JPH0464342B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel fiber-reactive compounds. More specifically, the present invention relates to the following general formula (1) [Wherein, R is an alkyl group having 1 to 4 carbon atoms, 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 group. Represents a substituted alkyl group or a sulfo-substituted alkyl group. A is a methyl group, an ethyl group, a methoxy group,
Phenylene residue or sulfonic acid group optionally substituted with one or two substituents selected from the group of ethoxy group, chlorine, bromine and sulfonic acid group 1
Represents a naphthylene residue optionally substituted with . Z represents a chlorine atom or a fluorine atom. X represents _a group _-SO2CH = _CH2 or _a group _-SO2CH2CH2Y . 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. When the anthraquinone compound represented by the above general formula (1) is used for dyeing or printing materials containing a hydroxyl group or an albonamide group, especially textile materials, it is preferably in the form of its salt, especially an alkali metal salt or an alkali metal salt. Used in the form of earth metal salts, they have excellent alkali stability, good build-up properties, good fiber affinity, and can provide dyed products with 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, [In the formula, X' represents a vinyl group, a β-thiosulfatoethyl group, or a β-sulfatoethyl group,
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 have the general formula (4) An anthraquinone compound represented by the formula (2) or a salt thereof is reacted with 2,4,6-trichlor or fluoro-S-triazine (cyanuric chloride or fluoride) in equimolar amounts. [In the formula, Z has the above-mentioned meaning. ] A dihalogenotriazinyl compound or a salt thereof is obtained, and this is expressed by the general formula (3). [In the formula, R, A and Z have the above-mentioned meanings. ] or react with an amino compound represented by
An anthraquinone compound represented by general formula (4) or a salt thereof and general formula (5) [In the formula, R, A, Z and X have the above meanings. ] It can be easily produced by reacting with a dihalogenotriazinyl compound represented by the following. The condensation of the anthraquinone compound represented by general formula (4) or its salt with cyanuric chloride or fluoride is generally carried out in an aqueous medium or an aqueous organic solvent at -5°C to +30°C.
3 to 9 °C, preferably at a temperature of 0 °C to +10 °C,
Preferably it is carried out at a pH of 5-8. 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 0 to 70
It can be carried out at a temperature of 0°C to 50°C, preferably 0°C to 50°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 at 0°C to 60°C, preferably in an aqueous medium, optionally in combination with an organic solvent. 0℃~
It is carried out at a temperature of 50°C and a pH of 3-9, preferably 5-8. Hydrogen chloride liberated in the condensation reaction can be treated with acid binders such as sodium or potassium hydroxide, carbonate, etc.
React with sodium or potassium bicarbonate, sodium acetate or basic sodium phosphate. Isolation of the compound of the invention of the general formula (1) 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 precipitation from the reaction medium with an electrolyte, such as sodium chloride or potassium chloride. This is carried out by evaporation of the solution, for example by spray drying (buffer substances can be added to the reaction solution). Examples of the substituent R in the amino compound represented by general formula (3) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, hydroxymethyl group, 2-hydroxyethyl group, 2- Hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 4-
Hydroxybutyl group, 1-methyl-2-hydroxypropyl group, cyanomethyl group, cyanoethyl group, methoxymethyl group, 2-methoxyethyl group,
3-methoxypropyl group, ethoxymethyl group, 2
-Ethoxyethyl group, chloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorobutyl group, carboxymethyl group, 2-carboxyethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 2-methoxycarbonylethyl group group, 2-ethoxycarbonylmethyl group, sulfomethyl group, 2-sulfoethyl group, etc., and as the formula residue A, for example,

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【formula】 [In the formula, the bond indicated with an asterisk is

[Formula] means a bond that leads to a group. ] and so on. and X is a group -SO ₂ CH=CH ₂ or a group -
represents SO ₂ CH ₂ CH ₂ Y, where Y is a group that is eliminated with an alkali, such as a sulfate ester group,
