JPH0717858B2 - Monoazo compound and method for dyeing or printing fiber material using the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a monoazo compound and a method for dyeing or printing a fiber material using the same.

Prior art Example 13 of Japanese Examined Patent Publication No. 55-39672 has the following formula The bluish red reactive dye represented by

Further, in Example 2 of Japanese Patent Publication No. 39-18184, the following formula The red reactive dye denoted by is shown.

Problems to be Solved by the Invention Conventionally, various reactive dyes have been widely used for dyeing and printing fiber materials. However, the above Japanese Patent Publication No. 55-3967
The dye of Example 13 of JP-B No. 2 is inadequate in terms of dyeing performance such as build-up property, and the dye of Example 2 of JP-B-89-18184 is a dye having solubility and build-up property. In view of high demands in terms of performance and fastness, it is not yet at a satisfactory level, and it is strongly desired to provide a further improved dye.

Excellent solubility means, for example, A dictionary of dyes
and dyeing, KG Ponting, p. 159, (1980), it is important for eliminating dyeing problems. Further, in recent years, an aqueous liquid composition of a dye has been attracting attention for reasons such as energy saving and automatic measurement, but it is also an important factor from the applicability.

It is well known that dyes having a high solubility generally have a low affinity for fibers and tend to be easily hydrolyzed with a reactive group, resulting in a poor build-up property.
That is, regarding the relationship between the solubility and the build-up property, it is generally considered that if one of them is improved, the other is sacrificed, and it is strongly desired to develop a compound having these properties at the same time and significantly improved.

The inventors of the present invention have satisfied the above-mentioned needs, have improved the above-mentioned drawbacks of the known dyes, and have conducted extensive studies with the aim of finding new compounds that can widely satisfy the requirements for dyes. The present invention has been completed.

Means for Solving the Problems The present invention provides the following general formula (I) in the form of a free acid. [In the formula, R is a hydrogen atom or an optionally substituted alkyl group, R ₁ and R ₂ are each independently a hydrogen atom, an optionally substituted lower alkyl group, an optionally substituted phenyl group, The naphthyl group which may be substituted or the benzyl group which may be substituted is shown. Z represents a group —SO ₂ CH═CH ₂ or a group —SO ₂ CH ₂ CH ₂ Y, and Y is a group capable of leaving by the action of an alkali. ] The monoazo compound shown by these, and the method of dyeing or printing a textile material using it.

In the general formula (I), when R is an alkyl group, a lower alkyl group, which is also preferably an alkyl group having 1 to 4 carbon atoms, is preferably a hydroxyl group, a cyano group,
It may be substituted with one or two substituents selected from the group consisting of an alkoxy group, a halogen atom, a carboxylic acid group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfonic acid group and a sulfamoyl group.

Preferred R is, for example, hydrogen atom, methyl group,
Ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group Group, 3-hydroxybutyl group, 4-hydroxybutyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, methoxymethyl group, ethoxymethyl Group, 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 2-hydroxy group,
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, 8-carbamoylpropyl group, 4-carbamoylbutyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, 2-methoxy Carbonylethyl group, 2-
Ethoxycarbonylethyl group, 3-methoxycarbonylpropyl group, 3-ethoxycarbonylpropyl group, 4-
Methoxycarbonylbutyl group, 4-ethoxycarbonylbutyl group, methylcarbonyloxymethyl group, ethylcarbonyloxymethyl group, 2-methylcarbonyloxyethyl group, 2-ethylcarbonyloxyethyl group, 3-
Methylcarbonyloxypropyl group, 3-ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, sulfone group Famoylmethyl group, 2
-Sulfamoylethyl group, 3-sulfamoylpropyl group, 4-sulfamoylbutyl group and the like can be mentioned.

Among them, particularly preferable R is a hydrogen atom, a methyl group or an ethyl group.

The lower alkyl group represented by R ₁ and R ₂ is selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, a chlorine atom, a phenyl group and a sulfate group. Alternatively, a lower alkyl group which may be substituted with 2 substituents and has 1 to 4 carbon atoms is preferable.

Among them, particularly preferably, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, β-hydroxyethyl group, β-sulfatoethyl group, β -Sulfoethyl group, β-methoxyethyl group, carboxymethyl group and the like are included.

