JPS63179969A - Water-soluble monoazo compound and dyeing or printing of fibrous material using said compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I {R1-R4 are H or (substituted)lower alkyl; R5 is H, (substituted)lower alkyl; R5 is H, (substituted) lower alkyl, acyl, etc.; A1 and A2 are (substituted)phenylene or (sulfonic acid- substituted) naphthylene; B is group shown by formula II (R6 is H, Cl, sulfonic acid, carboxylic acid, etc.) or group shown by formula III [Y1 and Y2 are -CH=CH2 of -CH2=CH2Z (Z is group eliminable by alkali action)]; m is 0 or 1}. EXAMPLE:A compound shown by formula IV. USE:Dye for dyeing OH group-containing material or carboxylic acid amide group-containing material in red - bluish red. PREPARATION:A compound shown by formula V and a compound shown by formula VI are reacted with cyanuric chloride, etc., the reaction product is diazotized and coupled with a compound shown by formula VII. The formed monoazo compound is condensed with a compound shown by formula VIII.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a water-soluble monoazo compound and a method for dyeing or printing textile materials using the same.

Conventional technology For example, in JP-A-57-199877, the following formula A red dye is shown.

Reactive dyes can be applied to various dyeing methods and have excellent characteristics such as vivid hues and good wet fastness of dyed products, so they are used for dyeing and printing cellulose fibers and polyamide fibers. It has been widely used as a dye.

However, when using reactive dyes for the purpose of obtaining richly dyed products, conventional dyes do not have sufficient build-up properties, resulting in a decrease in dyeing efficiency. They are expected to improve their level further.

In addition, red reactive dyes have low light fastness, and there is a strong demand for improvement.

Problems to be Solved by the Invention The present inventors have found a dye that improves the drawbacks of known dyes and has excellent dye properties such as fastness, level dyeing, and water solubility, as well as good build-up properties. As a result of intensive research aimed at this purpose, it was discovered that a specific compound had the desired performance.

Means for Solving the Problem The present invention provides a method for solving the problem in which the following general formula (I) [wherein R1
, R1, R11 and R4 each independently represent a hydrogen atom or an optionally substituted lower alkyl group, and R11 is a hydrogen atom, an optionally substituted lower alkyl group, an acyl group, or each independently represents a methyl group, a methoxy B represents a group, an ethyl group, an ethoxy group, a chlorine atom, a bromine atom, a phenylene group which may be substituted with a sulfonic acid group or a carboxylic acid group, or a naphthylene group which may be substituted with a sulfonic acid group; Sulfonic acid group, carbonic acid group, methyl group,
Indicates a methoxy group or an ethoxy group. ) or independently based on −
CH=CH! or -CH2CH2Z, where 2 is a group that is eliminated by the action of an alkali.

m represents 0 or 1. The present invention provides a water-soluble monoazo compound represented by the following and a method for dyeing or printing a fiber material using the same.

In general formula (I), the optionally substituted lower alkyl group represented by R1, Rg, Ra, R4 and R5 is preferably an alkyl group having 1 to 4 carbon atoms, even if substituted. Preferred examples of the group include a hydroxy group, a cyano group, an alkoxy group, a halogen group, a carboxy group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group, and a sulfamoyl group.

Preferred optionally substituted lower alkyl groups of R1, Rg, R8, R4 and RFI include, for example, methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 1so-butyl group. , 5eC-butyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 8-hydroxybutyl group, 4-hydroxybutyl group, 2.8-dihydroxypropyl group, 8,4-dihydroxybutyl group, cyanomethyl group, 2-cyanoethyl group,
3-cyanopropyl group, methoxymethyl group, ethoxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 8-methoxypropyl group, 8-ethoxypropyl group,
2-hydroxy group, 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, 8-carboxypropyl group, 4-carboxybutyl, 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, 8-ethoxycarbonylpropyl group, 4-methoxycarbonylbutyl group, 4-ethoxycarbonylbutyl group, methylcarbonyl Oxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 8-methylcarbonyloxypropyl group, 8
-Ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group, 8-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2 -sulfamoylethyl group, 8-sulf7
Examples include moylprobyl group and 4-sulfamoylbutyl group.

