KR100531409B1 - Mixture dyes of metal complex formazan derivatives and methods for reactive dyeing with them - Google Patents

Abstract

The present invention relates to a metal complex salt formazan mixture dye which can be used for dyeing a hydroxy group-containing material and a dyeing method using the same. The mixture dye according to the present invention is a dicyclic formazan derivative of Formula 1 (see specification) and Formula 2 ( It is composed of a certain amount of a tricyclic formazan derivative (see specification), such a mixture not only shows excellent solubility compared to the dye alone, but also using such a mixture dyes for hydroxy group-containing materials such as cotton, hemp, rayon, etc. When dyed, compared with the dyes of these compounds alone, it exhibits excellent color fastness, washing fastness, fastness of daylight, fastness of sweat, fastness of chlorine water, and fastness to build up.

Description

MIXTURE DYES OF METAL COMPLEX FORMAZAN DERIVATIVES AND METHODS FOR REACTIVE DYEING WITH THEM

The present invention relates to a dye mixture of metal complex salt formazan derivatives that can be used for dyeing of hydroxy group-containing materials and a method for preparing the same, and more particularly, to a bicyclic formazan derivative having a specific structure and a tricyclic formazan having a specific structure. As a mixture dye containing a certain amount of a derivative, such a mixture not only exhibits excellent solubility as compared with a single dye, but also when dyeing a hydroxyl group-containing material such as cotton, hemp, rayon, etc. using such a mixture dye, Compared to the above, it exhibits excellent fastness and build-up properties such as excellent dyeing rate, washing fastness, daylight fastness, daylight fastness and chlorine water fastness.

Metal complex salt formazan derivatives as reactive dyes are generally in the form of metal complex salts having a vinyl sulfone group or a vinyl sulfone group and a monochlorotriazine, and many derivatives of bicyclic and tricyclic structures are known in the art. It is.

For example, the bicyclic metal formazan derivative includes a compound having the structure as disclosed in British Patent No. 81-4783;

There is a compound of the structure disclosed in US Pat. No. 4,607,098.

These bicyclic formazan derivatives are not excellent in dyeing rate and overall fastness, and the bicyclic metal complex salt formazan derivatives having superior physical properties include compounds having the following structures disclosed in Korean Patent No. 134,648 of the applicant.

On the other hand, examples of the tricyclic metal complex salt formazan derivative include compounds of the following structures disclosed in Japanese Patent Application No. 1981-4783;

A compound having the structure disclosed in Japanese Patent Application No. 1980-12187,

A compound having the structure disclosed in U.S. Patent No. 3,926,942,

Compounds of the following structure disclosed in Korean Patent Laid-Open No. 1984-5461, and the like.

These tricyclic metal complex salt formazan derivatives have a problem in that dyeing rate is superior to dicyclic derivatives, but the manufacturing cost is high, and the fastness of washing with water and the like is not satisfactory.

As can be seen from above, the metal complex salt formazan dye compound has a basic skeleton is almost the same according to the dicyclic or tricyclic structure, it can be seen that the dyeing rate, color fastness and the like depending on the type and position of the substituent.

On the other hand, in recent years, due to the development of various kinds of fibers and the enhancement of consumer tastes, high-quality dyeings are required, and thus, a need for dyes having better dyeing properties and improved overall fastness than the dyes is increasing.

In addition, there is a high need for a dye having a high dyeing efficiency, that is, a dye capable of exerting a desired dyeing effect in a small amount.

Therefore, an object of this invention is to provide the reactive blue dye which solves these technical subjects at once.

The present inventors have conducted a number of experiments and comparative analyzes as a continuous study on the applicant's Korean Patent No. 134,648, and each of which includes a bicyclic metal complex salt formazan derivative and a tricyclic metal complex salt formazan derivative of a specific structure. It has been found that the mixture dyes provide higher dyeing rates than the average of the dyeing yields of the dyes obtained from the respective compound dyes, are also better at all other fastnesses and buildups, and are superior in solubility, leading to the present invention. It became. This synergistic effect is totally unexpected and shows excellent improved properties of the inventive mixture dyes when compared to the individual compound dyes in the mixture.