The phenyl group represented by R ₁ and R ₂ is a 1 or 2 substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, a sulfonic acid group, a carboxylic acid group and a chlorine atom. It may be substituted.

Among them, phenyl group, 2-, 3- or 4 is particularly preferable.
-Sulfophenyl group, 2-, 3- or 4-carboxyphenyl group, 2,4-, 3,5- or 2,5-disulfophenyl group, 2-, 3- or 4-methylphenyl group, 2- , 3-
Alternatively, a 4-ethylphenyl group and the like can be mentioned.

The naphthyl group represented by R ₁ and R ₂ includes a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a chlorine atom. It may be substituted with 1, 2 or 8 substituents selected from the group

Among them, particularly preferably, 2-, 3-, 4-, 5-, 6-, 7- or 8-sulfo-1-naphthyl group, 1-, 5-, 6-, 7- or 8
-Sulfo-2-naphthyl group, 2,4-, 5,7-, 6,8-, 4,8
-, 4,7-, 8,8-, 4,6-, 3,7- or 3,6-disulfo-
2-naphthyl group, 4,6,8-, 2,4,7- or 3,6,8-trisulfo-1-naphthyl group, 1,5,7-, 4,6,8- or 3,6, 8-
Examples thereof include a trisulfo-2-naphthyl group.

The benzyl group represented by R ₁ and R ₂ is selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group and a chlorine atom. It may be substituted with 1 or 2 substituents.

Among them, benzyl group, 2-, 3- or 4 is particularly preferable.
-Sulfobenzyl group and the like.

Further, particularly preferred R ₁ and R ₂ are those in which R ₁ is a hydrogen atom, a methyl group or an ethyl group, and R ₂ is a group. (R ₃ and R ₄ are each independently a hydrogen atom, a sulfonic acid group,
A carboxylic acid group, a methyl group, an ethyl group or a halogen atom is shown. ).

Z represents a group —SO ₂ CH═CH ₂ or a group —SO ₂ CH ₂ CH ₂ Y, and Y is a group capable of leaving with an alkali, such as a sulfate ester group, a thiosulfate group or a phosphate ester. A group, an acetate group, etc. correspond to this. -SO ₂ CH = CH ₂ and _{-SO 2 CH 2 CH 2 OSO 3} H and the like as a preferable Z.

The compound of the present invention may be present in the form of a free acid, but is preferably an alkali metal salt or an alkaline earth metal salt,
For example, sodium salt and potassium salt may be mentioned.

In the monoazo compound of the present invention represented by the general formula (I), the following general formula (II) in the form of a free acid and especially the general formula (III)
The monoazo compound represented by is particularly preferable.

[In the formula, R, R ₁ , R ₂ and Z have the above-mentioned meanings. ] [In the formula, R, R ₁ , R ₂ and Z have the above-mentioned meanings. The monoazo compound represented by the general formula (I) of the present invention can be produced, for example, as follows.

The following general formula (IV) in the form of free acid And a compound represented by the following general formula (V) [In the formula, R and Z have the above-mentioned meanings. ] In the aqueous medium, in any order, the compound represented by
PH to 1 to 10, preferably 2 to 7 at -50 ° C, preferably 0 to 30 ° C, and secondarily 0 to 70 ° C, preferably 10 to 50 ° C, pH 2 to 9 Then, it is condensed with cyanuric chloride or cyanuric fluoride while adjusting the pH to preferably 3 to 6. Then, the following general formula (VI) [In the formula, R ₁ and R ₂ have the above-mentioned meanings. ] In the aqueous medium and a compound represented by 50 ~ 100 ℃, preferably 70 ~ 1
The monoazo compound of the general formula (I) can be obtained by condensation at 00 ° C. while adjusting the pH to 2 to 9, preferably 3 to 7.

Alternatively, as an alternative, the compound of general formula (VI) and cyanuric chloride or cyanuric fluoride in an aqueous medium at −10 to 50 ° C.,
Preferably at 0-30 ° C, pH 1-10, preferably 2-7
After the primary condensation, the compounds of the general formulas (IV) and (V) are secondarily condensed in any order and then at 0 to 70 ° C.
And preferably at 10 to 50 ° C. to pH 2 to 9, preferably pH 3
By adjusting the pH to 6 and tertiaryly at 50 to 100 ° C., preferably 70 to 80 ° C., while adjusting the pH to 2 to 9, preferably pH 3 to 7, the general formula (I) A monoazo compound represented by can be obtained.