Among these, particularly preferred R1, Rg, Rs and R4 include a hydrogen atom, a methyl group, and an ethyl group.

It is more preferable that at least one of Rg and Rz is a hydrogen atom, and it is even more preferable that R8 is a hydrogen atom or a methyl group.

Examples of the acyl group for R6 include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group,
Isovaleryl group, hexanoyl group, heptanoyl group, acryloyl group, acetoacetate, thyl group, benzoyl group,
Anisoyl group, alanyl group, ethoxalyl group, carbazole group, carbamoyl group, glycoloyl group, glycyl group, glyceroyl group, crotonoyl group, salicyloyl group,
Examples include sarcosyl group, cyclohexanecarbonyl group, cyclohexylcarbonyl group, seryl group, toluoyl group, hydroatroboyl group, p-hydroxybenzoyl group, pyruvoyl group, phenylacetyl group, phenylcarbamoyl group, and lactoyl group.

Among these, particularly preferred R5 is a hydrogen atom, a methyl group, an ethyl group, an acetyl group, or a propionyl group.

In the general formula (I), a phenylene group represented by Al p A2 which may be independently substituted with a methyl group, a methoxy group, an ethyl group, an ethoxy group, a chlorine atom, a bromine atom, a sulfonic acid group or a carboxylic acid group; as,
For example, (l 4 ) (in the formula, the bond indicated by an asterisk means a -N- group or a bond connected to one group in the formula).

In addition, the naphthylene groups represented by At and Ag which may be independently substituted with sulfonic acid groups include, for example, * (wherein, the bond shown with an asterisk is a -N- group or -N-
means a bond that leads to a group. ) etc.

Among them, A1. It is preferred that A2 is a phenylene group which may be independently substituted with a methyl group or a methoxy group.

YlmatahaY2ka, -CH2CH*Z teh 'S tl
h is a group that is eliminated by the action of an alkali, such as a sulfuric acid ester group, a thiosulfuric acid ester group, a phosphoric acid ester group, a halogen atom, etc. Preferred Yl and Yyuzumi are both β- This is the case of sulf-1-toethyl, and some vinyl may be mixed therein.

In the general formula (I), B is, for example, a bond indicated by an asterisk in the E formula, which means a bond that is connected to the -N- group.

] etc. can be mentioned.

Particularly preferable monoazo compounds in the above general formula (I) include the following general formulas (II) and (II) in the form of free acids [wherein Ry, Re and RIG independently represent a hydrogen atom, a methyl group or an ethyl group]. and R9 represents a hydrogen atom, a sulfonic acid group or a chlorine atom.

Ro represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, or a propionyl group, and Rxi and Rss each independently represent a hydrogen atom, a methyl group, or a methoxy group. m has the above meaning. This is a monoazo compound represented by

The compounds of the present invention may exist in the form of free acids, but are preferably alkali metal salts or alkaline earth metal salts,
Examples include sodium and potassium salts.

The compound of the present invention can be produced, for example, as follows.

The following general formula (transformation) a HEN-B-NH (2) [wherein Rs and B have the above-mentioned meanings. ] and the following general formula (Mebo-At-5OgYx (g)L formula, Rlm
AI and Yl have the meanings given above. ] In any order, in an aqueous medium, at -10-50°C, preferably at 0-80°C, p
While adjusting H to 1 to 10, preferably 2 to 7, the p
H2 to 9, preferably 8 to 6, is condensed with cyanuric chloride or cyanuric fluoride to form the following general formula (
V) Rs R1 In the formula 1, R1, RB, AI, Yl and B have the above meanings, and X is a chlorine atom or a fluorine atom. ] is obtained.

