JPH0797532A - Water-soluble monoazo dye - Google Patents

Abstract

PURPOSE:To obtain a new dye useful as a water-soluble reactive orange-colored dye capable of dyeing a cellulose fiber material with excellent build up properties and with excellent wash off properties, exhibiting an excellent solubility in an aqueous solvent and, therefore, capable of readily preparing a stable high-concentration liquid state product. CONSTITUTION:A dye of formula [X is CH=CH2 or C2H4W (W is a group eliminable by an action with an alkali); A<1> and A<2> are each phenylene or naphthylene; R<1> is a 1 to 6C alkyl; Z is a halogen or a pyridinium salt], e.g. a compound of formula II. This dye is produced, e.g. by condensing a free acid compound of formula III and an amine of formula IV with a 2,4,6- trihalogeno-s-triazine. In addition, the compound of formula I in which Z is pyridinium is synthesized by condensing a compound of formula I in which Z is a halogen with a pyridine-based compound at pH6 to 7 and 90 to 95 deg.C in an aqueous solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an orange water-soluble monoazo dye having a novel structure. Specifically, it has three reactive groups in the structure, and especially cellulose fibers have build-up properties and wash-off (wash-off).
The present invention relates to a water-soluble monoazo dye excellent in property).

[0002]

2. Description of the Related Art Monoazo dyes having a triazinyl group and two vinylsulfone-based reactive groups in the same molecule are known, for example, in European Patent Publication No. 516298, but in terms of dyeing performance, for example, build-up and wash. The off property is not sufficient, and it is difficult to prepare a high-concentration liquid product, so that it cannot be said to be satisfactory.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide an orange water-soluble reactive dye having particularly good build-up properties and wash-off properties.

[0004]

As a result of various investigations by the present inventors to provide a water-soluble reactive dye having the above-mentioned characteristics, the novel monoazo compound having a specific structure has the above-mentioned object. The present invention has been completed and the present invention has been completed. That is, the gist of the present invention is the following formula [I] in the form of a free acid.

[0005]

[Chemical 2]

(In the formula, X is a -CH = CH ₂ group or -C ₂
Represents a H ₄ W group. However, W represents a group capable of leaving by the action of an alkali. A ¹ and A ² each represent a phenylene group or a naphthylene group which may have a substituent, and R ¹
Represents a C ₁ -C ₆ lower alkyl group, and Z represents a halogen atom or a pyridinium salt which may have a substituent. ) Exists in the water-soluble monoazo dye.

The present invention will be described in more detail. Each of the reactive dyes of the present invention is represented in the form of a free acid, but the salt is preferably an alkali metal such as lithium, sodium or potassium, particularly a lithium salt. In the above formula [I], X is -CH
= CH ₂ or -CH ₂ CH ₂ W. -CH -CH ₂ CH ₂ W from W-H is eliminated by the action of an alkali
Since = a CH ₂ -CH ₂ CH ₂ W and the -CH = CH ₂
Is an equivalent.

Examples of the group represented by W which is eliminated by the action of an alkali include a sulfuric acid ester group, a thiosulfuric acid ester group, a phosphoric acid ester group, an acetic acid ester group, a halogen atom and the like, and a sulfuric acid is particularly preferable. An ester group may be mentioned. As the halogen atom represented by Z,
Examples thereof include a fluorine atom, a chlorine atom and a bromine atom, but a fluorine atom or a chlorine atom is particularly preferable.

A ¹ and A ² in the above general formula [I]
The phenylene or naphthylene group which may have a substituent is preferably methyl group, ethyl group, methoxy group, ethoxy group, chlorine atom, 1 or 2 selected from the group of bromine atom and sulfo group. A phenylene group optionally substituted with one substituent or a naphthylene group optionally substituted with one sulfo group, for example

[0010]

[Chemical 3]

[0011]

[Chemical 4] Represents a bond that is present. ) And the like.

As the pyridinium salt represented by Z, which may have a substituent, 3-carboxypyridinium, 4-carboxypyridinium, 3-carbonamidopyridinium, 4-carbonamidopyridinium, 3-
Examples thereof include methylpyridinium and 3-sulfopyridinium, and 3-carboxypinidinium is particularly preferable.