In this method, the order of condensation is not particularly limited, but in view of the reaction yield and quality of the general formula (I), compounds having lower reactivity to cyanuric chloride or cyanuric fluoride are first selected. Is preferably condensed.

Examples of the compound represented by the general formula (VI) include emmonia, 1-aminobenzene, and 1-amino-2.
-, -3- or -4-methyl-benzene, 1-amino-
3,4- or -3,5-dimethylbenzene, 1-amino-2
-, -3- or -4-ethylbenzene, 1-amino-2
-, -3- or -4-chlorobenzene, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-
Methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, 5-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-
1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid, 4-amino-5-methylbenzene-1,2-disulfonic acid, 3- or 4-aminobenzoic acid, 5-aminobenzene-1 , 3-Dicarboxylic acid, N-methylaminobenzene, N-ethylaminobenzene, 1-methylamino-3
-Or-4-methylbenzene, 1-ethylamino-4-
Chlorobenzene, 1-ethylamino-3- or 4-methylbenzene, 1- (2-hydroxyethyl) -amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 2-aminonaphthalene-1- Sulfonic acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1- Sulfonic acid, 1-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic acid, 6-
Aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-
2-sulfonic acid, 7-ethylaminonaphthalene-2-sulfonic acid, 7-butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic acid, 4- Aminonaphthalene-1,3-disulfonic acid, 5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3
-Disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 8-aminonaphthalene-1,3-disulfonic acid,
2-aminonaphthalene-1,5-disulfonic acid, 3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,6
-Disulfonic acid, 8-aminonaphthalene-1,6-disulfonic acid, 4-aminonaphthalene-1,7-disulfonic acid,
3-aminonaphthalene-2,6-disulfonic acid, 4-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 4-aminonaphthalene-2,7
-Disulfonic acid, 6-aminonaphthalene-1,3,5-trisulfonic acid, 7-aminonaphthalene-1,3,5-trisulfonic acid, 4-aminonaphthalene-1,3,6-trisulfonic acid, 7 -Aminonaphthalene-1,3,6-trisulfonic acid,
8-aminonaphthalene-1,3,6-trisulfonic acid and 4
-Aromatic amines such as aminonaphthalene-1,3,7-trisulfonic acid, or methylamine, ethylamine, n-
Propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, dimethylamine, diethylamine, methylethylamine,
Allylamine, 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol, 2-methylaminoethanol, bis- (2-hydroxyethyl) -amine, 1-amino-2-propanol, 3-methoxypropylamine, 2-amino Ethanesulfonic acid, aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid, 3
-Amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, ε-aminocaproic acid, benzylamine, 2-, 3- or 4
-Chlorobenzylamine, 4-methylbenzylamine,
N-methylbenzylamine, 2-, 3- or 4-sulfobenzylamine, 2-phenylethylamine, 1-
Aliphatic amines such as phenylethylamine and 1-phenyl-2-propylamine may be mentioned.

Of these, particularly preferred compounds represented by general formula (VI) include, for example, aniline, N-methylaminobenzene, N-ethylaminobenzene, 3- or 4-aminobenzenesulfonic acid, 2- or 3-methylaminobenzene. Examples thereof include sulfonic acid, 2- or 3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, mono- or diethanolamine.

The following general formula (VII), which is a starting material (starting material) for the compound of general formula (IV) Examples of the compound represented by 2-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic acid, 6-
Aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonic acid, 6-aminonaphthalene-1,3-
Disulfonic acid, 7-aminonaphthalene-1,3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 3
-Aminonaphthalene-1,5-disulfonic acid, 3-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic acid, 6-aminonaphthalene-1,3,5
-Trisulfonic acid, 7-aminonaphthalene-1,3,5-trisulfonic acid, 7-aminonaphthalene-1,3,6-trisulfonic acid and the like can be mentioned.

Of these, particularly preferred are, for example, 2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, and 6-aminonaphthalene-1,3,5-trisulfonic acid. .

The following general formula (VIII), which is a raw material (starting material) for the compound of general formula (IV) Examples of the compound represented by 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and 1-amino-3
-Hydroxynaphthalene-4,6-disulfonic acid and the like can be mentioned.