Subsequently, the compound of the general formula (v) was diazotized at -10 to 20°C in a conventional manner to form the following general formula (■) [where R4, R
s and m have the meanings given above. ] at -10 to 50"C, preferably at 0 to 80"C, and at pH 1 to 7, preferably at pH 1.
Coupling is performed while adjusting to ~5, and the following general formula (
b) [In the formula, R1, RB, R4, R5, AI, Yt, B,
X and m have the meanings given above. ] A monoazo compound represented by the following can be obtained.

Furthermore, the monoazo compound represented by the general formula (4) is expressed by the following general formula (2) [wherein R2, A2 and Y8 have the above-mentioned meanings. 50 to io of the compound shown in aqueous medium.

"C, preferably at 70-100°C, to pH 2-9,
Preferably, the monoazo compound of general formula (I) can be obtained by condensation while adjusting to H3N2.

Alternatively, as an alternative method, the compound represented by the general formula Qn) is diazotized in a conventional manner at -10 to 20°C to form the compound represented by the general formula (Qn).
9) at -10 to 50°C, preferably θ to 30°C.
Coupling is carried out while adjusting the pH to 1 to 7, preferably 1 to 5, or by the following general formula (5).
) % formula % ( ) [wherein B has the above meaning. ] A compound represented by the following general formula (X) is diazotized by a conventional method, coupled with a compound of the general formula position), and then reduced at 40 to 100°C in the presence of sodium sulfide to form the following general formula (X) [in the formula , R8, R4, R5, B and r, i, i have the above meanings. ] A compound represented by is obtained.

Subsequently, the compound of the general formula (3) and the compound of the general formula (the cup) are mixed in an aqueous medium in an arbitrary order, and then -10 to 50
℃, preferably 0 to 80℃, adjusting to pH 1 to 10, preferably 2 to 7, and secondarily at 0 to 70℃, preferably 10 to 50℃, to pH 2 to 9, After condensing with cyanuric chloride or cyanuric fluoride while preferably adjusting the pH to 8 to 6, the compound represented by the general formula
The monoazo compound of general formula (I) can be obtained by condensation with H2-9, preferably while adjusting the pH to 8-7.

In these methods, the condensation order is not particularly limited, but considering the reaction yield and quality of general formula (I), compounds with low reactivity toward cyanuric chloride or cyanuric fluoride should be selected first. It is preferable to carry out the condensation first.

The above starting compounds can be acids and/or salts, depending on the reaction conditions.
It is used in particular in the form of alkali metal salts or alkali IJ earth metal salts.

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-containing fiber materials or regenerated products thereof 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, 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, especially 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, tribasic sodium phosphate, caustic soda, etc., optionally with the addition of a neutral salt, such as mirabilite or common salt,
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, it can be carried out 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. Printing 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 to cellulose fiber materials are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali upon heating. 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, and the like.

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 in acidic or slightly acidic dye baths under the control of the aph value, and then by 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 textile materials. It is particularly suitable for dyeing cellulose fiber materials, with excellent sunlight fastness, perspiration sunlight fastness and formalin resistance, excellent wet fastness, such as washing fastness, peracid washing fastness, and chlorine fastness. It has good fastness to chlorine bleaching, sweat fastness, acid hydrolysis fastness and alkali resistance, as well as good rub fastness and eye fastness. In addition, it has excellent build-up properties, level dyeing properties, and wash-off properties, as well as good solubility, high exhaustion, and fixation properties, and is not affected by changes in dyeing temperature, alkaline agent, inorganic salt addition amount, and dye bath ratio. It is characterized by the fact that it is difficult to obtain dyed products of stable quality.

In addition, the compound of the present invention exhibits excellent build-up properties and excellent alkali stability in cold patch-up dyeing, and there is almost no difference in density or hue between fixation at low temperatures and fixation at 25°C, and it also It has the ability to be resistant to hydrolysis.

