JPS59140266A - Anthraquinone compound, production thereof and dyeing or printing method using the same - Google Patents

Abstract

NEW MATERIAL:Anthraquinone compounds reactive with fibers and represented by formula I , wherein R is (hydroxy, cyano, phospho, etc.-substd.) C1-C4 alkyl; A is (methyl, methoxy, chlorine, sulfo group, etc.-substd.) phenylene, (sulfo group- substd.) naphthylene; Z is chlorine, fluorine; X is -SO2CH=CH2, -SO2CH2CH2Y (wherein Y is an alkali which can be removed as an anion). USE:Dyes which dye or print hydroxyl group- or carbamide-contg. fiber materials (e.g. cotton, viscose staple, wool, nylon, leather) yellow to blue. PREPARATION:An anthraquinone compd. of formula II is reacted with an equimolar amount of 2,4,6-trichloro (or fluoro)-S-triazine. The resulting dihalogenotriazinyl compd. of formula III is reacted with an amino compd. of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel fiber-reactive compound 1, more specifically, the present invention relates to a novel fiber-reactive compound represented by the following general formula +1) [wherein R is 1-4
a hydroxy-substituted alkyl group, a cyanogen-substituted alkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group, a carboxy-substituted alkyl group, a carbamoyl-substituted alkyl group, an alkoxycarbonyl-substituted alkyl group, or a sulfo-substituted alkyl group having 5 carbon atoms. represents. A is one phenylene residue or sulfonic acid group optionally substituted with ■ or two substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfonic acid group Fj represents an optionally substituted naphthylene residue. Z represents a chlorine atom or a fluorine atom. X is the group -8O2CH= CH2 or the group -502
Represents CH blind CH2Y.

Here, Y is a group that leaves as an anion with an alkali. ] The present invention relates to an anthraquinone compound or a salt thereof, a method for producing the same, and a method for dyeing or printing fiber materials using the same.

The anthraquinone compound represented by the above general formula +1+ is
When used for dyeing or printing materials containing hydroxy groups or carbonamide groups, especially textile materials, they are preferably used in the form of their salts, especially alkali metal salts or alkaline earth metal salts, which are alkaline-stable. It can provide dyed products with excellent build-up properties, good fiber affinity, and excellent various fastnesses and level dyeing properties.

Among the compounds of the present invention represented by the above general formula [1], the following general formula, [wherein X' represents a vinyl group, β-thiosulfatoethyl group or β-sulfatoethyl group, and R' represents a methyl group or an ethyl group, and M represents sodium or potassium. ] Compounds represented by these are particularly preferred.

These compounds of the present invention are prepared by reacting an anthraquinone compound represented by the general formula (4) or a salt thereof with 2,4,6-dolychlor or fluoro-S-triazine (cyanuric chloride or fluoride) in equimolar amounts. General formula (2) [in the formula Z
has the meaning given above. ] Obtain a dihalogenotriazinyl compound or a salt thereof,
This is reacted with an amino compound represented by the general formula (3) % formula % (31 [wherein R, A and Easily produced by reacting a metal compound or a salt thereof with a dihalogenotriazinyl compound represented by the general formula (5) [wherein R, A, Z and X have the above-mentioned meanings] can do.

The condensation of the anthraquinone compound represented by general formula (4) or a salt thereof with cyanuric chloride or fluoride is generally carried out in an aqueous medium or an aqueous organic solvent at -5°C to +30°C, preferably from O'C to +io°C. at a temperature of 8-9, preferably 5-8
Perform at a pH of . The condensation reaction between the dihalogenotriazinyl compound represented by general formula (2) or its salt and the aromatic amine represented by general formula (3) is carried out at θ°C to 70°C, preferably 0°C to 5°C.
It can be carried out at a temperature of 0°C. The reaction between the anthraquinone compound represented by the general formula (4) or its salt and the dihalogenotriazinyl compound represented by the general formula (5) is generally carried out in an aqueous medium at 0°C to 60°C, preferably in the presence of an organic solvent if necessary. At a temperature of 0°C to 50°C, 8 to 9, preferably 5 to 8
Perform at a pH of .

