylthio Examples include acyl compounds of mercapto organic acids such as glycolic acid and 2-acetylthio-propanesulfonic acid, or their sodium salts and potassium salts. In the present invention, the above-mentioned organic mercapto compound and organic sulfur compound may be used alone as the organic mercapto compound, or
You may use these together. When organic sulfur compounds are used as organic mercapto compounds, these organic sulfur compounds are easily converted to organic mercapto compounds during drying as described below. The amount of the above-mentioned organic mercapto compound to be used varies depending on the type of compound used, but it cannot be stated unconditionally, but it is generally sufficient to have it present in the dye solution in an amount of about 10 to 100 g, preferably about 20 to 30 g.

Further, in the present invention, it is necessary that urea be present in the dye solution. The presence of urea makes it possible to obtain uniform and deep dyeings. The amount of urea used is not particularly limited, but it is usually 50 to 400g/, preferably 100 to 400g/in the dye solution.
It is sufficient if it is present in an amount of about 200g/.

As the various auxiliaries added to the dye solution, various auxiliaries used for dyeing sulfur dyes or sulfur vat dyes can be widely used. Specifically, dye solubilizers such as ethylene glycol, diethylene glycol, thiodiethylene glycol, hydroxide Alkali hydroxides such as sodium and potassium hydroxide, alkali carbonates such as sodium carbonate, potassium carbonate, and sodium bicarbonate, inorganic salts such as sodium chloride and sodium sulfate, sodium dibasic phosphate, sodium triphosphate, sodium tripolyphosphate, etc. Phosphate, Sodium Subsulfate, Sodium Hydrogen Sulfide, Rongarit,
Examples include reducing agents such as sodium hydrosulfite, glucose, and sodium sulfite, wetting agents such as polyoxyethylene alkyl ether and polyoxyethylene alkyl allyl ether, and thickening agents such as starch, carboxymethyl cellulose, and sodium alginate. The amount of these various auxiliary agents to be used is not particularly limited, and may be added in an appropriate amount depending on the purpose of use, usually 100g/or less, preferably 30g/or less (singlely or in combination). do it.

Furthermore, as the sulfur dyes and sulfur vat dyes used in the present invention, any currently commercially available dyes can be used. The concentration of the dye in the dye solution is not particularly limited, but may be appropriately selected within the range of usually 1 to 200 g/, preferably 1 to 100 g/.

There are no particular limitations on the preparation of the dye solution used in the present invention, and it can be prepared according to conventionally known methods. For example, dissolve the specified organic mercapto compound, urea, and various auxiliary agents in water, then add the dye, stir well, heat from room temperature to 100°C for about 1 to 15 minutes to dissolve the dye, and then add the specified amount with water or warm water. It should be diluted to a concentration of The dye solution thus prepared
PH is generally about 8-13.

Furthermore, as the fiber material to be applied to the method of the present invention, a wide variety of fibers that have been dyed with sulfur dyes and sulfur vat dyes can be used, such as cotton, viscose rayon, cellulose fibers such as hemp, polyamide fibers, Examples include polyvinyl alcohol fibers, blended or interwoven fibers of these fibers, and the like.

In the present invention, the fiber material is first immersed in a dye solution. The appropriate temperature of the dye solution during dipping is usually room temperature to about 60°C. Further, the time for which the fiber material is immersed cannot be unconditionally determined depending on the dyeing machine used, but it is usually several seconds to about 5 minutes.

In the present invention, the fiber material is then dried. In order to facilitate drying, it is preferable to take out the fibrous material soaked in the dye solution and then squeeze it uniformly through a roller or the like. A wide variety of conventional drying devices can be used to dry the fiber material. In the present invention, when the fiber material is passed through the drying device, it is preferable to maintain the temperature in the drying device to be uniform, and if such a drying device is used, the subsequent dry heat treatment can be omitted. Oxidation treatment can be performed. Appropriate drying temperature is about 100 to 120°C, and drying time is usually about 1 to 3 minutes.

In the present invention, the above-mentioned fiber material may be subjected to dry heat treatment after drying. For the dry heat treatment, any conventionally known dry heat apparatus can be used, such as a general thermosol equipment, an infrared ray dryer, or a hot air dryer. The appropriate temperature for the dry heat treatment is about 120 to 180°C, and the dry heat treatment time is generally about 1 to 2 minutes. By the drying treatment or dry heat treatment, the sulfurized dye or sulfurized vat dye is fixed on the fiber material in the form of a leuco body.

