JPS59174649A - Monoazo compound and dyeing or textile printing using the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X is halogen; Y is -SO2CH=CH2 or -SO2CH2CH2Z (Z is group capable of being eliminated by alkali; A is (substituted) phenylene or naphthylene; B is (substituted) phenyl or napthyl; R1 is (substituted) lower alkyl; R2 is H or (substituted) lower alkyl; R3 is H, methyl, or sulfo; R4 is methyl, carboxy, etc.; R5 is OH or amino] and its salt. EXAMPLE:A compound of formula II. USE:Dye for dyeing esp. cellulose fibrous material yellow with high humidity and light resistance and high sweat resistance under sunlight. PREPARATION:For example, an aromatic sulfonic acid (salt) of formula III and another compound of formula IV are subjected, in an aqueous medium, to condensation with a trihalogenotriazine of formula V to prepare a compound of formula VI (or its salt while adjusting primarily at -10-40 deg.C and a pH 2-9 and secondarily at 20-70 deg.C and a pH 2-9. This compound is then diazotized followed by coupling, at -10-50 deg.C and a pH 4-10, with a pyrazolone derivative of formula VII.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a monoazo compound and a method of dyeing or printing using the same. For more details, refer to the following general formula (
I) (wherein, X is a halogen atom, Y is -502CH=CH
2 or -5O2CH2CH2Z, Z is a group that leaves by the action of an alkali, A is a phenylene group or naphthylene group which may have a substituent, B is a phenyl group or naphthyl group which may have a substituent. Representation, R
1 is an optionally unsubstituted lower alkyl group, R2 is a hydrogen atom or an optionally substituted lower alkyl group, R3 is a hydrogen atom, a methyl group or a sulfo group, R4 is a methyl group, a carboxyl group or a methoxycarbonyl group, represents a hydroxyl group or an amine group. ) The present invention relates to a monoazo compound or a salt thereof, and a method for dyeing or printing using the monoazo compound or a salt thereof.

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

Examples of the group represented by Z 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, and means, for example, a continuous bond. ), etc.

In addition to R1 and R2, the lower alkyl group is Teha, 1
- An alkyl group having 4 carbon atoms is preferred, and optionally substituted groups include a hydroxy group, a cyano group, an alkoxy group, a halogen group, a carboxy group, and a carbamoy group.

Preferred are a carbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, and a sulfamoyl group.

Particularly preferable R1' + R2 include, for example, a methyl group, an ethyl group, an n-propyl group, and is.

-probyl group, n-butyl group, 1so-butyl group, 5e
c-butyl group, 2-hydroboxydiethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxy group, thyl group, 2,3-dihydroxypropyl group Base, 3.
4-dihydroxybutyl group, cyanomethyl group, 2-cyanoethyl group, B-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxy Propyl group, 2-hydroxy-3-methoxypropyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group, 2-bromoethyl group, 3-chloropropyl group, 3-
Bromopropyl group, 4-chlorobutyl group, 4-bromobutyl group, carboxymethyl group, 2-carboxyethyl group, 8-carboxypropyl group, 4-carboxybutyl group, 1,2-dicarboxyethyl group, carbamoylmethyl group, 2 -Carbamoylethyl group, 3-carbamoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 3- Ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group, 4-ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxy 1-methyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 3- Methylcarbonyloxypropyl group, 3-ethylcarbonyloxypropyl group, 4-methylcarbonyloxyphthyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfobutyl group, 3-sulfopropyl group, 4-sulfobutyl group, A hydrogen atom can be mentioned only in the case of sulfamoylmethyl group, 2-sulfamoylethyl group, 3-sulfamoylpropyl group, 4-sulfamoylbutyl group and R2.

B is preferably selected from the group of methyl, ethyl, methoxy, halogen, sulfo and carboxy groups,
It is a phenyl group which may be substituted with 1 to 3 substituents, or a naphthyl group which may be substituted with 1 or 2 sulfo groups.

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, potash and carta l-salts.

The compound of the present invention can be produced, for example, by the following purifying process.

