JP2694825B2 - Triazine compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to materials containing hydroxyl groups and / or amide groups, in particular cellulose fibers,
The present invention relates to a triazine compound suitable for dyeing and printing natural or synthetic polyamide fibers, polyurethane fibers, leather and the like, as well as mixed fibers thereof.

[0002]

2. Description of the Related Art Reactive dyes having a monochlorotriazinyl group as a reactive group are known, but their dyeing performance, for example, build-up property, leveling property, or fastness is insufficient, and further improvement in level is required. Is desired.

[0003]

PROBLEM TO BE SOLVED BY THE INVENTION Hydroxyl group and / or
Or, the dyeing performance of the monochlorotriazinyl type reactive dye in dyeing or printing a material containing an amide group, especially the build-up property is not at a satisfactory level, and it is difficult to obtain a dyed or printed product with a high concentration. Therefore, the present inventors diligently made efforts to improve this level and found a triazine compound which can solve the above problems.

[0004]

The present invention provides a compound represented by the following general formula (I):

[0005]

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[In the formula, A represents a phenylene group or a naphthylene group which may have a substituent, R ₁ and R ₂ each independently represent a hydrogen atom or an optionally substituted lower alkyl group, D is the following formula (a)

[0007]

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(Wherein D ₀ is a bicyclic aryl group or
A monocyclic aryl group having a sulfonic acid group as a substituent at the ortho-position of the bond -N = N- and further substituted with a halogen atom, an alkyl group, an acylamino group or an alkoxy group, wherein the asterisk represents the general formula ( -N (R ₁ )-in I)
The group is bonded to the 6-, 7- or 8-position of the naphthalene nucleus. However, the naphthalene nucleus may have a sulfonic acid group as a substituent at the 5- or 6-position. ) Represents a monoazo organic dye residue. ] The triazine compound shown by these is provided. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The triazine compound represented by the general formula (I) has the following general formula (II):

[0010]

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(Wherein D ₀ , * and R ₁ have the same meanings as described above), and the following general formula (III) HN (R ₂ ) -A-SO ₂ CH ₂ CH ₂ A compound represented by OH (III) (wherein A and R ₂ have the above meanings) in an aqueous medium with cyanuric chloride in any order,
Primary temperature is 0 to 30 ℃, pH is 3 to 9, and secondary temperature is 20 to 60
It can be obtained by reacting at a temperature of 4 to 8 ° C.

In the general formula (II), D ₀ is a bicyclic aryl group or a monocyclic aryl group in which a sulfonic acid group is substituted at the ortho position of the bond —N═N—. The monocyclic aryl group is further substituted with, for example, a halogen atom such as a chlorine atom, an alkyl group such as a methyl group, an acylamino group such as an acetylamino group, or an alkoxy group such as a methoxy group. It is a phenyl group. Further, as the bicyclic aryl group, a bond-
A naphthyl group in which a sulfonic acid group is substituted at the ortho position of N = N- is preferable.

Specific examples of the compound represented by the above general formula (II) include the following compounds.

7-Methylamino-2- (4'-methoxy-2'-sulfophenylazo) -1-hydroxy-naphthalene-3-sulfonic acid. 8-Amino-1-hydroxy-2,2′-azonaphthalene-1 ′, 3,5 ′, 6-tetrasulfonic acid. 6-amino-1-hydroxy-2-
(4'-acetylamino-2'-sulfophenylazo)
-Naphthalene-3-sulfonic acid. 6-methylamino-1
-Hydroxy-2- (4'-methoxy-2'-sulfophenylazo) -naphthalene-3-sulfonic acid. 8-amino-1-hydroxy-2,2'-azonaphthalene-
1 ', 3,6-trisulfonic acid. 6-Amino-1-hydroxy-2- (4′-methoxy-2′-sulfophenylazo) -naphthalene-3-sulfonic acid. 8-amino-1
-Hydroxy-2,2'-azonaphthalene-1 ', 3,
5'-trisulfonic acid. 6-amino-1-hydroxy-
2,2'-azonaphthalene-1 ', 3,5'-trisulfonic acid. 6-methylamino-1-hydroxy-2,2 ′
-Azonaphthalene-1 ', 3,5'-trisulfonic acid.
7-Amino-1-hydroxy-2,2′-azonaphthalene-1 ′, 3-disulfonic acid.