The mixture dye according to the present invention for achieving the above object comprises a bicyclic formazan derivative of the general formula (1) and a tricyclic formazan derivative of the general formula (2) in a 99: 1 to 1: 99 (molar ratio).

Where

A ₁ is a substituted or unsubstituted phenylene group or naphthylene group having one or more sulfone groups (—SO ₃ M);

A ₂ is a substituted or unsubstituted phenylene group or a naphthylene group;

B is a straight or branched alkyl group, alkenyl group, substituted or unsubstituted phenyl group or naphthyl group or heterocyclic group;

D is a substituted or unsubstituted phenylene group or a naphthylene group;

M is a hydrogen atom or an alkali metal or alkaline earth metal;

Me is a metal ion of atomic number 27 to 29;

X is a group that provides solubility in hydrogen atoms or water;

Y is a halogen atom;

R is a straight or branched chain alkyl group or a hydroxy alkyl group;

Q is a -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ L, where L is a substituent which may be substituted or removed from the alkali and; And,

l, m and n are each an integer of 0-3.

Where

A ₁ is a substituted or unsubstituted phenylene group or a naphthylene group;

Z is -O- or;

A ₂ , B, D, Me, R, Q, X, Y, l, m and n are the same as in the general formula (1).

More detailed descriptions of Chemical Formulas 1 and 2 are as follows.

Substituents for the phenylene group or naphthylene group defined in A ₁ and A ₂ include halogen, nitro, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, sulfamoyl group, N-mono, N, N -Dialkyl (C1-4) sulfamoyl, C1-4 alkylsulfonyl group, phenylsulfonyl group, etc. are preferable, and chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, sulfamoyl or N, N-diethylsulfamoyl group and the like are more preferable.

When said B is a linear or branched alkyl group, a C1-C8 alkyl group is preferable and a C2-C8 alkyl group is more preferable.

When B is a phenyl group or a naphthyl group, it is preferable that a substituent is a halogen, a hydroxyl group, a nitro group, a C1-C4 alkyl group, a C1-C4 alkoxy group, and a C1-C4 carboalkoxy group.

In the case where B is a heterocyclic group, furan, thiophene, pyrrole, imidazole, indole, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, and the like are preferable, and are bonded to the ring carbon constituting the heterocycle. The hydrogen atom may be substituted with chlorine, phenyl, methyl, ethyl, methoxy, ethoxy, and the like, and the hydrogen atom bonded to the heteroatom of the heterocycle may be substituted with a substituent such as methyl, ethyl, benzyl, or the like.

When D is a phenylene group, unsubstituted or one or more hydrogen atoms may be substituted with a halogen element, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and among them, methyl, ethyl, methoxy and ethoxy More preferred is chlorine or bromine. When D is a naphthylene group, the case where it is unsubstituted or substituted by sulfonic acid group is preferable.

Me may be a metal having an atomic number of 27 to 29, but Cu having an atomic number of 29 is most preferred.

In the above X, sulfonic acid, carboxylic acid, phosphonic acid, and the like may be used as the substituents to provide solubility in water, and among these, sulfonic acid is most preferable, and these are those of A ₁ , A ₂ and B constituting the formazan ring. It may be substituted with a ring carbon atom or an aliphatic carbon atom substituted with a ring.

The halogen represented by Y is preferably fluorine, chlorine or bromine, and particularly preferably fluorine and chlorine.

R is preferably a lower alkyl group such as methyl, ethyl, propyl or butyl, which may be substituted with hydroxy, carboxy, sulfo, carbamoyl, methoxycarbamoyl and the like. In particular, methyl, ethyl, carbamoylethyl, hydroxyethyl, n-propyl, iso-propyl and the like are suitable.

It is preferable that the sum of l, m, and n is 2-3.

When Q is SO ₂ CH ₂ CH ₂ L, L is halogen such as chlorine or bromine, or ester group of organic carboxyl group or sulfonic acid such as acetyloxy group, benzoyloxy group, benzenesulfonyloxy group, lower alkanoyloxy group, etc. , it is preferred _{-OPO 3 H 2, -OSO 3 H} , -SSO 3 H , etc. are preferred, and particularly -OSO ₃ H. Thus, Q may be represented by -SO ₂ CH ₂ CH ₂ OSO ₃ H, some of which may have the form of -SO ₂ CH = CH ₂ in the form of sulfuric acid removed by alkali.