The hydrogen chloride liberated in the condensation reaction is reacted with an acid binder, such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium bicarbonate, sodium acetate or basic sodium phosphate. .

Isolation of the compounds of the invention of the general formula fl from the reaction solution is carried out according to generally known methods, for example by precipitation from the reaction medium with an electrolyte, such as sodium chloride or potassium chloride, or by evaporation of the reaction solution.
An example is carried out by spray drying (buffer substances can be added to the reaction solution).

Substituent in the amine compound represented by general formula (3)
Examples of R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5ec-butyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 8-hydroxypropyl group, 2-hydroxy Butyl group, 4-hydroxybutyl group, 1-methyl-2-hydroxypropyl group, cyanomethyl group, cyanethyl group, methoxymethyl group, 2-methoxyethyl group,
3-methoxypropyl group, ethoxymethyl group, 2-ethoxyethyl group, chloromethyl group, 2-chloroethyl group,
8-chloropropyl group, 4-chlorobutyl group, carboxymethyl group, 2-carboxyethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 2-ethoxycarbonylmethyl group, 2-ethoxycarbonylmethyl group, sulfomethyl group, 2- Examples of the acid residue A include a sulfoethyl group, and examples of the acid residue A include [In the formula, the bond indicated by an asterisk means a bond that is connected to the N-group. ] and so on.

and X is the group -5O2CH= CH2 or the group -502
CH2CH2Y represents a group in which Y is a group that can be eliminated with an alkali, such as a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, a halogen atom, etc. , has fiber reactivity and can be used for dyeing or printing hydroxy group-containing or carbonamide group-containing materials. Preferably, the material is used in the form of a fibrous material or a blend thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinyl alcohol. The cellulosic fiber material is preferably cotton, but also other vegetable w4#a such as linen, hemp, jute and ramie fibers. Examples of regenerated cellulose fibers include viscose staple and filament viscose.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-4. 1 The compound of the present invention can be dyed or printed on the above-mentioned materials, especially on the above-mentioned fiber materials, by a method depending on the physical and chemical properties. 'For example, when exhaust dyeing is carried out on cellulose fibers, in the presence of an acid binder such as soda carbonate, sodium phosphate, or caustic soda, neutral salts such as mirabilite or common salt are optionally added, and if desired, a solubilizing agent is added. Using agents, penetrants or leveling agents together,
It is carried out at relatively low temperatures. The neutral salts which accelerate the exhaustion of the dyestuff can be added only after the actual dyeing temperature has been reached, or even before then, optionally in portions. 1 When dyeing cellulose delicates according to the padding method, it can be padded at room temperature or at an elevated temperature, dried and then fixed by steaming or dry heat.

When printing cellulose fibers, printing is carried out either in one phase, e.g. by printing with a printing paste containing baking soda or other acid binders and then steaming at 100-160°C, or in two phases, e.g. This can be carried out by printing with an acidic or weakly acidic printing paste, passing it through a hot alkaline bath containing an electrolyte, or overpadding with a padding liquid containing an alkaline electrolyte and steaming or dry heat treatment.

Thickening agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used in the printing pastes, if desired in combination with customary printing aids and/or dispersants, such as, for example, urea.

Suitable acid binders for fixing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali under heated conditions. Particular mention may be made of alkali metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, among which preference is given to n, -da salts and potassium salts. Examples of such acid binders include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium acid, sodium silicate, sodium trichloroacetate and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers is first carried out by exhaustion under the control of P and H values from an acidic or weakly acidic dye bath, and then at a neutral or sometimes alkaline pH value for fixation. This can be done by changing. Dyeing is usually carried out at a temperature of 60 to 120'C, but in order to achieve leveling properties, conventional leveling agents, such as cyanuric chloride and
It is also possible to use condensation products of twice the molar amount of the amine benzene/sulfonic acid or aminonatutalenesulfonic acid or addition products of, for example, stearylamine and ethylene oxide.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials.It is particularly suitable for dyeing cellulose fiber materials, and has good light resistance, sweat resistance, sunlight resistance, and moisture resistance. It has properties such as washing resistance, peroxide washing resistance, chlorine water resistance, chlorine bleaching resistance, sweat resistance, acid hydrolysis resistance and alkali resistance, as well as good abrasion resistance and ironing resistance. In terms of build-up properties, level dyeing properties and wash-off properties, as well as good solubility and high exhaustion and fixation properties, dyed products with stable quality that are not affected by fluctuations in dyeing temperature and dye bath ratio are obtained. Has characteristics.