Examples of the compound represented by the general formula (V) include, for example, [In the formula, R and Z have the above-mentioned meanings. ] Etc. are mentioned.

Among them, particularly preferably, R is a hydrogen atom, a methyl group or an ethyl group, and Z is —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH.
₂ OSO ₃ H below formula The compound shown by is mentioned.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing a hydroxy group-containing or carbonamide group-containing material. The material is preferably used in the form of a fibrous material or of a blended material thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulosic fiber materials or regenerated products thereof and polyvinyl alcohol. Cellulosic fiber materials are cotton, as well as other vegetable fibers such as linen,
Hemp, jute and ramie fibers are preferred. Regenerated cellulosic fibers are, for example, viscose staples and filament viscose.

Carbonamide group-containing materials are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers such as wool and other animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-
It is 4.

The compound of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material by a method depending on physical and chemical properties.

For example, in the case of exhaustion dyeing on cellulose fibers, sodium carbonate, sodium phosphate tribasic, in the presence of an acid binder such as caustic soda, optionally a neutral salt, such as sodium sulfate or salt,
If desired, a solubilizing agent, a penetrating agent, or a leveling agent is used in combination, and the reaction is carried out at a relatively low temperature. The neutral salt, which accelerates the exhaustion of the dyestuff, can be added only after the original dyeing temperature has been reached or before, optionally in divided portions.

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

When printing on cellulose fibers, in one phase, for example with a printing paste containing baking soda or other acid binder, then by steaming at 100-160 ° C, or in two phases, for example medium. It can be carried out by printing with a neutral or weakly acidic printing paste, passing it through a hot electrolyte-containing alkaline bath, or overpassing with an alkaline electrolyte-containing padding solution, and steaming or dry heat treatment.

For printing pastes, pastes or emulsifiers, such as sodium alginate or starch ether, are used, if desired in combination with customary printing aids and / or dispersants, such as urea.

Suitable acid binders for fixing the compounds of the present 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 upon heating. In particular, alkali metal hydroxides and alkali metal salts of weak or medium-strength inorganic or organic acids are mentioned, of which soda salts and potassium salts are particularly preferable. Examples of such an acid binder include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, sodium dibasic or tribasic phosphate, sodium silicate, sodium trichloroacetate and the like.

Dyeing of synthetic and natural polyamide and polyurethane fibers should be carried out by first exhausting from an acidic or weakly acidic dyeing bath under the control of a pH value, and then changing it to a neutral, and possibly alkaline, pH value for fixing. Can be done by Dyeing is usually carried out at a temperature of 60 to 120 ° C., but in order to achieve level dyeing, a common leveling agent such as a condensation product of cyanuric chloride and 3 times moles of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, an addition product of stearylamine and ethylene oxide can be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing on fiber materials. It is especially suitable for dyeing cellulose fiber materials and has excellent fastness to sunlight, fastness to sweat and formalin, excellent fastness to wetness, for example, fastness to washing, fastness to peroxidative washing, fastness to chlorine, fastness to bleaching chlorine. , Fastness to sweat, fastness to acid hydrolysis and alkali resistance, and good fastness to rubbing and iron. Also extremely excellent build-up properties, level dyeing properties and wash-off properties, further good solubility and high exhaustion, point having dyeability, dyeing temperature, alkali agent, inorganic salt addition amount,
It is characterized in that it is hardly affected by fluctuations in the dyebath ratio and a dyed product of stable quality can be obtained.

Further, the compound of the present invention shows excellent build-up property and excellent alkali stability in cold batch up dyeing, and almost no difference in concentration and hue difference between fixation at low temperature and fixation at 25 ° C. It has the property of being less susceptible to hydrolysis by agents.

The present invention is described in detail below with reference to examples. In the examples, parts and% mean parts by weight and% by weight, respectively.

Example 1 The following formula in the form of free acid 63.4 parts of the compound represented by the above is dissolved in 500 parts of water, 18.5 parts of cyanuric chloride is added, and the mixture is stirred at 0 to 5 ° C for 5 hours while adjusting the pH to 2.5 to 3.5 using a 20% aqueous sodium carbonate solution, Terminate the first condensation.

Then, 41.1 parts of 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-sulfonic acid was added, and the pH was adjusted to 4 to 5 with a 20% aqueous sodium carbonate solution.
The temperature is raised to ℃, and the second condensation is completed by stirring at the same temperature and pH value for 10 hours.