In the present invention, the fiber material is then subjected to an oxidation treatment. When oxidizing the leuco body fixed to the fiber material, any conventional oxidation method and oxidation conditions can be applied. For example, the fiber material obtained above is treated with an oxidizing agent such as hydrogen peroxide-acetic acid, sodium dichromate-acetic acid, potassium iodate, or ammonium persulfate.
It may be immersed in a bath containing a concentration of 20 g/ml and treated at a temperature of room temperature to 80° C. for several seconds to 30 minutes.

Examples are given below to further clarify the present invention.

Example 1 Asashiosol Blue S/BC Conc [Trademark: Asahi Chemical Co., Ltd., CI Solbilized Sulfur Blue 7] 40g 50% sodium thioglycolate aqueous solution 40ml Urea 200g Sodium sulfite 5g contained in one A cotton cloth is dipped in the dye solution, wrung out, and then dried at 120°C for 2 minutes. then 60℃
Then, the color was developed by immersing it in an aqueous solution containing 1 ml of Asahi Oxy 50 [trademark; oxidizing agent, manufactured by Asahi Chemical Industries, Ltd.] and 5 ml of acetic acid, followed by thorough washing with water and drying. to obtain blue dyed cloth.

Example 2 Asashio Pure Blue 6G [Trademark; Manufactured by Asahi Chemical Industry Co., Ltd.]
CI Sulfui Blue 2] 50g Sodium 2-mercaptoethanesulfonate 30g Urea 200g Peretskus NB [Trademark; Wet, manufactured by Kao Atlas Co., Ltd.
A cotton cloth is dipped in a dye solution containing 2 g of penetrant, wrung out, dried at 120°C for 2 minutes, and then subjected to dry heat treatment at 150°C for 2 minutes. Next, wash with hot water at 60℃, then Asahi Oxy 50 [trademark; oxidizing agent manufactured by Asahi Chemical Industry Co., Ltd.] 1
ml and acetic acid in an aqueous solution containing 5 ml of acetic acid in 1 to develop color, thoroughly washed with water, and dried to obtain a blue dyed cloth.

Example 3 Asashio Sol Yellow S-RR [Trademark; Asahi Chemical Industry
Co., Ltd.] 50 g β-mercaptopropionic acid 20 g Sodium hydroxide 10 g Longalit C 5 g Urea 150 g Sodium alginate 2 g A cotton cloth was dipped in a dye solution containing 1 g, wrung out, and dried at 120°C for 2 minutes. and further 140℃
Dry heat treatment for 2 minutes. After washing thoroughly with water, use an oxidation bath [5 ml of hydrogen peroxide (30%) and 5 ml of acetic acid (98%)]
1) at 40°C, followed by washing with water and drying to obtain a yellow dyed cloth.

Example 4 Asashio Blue BB [Trademark: CI Sulfur Blue 7 manufactured by Asahi Chemical Co., Ltd.] 50g Monothioglycerol 20g Sodium carbonate 5g Urea 250g Glucose 5g Salt 50g Wetting and penetrating agent 2g Dye solution containing 1 g Example 1
Process according to the procedure to obtain blue staining.

Example 5 Asashio Sol Red Brown S-6B [Trademark: CI Solbilized Red 2 manufactured by Asahi Chemical Industry Co., Ltd.] 60 g 1,3-dithioglycerol 15 g Sodium diphosphate 5 g Urea 200 g Sodium sulfate 50 g Starch glue 10 g Viscose rayon is immersed in a dye solution containing 1 and treated according to the example to obtain a reddish-brown dyeing.

Example 6 Asashio Maroon 2R [trademark; manufactured by Asahi Chemical Industry Co., Ltd.]
Cotton is immersed in a dye solution containing 50 g of dithiodiglycolic acid, 20 g of sodium hydroxide, 5 g of sodium sulfite, and 200 g of urea, and then treated in accordance with Example 1 to obtain a brown dye.

Example 7 Asashio Orange Brown S・9R [Trademark: Asahi Chemical Co., Ltd., CI Solbilized Sulfur Brown 52] 40 g β, β'-sodium dithiopropionate 15 g Sodium carbonate 5 g Urea 200 g Sodium sulfite 5 g Cotton is immersed in the dye solution contained in Example 1 and treated according to Example 2 to obtain a brown dye.

Example 8 Asashio Solpiable Blue-S-GL [Trademark: CI Solbilized Blue-2, manufactured by Asahi Chemical Industry Co., Ltd.] 50g Dithiodiethanol 15g Sodium sulfite 5g Potassium carbonate 5g Urea 200g Dye solution containing in one part Cotton is soaked in and treated according to Example 2 to obtain a blue dyeing.