The present invention will be explained in detail below with reference to Examples.

In the examples, parts and % represent parts by weight and weight Ji%, respectively.

Example 1 1-amino-4-(8'-amino-2
/ , 4/ , 6'-trimethyl-57-sulfophenylamino)-anthraquinone-2-sulfonic acid 58
, (pH-value 7.5-8.0) is added dropwise to a suspension containing 19 parts of cyanuric chloride in 150 parts of ice water.

The temperature of the reaction mixture is cooled to 0-5 DEG C. and the pH value is simultaneously maintained at 6-7 by dropwise addition of sodium carbonate solution.

Stirring is continued for a further 2 hours at this temperature and this pH value until the condensation is complete. A neutral solution containing 82 parts of N-methylaniline-8-β-sulfatoethylsulfone in about 150 parts of water is then added to this mixture. The reaction mixture is heated to 60° C. and stirred at this temperature for 2 hours. The pH value was then adjusted to 6.0 by dropwise addition of aqueous sodium carbonate solution.
5-7, keep it at 0. Then 5 parts of disodium phosphate are added and the synthesized compound is isolated by spray drying.

A black-blue electrolyte-containing powder is thus obtained, which contains the sodium salt of the compound of formula. This anthraquinone compound is eminently suitable as a dye. This can be applied and fixed on the textile materials mentioned in the specification according to the application-and fixing-methods customary in the art for fiber-reactive dyes. Due to its reactive nature, clear blue dyeings and reddish prints are obtained, for example on cotton. It is extremely light and wash resistant.

Example 2 Process according to Example 1. However, in the second condensation step, N-
Methylaniline-4-β-sul compound (general formula (3))
Use the equivalent weight of The compounds prepared according to the invention dye wool or cotton, for example, in clear reddish-blue tones which likewise have very good wet resistance.

Example Amino compound (3) 4 N-methylaniline-3-β-thiosulfatoethylsulfone 5 N-ethylaniline-8-β-chloroethylsulfone 6 N-β-hydroxyethylaniline-4-β-sulfone Artethylsulfone 7 N-β-cyanoethylaniline-3-β-sulfa-toethylsulfone 8 N-methoxycarbonylethylaniline-3-β-
Sulfatoethylsulfone 9 N-β-carboxyethylaniline-4-β-sulfatoethylsulfone 10 N-β-ethoxyethylaniline-3-β-sulfatoethylsulfone 11 N-ethylaniline-3-β- Phosphate ethyl sulfone 12 N-ethylaniline-8-β-acetoxyethyl sulfone 1B 2' -N-ethylaminonaphthalene-6-β
-Sulfatoethylsulfone 142-N-methylamino-6-sulfonaphthalene-8
-β-Sulfatoethylsulfone 152-N-ethylaminonaphthalene-8-β-hinylsulfone 162-N-β-carbamoylethylamino-8-sulfonaphthalene-6-β-sulfatoethylsulfone Usage Example 1 Example Compound 15 according to the invention (f15 to urea 50
1 part in 200 parts of hot water.

Add 40 parts of sodium alkinate and 9 parts of water to the solution with stirring.
400 parts of glue consisting of 60 parts and 2 parts of sl-IJum bicarbonate
Add 0 parts. The mixture is then made up to 1000 parts with water and glue. This printing paste is used to print cotton fabrics. After drying, steam at 101-IO3°C for 5 minutes, wash with cold water, then hot water, boil soap, wash again and dry. A reddish-blue print is thus obtained which has very good wet fastness properties.

Usage example 2: 100 parts of wool top was pre-washed using a conventional method and treated with C12C.
14 - Added at 40 DEG C. to 8000 parts of an aqueous dyebath containing 1 part of an auxiliary agent prepared by oxyethylation of a 14-fatty amine with 5 mol of ethylene oxide and 2 parts of ammonium acetate.

A pH value of 4.8-5 is set using acetic acid.

Process the material in this bath for 5 minutes. 1.5 parts of the compound according to the invention (Example 8) dissolved in the hedge water are then added. Heat the dye liquor to boiling temperature within 30 minutes and leave the product at 60%
Dye at this temperature for minutes. The dyeing obtained is then washed with water, acidified, washed again and dried. The resulting dyeing of the wool top exhibits a clear deep blue color with a reddish tone, which has very good light and wet fastness and excellent leveling properties.

Claims (1)

[Claims] 1) General formula +1) [In the formula, R is an alkyl group having 1-4 carbon atoms,
It represents a hydroxy-substituted alkyl group, a cyano-substituted alkyl group, an alkoxy-substituted alkyl group, a halogen-substituted alkyl group, a carboxy-substituted alkyl group, a carbamoyl-substituted alkyl group, an alkoxycarbonyl-substituted alkyl group, or a sulfo-substituted alkyl group. A is selected from the group consisting of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine and sulfonic acid group, or ③ is substituted with two substituents and is a temoyoiphenylene residue or one sulfonic acid group; Represents an optionally substituted naphthylene residue. Z represents a chlorine atom or a fluorine atom. X is the group -5O2CH=CH
2 or a group ~5O2CH2CH2Y. Here, Y is a group that leaves as an anion with an alkali. ] An anthraquinone compound or a salt thereof. 2) General formula (2) [In the formula, Z represents a chlorine atom or a fluorine atom. ] An anthraquinone compound represented by or a salt thereof and general formula (3) R H-N-A-x
(3) [wherein, R
-Alkyl group having 4 carbon atoms, hydroxy-substituted alkyl group, cyanogen-substituted alkyl group, alkoxy-substituted alkyl group, halogen-substituted alkyl group, carboxy-substituted alkyl group, carbamoyl-substituted alkyl group, alkoxycarbonyl-substituted alkyl group , or represents a sulfo-substituted alkyl group. A is a methyl group, an ethyl group, a methoxy group,
Represents a phenylene residue optionally substituted with one or two substituents or a naphthylene group optionally substituted with one sulfonic acid group selected from the group of ethoxy group, chlorine, bromine, and sulfonic acid group . X is a group -5O2CH=
Represents CH2 or the group -502CH2CH2Y. Here, Y is a group that leaves as an anion with an alkali. ] or an anthraquinone compound represented by the general formula (4), or a salt thereof, and the general formula (6) [wherein RlA, Z and X have the above-mentioned meanings. ] General formula (1) characterized by reacting with a dihalogenotriazinyl compound represented by [In the formula, R, A, Z and X have the above-mentioned meanings. ] A method for producing an anthraquinone compound or a salt thereof. 3) General formula (1) [wherein R is an alkyl group having 1-4 carbon atoms,
Hydroxy-substituted alkyl group, cyanogen-substituted alkyl group,
Alkoxy-substituted alkyl group, halogen-substituted alkyl group,
It represents a carboxy-substituted alkyl group, a carbamoyl-substituted alkyl group, an alkoxycarbonyl-substituted alkyl group, or a sulfo-substituted alkyl group. A is one phenylene residue or sulfonic acid group optionally substituted with one or two substituents selected from the group of methyl group, ethyl group, methoxy group, ethoxy group, chlorine, bromine, and sulfonic acid group represents a naphthylene residue which may be substituted with Z represents a chlorine atom or a fluorine atom. X is a group -802CH, -CH
2 or the group -502CH2CH2Y. Here, Y is a group that leaves as an anion with an alkali. ] A method for dyeing or printing a hydroxy and/or carbonamide group-containing material, characterized by using an anthraquinone compound or a salt thereof.