Next, 9.3 parts of aniline was added, and the pH was raised to 80 ° C while adjusting the pH to 4 to 5 using a 20% aqueous sodium carbonate solution, and the mixture was stirred at the same temperature and the same pH value for 6 hours to complete the third condensation. After that, 25 parts of sodium chloride was added to precipitate crystals,
After suctioning, washing and drying at 60 ° C, the following formula (1) in the form of free acid is used. A monoazo compound represented by

Examples 2-37 In Example 1 Instead of, the compound (IV) shown in the second column of the following table was replaced with 2-aminonaphthalene-6-β-sulfatoethylsulfone-1.
-Compound (V) in column 3 below, instead of sulfonic acid
Was synthesized in the same manner as in Example 1 except that the compound (VI) shown in the fourth column of the following table was used instead of aniline to obtain a monoazo compound of 2-37.

Example 38 18.5 parts of cyanuric chloride was dispersed in 500 parts of ice water, 41.1 parts of 2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid was added thereto, and the pH was adjusted to 3 using a 20% aqueous sodium carbonate solution. Adjusting to ~ 4, 0 ~ 5 ℃
Stir for 5 hours to complete the first condensation.

Then, in the form of the free acid, 55.8 parts of the compound shown in is added, the temperature is raised to 40 ° C. while adjusting the pH to 4 to 5 using a 20% aqueous sodium hydrogen carbonate solution, and the second condensation is completed by stirring at the same temperature and the same pH value for 10 hours. Let

Next, 12.1 parts of N-ethylaniline was added, and the temperature was raised to 80 ° C. while adjusting the pH to 4 to 5 with a 20% aqueous sodium hydrogen carbonate solution, and the mixture was stirred at the same temperature and the same pH value for 10 hours and the third mixture was added. After completing the condensation, add 20 parts of sodium chloride for salting out, suctioning and washing, and then drying at 60 ° C to obtain the free acid in the form of the following formula (38). A monoazo compound represented by

Examples 39-56 In Example 38 Instead of, the compound (IV) shown in the second column of the following table was replaced with 2-aminonaphthalene-8-β-sulfatoethylsulfone-6.
-In the same manner as in Example 38, compound (V) in the third column of the following table was used instead of sulfonic acid, and compound (VI) in the fourth column of the following table was used instead of N-ethylaniline. , 39 ~
56 monoazo compounds were obtained.

Dyeing Example 1 0.3 part of the monoazo compound (1) obtained in Example 1 is dissolved in 200 parts of water, 20 parts of Glauber's salt is added, 10 parts of cotton is added, and the temperature is raised to 50 ° C. Then, after 30 minutes, 4 parts of sodium carbonate is added and dyeing is carried out at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a dyed product having a high red color density, which was excellent in various fastnesses, particularly chlorine fastness, sunlight fastness and sweat / sunlight fastness, and which had good build-up properties.

Dyeing Example 2 0.3 part of the monoazo compound obtained in Example 38 is dissolved in 150 parts of water, 80 parts of Glauber's salt is added, 10 parts of cotton are added, and the temperature is raised to 60 ° C. Then, after 20 minutes, 4 parts of sodium carbonate is added and dyeing is carried out at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a dyed product having a high red color density, which was excellent in various fastnesses, particularly chlorine fastness, sunlight fastness and sweat / sunlight fastness, and which had good build-up properties.

Dyeing Example 3 0.3 part of each of the monoazo compounds obtained in Examples 1 to 37
Dissolve in 00 parts of water, add 30 parts of Glauber's salt, add 10 parts of cotton,
Raise the temperature to 60 ° C. Then, after 20 minutes have passed, 5 parts of sodium carbonate is added and dyeing is carried out at the same temperature for 1 hour. After completion of dyeing, washing with water and soaping are performed to obtain various fastnesses, especially chlorine fastness,
A dyed product having a high red color and excellent fastness to sunlight and fastness to sweat and good build-up properties was obtained.