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

In the examples, parts and % mean parts by weight and % by weight, respectively.

Example 1 18.5 parts of cyanuric chloride and 18.8 parts of 2,4-diaminobenzenesulfonic acid were first mixed with I) H3N at 2.0 to 5°C.
After condensation, 28.1 parts of 1-aminobenzene-8-β-sulfatoethylsulfone was added to adjust the pH to 4 to 6.
．． A second condensation was carried out at 10-20°C.

Then, after diazotizing the above reaction solution by a conventional method, 7-
28.9 parts of amino-1-naphthol-8-sulfonic acid was added and coupling was performed at pH 1-8.0-5°C. After the reaction, 88.1 parts of N-ethylaniline-8-β-sulf-1-toethylsulfone was added, and the pH was adjusted to 4-6.50.
The eighth condensation was carried out at 80° C., and a monoazo compound having the following structure was obtained in the form of an isolated free acid.

Examples 2 to 105 In Example 1, 7-amino-1-naphthol-8-
Instead of sulfonic acid, compound (6) in column 2 of the table below,
8th instead of 2,4-diaminobenzenesulfonic acid
Compound (I1') in column 4 was replaced with N-ethylaniline-8-β-sulfate in place of 1-aminobenzene-8-β-sulfatoethylsulfone.
Synthesis was carried out in the same manner as in Example 1 using the compound in column 5 instead of toethylsulfone to obtain the corresponding monoazo compounds, and column 6 shows the color tone of the compound on cellulose fiber. Indicated.

Example 106 2-methoxy-4-nitroaniline-5-sulfonic acid 2
After diazotizing 4.8 parts by a conventional method, 7-amino-1
- Add 28.9 parts of naphthol-8-sulfonic acid and adjust the pH.
Coupling was carried out at 1-8, 0-5°C. After the reaction was completed, the pH was adjusted to 8 to 10, 10.7 parts of sodium sulfide was added, and reduction was performed at 60"O, followed by salting out to obtain a wet cake. This wet cake was dissolved in water, and cyanuric chloride 16 Add 7 parts of ゜ and adjust the pH to 2-5.0-10℃.
The first condensation is carried out with 2-aminonaphthalene-
87 parts of 6-β-sulfur-1-toethylsulfonic acid-1-sulfonic acid was added, and the second bonding was carried out at pH 8-6.20-80°C. After the reaction, N-ethylaniline-8-β-
Add 80 parts of sulfur-1-toethyl sulfone and adjust the pH to 8-7.
．． The eighth bond was carried out at 50 to 80°C and the monoazo compound having the following structure was obtained in the form of a free acid by isolation.

(λmax 550 nm) Examples 107 to 126 In Example 106, 7-amino-1-naphthol-
In place of 8-sulfonic acid, compound (9) in column 2 of the table below, in place of 2-methoxy-4-nitroaniline-5-sulfonic acid, compound (transformed) in column 8, and in place of 2-aminonaphthalene. -In place of 6-β-sulfatoethylsulfone-1-sulfonic acid, the compound (b) of column 4 was added, and in place of N-ethylaniline-8-β-sulf-1-toethylsulfone, compound Example 10 using the compound (■) in column
The corresponding monoazo compounds were synthesized in the same manner as in Example 6, and the color tone of the compounds on cellulose fibers is shown in column 6.

(FIR) Dyeing Example 1 0.8 parts of the monoazo compound obtained in Example 1 was dissolved in 200 parts of water, 20 parts of Glauber's salt was added, and 10 parts of cotton was added.
Raise the temperature to 0°C. Then, after 80 minutes had elapsed, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a dyed product with a high concentration of red color and excellent build-up properties in various fastnesses, especially chlorine fastness, sunlight fastness, and sweat/sunlight fastness.