This includes a thiosulfate group, a phosphate group, an acetate group, a halogen atom, and the like. The compound of the present invention 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 fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, 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. It is. The compounds of the present invention can be dyed or printed on the above-mentioned materials, in particular on the above-mentioned fiber materials, in a manner depending on their 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, caustic soda, etc., a neutral salt, such as mirabilite or common salt, is optionally added and, if desired, dissolved. It is carried out at relatively low temperatures using auxiliaries, penetrants or leveling agents. 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. When dyeing cellulose fibers according to the padding method, after padding at room temperature or elevated temperature and drying,
It can be fixed by steaming or dry heat. When printing is carried out on cellulose fibers, it can be carried out in one phase, for example by printing with a printing paste containing baking soda or other acid binders and then steaming at 100-160°C, or in two phases. For example, it can be carried out by printing with a neutral 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, followed by 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 auxiliaries 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 moderate inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Such acid binders include, for example, caustic soda, caustic potash, baking soda, soda carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium phosphate,
Examples include sodium silicate and sodium trichloroacetate. Dyeing of synthetic and natural polyamide and polyurethane fibers begins with an acidic or weakly acidic dye bath.
This can be carried out by controlling the pH value of the pH and then changing the pH value to neutral, or even alkaline, for fixation. Dyeing is usually carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, conventional leveling agents such as a condensation product of cyanuric chloride and 3 times the mole of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, addition products of stearylamine and ethylene oxide can also be used. The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing textile materials.
Especially suitable for dyeing cellulose fiber materials, good light fastness and sweat resistance, good moisture resistance, such as washing resistance, peroxidation washing resistance, chlorine water resistance, chlorine bleaching resistance, sweat resistance , has acid hydrolysis resistance and alkali resistance, as well as good abrasion resistance and ironing resistance. In addition, it has excellent build-up properties, level dyeing properties, and wash-off properties, as well as good solubility and high exhaustion and fixation properties, making it possible to produce dyed products of stable quality that are less affected by fluctuations in dyeing temperature and dye bath ratio. It is characterized by the fact that it is The present invention will be explained in detail below with reference to Examples. In the examples, parts and % represent parts by weight and % by weight, respectively. Example 1 1-Amino-4-(3'-amino-
A solution containing 53.1 parts of 2',4',6'-trimethyl-5-sulfophenylamino)-anthraquinone-2-sulfonic acid (PH-value 7.5-8.0) was mixed with 19 parts of cyanuric chloride in 150 parts of ice water. dropwise into the containing suspension. 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 32 parts of N-methylaniline-3-β-sulfatoethylsulfone in about 150 parts of water is then added to this mixture. Reaction mixture at 60℃
and stir at this temperature for 2 hours. At this time, PH
− value by dropwise addition of aqueous sodium carbonate solution.
Keep it between 6.5 and 7.0. 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 has the formula It contains a sodium salt of a compound [λ _nax =630 nm (in an aqueous medium, the same applies hereinafter)]. 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 their reactive nature, clear blue dyes 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, instead of N-methylaniline-4-β-sulfatoethylsulfone, N-ethylaniline-
35 parts of 4-β-thiosulfate ethyl sulfone are used. After the end of the reaction, the reaction solution is cooled to room temperature, the synthesized compound is precipitated with 80 parts of potassium chloride, suctioned off, washed with 20% aqueous potassium chloride solution, dried at 60° C. under reduced pressure and ground. A black-blue electrolyte-containing powder is thus obtained, which has the formula The sodium/potassium salt of the compound (λ _nax =
630nm). The anthraquinone compounds are eminently suitable as dyes, for example on cotton and wool from aqueous-alkaline or weakly acidic dye liquors according to the customary exhaustion and padding methods or as print dyes. Produces blue staining or reddish printing. Example 3 Process according to Example 1. However, in the second condensation step, 27 parts of N-carbamoylaniline-4-vinylsulfonylaniline are used instead of N-methylaniline-3-β-sulfatoethylsulfone. The post-treatment was carried out according to Example 1, and a dye powder was obtained, which had the formula Contains the sodium salt of the compound (λ _nax =630 nm). This is normal dyeing for reactive dyes.