In Formulas 1 and 2, the moiety represented by Formula 3 may be substituted with any part of phenyl, naphthyl, alkyl, alkenyl, phenylene, naphthylene, heterocyclic or branched carbon atom, but is substituted with phenyl or phenylene group. The case is preferred.

The bicyclic formazan derivative of Formula 1 and the tricyclic formazan derivative of Formula 2 are preferably compounds defined by the following Formulas 4 and 5, respectively.

In Formulas 4 and 5, D, M, R, Q, and Y are the same as in Formula 1, p, q, and r are each 0, 1 or 2, and the sum thereof is an integer of 2 to 3.

The mixture dyes of the formulas (1) and (2) according to the present invention exhibit excellent dyeing properties, solubility, overall fastness, buildup properties and the like compared to the dyes of the compounds of formulas (1) and (2) alone. For example, the dyeing rates of dyes obtained from mixture dyes could be higher than the average of the sum of the dyeing rates of dyes obtained from each compound dye, in particular their solubility obtained from the individual dyes or their sum It was much higher, and the fastness and buildup were also excellent. This is a unique synergistic effect of the present invention which is not at all unexpected in the past.

In order to exert the synergistic effect according to the present invention, the content of each component of the formulas (1) and (2) in the mixture of dyes should be at least 1% in molar ratio, preferably the molar ratio of the formulas (1) and (2) is 20:80 to 80: 20, More preferably, it is 30: 70-70: 30. At this time, the components corresponding to the formulas (1) and (2) may each be one kind of compound or a combination of two or more kinds of compounds.

The mixture dye according to the present invention may include various compounds, mixtures, complexes, and the like, which are known in the art, in order to increase the properties of the dye or the efficiency of the dyeing process, so long as the effects of the present invention are not impaired.

The preparation method of the bicyclic formazan derivative of Formula 1 and the tricyclic formazan derivative of Formula 2 which are constituents of the mixture dye according to the present invention are as follows.

The bicyclic formazan derivative of Chemical Formula 1 is prepared by reacting a formazan compound represented by Chemical Formula 6 with 1,3,5-trihalogeno-s-triazine represented by Chemical Formula 6 below. After the condensation reaction with the amine compound of Formula 8 it can be prepared. Alternatively, the compound of formula 9 obtained by reacting 1,3,5-trihalogeno-s-triazine with an amine compound of formula 8 may be prepared by reacting with a bicyclic formazan pigment group of formula 6 .

In Formulas 6 to 9, the definitions of A ₁ , A ₂ , B, D, M, Me, R, Q, X, Y, l, m, and n are the same as in Formula 1.

The tricyclic formazan derivative of Chemical Formula 2 is prepared by reacting the tricyclic formazan pigmented body represented by the following Chemical Formula 10 with 1,3,5-trihalogeno-s-triazine to form the Formazan compound of Chemical Formula 11 After the condensation reaction with the amine compound of Formula 8 can be prepared again. Alternatively, the compound of Formula 9 obtained by reacting 1,3,5-trihalogeno-s-triazine with an amine compound of Formula 8 may be prepared by reacting with a tricyclic formazan pigment group of Formula 10 below. .

In Formulas 10 and 11, the definitions of A ₁ , A ₂ , B, D, Me, R, Q, X, Y, Z, l, m, and n are the same as in Formula 2.

The reaction conditions of the compounds of Chemical Formulas 1 and 2 are not particularly limited, and in the case of the condensation reaction, the reaction may be performed at -5 to 70 ° C at pH 2 to 8, preferably at 0 to 60 ° C at pH 3 to 6. Can be. The first condensation reaction and the second condensation reaction can be carried out under different conditions. The second condensation reaction can be carried out at a higher pH and temperature than the first condensation reaction. For example, the first condensation reaction is carried out at -2 to 20 ° C at pH 2 to 4, and the second condensation reaction is carried out at 20 to 70 ° C at pH 4 to 8.