Dyeing Example 2 0.8 part of the monoazo compound obtained in Example 106 was added to 15
Dissolve in 0 parts of water, add 80 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 60°C. After 20 minutes, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After dyeing, wash with water and soap to improve various fastnesses, especially chlorine fastness.
A dyed product with a high density of red color having excellent sunlight fastness and sweat/sweat sunlight fastness and good build-up properties was obtained.

Dyeing Example 8 Each of the monoazo compounds obtained in Examples 1 to 105 was 0.
Dissolve 8 parts in 800 parts of water, add 80 parts of mirabilite, and add 1 part of cotton.
Add 0 parts and raise the temperature to 60°C. Then, after 20 minutes,
Add 5 parts of soda carbonate and dye at the same temperature for 1 hour. After dyeing, washing with water and soaping are performed to determine the color fastness,
In particular, a dyed product with a high concentration of red color, which has excellent chlorine fastness, sunlight fastness and perspiration/sunlight fastness, and good build-up properties was obtained.

Dyeing Example 4 0.8 parts of each of the monoazo compounds obtained in Examples 106 to 125 were dissolved in 200 parts of water, 80 parts of Glauber's salt was added,
Add 10 parts of cotton and raise the temperature to 50°C. After 80 minutes, 4 parts of tribasic sodium phosphate was added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were carried out to obtain a dyed product with a high concentration of red color and excellent build-up properties in various fastnesses, especially chlorine fastness, sunlight fastness, and sweat/sunlight fastness.

Dyeing example 5 Color paste composition Urea 5 parts Algi soda (5%) Base paste 50 parts Hot water
25 parts baking soda
2 parts Balance 18 parts A colored paste having the above composition is printed on mercerized 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 red printed product was obtained which had a high fixation rate, was excellent in various fastnesses, especially chlorine fastness, sunlight fastness and perspiration/sunlight fastness, and had good build-up properties.

t Shin Fl) Dyeing example 6 Color paste composition Urea 5 parts AlgiΔ
Soda (6%) 50 parts hot water 25 parts weight W
2 parts balance 14 parts A colored paste having the above composition is printed on mercerized cotton broadcloth, and after intermediate drying, steaming is performed at 120° C. for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying to finish.

In this way, a red printed product was obtained which had a high fixation rate, was excellent in various fastnesses, especially chlorine fastness, sunlight fastness and perspiration/sunlight fastness, and had good build-up properties.

Dyeing Example 7 25% of each of the monoazo compounds obtained in Examples 1 to 106
part is dissolved in hot water and cooled to 25°C. 82.5 to this
Add 6.5 parts of 96% caustic soda aqueous solution and 150 parts of 50° Baume water glass, and then add water to bring the total volume to 2.
Immediately after being made up to 1,000 parts at 5°C, this liquid is used as a padding liquid to roll up a cotton fabric, sealed with polyethylene film and stored in a room at 20°C.

The mta material, padded in the same manner and sealed with rolled polyethylene film, is stored indoors at 5°C.

After each padding cloth has been left to stand for 20 hours, the dyeing is finished by washing in cold water, hot water, soaping in boiling detergent, washing in cold water and drying.

We investigated the difference in hue and density between dyed products left at 20°C for 20 hours and dyed products left at 5°C for 20 hours.
It was hardly recognized. In addition, a dyed product with good build-up properties was obtained by cold patch-up dyeing.

Dyeing Example 8 Using 25 parts of each of the monoazo compounds obtained in Examples 106 to 125, dyeing was carried out by the cold batch-up method in the same manner as in Dyeing Example 7, and a dyed product with good build-up properties was obtained. When the difference in density and hue of the dyed product left at 5° C. and the dyed product left at 5° C. were examined, almost no difference was observed.

Dyeing Example 9 25% of each of the monoazo compounds obtained in Examples 1 to 105
Dissolve the portion in hot water and cool to 25"C. Add 82.
10 parts of 5% caustic soda aqueous solution and go parts of anhydrous sodium sulfate! Add water and bring the total volume to 1 at 25°C.
．． Immediately after making 000 parts, this liquid is used as a padding liquid to pad a viscose rayon fabric. The padded viscose rayon fabric is rolled up, sealed with polyethylene film and stored indoors at 20°C.