Aromatic sulfonic acid or its salt represented by the following general formula (Ill (in the formula, R2 and R3 have the above-mentioned meanings) and the following general formula (III 1 " HN-A-Y (Ill (in the formula, R1 ，
A and Y have the above meanings. ) in an aqueous medium in any order, then at a temperature of -10°C to 40°C to a pH of 2 to pH 9, secondarily at a temperature of 20°C to 70°C. pH2 to pH9
While adjusting to , Y has the above-mentioned meaning 2) or a salt thereof is obtained.Then, the compound of general formula (V) or a salt thereof is diazotized in an aqueous medium by a conventional method to obtain the following general formula (VD( In the formula, R4+ R5+
B has the meaning given above. ) at a temperature of -10°C to 50°C and a pH of 4 to 50°C.
The compound of general formula (I) or a salt thereof can be obtained by coupling while adjusting the amount of 1O.

Alternatively, an aromatic sulfonic acid represented by general formula (II) or a salt thereof and a trihalogenotriazine represented by general formula (W) are mixed in an aqueous medium at a temperature of -1θ°C to 40°C, p
After condensation while adjusting the pH between H2 and pH 9, diazotization is carried out using a conventional method, and coupling is performed with a pyrazolone derivative represented by the general formula (Vl) at a temperature of -10°C to 50°C while adjusting the pH between 4 and 1O, Then, the compound represented by the general formula (1) or a salt thereof can also be obtained by condensing the compound represented by the general formula (2) at a temperature of 20° C. to 70° C. while adjusting the pH to 2 to 9.

Alternatively, a monoacyl compound of the compound represented by the general formula (III) is diazotized and coupled with a pyrazolone derivative represented by the general formula (Vll) at a temperature of -10°C to 50°C while adjusting the pH to 4 to 1O, followed by acid or The acyl group is hydrolyzed at a temperature of 50°C to 100°C in the presence of an alkali to form the following general formula (to) (where Rz
, Rs + R< + R5, B has the above-mentioned meaning 1,) to obtain a compound (or a salt thereof). Then, the formula
or a salt thereof and a compound represented by general formula (2) in an aqueous medium in any order at a temperature of -10
℃ to 40℃ while adjusting the pH to 1) R2 to pH 9, and secondarily adjusting the pH to 2 to 70℃ at a temperature of 20℃ to 70℃.
The compound of general formula (I) or a salt thereof can also be obtained by condensation with trihalogenotriazine represented by general formula (IV) while adjusting to H9.

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 0 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, in the case of exhaust dyeing on cellulose fibers, in the presence of an acid binder such as soda carbonate, sodium phosphate or caustic soda, a neutral salt such as mirabilite or common salt is optionally added, and if desired, a solubilizer is added. , use a penetrant or leveling agent together,
It is carried out at relatively low temperatures. Neutral salts which accelerate the exhaustion of the dyestuff can optionally be added in portions only after or even before the ``actual dyeing temperature'' has been reached.

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.

Such acid binders include, for example, caustic soda, caustic potash, baking soda, soda carbonate, sodium formate, potassium carbonate,
Examples include secondary or tertiary sodium phosphate, sodium silicate, and sodium trichloroacetate.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out first by exhaustion under pH control from an acidic or slightly acidic dye bath, and then by changing the pH value to a neutral or even alkaline one for fixation. It can be done by 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 a synthesis product of cyanuric chloride and 3 times the mole of amine benzenesulfonic 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. Particularly 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 alkali resistance, Furthermore, it has good abrasion resistance and ironing resistance. In addition, it has excellent build-up properties, level dyeing properties, O/wash-off properties, good solubility, high exhaustion/fixation properties, and stable quality dyed products that are not affected by fluctuations in dyeing temperature or dye bath ratio. It is characterized by the fact that it can be obtained.

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 10.1 parts of cyanuric chloride is added to 100 parts of water at 0 to 10°C and dispersed. A suspension of 9.4 parts of 2,4-diaminobenzenesulfonic acid and 100 parts of water, adjusted to pH 6 to 9 with a caustic sorter aqueous solution, was added dropwise at 0 to 5°C.

After dropping, add 20% carbonate sorter solution to pH 7~
Adjust to 8. Next, 35 parts of sodium nitrite is added and dissolved, and 12.7 parts of concentrated hydrochloric acid is injected at 0 to 5°C to diazotize.