and according to the printing process produces reddish-blue tones with very good wet resistance on cotton and wool. Examples 4-16 Process according to the process described in the above examples. In this case, an equivalent amount of the amino compound (general formula (3)) described below is used in the second condensation step. The compounds prepared according to the invention dye, for example, wool or cotton 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-3-β-chloroethylsulfone 6 N-β-hydroxyethylaniline-4-β
-Sulfatoethylsulfone 7 N-β-cyanoethylaniline-3-β-sulfatoethylsulfone 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-phosphatoethylsulfone 12 N-ethylaniline-3-β-acetoxyethylsulfone 13 2-N-ethylaminonaphthelene-6-β-
Sulfatoethylsulfone 14 2-N-methylamino-6-sulfonaphthalene-8-β-sulfatoethylsulfone 15 2-N-ethylaminonaphthalene-8-β-
Vinyl sulfone 16 2-N-β-carbamoylethylamino-8
-Sulfonaphthalene-6-β-sulfatoethylsulfone The compounds according to the invention in Examples 4 to 16 are all λ _nax
=630nm. Application Example 1 15 parts of the compound according to the invention from Example 1 are dissolved together with 50 parts of urea in 200 parts of hot water. 400 parts of a glue consisting of 40 parts of sodium alginate and 960 parts of water and 20 parts of sodium bicarbonate are added to the solution with stirring. 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 101-103°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: Wash 100 parts of wool top in advance using the usual method and apply C ₁₂
The _-C14 -fatty amine is added at 40 DEG C. to 3000 parts of an aqueous dyebath containing 1 part of the auxiliary prepared by oxyethylation with 5 mol of ethylene oxide and 2 parts of ammonium acetate. The pH value is adjusted to 4.8-5 using acetic acid. Process the material in the bath for 5 minutes. 1.5 parts of the compound according to the invention (Example 3) dissolved in a small amount of water are then added. The dye liquor is heated to boiling temperature within 30 minutes and the product is dyed at this temperature for 60 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) [Wherein, R is an alkyl group having 1 to 4 carbon atoms, 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 group. Represents a substituted alkyl group or 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 selected from the group of ethoxy group, chlorine, bromine, and sulfonic acid group, or a naphthylene residue optionally substituted with one sulfonic acid group . Z represents a chlorine atom or a fluorine atom. X represents _a group _-SO2CH = _CH2 or _a group _-SO2CH2CH2Y . 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) [Wherein, R is an alkyl group having 1 to 4 carbon atoms, 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 group. Represents a substituted alkyl group or 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 selected from the group of ethoxy group, chlorine, bromine, and sulfonic acid group, or a naphthylene group optionally substituted with one sulfonic acid group.
X represents _a group _-SO2CH = _CH2 or _a group _-SO2CH2CH2Y . Here, Y is a group that leaves as an anion with an alkali. ] or react with an amino compound represented by formula (4) An anthraquinone compound represented by or a salt thereof and general formula (5) [In the formula, R, A, Z and X have the above meanings. ] General formula (1) characterized by reacting with a dihalogenotriazinyl compound represented by [In the formula, R, A, Z and X have the above meanings. ] A method for producing an anthraquinone compound or a salt thereof. 3 General formula (1) [Wherein, R is an alkyl group having 1 to 4 carbon atoms, 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 group. Represents a substituted alkyl group or 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 selected from the group of ethoxy group, chlorine, bromine, and sulfonic acid group, or a naphthylene residue optionally substituted with one sulfonic acid group . Z represents a chlorine atom or a fluorine atom. X represents _a group _-SO2CH = _CH2 or _a group _-SO2CH2CH2Y . 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.