In a similar manner, viscose rayon fabric sealed with padded rolled polyethylene film is stored in a 5''C room.

After each padding cloth has been left for 20 hours, the dyeing is washed in cold and then hot water, soaped in boiling detergent,
Finish by washing with cold water and drying.

When the differences in density and hue were examined between a dyed product left at 20°C for 20 hours and a dyed product left at 5°C for 20 hours, almost no differences were observed.

Dyeing Example 10 Using 20 parts of each of the monoazo compounds obtained in Examples 106 to 125, dyeing was carried out by the cold batch-up method in the same manner as in Dyeing Example 9, and a dyed product with good build-up properties was obtained. 5 for dyed items left in
When we examined the difference in density and the difference in density and hue of the dyed products left at ℃, almost no difference was observed.

Dyeing Example 11 Dyeing was carried out in the same manner as in Dyeing Example 8, except that the amount of sodium carbonate used was changed from 5 parts to 8 parts, and the dyeing obtained in Dyeing Example 8 was carried out for each of the monoazo compounds 1 to 105 used. A dyed product with quality equivalent to that of the dyed product was obtained.

Dyeing Example 12 Dyeing was carried out in exactly the same manner as in Dyeing Example 8 except that the temperature was changed from 60°C to 50°C, and the quality was equivalent to that of the dyed product obtained in Dyeing Example 8 for each of the monoazo compounds 1 to 105 used. A dyed product was obtained. The same thing happened when the temperature was set to 70°C.

Dyeing Example 18 Dyeing was carried out in exactly the same manner as in Dyeing Example 8, except that the amount of Glauber's salt used was changed from 80 parts to 16 parts, and the dyed products obtained in Dyeing Example 8 were obtained for each of the monoazo compounds 1 to 105 used. A dyed product with quality equivalent to that of the dyed product was obtained.

Dyeing Example 14 Dyeing was carried out in the same manner as in Dyeing Example 4 except that the amount of water used was changed from 200 parts to 150 parts and the amount of Glauber's salt used was changed from 80 parts to 28 parts, and the monoazo compound used was 106 to 125 parts. For each dyed product, a dyed product having the same quality as the dyed product obtained in Dyeing Example 4 was obtained.

Procedural amendment (spontaneous) 1. Indication of the case 1988 Patent Application No. 11664 2. Name of the invention Water-soluble monoazo compound and method of dyeing or printing textile materials using the same 8. Person making the amendment Related Patent Applicant Address 5-15 Kitahama, Higashi-ku, Osaka Name (20
9) Sumitomo Chemical Co., Ltd. Representative: Hideo Mori 4, Agent address: Sumitomo Chemical Co., Ltd., 5-15 Kitahama, Higashi-ku, Osaka City, 5, Column 6 for detailed description of the invention in the specification to be amended, Amendment Contents (I) “Ku0oc practice” (2) on page 14, line 5 of the specification
8th and 2nd lines from the bottom of page 19 of the specification;
On page 1, lines 8 and 4, it is stated that ``pH 1-7 preferably pH
pH 1 to 5” is replaced with “pH 1 to 5, preferably pH 1 to 5.”
8,” he corrected.

(8) On page 28, line 7 of the specification, the word "fiber" is amended to read "fiber."

(4) The phrase "steaming" on page 25, line 8 of the specification is amended to read "steaming."

(5) Lines 8 and 2 from the bottom of page 27 of the specification indicate “
"pH2-6.0-5℃" means rpH2-6.0-5
°C".

(6) Page 56, line 2 of the specification “pH 1-8,0~
5" is corrected to "pH 1-8, o-5."