This diazo suspension was mixed with 1-(4', 8'-disulfo-
21-Naphthyl)-3-methylpyrazolone (19.2 parts) is dissolved in 150 parts of water at pH 7-8 and added at 0-5°C. During this time, add a 20% sodium carbonate aqueous solution to pH 5-6.
Adjust to. After injecting the diazo suspension, stir at 0 to 5°C until coupling is completed.

Next, 18.6 parts of 1-N-ethylaminobenzene-8-β-sulfatoethyl sulfone was added to adjust the pH to 5-6.
The temperature was raised to 40°C in 2 steps, and the mixture was stirred at the same temperature for 5 hours. 60 parts of sodium chloride was added to this solution to precipitate the product, which was suction filtered, washed, and dried at 60°C to obtain a monoazo compound having the following structural formula.

Examples 2 to 18 In place of 2.4-diaminobenzenesulfonic acid in Example 1, a compound of the general formula (II) having the following structure was used, and in place of l-N~ethylaminobenzene-3-~sulfatoethylsulfone In order to replace the compound on the general formula side of the structure with cyanuric chloride, the compound with the general formula (IVI) of the following structure, l(4F,
Corresponding monoazo compounds were prepared in the same manner as in Example 1, using a compound of general (VD) having the following structure in place of sf-disulfo-2'-naphthyl)-3methylpyrazolone.

Example 19 Monoazo compounds O1, 0, 8 and 0 described in Example 1
, 6 parts each in 200 parts of water, 10 parts of Glauber's salt and 1 part of cotton.
Add 0 parts, raise the temperature to 60℃, add 4 parts of soda carbonate, and add 1 part.
Time staining. After washing with water, soaping, rinsing with water and drying, a bright yellow dyed product was obtained which was excellent in various fastnesses, particularly fastness to sunlight, perspiration and sunlight, and had extremely good build-up properties and good dischargeability.

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

Example 20 200 parts of 0.3 parts of the monoazo compound described in Example 4 are added, 10 parts of cotton are added, and the temperature is raised to 50°C. Then 8
After 0 minutes. Add 4 parts of soda carbonate and dye at the same temperature for 1 hour. After dyeing, washing with water and soaping yielded a bright yellow dyed product with excellent fastness to sunlight, sweat and sunlight.

Example 21 9.2 parts of cyanuric chloride was dispersed in 200 parts of water at 0 to 5°C, and 9.4 parts of 2,4-dicyanobenzenesulfonic acid was added to the solution.
A solution prepared by adjusting the pH to 7 with a caustic soda solution in 100 parts of water is added dropwise at 0 to 5°C over 1 hour.

After dropping, add 20% sodium carbonate aqueous solution to adjust the pH.
Adjust to 7-8. Next, 35 parts of sodium nitrite is added and dissolved, and 12.7 parts of concentrated hydrochloric acid is injected at 0 to 5°C to diazotize. This perilla solution is added at 0 to 5°C to a solution prepared by dissolving 14 parts of 1-(4'-sulfophenyl)-3-carboxypyrazolone in 150 parts of water at a pH of 7 to 8. During this time,
Adjust the pH to 5-6 with an aqueous IJ solution (20% carbonic acid). After injecting the diazo solution, stir at 0-5°C until coupling is completed.

Next, 18 parts of 1-N-methylaminobenzene-3-β-sulfatoethylsulfone was processed, and the temperature was raised to 40° C. while adjusting the pH to 5 to 6, and the mixture was stirred at the same temperature for 5 hours. Add 70 parts of sodium chloride to this solution to precipitate crystals,
The mixture was filtered under suction, washed, and dried at 60°C to obtain a monoazo compound having the following drawing formula.

Examples 22 to 38 In place of 2,4-diaminobenzenesulfonic acid in Example 21, a compound of general formula (If) having the following structure was used as ■-N
-Methylaminebenzene-8-β-Sulfatoethylsulfone is replaced with a compound of the general formula (III) shown below, and chloride anur is replaced with a compound of the general formula (IY
) compound, 1-(4'-sulfophenyl)-8-
In place of carboxypyrazolone, the following general formula (Vl
) using the same method as in Example 21,
The corresponding monoazo compounds were obtained.