C represented by R ¹ in the general formula [I]
₁ Examples of the alkyl group -C ₆ methyl group, an ethyl radical, n
-Propyl group, iso-propyl group, n-butyl group, s
ec-butyl group, iso-butyl group, n-amyl group, n
Examples thereof include a -hexyl group and an iso-hexyl group, with a C ₁ -C ₄ linear alkyl group being particularly preferable. In the general formula [I], as a particularly preferred structure,

[0014]

[Chemical 5]

[0015]

[Chemical 6]

(Wherein Z ¹ represents a chlorine atom or a fluorine atom, and R ^1-1 represents a C _{1 to} C ₄ linear alkyl group) and the like. The monoazo dye of the present invention can be produced, for example, as follows. That is, the following general formula [II] in the form of free acid

[0017]

[Chemical 7]

(Wherein, X and A ¹ have the same meanings as described above) and the following general formula [III]

[0019]

[Chemical 8]

By condensing the amine represented by the formula (wherein R ¹ , X and A ² have the same meanings as described above) with 2,4,6-trihalogeno-s-triazine,
A compound represented by the general formula [I] can be obtained.
Alternatively, alternatively, 2,4,6-trihalogeno-s-
Triazine is condensed with sulfo-J-acid (2-amino-5-naphthol-1,7-disulfonic acid) or a compound represented by the general formula [III], and then the resulting condensate is condensed with sulfo-J. - after another by condensing a compound represented by the acid or formula (III), the following formula _{^{XO 2 S-a 1 -NH 2}} ... [IV] (wherein X and a ¹ has the same meaning as defined above. A monoazo dye represented by the general formula [I] can be obtained by coupling a diazotized amino compound represented by the formula (1).

Considering the reaction yield and quality of the general formula [I], it is preferable to condense 2,4,6-trihalogeno-s-triazine from a compound having a low reactivity. The reaction conditions are also not particularly limited, but primarily, the temperature is -10 to 20 ° C, especially 0 to 10 ° C, and the pH is 2 to 9, especially 3 to 10.
6, secondarily at a temperature of 0 to 60 ° C, especially 20 to 40 ° C, p
The compound represented by the general formula [I] or a salt thereof can be obtained by condensation while adjusting to H2-9, especially 4-7.

In the general formula [I], when Z is a pyridinium salt, it is produced by condensing a homologous compound in which Z is a halogen atom with an pyridine compound in an aqueous solvent at a temperature of 90 to 95 ° C. and a pH of 6 to 7. can do.

[0023]

The monoazo dye of the present invention can be widely used as a dye for dyeing fibers and cloths, a dye for coloring paper and synthetic resins, and a dye for inkjet printers. Excellent suitability as a dye for cellulose fibers. When dyeing with the monoazo dye of the present invention, the target fibers include cotton, viscose rayon, cupraammonium rayon, cellulosic fibers such as hemp, and further nitrogen-containing fibers such as polyamide, wool and silk. Of these, cellulose fibers are particularly desirable. Further, these fibers may be used as a mixed fiber of polyester, triacetate, polyacrylonitrile, etc., for example.

To dye cellulose or nitrogen-containing fibers with the monoazo dye of the present invention, an acid binder consisting of an inorganic alkali such as sodium bicarbonate and sodium carbonate, or an organic base such as triethylamine is usually used. Staining can be carried out in the presence of a binder according to a conventional method. As the dyeing method using the dye of the present invention, the dip dyeing method is suitable, and the dyeing temperature is usually about 40 to 80 ° C.

Further, a usual dyeing method such as a cold pad batch method, a pad steam method and a textile printing method can be applied, but a dipping method, a cold pad batch method and a pad steam method are particularly preferable.

[0026]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to the description of the examples as long as the gist thereof is not exceeded. The build-up property and level dyeing property were measured as follows. <Measurement of build-up property> The surface reflectance of the obtained dyed cloth was measured by a dye meter (manufactured by Nippon Denshoku Industries Co., Ltd.) to determine the dyeing density. Regarding the build-up property, the dyeing concentration when 1.2 g of the dye was used with respect to the dyeing concentration when 0.3 g of each dye was used, was expressed as a relative value.