A is preferably a phenylene group optionally substituted by 1 or 2 substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo, or substituted by 1 sulfo. A naphthylene group which may be present, for example

[0016]

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[0017]

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[In the formula, the bond indicated by an asterisk is -N
It means a bond leading to the (R ₂ ) -group. ] Etc. can be mentioned.

In R ₁ and R ₂ , the lower alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and the group which may be substituted is a hydroxy group, a cyano group, an alkoxy group or a halogen group. A carboxy group, a carbamoyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a sulfo group and a sulfamoyl group are preferred.

Particularly preferred R ₁ and R ₂ are, for example, hydrogen atom, methyl group, ethyl group, n-propyl group,
i-propyl group, n-butyl group, i-butyl group, s-butyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl 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-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, 3-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 Methyl carbonyloxy methyl group, ethyl carbonyloxy methyl group, 2-methyl carbonyloxy methyl group, 2-ethyl carbonyl oxymethyl group, 3-methyl-carbonyloxy propyl group, 3-
Ethylcarbonyloxypropyl group, 4-methylcarbonyloxybutyl group, 4-ethylcarbonyloxybutyl group, sulfomethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, sulfamoylmethyl group, 2-sulfur Examples thereof include famoylethyl group, 3-sulfamoylpropyl group, and 4-sulfamoylbutyl group.

The compound of the present invention can be made into a liquid product by removing an inorganic salt and optionally adding a stabilizer or a dyeability improving agent, or the liquid product or the reaction solution is evaporated. For example, it can be made into a powder product by spray drying, and can also be made into a liquid product or a powder product through salting-out separation by addition of an electrolyte by a generally known method.

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 a blend thereof. The hydroxy group-containing material is a natural or synthetic hydroxy group-containing material, such as a cellulose fiber material or a regenerated product thereof, and polyvinyl alcohol. The cellulosic fiber material is preferably cotton and other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose staples and filament viscose. Carbonamide-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6.
6, polyamide-6, polyamide-11, polyamide-
4.

The compound of the present invention is applied on the above-mentioned material, particularly on the above-mentioned fiber material, in a manner depending on the physical and chemical properties,
It can be dyed or printed. For example, in the case of exhaustion dyeing on cellulose fibers, a neutral salt such as sodium sulfate or sodium chloride is optionally added in the presence of an acid binder such as sodium carbonate, sodium tertiary phosphate, caustic soda, etc. It is carried out at a relatively high temperature using an agent, a penetrant or a leveling agent in combination. Neutral salts which promote the exhaustion of the dye can be added only after the original dyeing temperature has been reached or before, optionally in portions. When dyeing cellulose fibers according to the padding method, they can be padded at room temperature or at an elevated temperature, dried, and then fixed by steaming or dry heat. When printing on cellulose fibers, in one phase, for example with a printing paste containing baking soda or other acid binder, then 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 over-padding with an alkaline electrolyte-containing padding solution, and steaming or dry heat treatment. In the printing paste, a sizing or emulsifying agent such as, for example, sodium alginate or starch ether is used, if desired, in combination with a usual printing aid and / or dispersant such as, for example, urea.

Suitable acid binders for fixing the compounds according to the invention on cellulose fibers are, for example, water-soluble bases of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali on heating. . In particular, mention may be made of hydroxides of alkali metals and alkali metal salts of inorganic or organic acids of weak to moderate strength, of which soda salts and potassium salts are particularly preferred. Examples of such an acid binder include caustic soda, caustic potash, baking soda, sodium carbonate,
Examples thereof include sodium formate, potassium carbonate, first, second or third sodium phosphate, sodium silicate, sodium trichloroacetate and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out by first exhausting from an acidic to slightly acidic dyeing bath under controlled pH values, and then to neutral, and possibly alkaline, pH values for fixing. It is done by changing. Dyeing can usually be carried out at a temperature of from 60 to 120 ° C., but in order to achieve levelness, a conventional leveling agent, for example, the condensation product of cyanuric chloride with 3 times the molar amount 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 exerts excellent performance on fiber materials, and is particularly suitable for dyeing cellulosic fibers. It exhibits high exhaustion and fixation, extremely excellent build-up properties, leveling properties and detergency, and is suitable for obtaining dense dyeings. It also shows high coloring power in printing. Furthermore, it has a feature that it is hardly affected by the dyeing property even if the dyeing conditions such as temperature, bath ratio, salt concentration and the like slightly change, and also has light resistance, sweat light resistance, sweat resistance, acid hydrolysis resistance, Excellent washing resistance, chlorine resistance, etc.