Dyeing Example 4 0.3 part of each of the monoazo compounds obtained in Examples 38 to 56 was added to 2 parts.
Dissolve in 00 parts of water, add 30 parts of Glauber's salt, add 10 parts of cotton,
Raise the temperature to 50 ° C. Then, after 30 minutes have passed, 4 parts of sodium phosphate tribasic is added and dyeing is carried out at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were carried out to obtain a dyed product having a high red color density, which was excellent in various fastnesses, particularly chlorine fastness, sunlight fastness, and sweat / sunlight fastness and had good build-up properties.

Dyeing Example 5 Color paste composition Each of the monoazo compounds obtained in Examples 1-37 5 parts Urea 5 parts Sodium alginate (5%) Original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts Color paste having the above composition Is printed on mercerized cotton broad cloth, 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 print having a high fixing rate and various fastnesses, especially chlorine fastness, fastness to sunlight and fastness to sweat and sunlight and good build-up properties was obtained.

Dyeing Example 6 Color paste composition Each of the monoazo compounds obtained in Examples 38 to 56 4 parts Urea 5 parts Sodium alginate (5%) Original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 14 parts Color paste having the above composition The product is printed on mercerized cotton broad cloth, and after intermediate drying, steaming is performed for 5 minutes at 120 ° C, followed by hot water washing, soaping, hot water washing, and drying to finish.

In this way, a red print having a high fixing rate and various fastnesses, especially chlorine fastness, fastness to sunlight and fastness to sweat and sunlight and good build-up properties was obtained.

Dyeing Example 7 25 parts of each of the monoazo compounds obtained in Examples 1-37 are dissolved in hot water and cooled to 25 ° C. To this, 5.5 parts of 32.5% caustic soda solution and 150 parts of water glass with 50 degree baume were added, and further, water was added to bring the total amount to 1,00 parts at 25 ° C. Roll up cotton fabric, seal with polyethylene film and store in a room at 20 ° C.

The cotton fabric padded in the same manner and rolled up and sealed with a polyethylene film is stored in a room at 5 ° C. After leaving each padding cloth for 20 hours, the dyed product is washed with cold water and then with hot water, soaped in boiling detergent, further washed with cold water and dried to finish.

When the difference in density and the difference in density between the dyed product left at 20 ° C. for 20 hours and the dyed product left at 5 ° C. for 20 hours were examined, almost no difference was observed. In addition, a dyed product having good build-up properties was obtained by cold batch-up dyeing.

Dyeing Example 8 Using 25 parts of each of the monoazo compounds obtained in Examples 38 to 56, dyeing was carried out by the cold batch-up method in the same manner as in Dyeing Example 7 to obtain a dyed product having a good build-up property. When the difference in density and the difference in hue between 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 parts of each of the monoazo compounds obtained in Examples 1-37 are dissolved in hot water and cooled to 25 ° C. To this, 10 parts of 32.5% caustic soda aqueous solution and 30 parts of anhydrous sodium sulfate were added,
Immediately after adding water to make 1,000 parts at 25 ° C,
A viscose rayon fabric is padded using this solution as a padding solution. The padded viscose rayon fabric is rolled up, sealed with a polyethylene film and stored in a room at 20 ° C.

In the same manner, the viscose rayon fabric padded, rolled up and sealed with a polyethylene film is stored in a room at 5 ° C.

After leaving each padding cloth for 20 hours, wash the dyed product with cold water, then with hot water, and soap in boiling detergent,
Further, it is washed with cold water and dried to finish.

As a result of examining the density hue difference and the density difference between the dyed product left for 20 hours at 20 ° C. and the dyed product left for 20 hours at 5 ° C., almost no difference was observed.

Dyeing product 10 Using 20 parts of each of the monoazo compounds obtained in Examples 38 to 56, dyeing was carried out by the cold batch-up method in the same manner as in Dyeing Example 9 to obtain dyeings having good build-up properties,
Further, when the difference in the density and the difference in density of the dyed product left at 5 ° C. with respect to the dyed product left at 20 ° C. were examined, almost no difference was observed.

Dyeing example 11 Dyeing was carried out in exactly the same manner as in Dyeing example 3 except that the amount of sodium carbonate used was changed from 5 parts to 3 parts, and the dyes obtained in dyeing example 3 were used for each of the monoazo compounds 1-37 used. A dyed product having the same quality as the product was obtained.

Dyeing example 12 Dyeing example 3 was dyed in exactly the same manner except that the temperature was changed from 60 ° C. to 50 ° C., and the same quality as the dyed product obtained in dyeing example 3 for each of the monoazo compounds 1 to 37 used. A dyed product having The same was true when the temperature was 70 ° C.