<Wash-off property> 1.2 g of dye mixture
After squeezing the dyed fabric dyed using the method of Example 1 to a draw ratio of 100%, the dyeing cloth was treated as follows, and the coloring degree of the second soaping liquid was measured according to the following criteria. As the soaping agent, the product name Hostapearl CT40 (manufactured by Hoechst Japan Co., Ltd.) was used.

[0028]

[Table 1] Water wash 30 ° C x 5 minutes ↓ Bath ratio 1:20 Hot water wash 60 ° C x 10 minutes ↓ Bath ratio 1:20 First soaping 60 ° C x 10 minutes ｜ Bath ratio 1:20 ↓ Soaping agent 2g / l Second soaping 60 ° C. × 10 minutes Bath ratio 1:20 Soaping agent 2 g / l

<Judgment Criteria> ○: Almost no coloring ×: Very coloring

Example 1, Comparative Example 1 0.3 g or 1.2 g of each monoazo dye represented by the following structural formulas [I-1] and [A-1] in the form of a free acid was dissolved in 300 ml of water, 15 g of unmercerized cotton cloth was immersed in a dye bath prepared by adding 20 g of sodium sulfate and dissolving it, and the temperature was raised to 60 ° C. in 30 minutes. Then, 4.5 g of sodium carbonate was added and dyed at 60 ° C. for 1 hour, followed by washing with water, soaping, washing with water and drying to obtain an orange dyed product.
The build-up property was evaluated, and the results are shown in Table-1.
-1] and each of the monoazo dyes represented by [A-1] 1.
Dissolve 2g of each in 300ml, add 20g of Glauber's salt and dissolve it into the dye bath. 15g of unmercerized cotton cloth
Was soaked and the temperature was raised to 60 ° C. over 30 minutes. Then, 4.5 g of sodium carbonate was added, and after dyeing at 60 ° C. for 1 hour, evaluation was carried out based on the method described above, and the results are shown in Table 1.

[0031]

[Chemical 9]

[0032]

[Chemical 10]

[0033]

[Table 2]

The monoazo dye of the present invention represented by the structure [I-1] is represented by the following structural formula [I-2] in the form of free acid.

[0035]

[Chemical 11]

1 mole ratio of the monoazo compound represented by
1.1 mol ratio of-(β-hydroxyethyl) sulfonyl-N-ethylaniline sulfuric acid ester was added in an aqueous medium at 35 ° C.
It was obtained by keeping H 5.0 to 5.5 and reacting for 10 hours, and salting out with sodium chloride. Λmax of the obtained compound was 491 nm (in an aqueous medium).

Example 2 In the form of a free acid, 25 g and 50 g of a monoazo dye represented by the following structural formula [II-1] are dissolved in hot water and cooled to 25 ° C. 5.5 g of 32.5% caustic soda solution
Immediately after adding 150g of water glass of 50 degree Baume and further adding water to make the total amount 1.000g at 25 ° C, use this solution as a padding solution to pad on cotton fabric, roll up and seal with polyethylene film. Then 20
Store at room temperature for 20 hours. Then dye the dyed water in cold water,
Next, it is washed with hot water, soaped in a boiling soaping bath, washed with cold water and dried to finish. As a result, an orange dyed product with good build-up properties was obtained.
This is due to its excellent solubility in alkaline water.

[0038]

[Chemical 12]

The monoazo dye was produced according to the method of Example 1. Examples 3-1 to 3-15 The monoazo dyes of the present invention shown in Table 2 (shown in the form of free acid) were synthesized according to the method of Example 1, and cotton cloth was produced in the same manner as in Example 1. When dyed, each has build-up properties,
The wash-off property was remarkably good.

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

The orange water-soluble monoazo dye of the present invention is
In particular, cellulose fiber materials can be dyed with good build-up properties and wash-off properties. Further, it has excellent solubility in an aqueous solvent, and a stable high-concentration liquid product can be easily prepared.

Claims (1)

[Claims] 1. A compound represented by the following general formula [I] in the form of a free acid: (In the formula, X represents a —CH═CH ₂ group or a —C ₂ H ₄ W group, provided that W represents a group capable of leaving by the action of an alkali. A ¹ and A ² each have a substituent. Optionally represents a phenylene group or a naphthylene group, and R ¹ is C _{1 to} C ₆
Represents a lower alkyl group, and Z represents a halogen atom or a pyridinium salt which may have a substituent. ) Water-soluble monoazo dyes represented by.