A method for preparing a bicyclic formazan pigmented parent of Formula 6 and an amine compound of Formula 8 is disclosed in Korean Patent No. 135,648 of the applicant described above, which is incorporated herein by reference. In addition, the preparation method of the tricyclic formazan pigmented parent of Formula 10 is the same as the method of preparing the dicyclic formazan pigmented mother, except that the formula 12 of the following formula used when preparing the bicyclic formazan pigmented mother The only difference is that the compound of formula 13 is used instead of the compound.

A ₁ , M, X ₁ and Z in Formulas 12 and 13 are the same as in Formulas 1 and 2.

Mixture dyes according to the invention can be prepared in powders, granules and mixed solutions, and can be used by mixing respective dye compounds immediately before dyeing. These mixture dyes are prepared by mechanically mixing the respective dye compounds of Formulas 1 and 2, or by chemical synthesis at one reaction port, e.g., reaction raw materials common to one reaction batch and individual reaction raw materials together. It can also be prepared by using their individual condensation reaction.

The two kinds of components constituting the mixture dye may be added with other components required for dyeing. For example, the powder mixture contains inorganic salts in the range of 20 to 30% by weight, based on the total weight of the mixture dye. Preferably, as the inorganic salt, 15 to 20% by weight of an electrolyte salt and 5 to 10% by weight of a buffer salt may be used. Representative examples of the electrolyte salt may include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, and the like, and the buffer salt is a salt for adjusting the pH of an aqueous solution in which a mixture dye is dissolved to 3 to 7, and representative examples thereof include sodium carbonate, Sodium bicarbonate, sodium acetate, sodium borate, sodium citrate, sodium monohydrogen phosphate and sodium dihydrogen phosphate.

When the powder mixture is converted to an aqueous solution and stained, the mixture is adjusted to dissolve 5 to 15 wt% based on the total weight of the aqueous solution.

The invention also relates to a method of dyeing a hydroxy group containing material in blue using the mixture dye. Examples of the hydroxy group-containing material include natural cellulose fibers such as cotton, flax and hemp, pulp and recycled or synthetic cellulose, and blended fibers with other synthetic fibers.

Mixture dyes according to the invention can be used in a variety of known ways, in particular in the form of an aqueous dye solution can be applied to the fiber material or fixed to the fiber. For example, an aqueous solution of these dye mixtures (which may contain salts and alkalis) is impregnated with fibers, and the salts are fixed with the action of salts with alkali, or CPB for storage and fixation at room temperature for several to several tens of hours; Suitable for both continuous dyeing.

When the dye mixture according to the invention is used for the dyeing of cellulose fibers, it is characterized by high fixing strength. After conventional post-treatment by washing to remove non-fixed dyes, the cellulose fiber dyeings show good wet fastness, especially since the non-fixed dye portions have good solubility in cold water and can be easily washed. . In particular, daylight fastness, sweatfastness fastness, washing fastness, chlorine water fastness and sweat fastness has very excellent characteristics.

Hereinafter, specific experimental examples of the present invention will be described with reference to Examples, but these are merely illustrative of the present invention, and the scope of the present invention is not limited thereto. In the following examples, "parts" means parts by weight unless otherwise specified.

Example 1

A bicyclic formazan derivative (A) corresponding to Formula 1 and a tricyclic formazan derivative (B) corresponding to Formula 2 were prepared by the method described in or similar to Korean Patent No. 135,648 of the applicant. A mixture of each of the formazan derivatives and the inorganic salts (A 'and B') was prepared to include 20% by weight of inorganic salt (sodium chloride) based on the total weight of the mixture, and then, these were mixed in 50 parts and 50 parts to 100 parts of A mixture dye was made. As a result of dyeing the cellulose fibers according to the following dyeing and fixing method, the resultant dye mixture was obtained as a blue dye having excellent dyeing rate and light and water fastness.

[Compound A]

[Compound B]

(Dyeing and Fixing Method)

Two parts of the resulting mixture dye were dissolved in 398 parts of water, and a saline solution was prepared by adding 1500 parts of a solution containing 50 parts of sodium chloride per 1000 parts. 100 parts of cotton fabrics were put into this solution at 35 degreeC, and after 20 minutes, 100 parts of solutions containing 16 parts of sodium hydroxide and 20 parts of sodium carbonate were added per 1000 parts. The temperature of the salt bath was maintained at 35 ° C. for an additional 15 minutes, then the temperature was raised to 60 ° C. over 20 minutes and then at 60 ° C. for an additional 40 minutes. The dyeings were then washed with cold water, soaped at 100 ° C. for 30 minutes, then washed and dried.