Example 9 Cotton was immersed in a dye solution containing 100 g of Kayaku Carbon D (trademark: CI Sulfur Black 11 manufactured by Nippon Kayaku Co., Ltd.), 20 g of trithiodiethanol, 5 g of potassium hydroxide, and 200 g of urea. A black stain is obtained.

Example 10 Asashiosol Green S-GO [Trademark: Solbilized Sulfur Green 3 manufactured by Asahi Chemical Industry Co., Ltd.]
Cotton is immersed in a dye solution containing 50 g 4-sulfobenzene isothiocyanate 20 g sodium carbonate 5 g sodium sulfite 5 g urea 200 g and treated according to Example 3 to obtain a blue-green dyeing.

Example 11 Asashio Red Brown 3B [Trademark: Asahi Chemical Co., Ltd.]
Cotton was immersed in a dye solution containing 50 g of S-(2-sulfoethyl)thiuronium 20 g, 5 g of sodium carbonate, and 200 g of urea and treated according to Example 3 to obtain a reddish brown dye.

Example 12 Kayaku Homodai Blue BGF-S [Trademark: Nippon Kayaku
Cotton is immersed in a dye solution containing 50 g of CI Sulfur Blue 13 (manufactured by Co., Ltd.), 20 g of methylxanthogenacetic acid, 5 g of sodium carbonate, and 200 g of urea, and treated according to Example 3 to obtain blue dyeing.

Example 13 Asashio Orange OA [trademark; manufactured by Asahi Chemical Industry Co., Ltd.]
Cotton is immersed in a dye solution containing 50 g 2-acetylthiopropanesulfonic acid 20 g sodium carbonate 5 g urea 150 g and treated according to Example 2 to obtain a yellow-brown dyeing.

Example 14 (A) Asasiozole according to the method of the present invention. Black SB-N [Trademark: Asahi Chemical Co., Ltd., CI Solbilized Sulfur Black-1] Dip a cotton cloth in a dye solution containing 40 g of 50% sodium thioglycolate 50 ml of urea 200 g. After squeezing, dry at 120℃ for 2 minutes, then dry at 150℃ for 2 minutes.
Process in minutes. Next, wash with hot water at 60℃, and 1 ml of Asahi Oxy 50 [trademark; oxidizing agent, manufactured by Asahi Chemical Industry Co., Ltd.]
After immersing the fabric in an aqueous solution containing 5 ml of acetic acid in 1 to develop color, the fabric was thoroughly washed with water and dried to obtain a black dyed fabric.

(B) Comparison method asasiozole. A cotton cloth was dipped in a dye solution containing 40 g of Black SB-N, 50 ml of 50% sodium thioglycolate, and 5 g of sodium carbonate, wrung out, and then heated with moist heat at 102°C for 2 minutes. then 60
Wash with hot water at ℃, add 1 ml of Asahi Oxy 50 [trademark; oxidizing agent, manufactured by Asahi Chemical Industry Co., Ltd.] and 5 ml of acetic acid.
After immersing the cloth in the aqueous solution contained in the cloth to develop color, the cloth is sufficiently washed with water and dried to obtain a black dyed cloth.

The obtained dyed fabric has a significantly larger density difference between the first dyed part and the last dyed part compared to that obtained by method A. Also, C
Compared to method A, method
It is very dirty and is not practical.

(C) Comparative method Using the dye solution of B, a dyed cloth was obtained in the same manner as method A. However, the dyed fabric obtained had a dyeing degree of only about 70, assuming that the dyeing degree of the dyed fabric obtained in A was 100.

(D) Comparative method A dyed fabric was obtained in the same manner as in method A using a dye solution containing 40 g of Asashiozole, Black SB-N, 50 ml of 50% sodium thioglycolate, 5 g of sodium sulfite, and 5 g of sodium hydroxide. However, the dyeing degree of the obtained dyed cloth was only about 70, assuming that the dyeing degree of the dyed cloth A was 100.

Claims (1)

[Claims] 1. An organic mercapto compound having at least one -SM ₁ group (M ₁ is a hydrogen atom or an alkali metal atom) in the molecule and/or an organic sulfur compound capable of forming a mercapto group under heating conditions. A dyeing method using a sulfur dye or a sulfur vat dye, which comprises immersing a fiber material in an alkaline dye solution containing a compound and urea, drying the fiber material, and further performing an oxidation treatment. 2 Contains an organic mercapto compound having at least one -SM ₁ group (M ₁ is a hydrogen atom or an alkali metal atom) in the molecule and/or an organic sulfur compound capable of producing a mercapto group under heating conditions and urea After soaking the textile material in an alkaline dye solution, the textile material is dried and then subjected to a dry heat treatment,
A dyeing method using a sulfur dye or a sulfur vat dye, which is characterized by further performing an oxidation treatment.