Example 39 0.1, 0.8 and 0.6 parts of the monoazo compounds described in Example 21 were each dissolved in 200 parts of water, 20 parts of Glauber's salt was added, 10 parts of cotton was added, and the temperature was raised to 70°C. do. Then 3
After 0 minutes, 3 parts of soda carbonate is added and dyed at the same temperature for 1 hour.

After dyeing, washing with water and soaping were carried out to obtain a yellow dyed product having excellent fastness properties, especially fastness to sunlight, sweat and sunlight, extremely good build-up properties, and good dischargeability.

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

Example 40 0.8 parts of the monoazo compound described in Example 22 is dissolved in 200 parts of water, 20 parts of Glauber's salt are added, 10 parts of cotton are added, and the temperature is raised 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 were performed to obtain a yellow dyed product with excellent fastness.

Example 41 Color paste composition Monoazo compound described in Example 1 5 parts urea
5 parts Sodium alginate (5%) Base glue 50 parts Heat expansion
25 parts baking soda
2 part balance
13 parts Color paste having the above composition is printed on a mercerized wire broadcloth, and after intermediate drying, 10 parts
Steam for 5 minutes at 0°C, wash with hot water, soap, wash with hot water, and finish.

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

Procedural amendments (nine) April 1980 Commissioner of the Patent Office, April 22nd, 1981, Showa evening and year Patent application No. 0/No. 2, Name of the invention Monoazo compound and dyeing or printing using the same Law 3, Relationship with the amendment person case Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative: Takeshi Hijikata 4, Agent address: Kita @ 5-15-5, Higashi-ku, Osaka City, Claims and Detailed Description of the Invention column 6 of the specification to be amended, Amendment Contents 1) Amend the claims of the specification as shown in the attached sheet.

2) General formula (1) described on page 3, line 9 of the specification is amended as follows.

l) The following general formula (wherein, X is a halogen atom, Y is -8O20■, =OH
2;i? . represents a naphthyl group, R1 is an optionally substituted lower alkyl group, bird is a hydrogen atom, and both are optionally substituted lower alkyl groups,
R3 is a hydrogen atom, a methyl group, a sulfo group, a methyl group, a carboxy group or a methoxycarbonyl group, R
S represents a hydroxyl group or an amino group. ) or a salt thereof.

2) The following general formula (wherein, X is a halogen atom, Y is -802CH=O) [
, t i barso□an2an, z, z are groups that are eliminated by the action of an alkali, A is a phenylene group or naphthylene group which may not have a substituent, B is an yoiphenyl group even if it has a substituent. Matko represents a naphthyl group,
几1 is an optionally substituted lower alkyl group, R2 is a hydrogen atom or an optionally unsubstituted lower alkyl group, R
3 represents a hydrogen atom, a methyl group or a sulfo group, R4 represents a methyl group, a carboxyl group or a methoxycarbonyl group, and a circle represents a hydroxyl group or an amino group. ) A method of dyeing or printing using the monoazo compound □ or its salt.

356

Claims (1)

[Claims] ■) The following general formula (wherein, X is a halogen atom, Y is -802CH=CH2
or -802CH2CH2Z SZ is a group that is eliminated by the action of an alkali, A is a phenylene group or naphthylene group which may have a substituent group, and B is a phenyl group or naphthyl group which may have a substituent group. , R1 is an optionally substituted lower alkyl group, R2 is a hydrogen atom or an optionally substituted lower alkyl group, R3 is a hydrogen atom, a methyl group or a sulfo group, R
4 represents a methyl group, a carboxy group or a methoxycarbonyl group, and R5 represents a hydroxyl group or an amine group. ) A monoazo compound or a salt thereof. 2) The following general formula (wherein, X is /% rogen atom, Y is -802CH=CH
z or -5O2CH2CH2Z, Z is a group that leaves by the action of an alkali, A is a phenylene group or naphthylene group which may also have a substituent, B is a phenyl group or naphthyl group which may have a substituent. Representation, R
1 is an optionally substituted lower alkyl group, R2 is a hydrogen atom or an optionally substituted lower alkyl group, 1 is a hydrogen atom, a methyl group or a sulfo group, R4 is a methyl group,
A carboxyl group or a methoxycarbonyl group, R5 represents a hydroxyl group or an amino group. ) A method of dyeing or printing using a monoazo compound or a salt thereof.