JPS6092357A - Anthraquinone compound and dyeing or printing method using the same - Google Patents

Abstract

NEW MATERIAL:Anthraquinone compounds of formula I wherein X is halogen; Y is -SO2CH=CH2, -SO2CH2CH2Z (whrerin Z is a group which can be removed by the action of an alkali); A is (substd.)phenylene, (substd.)naphthylene; R1 is H, (substd.)alkyl; m is 0, 1; n is 2-6; and salts thereof. USE:Reactive dyes which dye or print materials contg. hydroxyl or carbonamide groups such as cellulose fiber materials, polyamide fiber materials and wool blue. PREPARATION:An anthraquinone compd. (salt) of formula II, a compd. of formula III and a trihalogenotriazine are condensed together in an aq. medium at a pH of 2-9.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anthraquinone compound and a method for dyeing or printing using the anthraquinone compound. Y is -8O2CH=CH2
i Taha-802CH2CH2Z, Z Hi Luka!
j (7) A group which is eliminated by action, A is a phenylene group or a naphthylene group which may have a substituent, and Rx is a hydrogen atom or a lower alkyl group which may be substituted. m represents o, l or 2, and n represents an integer from 2 to 6. ) and a method for dyeing or printing textile materials using the anthraquinone compound or its salt.

In the general formula α), the halogen atom represented by X is particularly preferably chlorine, bromine or fluorine.

Examples of the group represented by 2 which is eliminated by the action of an alkali include a sulfate ester group, a thiosulfate ester group, a phosphate ester group, an acetate ester group, and a halogen atom.

A is preferably selected from the group of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo groups,
A phenylene group which may be substituted with one or two substituents or a naphthylene group which may be substituted with one sulfo group, such as 1 (in the formula, the bond shown with an asterisk is -N - refers to a bond that leads to a group.] etc.

In R1, the lower alkyl group is preferably an alkyl group having -4 carbon atoms, and the optionally substituted groups include a hydroxy group, a cyano group, an alkoxy group, a halogen group, a carboxy group, and a carbamoyl group. , alkoxycarbonyl group, alkylcarbonyloxy group,
A sulfo group and a sulfamoyl group are preferred.

Particularly preferable examples of R1 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a 1so-propyl group,
11-butyl group, 1so-butyl group, 5ee-butyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 8-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group ,
2.3-dihydroxypropyl group, 8.4-dihydroxybutyl group, cyanomethyl group, 2-cyanoethyl group, 8
-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group,
8-methoxypropyl group, 8-ethoxypropyl group, 2
-Hydroxy-8-methoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 8-chloropropyl group, 8-bromopropyl group, 4-chlorobutyl group, 4-bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 1,2-dicarboxyethyl group, carbamoylmethyl group, 2-carbamoylethyl group, 8-carbamoylpropyl group, 4-carbamoylbutyl group , methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 8-methoxycarbonylpropyl group, 3-ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group, 4-ethoxy Carbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 3-methylcarbonyloxypropyl group, 8-
Ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-4sulfobutyl group, sulfamoylmethyl group, 2 -sulfamoylethyl group, 8-sulfamoylpropyl group, and 4-sulfamoylbutyl group.

The compounds of the invention are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts, especially the soda, potassium and calcium salts.

The compound of the present invention can be produced, for example, in the following manner.

An aminoanthraquinone compound or a salt thereof represented by the following general formula (II) (wherein m and n have the above-mentioned meanings) and the following general formula (III) 1 (wherein R1, A, and Y are the above-mentioned ) in any order in an aqueous medium, secondly at a temperature of -1oC to 40'C with adjustment to pH 2 to pH 9, secondarily at a temperature of 20C to 70C. I) II at °C
The compound of general formula (i) or a salt thereof is condensed with a trihalogenotriazine represented by the following general formula (IV) (wherein, X has the above-mentioned meaning) while adjusting the pH to 2 to 9. Obtainable.

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 AM 1m material or its regenerated products and polyvinyl alcohol. The cellulose fibers are preferably made of cotton, and other vegetable fibers, such as linen, hemp, jute, and wool E-mW. Regenerated cellulose fibers are, for example, hiscose stable 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.

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 m-fibers, in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate, or caustic soda, a neutral salt such as mirabilite or common salt is optionally added.
If desired, solubilizers, penetrants or leveling agents are used in combination and the process 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.

When dyeing cellulose fibers according to the padding method, it can be padded at room temperature or at an elevated temperature and, after drying, fixed by steaming or dry heat.

When printing is carried out on cellulose fibers, 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, 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 medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Examples of such acid binders include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary, or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate, and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers involves first exhaustion under pH control from an acidic or slightly acidic dye bath and then changing to a neutral or even alkaline pH value for fixation. This can be done by Dyeing can usually be 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 8 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 mia materials. Especially suitable for dyeing cellulose fiber materials, good light fastness and sweat resistance, good moisture resistance, such as washing resistance, peroxidation washing resistance, sweat resistance, acid hydrolysis resistance and It is alkaline and also has 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 parts represent parts by weight and i% by weight, respectively.

Example 1 9.2 parts of cyanuric chloride is added to 100 parts of water at 5 to 10°C and dispersed.