Dyeing Example 13 Dyeing products obtained in Dyeing Example 3 were dyed in exactly the same manner as in Dyeing Example 3 except that the amount of Glauber's salt used was changed from 30 parts to 15 parts. A dyed product having the same quality as

Dyeing Example 14 Dyeing Example 4 was carried out in exactly the same manner 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 30 parts to 28 parts. A dyed product having the same quality as the dyed product obtained in Dyeing Example 4 was obtained for each.

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Claims (5)

[Claims] 1. The following general formula (I) in the form of a free acid. [In the formula, R represents a hydrogen atom, or is selected from the group consisting of a hydroxyl group, a cyano group, an alkoxy group, a halogen atom, a carboxylic acid group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfonic acid group and a sulfamoyl group. Represents an alkyl group which may be substituted with one or two selected substituents; R ₁ and R ₂ each independently represent a hydrogen atom, or 1 to 4
A lower alkyl group optionally substituted by 1 or 2 substituents selected from the group consisting of alkoxy groups having 1 carbon atom, sulfonic acid group, carboxylic acid group, hydroxyl group, chlorine atom, phenyl group and sulfate group. Represent or 1
An alkyl group having 4 to 4 carbon atoms, a sulfonic acid group,
Represents a phenyl group which may be substituted with 1 or 2 substituents selected from the group consisting of a carboxylic acid group and a chlorine atom, or represents a hydroxyl group, a carboxylic acid group, a sulfonic acid group, 1 to
Does it represent a naphthyl group which may be substituted with 1, 2 or 3 substituents selected from the group consisting of alkyl groups having 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms and chlorine atoms? Or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group, and 1 or 2 substituents selected from the group of chlorine atoms Represents a good benzyl group: Z represents a group —SO ₂ CH═CH ₂ or a group —SO ₂ CH ₂ CH ₂ Y,
Here, Y is a group capable of leaving with an alkali. ] The monoazo compound shown by these. 2. The following general formula (II) in the form of a free acid. [In the formula, R, R ₁ , R ₂ and Z have the meanings defined in claim 1. ] The monoazo compound of Claim 1 shown by these. 3. The following general formula (III) in the form of a free acid. [In the formula, R, R ₁ , R ₂ and Z have the meanings defined in claim 1. ] The monoazo compound of Claim 1 shown by these. 4. R and R ₁ are each independently a hydrogen atom, a methyl group or an ethyl group, and R ₂ is a group. (R ₃ and R ₄ are each independently a hydrogen atom, a sulfonic acid group,
A carboxylic acid group, a methyl group, an ethyl group or a halogen atom is shown. ) Claims which are) Claim 1, Claim 2 or Claim 3
The monoazo compound according to the item. 5. The following general formula (I) in the form of a free acid. [In the formula, R represents a hydrogen atom, or is selected from the group consisting of a hydroxyl group, a cyano group, an alkoxy group, a halogen atom, a carboxylic acid group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfonic acid group and a sulfamoyl group. Represents an alkyl group which may be substituted with one or two selected substituents; R ₁ and R ₂ each independently represent a hydrogen atom, or 1 to 4
A lower alkyl group optionally substituted by 1 or 2 substituents selected from the group consisting of alkoxy groups having 1 carbon atom, sulfonic acid group, carboxylic acid group, hydroxyl group, chlorine atom, phenyl group and sulfate group. Represent or 1
An alkyl group having 4 to 4 carbon atoms, a sulfonic acid group,
Represents a phenyl group which may be substituted with 1 or 2 substituents selected from the group consisting of a carboxylic acid group and a chlorine atom, or represents a hydroxyl group, a carboxylic acid group, a sulfonic acid group, 1 to
Does it represent a naphthyl group which may be substituted with 1, 2 or 3 substituents selected from the group consisting of alkyl groups having 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms and chlorine atoms? Or 1 selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group and a chlorine atom.
Or represents a benzyl group which may be substituted with two substituents; Z represents a group —SO ₂ CH═CH ₂ or a group —SO ₂ CH ₂ CH ₂ Y,
Here, Y is a group capable of leaving with an alkali. ] The dyeing or printing method of the textile material characterized by using the monoazo compound shown by these.