(7) In the table on page 58 of the specification, Example number 107, (
8) In the table on page 61 of the specification, Example number 122, (9
) Example number 12o in the table on page 61 of the specification.

121 and 122, respectively in the column of the compound with the general formula
” are respectively corrected as and [H,N O8O□C8CH2Cl J.

that's all (4 complete)

Claims (1)

[Claims] 1) In the form of a free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1, R_2, R_3 and R_4 each independently represent a hydrogen atom or Indicates an optionally substituted lower alkyl group, and R_5 represents a hydrogen atom, an optionally substituted lower alkyl group, an acyl group, or a group ▲There are numerical formulas, chemical formulas, tables, etc.▼. A_1 and A_2 are independently substituted with a methyl group, a methoxy group, an ethyl group, an ethoxy group, a chlorine atom, a bromine atom, a phenylene group which may be substituted with a sulfonic acid group or a carboxylic acid group, or a sulfonic acid group. represents a naphthylene group which may be represented by the formula ▲numerical formula,
There are chemical formulas, tables, etc. ▼ (R_6 indicates a hydrogen atom, chlorine atom, sulfonic acid group, carboxylic acid group, methyl group, methoxy group, or ethoxy group) or formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Indicates the divalent group that can be used. Y_1 and Y_2 are -CH independently of each other
=CH_2 or -CH_2CH_2Z, where Z
is a group that is eliminated by the action of an alkali. m represents 0 or 1. ] A water-soluble monoazo compound represented by: 2) In claim 1, wherein R_1, R_2, R_3 and R_4 are each independently a hydrogen atom, a methyl group or an ethyl group, and R_5 is a hydrogen atom, a methyl group, an ethyl group, an acetyl group or a propionyl group. Monoazo compounds as described. 3) The monoazo compound according to claim 1 or 2, wherein A_1 and A_2 are independently a phenylene group optionally substituted with a methyl group or a methoxy group. 4) The monoazo compound according to claim 1, 2 or 3, wherein Y_1 and Y_2 are both β-sulfatoethyl groups. 5) The divalent group represented by B is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲There are mathematical formulas, chemical formulas, tables, etc.▼or▲Mathematical formulas, chemical formulas , tables, etc. ▼ [In the formula, the bond indicated by an asterisk means a bond that leads to the -N- group. ] The monoazo compound according to any one of claims 1, 2, 3, or 4. 6) In the form of a free acid, the following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, R_7, R_8 and R_1_0 independently represent a hydrogen atom, a methyl group or an ethyl group, R_9 represents a hydrogen atom, a sulfonic acid group, or a chlorine atom. R_1_1 represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, or a propionyl group, and R_1_2 and R_1_3 each independently represent a hydrogen atom, a methyl group, or a methoxy group. m has the meaning given in claim 1. ] The monoazo compound according to claim 1, which is represented by: 7) In the form of a free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1, R_2, R_3 and R_4 may be independently hydrogen atoms or substituted. It represents a lower alkyl group, and R_5 represents a hydrogen atom, an optionally substituted lower alkyl group, an acyl group, or a group ▲Numerical formula, chemical formula, table, etc. are available. A_1 and A_2 are independently substituted with a methyl group, a methoxy group, an ethyl group, an ethoxy group, a chlorine atom, a bromine atom, a phenylene group which may be substituted with a sulfonic acid group or a carboxylic acid group, or a sulfonic acid group. represents a naphthylene group, which may be a naphthylene group, and B is a group ▲ formula,
There are chemical formulas, tables, etc. ▼ (R_6 indicates a hydrogen atom, chlorine atom, sulfonic acid group, carboxylic acid group, methyl group, methoxy group, or ethoxy group) or the group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ . Y
_1 and Y_2 are -CH=CH_2 or - independently of each other
CH_2CH_2Z is shown, where Z is a group that is eliminated by the action of an alkali. m represents 0 or 1. ] A method for dyeing or printing textile materials, characterized by using a water-soluble monoazo compound represented by the following.