A solution prepared by dissolving 14 parts of 1-aminobenzene-4-β-sulfatoethyl sulfone in 1.00 parts of water at a pH of 4 to 5 was added to this solution for 1 hour while adjusting the pH to 4 to 5 with a 20% aqueous sodium carbonate solution. and stirred at the same temperature for an additional 8 hours.

Then, sodium 1-amino-4-(8'-aminopropylamino)-anthraquinone-2-sulfonate 20
A suspension of 200 parts of water was added to the above reaction solution at a temperature of 40 to 50°C while adjusting the pI (6 to 7) with a 20% aqueous sodium carbonate solution. Stir for an additional 5 hours.

40 parts of sodium chloride was added to this solution to precipitate crystals, which were filtered under suction, washed, and dried at 60° C. to obtain an anthraquinone compound having the structural formula of the manure.

Ul (λmax 53Qnm) Examples 2 to 17 In place of 1-amino-4-(8'-aminopropylamino)-anthraquinone-2-sulfonic acid of Example 1, a compound of general formula (II) having the following structure, In place of 1-aminobenzene-4-β-sulfatoethyl sulfone, a compound of general formula (II') having the following structure can also be carried out using a compound of general formula (IV) having the following structure in place of cyanuric chloride. Corresponding anthraquinone compounds were obtained in the same manner as in Example 1.

(15) (16) Example 18 Anthraquinone compound o, t, o, a described in Example 1
and 0.6 parts of each were dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, the temperature was raised to 60°C, 4 parts of soda carbonate was added, and dyeing was carried out for 1 hour. After washing with water, soaping, washing and drying, it has excellent fastness to sunlight, sweat, and sunlight.
A bright blue dyed product with good build-up properties was obtained.

This compound has good level dyeing properties and dyeing reproducibility.

Example 19 0.8 part of the anthraquinone compound described in Example 4 was added to 20
Add 0 parts, add 10 parts of cotton, and raise the temperature to 50°C. After 30 minutes, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping yielded a bright blue dyed product with excellent fastness to sunlight, sweat and sunlight.

Example 20 1-N-ethylaminobenzene-4-β- in 200 parts of water
15.5 parts of sulfate ethyl sulpone at p'E14~
5 and cooled to 5-10°C, cyanuric chloride 9
．． Add 2 parts p)I4 with 15% aqueous sodium carbonate solution.
Stir at 5-10° C. for 8 hours while adjusting the temperature to 5-5.

Then, sodium 1-amino-4-(6'-aminohexylamino)-anthraquinone-2-sulfonate 21
1 part suspended in 200 parts of water was added to the above reaction solution, and 1
Stir at 80-85° C. for 8 hours while adjusting the pH to 6-7 with a 5% aqueous sodium carbonate solution. 60 parts of sodium chloride was added to this solution to precipitate crystals, which were filtered under suction, washed, and dried at 60°C to obtain an anthraquinone compound having the following structural formula.

Examples 21 to 28 In place of 1-amino-4-(6'-aminohexylamino)-anthraquinone-2-sulfonic acid in Example 20, a compound of general formula (II) having the following structure was substituted with 1-N-ethyl Example 20 was carried out by using a compound of general formula (m) having the following structure in place of aminobenzene-4-β-sulfatoethyl sulfone and a compound having general formula (IV) having the following structure in place of cyanuric chloride. Corresponding anthraquinone compounds were obtained in the same manner.

Example 29 Anthraquinone compound described in Example 20 0.110.
8 and 0.6 parts each in 200 parts of water, and 20 parts of Glauber's salt.
1 part, add 10 parts of cotton, and raise the temperature to 70°C. Then, after 80 minutes had passed, 8 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were carried out to obtain a bright blue dyed product having excellent fastness to sunlight, sweat and old light, and good build-up properties.

This compound also has excellent solubility, and has good level dyeing and dyeing reproducibility.

Example 80 0.8 part of the anthraquinone compound described in Example 22 was added to 2
Dissolve in 0.00 parts of water, add 20 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 60'C. Then, after 20 minutes, 8 parts of tribasic sodium phosphate is added. Dye for 1 hour at that temperature.

After dyeing, washing with water and soaping yielded a bright blue dyed product with excellent fastness (25).

Example 31 Color paste composition Anthraquinone compound described in Example 1 5 parts Urea 5 parts Sodium alginate (5 parts) Base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 18 parts The color paste having the above composition was mercerized. The print is printed on processed cotton broadcloth, and after intermediate drying, steaming is performed at 100°C for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying to finish.

In this way, a bright blue print with excellent color fastness was obtained.

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Claims (1)

[Claims] 1) The following general formula (wherein, X is a halogen atom, Y is -8020H=CH2
t f: bar 8020H20H2Z, Z is a group that leaves by the action of alkali, A is a phenylene group or naphthylene group that may have a substituent, lh is a hydrogen atom or a lower alkyl group that may be substituted . m represents 0.1 or 2, and n represents an integer from 2 to 6. ) (1) An anthraquinone compound or a salt thereof. 2) The following general formula (wherein, X is a halogen atom, Y is -802CH=OH2
t t knee bar 802CH2CH2Z 1Z huff
# A group that is eliminated by the action of potash, A is a phenylene group or naphthylene group that may also have a substituent, R1
represents a hydrogen atom or an optionally substituted lower alkyl group. m represents 0, 1 or 2, and n represents an integer from 2 to 6. ) A method of dyeing or printing textile materials using an anthraquinone compound or its salt.