Example 2

100 parts of the mixture dye was prepared in the same manner as in Example 1, except that 20 parts of the mixture (A ') and 80 parts of the mixture (B') of Example 1 were mechanically mixed. This mixture dye was dyed in the same manner as in Example 1 to obtain a blue dye having excellent dyeing rate, daylight and washing fastnesses.

Example 3

100 parts of the mixture dye were prepared except that 70 parts of the mixture A 'of Example 1 and 30 parts of the mixture B' were mechanically mixed. This mixture dye was dyed in the same manner as in Example 1 to obtain a blue dye having excellent dyeing rate, daylight and washing fastnesses.

Example 4

In the same manner as in Example 1, a tricyclic formazan derivative of the following compound C was prepared, and 40 parts of the mixture (C ′) in which 20% by weight of sodium chloride was mixed based on the total weight of the mixture, and the mixture of Example 1 60 parts of (A ') were mixed and 100 parts of mixture dyes were obtained. This mixture was dyed in the same manner as in Example 1 to obtain a light blue dye having excellent dyeing rate, daylight and wash fastnesses.

[Compound C]

Example 5

100 parts of the mixture dye was prepared in the same manner as in Example 1, except that 30 parts of Mixture A 'of Example 1, 40 parts of Mixture B' and 30 parts of Mixture C 'of Example 4 were mixed. This mixture was dyed in the same manner as in Example 1 to obtain a light blue dye having excellent dyeing rate, daylight and wash fastnesses.

[Examples 6 to 100]

To prepare a mixture dye combining the dye compounds (compounds D-X) and compounds A, B, C of the following Table 1 corresponding to the formulas 4 and 5 in the proportions defined in Tables 2 to 4, using Example 1 Cellulose fibers were dyed in the same manner as in to obtain a blue dye. At this time, the structures of the formazan pigment matrix corresponding to the formulas (6) and (10) are represented by the following I, II and III.

[Color pigment Ⅰ]

[Color Pigment II]

[Color Pigment III]

Comparative Example 1

In order to compare the physical properties of the dicyclic formazan derivative dye alone selected from Formula 1 with the properties of the mixture dye according to the present invention, the compound dye of Formula A (see Example 1) was dyed in the same manner as in Example 1 The results in Example 1 are compared with Table 6 below.

Comparative Example 2

In order to compare the physical properties of the tricyclic formazan derivative dye alone selected from Formula 2 with the properties of the mixture dye according to the present invention, the compound dye of Formula B (see Example 1) was dyed in the same manner as in Example 1 The results in Example 1 are compared with Table 5 and shown.

First, the method of measuring the dyeing rate, solubility, various fastnesses and buildup properties are as follows, and the grades for each evaluation criteria are shown in Table 5 below.

[Measuring method of dyeing rate, solubility, various fastnesses and buildup properties]

1. Dyeing rate : After drying the fabric (cloth) dyed by the dyeing method, and measuring the front and back of the dyed cloth evenly eight times or more using a colorimeter to obtain an average, based on the dyeing rate of Example 1 ( 100) is shown.

2. Solubility : The dye was added and dissolved in 50 g / L sodium sulfate and 20 g / L sodium carbonate mixed solution at 60 ° C. in 5 g / L units, and then filtered through a filter paper to determine the maximum value of insoluble dye particles.

3. Wash fastness : Put the dye cloth and white cloth in the solution containing 5 g / L of soap solution and 2 g / L of soda ash, and put 10 steel balls into it and attach it to the laundry fastness measuring instrument. The operation was measured for 30 minutes at. The measurement results were divided into 5 grades.

4. Daylight Fastness : Experimented by ISO-B02. The measurement results were divided into 5 grades.

5. Sweat daylight fastness : Experiment by JIS 0888. The measurement results were divided into 5 grades.

6. Chlorine water fastness : The test was performed according to ISO-E03. The measurement results were divided into 5 grades.

7. Acid sweat fastness : L-histidine hydrochloride 0.5 g / L mixed with sodium monophosphate and sodium chloride to adjust the pH to 5.5, then put the dyeing cloth between the glass plate and maintained at a constant pressure of 30 ℃ constant temperature for 4 hours, 60 Dried at ° C. The measurement results were divided into 5 grades.

8. Alkaline sweat fastness : After adjusting the pH of 8 by mixing sodium diphosphate and sodium chloride with 0.5 g / L of L-histidine hydrochloride, it was measured in the same manner as the acid sweat fastness measurement method. The measurement results were divided into 5 grades.

9. Build-up property : After drying the cloth (cloth) dyed at each designated concentration by the dip dyeing method, the front and the back of the dyed tip were measured evenly eight times or more using a colorimeter, and then averaged. Relative values based on 8% dyeing (100) are shown in FIG. 1.

As can be seen in the comparative results of Table 6, when the dye using the compound dye alone (Comparative Examples 1 and 2), while the dyeing rate is 90 or 96, the mixture of Example 1 according to the present invention in the same amount When the dye is used, the dyeing rate is 100, and it can be seen that the mixture dye according to the present invention shows a better dyeing rate than the arithmetic mean value for the dyes of the compound alone. In particular, it was confirmed that the solubility (100) of the mixture dye of Example 1 according to the present invention was significantly higher than the solubility (50, 40) of the dye alone or the sum thereof. When the solubility of the dye is low, the amount of the dye used to dissolve in water for dyeing is increased and the amount of the discarded dye is increased, and thus there is a problem in that the overall efficiency is lowered, such as poor dyeing efficiency. In addition, it was confirmed that the mixture dye of Example 1 according to the present invention has better daylight fastness, sweat sunfastness, chlorine water fastness, sweat fastness, and the like, than the dye of the compound alone. On the other hand, as can be seen in Figure 1, it can be seen that the dye of Example 1 is significantly superior to the dye of the compound alone in terms of build-up (Build-Up). This indicates that excellent dyeing rates can be obtained even with a small amount of dyes at high concentrations, and thus have a special effect in reducing the amount of dye used, reducing the waste dyes and suppressing the generation of waste water.

Those skilled in the art to which the present invention pertains may make various applications and modifications within the scope of the present invention based on the above contents.

The mixture dye of the dicyclic formazan derivative of Formula 1 and the tricyclic formazan derivative of Formula 2 according to the present invention has excellent dyeing rate and solubility compared to the dye of each of these compounds alone, It has excellent fastness and buildup.

1 is a comparative graph of buildup properties of the dye of Example 1 of the present invention and the dye of the compound alone.

Claims (10)

A metal complex salt formazan mixture dye, comprising a bicyclic formazan derivative of Formula 1 and a tricyclic formazan derivative of Formula 2 at 99: 1 to 1:99 (molar ratio). (One) Where A ₁ is a substituted or unsubstituted phenylene group or naphthylene group having one or more sulfone groups (-SO ₃ M), wherein the substituted phenylene group or naphthylene group is chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy A phenylene group or a naphthylene group substituted with a sulfamoyl or N, N-diethylsulfamoyl group; A ₂ is a substituted or unsubstituted phenylene group or a naphthylene group, wherein the substituted phenylene group or naphthylene group is chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, sulfamoyl or N, N-diethylsulfamo Phenylene group or naphthylene group substituted with a diary; B is a linear or branched alkyl group having 2 to 8 carbon atoms, an alkenyl group, a substituted or unsubstituted phenyl group or a naphthyl group or a heterocyclic group, and the substituents of the substituted phenyl group or naphthyl group are halogen, hydroxy group, nitro group and alkyl group having 1 to 4 carbon atoms. , An alkoxy group having 1 to 4 carbon atoms, or a carboalkoxy group having 1 to 4 carbon atoms, wherein the heterocyclic group is furan, thiophene, pyrrole, imidazole, indole, pyrazole, pyridine, pyrimidine, quinoline, or benzimi Doazole; D is a substituted or unsubstituted phenylene group or a naphthylene group, wherein the substituted phenylene group is a phenylene group substituted with methyl, ethyl, methoxy, ethoxy, chlorine or bromine, and the substituted naphthylene group is a naphthalene group substituted with a sulfonic acid group ; M is a hydrogen atom or an alkali metal or alkaline earth metal; Me is a metal ion of atomic number 27 to 29; X is a group that provides solubility in hydrogen atoms or water; Y is a halogen atom; R is a straight or branched chain alkyl group or a hydroxy alkyl group; Q is a -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ L, where L is a substituent which may be substituted or removed from the alkali and; And, l, m and n are each an integer of 0-3. (2) Where A ₁ is a substituted or unsubstituted phenylene group or a naphthylene group, wherein the substituted phenylene group or naphthylene group is chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, sulfamoyl or N, N-diethylsulfamo Phenylene group or naphthylene group substituted with a diary; Z is -O- or; A ₂ , B, D, Me, R, Q, X, Y, l, m and n are the same as in the general formula (1). The method of claim 1, Me is Cu; The substituent providing solubility in water at X is sulfonic acid; Halogen in Y is fluorine or chlorine; R is methyl, ethyl, carbamoylethyl, hydroxyethyl, n-propyl, or iso-propyl; The sum of l, m and n is 2 to 3; Metal complex salt formazan mixture dye, wherein Q is -SO ₂ CH ₂ CH ₂ OSO ₃ H. The metal complex salt formazan mixture dye according to claim 1, wherein the dicyclic formazan derivative of Formula 1 and the tricyclic formazan derivative of Formula 2 are compounds represented by the following Formulas 4 and 5. (4) (5) In Formulas 4 and 5, D, M, R, Q, and Y are the same as in Formula 1, p, q, and r are each 0, 1 or 2, and the sum thereof is an integer of 2 to 3. The metal complex salt formazan mixture dye according to claim 1, wherein the moiety represented by the following Chemical Formula 3 in Chemical Formulas 1 and 2 is substituted with a phenyl or phenylene group. (3) The metal complex salt formazan mixture dye according to claim 1, wherein the mixing ratio of the dicyclic formazan derivative of Formula 1 and the tricyclic formazan derivative of Formula 2 is 20:80 to 80:20 in molar ratio. The metal complex salt form according to claim 1, wherein the dicyclic formazan derivative component of Formula 1 and the tricyclic formazan derivative component of Formula 2 are each one kind of compound selected from these formulas, or a combination of two or more kinds of compounds. Marzan mixture dye. According to claim 1, wherein the bicyclic formazan derivative of Formula 1 is reacted with the bicyclic formazan pigments represented by Formula 6 and 1,3,5-trihalogeno-s-triazine to form the After preparing a marzan compound, the compound of Formula 9 obtained by condensation reaction with an amine compound of Formula 8 or by reacting 1,3,5-trihalogeno-s-triazine with an amine compound of Formula 8 A metal complex salt formazan mixture dye, which is prepared by reacting with a bicyclic formazan pigment matrix of 6. (6) (7) (8) (9) In Formulas 6 to 9, the definitions of A ₁ , A ₂ , B, D, Me, R, Q, X, Y, l, m, and n are the same as in Formula 1. According to claim 1, wherein the tricyclic formazan derivative of formula (2) is reacted with the tricyclic formazan pigments represented by the formula (10) and 1,3,5-trihalogeno-s-triazine to form the After preparing a marzan compound, the compound of Formula 9 obtained by condensation reaction with an amine compound of Formula 8 or by reacting 1,3,5-trihalogeno-s-triazine with an amine compound of Formula 8 A metal complex salt formazan mixture dye, which is prepared by reacting with a tricyclic formazan pigment matrix of 10. 10 (11) In Formulas 10 and 11, the definitions of A ₁ , A ₂ , B, D, Me, R, Q, X, Y, Z, l, m, and n are the same as in Formula 2. The metal complex salt formazan mixture dye according to claim 1, further comprising 15 to 20% by weight of an electrolyte salt and 5 to 10% by weight of a buffer salt, based on the total weight of the mixture. A dyeing method comprising dyeing a hydroxy group-containing material in blue using a metal complex salt formazan mixture dye according to any one of claims 1 to 9.