[0027]

EXAMPLES Next, the present invention will be described in more detail by way of examples. In the text, "parts" indicates parts by weight.

Reference Example 1 Diazotized 2-aminonaphthalene-3,6,8-
3.7 parts of cyanuric chloride was added to a neutral solution of the amino dye obtained in 200 parts of water by coupling 7.7 parts of trisulfonic acid with 3.0 parts of 3-ureidoaniline by a conventional method.
Stir until the condensation is complete. Next, 4.0 parts of aniline-3-β-hydroxyethyl sulfone was added to this solution, and the mixture was stirred until the condensation was completed. Then, salt was added to precipitate crystals, which was separated by filtration and dried to give a free acid form. A reddish yellow dye having the following structural formula was obtained.

[0029]

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Example 1 6.4 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid was dissolved in 150 parts of water to obtain 3.7 parts of cyanuric chloride.
Part under acidic conditions, and then reacted with aniline-3-
Add β-hydroxyethyl sulfone 4.0 parts,
The mixture was stirred under weak acidity until the condensation was completed. 2-aminonaphthalene-1, which was diazotized to this reaction solution by a conventional method,
6.1 parts of 5-disulfonic acid was added and coupled. Furthermore, sodium chloride was added to this solution to crystallize,
It was then filtered off and dried to give a red dye of the following structural formula, expressed in free acid form.

[0031]

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Example 2 In place of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, the coupling component in column 1 of the following Table 1 was used instead of aniline-3-β-hydroxyethylsulfone. Corresponding to the amine in the second column of Table 1 by the same method as in Example 1 using the diazo component in the third column of the following Table 1 instead of 2-aminonaphthalene-1,5-disulfonic acid. A red triazine compound was obtained.

Further, the amino dyes listed in the second column of the following Table 2 are condensed with an equivalent amount of cyanuric chloride and then the amines listed in the third column in the same manner as in Reference Example 1 to give the corresponding triazine compounds. Got

[0034]

[Table 1]

[0035]

[Table 2]

Example 3 2-amino-5-hydroxynaphthalene-7-sulfonic acid (4.8 parts) was dissolved in water (150 parts) and reacted with cyanuric chloride (3.7 parts) under acidic conditions by a conventional method. 4.1 parts of 4-methoxyaniline-2-sulphonic acid, which had been derivatized, were added for coupling, and then N-ethylaniline-3-β-hydroxyethylsulfone 4.6 was added under mild acidity.
Parts were added and stirred until the condensation was complete. The reaction solution was vacuum dried to obtain a deep red dye having the following structural formula when expressed in the form of a free acid.

[0037]

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Dyeing Example 1 0.1, 0.3 and 0.6 parts of the compound described in Example 3 were each added to water.
Dissolve in 200 parts, add 30 parts of Glauber's salt, add 10 parts of cotton, and add 80 parts.
Heat to ° C. Then, after a lapse of 30 minutes, 3 parts of sodium carbonate are added, and the mixture is dyed at the same temperature for 1 hour. After the completion of dyeing, washing with water and soaping were performed to obtain a bright scarlet dyed product having various fastnesses and good build-up properties.

Dyeing Example 2 Color paste composition Compound described in Example 1 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 mercerized After printing on cotton broad cloth, intermediate drying, steaming at 120 ℃ for 5 minutes, wash with hot water, soaping, hot water and dry to finish.
In this way, a clear red printed matter having various fastnesses was obtained.

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I): [In the formula, A represents a phenylene group or a naphthylene group which may have a substituent, R ₁ and R ₂ each independently represent a hydrogen atom or an optionally substituted lower alkyl group, and D represents the following. Formula (a): (In the formula, D ₀ is a bicyclic aryl group or a bond —N═N
-Has a sulfonic acid group as a substituent at the ortho position, and further represents a monocyclic aryl group substituted with a halogen atom, an alkyl group, an acylamino group or an alkoxy group,
Mark *, -N in the general formula (I) (R ₁₎ - group, a naphthalene nucleus 6, indicating that it is bound to the 7 or 8-position. However, the naphthalene nucleus may have a sulfonic acid group as a substituent at the 5- or 6-position. ) Represents a monoazo organic dye residue. A triazine compound represented by the formula: