KR100688310B1 - Metal complex reactive azo dyes, preparation method thereof and composition comprising the same - Google Patents

Abstract

Provided is an azo-based metal complex reactive dye, which has advantages of both azo-based metal complex dyes and reactive dyes, and shows an improved sunlight fastness and a high fixation ratio. The azo-based metal complex reactive dye is represented by a formula of MxAyBz, wherein M represents a metal selected from the group consisting of Cr, Co, Fe, Cu and Ni; each of x and y represents 1 or 2, and z is 1, 2 or 3; A is selected from tridendate ligands represented by formulae 7-13; B represents H2O or is selected from tridendate ligands represented by the formulae 7-13; each of R1 and R2 is selected from the group consisting of -OH, -NH2, -COOH, -NHCOCH2COCH3 and -NH-(C6H5); and at least one of R3-R9 is -NHCOCHBrCH2Br or -NHCOCBr=CH2, and each of the remaining substituents of R3-R9 is selected from the group consisting of -H, -NH2, -SO3H, -OH, -COOH, -CH3, -OCH3, -NH-(C6H5), -NH-(C6H5)CH3, -NHSO2-(C6H5), -NHSO2-(C6H5)Cl, -NHSO2-(C6H5)COOH, -NHCOCH3, -NH2CH3, -SO2NH2, -NHSO2CH3, -N(CH3)2, -N(C2H5)2, -NO2, -NHCONH2, -CONH2, -N(C2H4OH)2 and -OC2H5.

Description

Azo-based metal complex reactive dyes, a method for preparing the same, and a composition comprising the same {METAL COMPLEX REACTIVE AZO DYES, PREPARATION METHOD THEREOF AND COMPOSITION COMPRISING THE SAME}

The present invention relates to an azo-based metal complex reactive dye, a method for preparing the same, and a composition comprising the same.

Azo metal complex dyes are broadly classified into 1: 1 metal complex dyes, 1: 2 symmetric metal complex dyes, and 1: 2 asymmetric metal complex dyes.

Formulas 1 to 4 below illustrate azo-based metal complex dyes listed in the Color Index (C.I.) and disclosed to the public.

Formula 1 is a 1: 1 chromium complex dye. No. Acid Blue 158, Formula 2, is an example of a 1: 2 symmetric chromium complex dye. No. Acid Black 172, Formula 3, is an example of a 1: 2 asymmetric chromium complex dye. No. Acid Red 405, Formula 4 is an example of a 1: 2 symmetric cobalt complex dye.

In addition, one of the inventors of the present invention has recently invented a new type of asymmetric chromium complex dye, which has a structure and a manufacturing method different from the conventionally known azo-based metal complex dye, and has applied for the patent. (International Application Publication No. WO 2002/79326).

Azo-based metal complex dyes are applied in acid dyes, and the properties of these dyes are similar to acid dyes. That is, these are compounds in which chromium, cobalt, or other metal molecules are present in the dye molecule, and the metal is dyed to the fiber, and thus, the fastness to friction, sweat, especially sunlight, and the water resistance are also evaluated. Therefore, the azo-based metal complex dyes currently on the market are widely used in the nylon and wool fiber markets due to their high daylight fastness and deep color characteristics.

However, since they are acid dyes, they are not a problem when dyeing fibers such as nylon, but when used for wool fibers, more dyes remain after dyeing than reactive dyes, which may cause wastewater treatment.

Reactive dyes structurally include leaving groups capable of nucleophilic substitution reactions with hydroxyl groups of cellulose or activated carbon-carbon double bonds capable of nucleophilic addition reactions. Therefore, reactive dyes are not only vividly dyed, but are also dyed through chemical covalent bonds, and thus generally have high dyeing rates and excellent fastnesses such as washing and rubbing compared to other dyes. Since these dyes are fixed through chemical covalent bonds with fibers, the dyeing properties of the dyes are largely determined by the reactive group used. The binding properties and stability between the dye and the fiber molecules before dyeing depend on the reactor of the dye, and the wet fastness of the dye can be seen as a function of the stability of the dye-fiber intermolecular bonds during washing or washing.

Formula 5 shows an example of a bromoacyl-based intermediate that is currently used in large quantities in the manufacture of reactive dyes.

It is an object of the present invention to provide an azo-based metal complex reactive dye having the advantages of both an azo-based metal complex dye and a reactive dye, a preparation method thereof, and a composition comprising the same.

Another object of the present invention is to solve the daylight fastness problem of the reactive dye using the high daylight fastness of the azo-based metal complex dyes, metal complex salt-based bifunctional reactive dyes, which can also maintain a high fixation rate of the metal complex dye, the preparation thereof It is to provide a method and a composition comprising the same.

An object of the present invention described above is to reduce a nitro group substituted in an aromatic ring of an azo metal complex dye having a nitro group to an amine group, a metal complex salt-based bifunctional reactive dye having a bifunctional reactor introduced therein, and a method for preparing the same It is achieved by providing a dye composition comprising.

Therefore, the azo-based metal complex reactive dye according to the present invention is a halogenated acrylic intermediate bonded to the azo-based metal complex dye, the structure is represented by the following formula (6).

In the above formula,

M is a metal selected from the group consisting of Cr, Co, Fe, Cu and Ni,

x and y are each 1 or 2, z is 1, 2 or 3,

A is selected from tridentate ligands having the structures shown in Formulas 7-13,

B is H ₂ O or selected from tridentate ligands having the structure shown in Formulas 7 to 13,

In Formulas 7 to 13, R ₁ and R ₂ are each selected from the group consisting of -OH, -NH ₂ , -COOH, -NHCOCH ₂ COCH ₃ and -NH- (C ₆ H ₅ ), R ₃ to R ₉ as necessary during the substituent -NHCOCHBrCH or ₂ Br -NHCOCBr = CH ₂ that is contained at least one, or -NHCOCHBrCH ₂ Br -NHCOCBr = CH ₂ R ₃ to the rest of the R ₉ substituent is not -H, - NH ₂ , -SO ₃ H, -OH, -COOH, -CH ₃ , -OCH ₃ , -NH- (C ₆ H ₅ ), -NH- (C ₆ H ₅ ) CH ₃ , -NHSO _2- (C ₆ H ₅ ), -NHSO _2- (C ₆ H ₅ ) Cl, -NHSO _2- (C ₆ H ₅ ) COOH, -NHCOCH ₃ , -NH ₂ CH ₃ , -SO ₂ NH ₂ , -NHSO ₂ CH _{3 , -N (CH 3) 2,} -N (C 2 H 5) 2, -NO 2, -NHCONH 2, -CONH 2, -N (C 2 H 4 OH) ₂ and the group consisting of -OC ₂ H ₅ Will be selected.

In the halogenated acrylic intermediate, the halogen atom may be fluorine, chlorine, bromine or iodine.

In Chemical Formula 6, when x = y = 1, z = 3, A is selected from tridentate ligands having the structures shown in Chemical Formulas 7 to 13, and B is H ₂ O, these compounds are 1 It becomes a: 1 metal complex reactive dye.

When x = y = z = 1, the A and B may be the same or different from each other selected from those having a structure shown in the formulas (7) to 13, the same compound A and B are 1: 2 symmetry A metal complex reactive dye, a compound in which A and B differ from each other, becomes a 1: 2 asymmetric metal complex reactive dye.

On the other hand, when x = y = z = 2, two A may be the same tridentate ligand selected from Formula 7 to 13, two B may be a different tridentate ligand selected from Formula 7 to 13, In particular, the two A may be a ligand having Formula 13, one of two B may be a ligand represented by Formula 7, and the other one may be a ligand represented by Formula 9.

The compound represented by Chemical Formula 6 may be selected from Cr, Co, Fe, Cu, and Ni, and one, two, or four three or the same or different from each other selected from compounds having one or more nitro groups, represented by the following Chemical Formulas 7a to 13a: The nitro group of the azo-based metal complex compound in which the site ligand is coordinated can be prepared by reducing an amine group and introducing a bromoacrylic intermediate into the amine group.

Therefore, according to the present invention, the method for preparing the azo-based metal complex reactive dye of Formula 6,

(1) The nitro group of a compound in which one, two or four tridentate ligands identical or different from each other represented by the following Chemical Formulas 7a to 13a are coordinated with a metal selected from Cr, Co, Fe, Cu and Ni is selected as an amine group. Reducing to obtain an amine compound,

(2) reacting the product of step (1) with a 2,3-dihalogenated propionyl halide to obtain a compound having a 2,3-dihalogenated acyl group introduced therein;

In Chemical Formulas 7a to 13a,

R ₁ and R ₂ are each selected from the group consisting of -OH, -NH ₂ , -COOH, -NHCOCH ₂ COCH ₃ and -NH- (C ₆ H ₅ ),

Any one of R ₃ to R ₉ is necessarily a nitro group, and the remaining R ₃ to R ₉ substituents which are not nitro groups are -H, -NH ₂ , -SO ₃ H, -OH, -COOH, -CH ₃ , -OCH ₃ , -NH- (C ₆ H ₅ ), -NH- (C ₆ H ₅ ) CH ₃ , -NHSO _2- (C ₆ H ₅ ), -NHSO _2- (C ₆ H ₅ ) Cl, -NHSO _2- (C ₆ H ₅ ) COOH, -NHCOCH ₃ , -NH ₂ CH ₃ , -SO ₂ NH ₂ , -NHSO ₂ CH ₃ , -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -NO ₂ , -NHCONH ₂ , -CONH ₂ , -N (C ₂ H ₄ OH) ₂ and -OC ₂ H ₅ .

Examples of 2,3-dihalogenated propionyl halides used as reactants in step (2) include 2,3-dibromopropionyl chloride.

In the present invention, the compound obtained in step (2) may be further converted to a compound having a halogenated acrylic group by dehydrohalogenation under basic conditions, and the converted compound is more preferable in terms of the user's dyeing environment. You may.

In general, an aromatic nitro compound can be reduced to an amino compound by iron reduction, zinc reduction, hydrogen catalytic reduction, hydrazine reduction, a reduction method using Na ₂ S and NaSH, and the like. Among them, such as iron reduction, a method using a metal or a metal oxide is not only inconvenient in process because it requires filtering a large amount of metal oxide produced after the reaction, and is also disadvantageous in terms of environment and economics because it is not easy to process the metal oxide. It is rarely used in recent years except for.

If fully equipped, catalytic hydrogen reduction is the most economical and industrially advantageous method. However, this method may not be practically suitable for mass production, in which case a reduction method using hydrazine hydrate may be used.

When hydrazine hydrate is used as the reducing agent, the use of Pd / C, Raney nickel, or the like as a catalyst can complete the reaction in a short time under mild conditions. However, since it is not easy to handle these catalysts on an industrial scale, inexpensive and industrially easy catalysts such as Fe ³⁺ and Cu ²⁺ can be used in consideration of economic aspects. In this case, the reaction is completed by stirring water for about 4 to 24 hours under reflux conditions using water as a solvent.

The use of cobalt ions with hydrazine hydrate as a catalyst is not preferred because it produces only decomposed by-products instead of a reduction reaction. Therefore, when cobalt ions are used as a catalyst, an amine compound can be obtained when Na ₂ S or NaSH is used as a reducing agent and water is used as a solvent and stirred at 50 to 60 ° C. for about 2 to 12 hours.

Scheme 1 below shows a reaction of reducing the compound of Formula 2 to obtain an amine compound which is one of the intermediates for producing a 1: 2 symmetric complex according to the present invention as one embodiment of the present invention.

By reacting the amine compound obtained by the reaction of Scheme 1 with 2,3-dibromopropionyl chloride which is a bromoacrylic reactor, the following Chemical Formula 14 having high dyeing rate and daylight fastness is obtained.

As a result of dyeing the compound of Chemical Formula 14 in wool, nylon, etc., the color of darkish navy blue is obtained, and C.I. No. Compared with Acid Black 172, it has improved washing and water fastness by about 2 grades, and it has been confirmed that it has about 2 grades of improved color fastness compared to conventional wool fiber dyes.

For comparison, the dyeing properties were tested using the compounds of formula 2 and formula 14, respectively, as starting materials. As a result, the fastness of the compound of the formula (14) was all 5 or more than the compound of the formula (2). The remaining bath is also excellent, and it shows a saturation value that can no longer be dyed to the fiber at a salt concentration of about 2%. In the case of thick blanket, the dye can be dyed to the fiber so that it is easy to obtain a deep dark color. It was. Nylon was dyed as well as the existing metal dyes, and it had excellent physical properties such as fastness, and the light fastness was better than the wool reactive dyes by 1 and 2 grades. In addition, it showed solubility values similar to those of the formula (2). Specifically, the compound of formula 14 exhibited a solubility of 30 to 100 g / L in water (dissolved at 99 ° C. for 3 minutes and then passing through Watman No. 2 filter paper within 3 minutes).

The compound of Formula 14 obtained by converting the compound of Formula 14 into a vinyl group by dehydrobromination at the end of the reactor using an excess of base in low temperature conditions showed better dyeing characteristics under alkaline conditions. Therefore, the compound of Formula 15 is not particularly different from the compound of Formula 14 in terms of quality, such as color fastness, but may be more preferable in terms of the user's dyeing environment.

Specific examples of azo-based metal complex reactive dyes which may be prepared by a method comprising a reduction reaction of nitro groups and a condensation reaction with a halogenated acrylic reactor using the azo metal complex dye as a starting material according to the present invention Formulas 16a-16g, 17a-17g and Table 1 (18a-18u) are shown.

Formulas 16a to 16g show examples of compounds of formula 6 according to the invention, which can be synthesized using a 1: 1 metal complex whose central metal is chromium as starting material.

In Chemical Formulas 16a to 16g,

R ₁ and R ₂ are each selected from the group consisting of -OH, -NH ₂ , -COOH, -NHCOCH ₂ COCH ₃ and -NH- (C ₆ H ₅ ),

R ₃ to R ₉ are essentially -NHCOCHBrCH ₂ or Br -NHCOCBr = CH ₂ a is to contain at least one, or -NHCOCHBrCH ₂ Br -NHCOCBr = CH ₂ R ₃ to the rest of the R ₉ substituent is not -H, - NH ₂ , -SO ₃ H, -OH, -COOH, -CH ₃ , -OCH ₃ , -NH- (C ₆ H ₅ ), -NH- (C ₆ H ₅ ) CH ₃ , -NHSO _2- (C ₆ H ₅ ), -NHSO _2- (C ₆ H ₅ ) Cl, -NHSO _2- (C ₆ H ₅ ) COOH, -NHCOCH ₃ , -NH ₂ CH ₃ , -SO ₂ NH ₂ , -NHSO ₂ CH _{3 , -N (CH 3) 2,} -N (C 2 H 5) 2, -NO 2, -NHCONH 2, -CONH 2, -N (C 2 H 4 OH) ₂ and the group consisting of -OC ₂ H ₅ Will be selected.

Formulas 17a to 17g illustrate the structure of the compound of formula 6 according to the present invention, which can be synthesized using a 1: 2 metal complex in which the central metal is chromium as a starting material.

In Chemical Formulas 17a to 17g,

R ₁ and R ₂ are each selected from the group consisting of -OH, -NH ₂ , -COOH, -NHCOCH ₂ COCH ₃ and -NH- (C ₆ H ₅ ),

R ₃ to R ₉ are essentially -NHCOCHBrCH ₂ or Br -NHCOCBr = CH ₂ a is to include two or more, or -NHCOCHBrCH ₂ Br -NHCOCBr = CH ₂ R ₃ to the rest of the R ₉ substituent is not -H, - NH ₂ , -SO ₃ H, -OH, -COOH, -CH ₃ , -OCH ₃ , -NH- (C ₆ H ₅ ), -NH- (C ₆ H ₅ ) CH ₃ , -NHSO _2- (C ₆ H ₅ ), -NHSO _2- (C ₆ H ₅ ) Cl, -NHSO _2- (C ₆ H ₅ ) COOH, -NHCOCH ₃ , -NH ₂ CH ₃ , -SO ₂ NH ₂ , -NHSO ₂ CH _{3 , -N (CH 3) 2,} -N (C 2 H 5) 2, -NO 2, -NHCONH 2, -CONH 2, -N (C 2 H 4 OH) ₂ and the group consisting of -OC ₂ H ₅ Will be selected.

On the other hand, since there are a myriad of azo-based metal complex reactive dyes that can be synthesized using a 1: 2 asymmetric metal complex dye as a starting material, for simplicity, an example of a compound in which the center metal is chromium is shown in Table 1 below. It was arranged as follows. That is, when referring to the structure of the formula 17a to 17g to the 1: 1 metal complex dye of the formula (16a to 16g) can be represented as shown in the formula (18a to 18u). In Table 1, the azo compound means a structure in which any one of the ligands represented by Formulas 8 to 13 is bonded to chromium in the structure of Formulas 16a to 16g instead of three water molecules.

Chemical formula number 1: 1 chromium complex dye Azo compounds 18a Formula 16a Formula 8 18b Formula 16a Formula 9 18c Formula 16a Formula 10 18d Formula 16a Formula 11 18e Formula 16a Formula 12 18f Formula 16a Formula 13 18g Formula 16b Formula 9 18h Formula 16b Formula 10 18i Formula 16b Formula 11 18j Formula 16b Formula 12 18k Formula 16b Formula 13 18l Formula 16c Formula 10 18m Formula 16c Formula 11 18n Formula 16c Formula 12 18o Formula 16c Formula 13 18p Chemical Formula 16d Formula 11 18q Chemical Formula 16d Formula 12 18r Chemical Formula 16d Formula 13 18s Chemical Formula 16e Formula 12 18t Formula 16e Formula 13 18u Formula 16f Formula 13

In Chemical Formulas 18a to 18u,

M is a metal selected from the group consisting of Cr, Co, Fe, Cu and Ni,

R ₁ and R ₂ are each selected from the group consisting of -OH, -NH ₂ , -COOH, -NHCOCH ₂ COCH ₃ and -NH- (C ₆ H ₅ ),

R ₃ to R ₉ are essentially -NHCOCHBrCH ₂ or Br -NHCOCBr = CH ₂ a is to contain at least one, or -NHCOCHBrCH ₂ Br -NHCOCBr = CH ₂ R ₃ to the rest of the R ₉ substituent is not -H, - NH ₂ , -SO ₃ H, -OH, -COOH, -CH ₃ , -OCH ₃ , -NH- (C ₆ H ₅ ), -NH- (C ₆ H ₅ ) CH ₃ , -NHSO _2- (C ₆ H ₅ ), -NHSO _2- (C ₆ H ₅ ) Cl, -NHSO _2- (C ₆ H ₅ ) COOH, -NHCOCH ₃ , -NH ₂ CH ₃ , -SO ₂ NH ₂ , -NHSO ₂ CH _{3 , -N (CH 3) 2,} -N (C 2 H 5) 2, -NO 2, -NHCONH 2, -CONH 2, -N (C 2 H 4 OH) ₂ and the group consisting of -OC ₂ H ₅ Will be selected.

In the present invention, there is also provided a dye composition in which a dye prepared according to the above-described method is mixed in order to exhibit various colors.

The dye composition is a dye represented by (a) 80 to 90% by weight of one compound selected from the compound represented by the formula (6) according to the present invention, and (b) a compound represented by the formula (6) is not the same as the above (a) As a mixture of 1 to 20% by weight of the compound or other colored dye compounds, such acidic azo chromium complex dye compositions exhibit excellent fastness, deep feeling of black color and excellent properties in high concentration dyeing.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention thereto.

In the following examples, the respective fastnesses (according to grading criteria classified by ISO or AATCC engines, etc.) were determined under the following conditions.

-Wash fastness (ISO 105 / CO3 60 ℃)

Apparatus: Lauder-O-Meter, Temperature: 60 ° C ± 2 ° C × 30 minutes, Liquid ratio: 50: 1

Water fastness (ISO 105 / E01)

Device: Perimeter (4.5 kg pressure), Temperature: 37 ° C ± 2 ° C × 4 hours

-Sweat fastness (ISO 105 / E04)

Device: Persistence Tester, Temperature: 30 ℃ ± 2 ℃ × 4 hours

Chlorine fastness (KS K 0725)

Daylight fastness (ISO 105 B02, Xenon-arc-lamp, ISO Blue scale)

Example 1 Preparation of a Compound of Formula 19

[Formula 19]

Into 300 parts of water (40 ° C.), 57.8 parts of 6-nitro-2-aminophenol-4-sulfonic acid and 1- (3'-chlorophenyl) -3-methyl-5-pyrazolone were added for 2 hours. After stirring, a green chrome formate liquid obtained by mixing 4.5 parts of CrO ₃ , 15 parts of water (room temperature) and 25 parts of formic acid was prepared and slowly added thereto. The pH is adjusted to 5 using 10% sodium hydroxide solution and maintained for 1 hour, and the temperature is raised to 100-105 ° C over 2 hours. After stirring for 4 hours while maintaining at this temperature, it was confirmed by TLC that all of the starting mono azo compound was consumed and naturally cooled to 70 ° C. 750 parts of NaCl are added to form particles, further stirred for 1 hour, then filtered by suction, washed with 100 parts of saturated KCl solution and dried in vacuo.

95.8 parts of the chromium compound prepared as described above was added to 800 parts of water at room temperature, dispersed for 2 hours, 10 parts of activated carbon and FeCl ₃ .6H ₂ O were added thereto, and the temperature was gradually increased to 70 ° C. After 30 parts of hydrazine monohydrate was diluted with 160 parts of water at room temperature and quenched in the reaction solution for 4 hours, the temperature of the reaction was raised to 98-102 ° C. The mixture was heated to reflux for 4 hours, and the reaction mixture was naturally cooled to 90 to 95 ° C. when thin layer chromatography (TLC) confirmed that all the nitro groups of the chromium compound were reduced. 20 parts of diatomaceous earth are added, stirred for 10 minutes, followed by suction filtration, the filtrate is neutralized to pH 3 with concentrated hydrochloric acid at around 70 ° C., and the precipitated solid is filtered.

The cake obtained by filtration was put in 500 parts of water at room temperature and dispersed for 2 hours, and then the pH was fixed at 7 with 10% Na ₂ CO ₃ solution. Ice was added to bring the temperature down to 10 ° C., 50 parts of 2,3-dibromopropionyl chloride was dissolved in 120 parts of acetone and added dropwise while maintaining the pH at 6.5 to 7.0 with 10% Na ₂ CO ₃ solution for 1 hour. do. It is salted and crystallized using 80 parts of NaCl at around 10 ° C, followed by suction filtration. Oven drying at 70 ℃ to obtain a dye compound represented by the formula (19) in a yield of 92%.

The color of the compound of Formula 19 is greenish red, and has a high rate of absorption as a result of dyeing on nylon and wool fibers. It can be seen that it is well dyed on thick fabrics. In addition to excellent washing and water fastness, high daylight fastness of more than 4 grades was shown.

The removal rate was determined by the following method. The UV absorbance of the salt solution of 0.2 g of the compound of Formula 19 in 100 ml of water was 1.49330 at 513 nm, and the absorbance at the same UV peak after dyeing to wool fibers was 0.0034759. On the other hand, when dyed to nylon with 1% salt solution, the absorbance at the same UV peak decreased to 0.058557. That is, it was confirmed that the residual dye amount of the compound of formula 19 was 1 to 0.01% or less, and the removal rate was 99% or more.

Example 2: Preparation of Compound 20

[Formula 20]

1: 1 chromium complex prepared using mono-azo compound of 1-diazo-2-naphthol-4-sulfonic acid and 1-phenyl-3-methyl-5-pyrazolone and an equivalent amount of chromium formate (chrome complex) 35 parts of mono azo compounds prepared by coupling a 49 parts dye and a diazo compound of 5-nitro-2-aminophenol and 1-phenyl-3-methyl-5-pyrazolone at 900 ° C. It is added together with water to disperse well, reacted at pH 8 and 80 ° C, and then crystallized by adding 100 parts of NaCl, suction filtered and dried under vacuum at 50 ° C.

84 parts of obtained chromium compounds are disperse | distributed to 950 parts of water at normal temperature, 10 parts of activated carbon are put, and it heats up to 80 degreeC. 10 parts of FeCl ₃ · 6H ₂ O is added, 20 parts of hydrazine monohydrate is diluted in 90 parts of water (room temperature), followed by washing with the reaction solution for 5 hours, and then raising the temperature to 90 ° C. and reacting for 5 hours. 15 parts of celite is added and suction filtered while maintaining a hot temperature. 200 parts of NaCl was added to the filtrate to crystallize, and after confirming the particle state and filtered. The reaction product, which is not dried, is poured into 800 parts of water (room temperature) and dispersed well. Then, ice is added to adjust the temperature to around 10 ° C. 25 parts of 2,3-dibromopropionyl chloride are dissolved in 60 parts of acetone and added dropwise while maintaining the pH of 6.5-7.0 with 10% Na ₂ CO ₃ solution for 1 hour. Around 10 ° C., salted, crystallized and suction filtered using 80 parts of NaCl. The obtained solid was oven dried at 70 ° C. to obtain a Bluish Red dye represented by Chemical Formula 20 in a yield of 90%.

It was well dyed to wool fibers and showed a wash fastness of at least 4-5 grades similar to other wool reactive dyes, and was found to have a high daylight fastness as high as 4-7 grades.

Example 3: Preparation of Compound of Formula 14

[Formula 14]

97 parts of the compound of formula 2 (CI No. Acid Black 172, powder, manufactured by China BSI Co., Ltd.) were added to 400 parts of water (room temperature), mixed well, and 5 parts of activated carbon and FeCl ₃ · 6H ₂ O were added thereto, and then 85 ~ It heats up to 90 degreeC over 1 hour. 7.5 parts of NH ₂ H ₂ O are diluted in 50 parts of water (room temperature) and slowly added to the solution for 2 hours. The temperature of the reactant is raised to 100 ° C., reacted by stirring for 2 hours while heating to reflux, and naturally cooled to 90 ° C. Oxalic acid and acetic acid were each added 2.5 parts, and the mixture was further stirred for 2 hours while maintaining the temperature at about 90 ° C. After adding 20 parts of diatomaceous earth, suction filtration is carried out while maintaining the temperature at 90 ° C. or higher. The filtrate is heated to 70 ° C., and then crystallized with 60 parts of NaCl and filtered to obtain an amine compound.

The undried amine compound was dispersed in 600 parts of water (40 ° C.), cooled to 10 ° C. or less by adding ice, and then a solution obtained by diluting 7.5 parts of 2,3-dibromopropionyl chloride in 10 parts of acetone was obtained. The mixture is reacted with stock for 1 hour while maintaining the pH below 7 with a 10% Na ₂ CO ₃ solution. 30 parts of KCl was added thereto, salted out, filtered, and dried in an oven at 70 ° C. or lower to obtain a compound of Formula 14 in a yield of 92%. When dyeing wool, nylon, etc., it shows dark navy blue color and is the starting material CI No. Compared to Acid Black 172, it has improved washing fastness and water fastness by about 2 grades, and has improved light fastness by about 2 grades compared to conventional wool fiber dyes.

Example  4

29.5 parts of 1-diazo-2-naphthol-6-nitro-4-sulfonic acid, 100 parts of water and 100 parts of ice were mixed at 10 ° C. After stirring for 30 minutes, 2 parts of zinc chloride (ZnCl ₂ ) was added thereto, and a solution of 20 parts of sodium acetate (CH ₃ COONa) in 100 parts of water was added to neutralize the pH to 3.0. 15 parts of 2-naphthol (β-Naphthol) was added to 150 parts of water at 80 ° C., and the mixture was completed with 10N NaOH solution, 150 parts of ice was added thereto, cooled to 30 ° C., added to the solution, mixed, neutralized to pH 10, and neutralized to 40 ° C. The mixture was stirred for 5 hours at. After completion of the reaction, the product crystallized by saturated sodium chloride solution was suction filtered through a black needle, washed with 5% sodium chloride solution and dried under vacuum at about 50 ° C. to prepare a monoazo compound.

43.9 parts of the dried monoazo compound was added to 300 parts of water, dissolved by adding a 10N NaOH solution, and a solution of 10 parts of CrO₃ dissolved in 20 parts of water was added thereto. System compound was obtained. The chromium compound was then salted out, crystallized and suction filtered with a saturated saline solution, washed with 5% sodium chloride solution and dried in vacuo.

Meanwhile, 30.8 parts of 4-nitro-2-aminophenol, 150 parts of water, and 150 parts of ice were mixed, stirred for 30 minutes, 40 parts of concentrated hydrochloric acid was added thereto, and 14 parts of sodium nitrite were mixed with water. A solution dissolved in 40 parts was added and stirred at 10 ° C. for 30 minutes. Excess nitrite was removed and 31.5 parts of 6-amino-N-phenyl-3-sulfon-naphthol dissolved in 10N NaOH, 200 parts of water and 100 parts of ice were mixed. The mixture cooled to 10 ° C. was added, a coupling reaction was performed at pH 10, stirred for 5 hours, salted out, suction filtered, washed with saturated brine, and dried in vacuo to obtain a disazo compound.

108.6 parts of the chromium compound prepared as described above and 64.5 parts of the disazo compound were added to 500 parts of water, and reacted at 80 ° C. and pH 9 for 4 hours. After completion of the reaction, the product crystallized in NaCl and sucked into a black needle was sucked. Filtered and dried in vacuo at 50 ° C.

154 parts of DKC's Uniset Black ACE product manufactured by the above method was added to 600 parts of water (room temperature) and mixed well. Then, 14 parts of activated carbon and FeCl ₃ · 6H ₂ O were added each, and 85 to 2 hours were added. It heats up to 90 degreeC. 23 parts of NH ₂ H ₂ O is diluted in 100 parts of water (room temperature) and added slowly to the solution for 2 hours. The reaction was stirred for 6 hours while heating to reflux to 100 ° C, and naturally cooled to 90 ° C. 10 parts each of oxalic acid and acetic acid are added, and the mixture is further stirred for 4 hours or more while maintaining at around 90 ° C. 50 parts of diatomaceous earth were added, suction filtration was maintained at a temperature of 90 ° C. or higher, the filtrate was heated to 70 ° C., crystallized with 60 parts of NaCl, and filtered to obtain a diazo chromium complex having a nitro group.

The undried product was dispersed in 600 parts of water (40 ° C.), cooled to 10 ° C. or less by adding ice, and then diluted with 14 parts of 2,3-dibromopropionyl chloride in 30 parts of acetone. After the reaction, the mixture was neutralized to a pH of 8 or less with a 10% Na ₂ CO ₃ solution, 200 parts of water was added thereto, and then spray-dried at a maximum temperature of 200 ° C. or a minimum temperature of 110 ° C. or more to obtain powder particles.

200 parts of water was added again to dissolve all of them, and a solution of 30 parts of sodium hydroxide dissolved in 300 parts of water was maintained while maintaining the temperature at 5 ° C. or lower. After 30 minutes, the solution was gradually neutralized to pH 8 again with hydrochloric acid. 200 parts of water was added again and spray dried at a temperature of 110 ° C to 200 ° C to obtain a compound in the form of particles. This compound has no difference in other fastnesses, but it can obtain grade 5 or higher. Daylight fastness is improved by 2nd grade and shows strong dyeing stability under alkaline conditions.

Example 5: Preparation of Compound of Formula 21

[Formula 21]

Into 300 parts of water (40 ° C.), 57.8 parts of 4-nitro-2-aminophenol-6-sulfonic acid and 1- (2'-chlorophenyl) -3-methyl-5-pyrazolone were added for 2 hours. After dispersing, 14 parts of CoSO ₄ · 7H ₂ O is dissolved in 40 parts of water, added to the dispersion, and then the temperature of the reaction mixture is gradually raised to 80 ° C. After neutralizing the pH to 6.5-7.0 with 10% sodium hydroxide solution, the mixture was stirred vigorously for 2 hours to synthesize cobalt dye, crystallized by adding 60 parts of NaCl, and filtered and dried under vacuum at 50 ° C. to obtain the compound of Formula 4.

Subsequently, 96 parts of the compound of formula 4 are added to 1000 parts of water (room temperature), stirred to disperse, and the temperature of the reaction mixture is raised to 60 ° C. In a temperature range of 60-70 ° C., 210 g of Na ₂ S was slowly reacted over 1 hour with reduction, followed by further stirring for 1 hour. Add 30 parts of celite, disperse well for 10 minutes, and filter while being careful not to lower the temperature. The filtrate is salted out with 200 parts of NaCl, filtered and washed with 50 parts of saturated KCl solution. The product obtained here was dispersed in 1000 parts of water (room temperature) without drying, neutralized to pH 6.5-7.0 with 10% Na ₂ CO ₃ solution, cooled to 10 ° C or less with ice, and then 30 parts of 2, A solution of 3-dibromopropionyl chloride in 45 parts of acetone was added dropwise for 1 hour while maintaining a pH of 6.5-7.0 with a 10% Na ₂ CO ₃ solution. It was salted out, crystallized using 100 parts of NaCl at around 10 DEG C, and suction filtered. Drying in an oven at 70 ° C. yielded a greenish yellow dye represented by Chemical Formula 21. The yield is 84%.

Example 6

A dye composition was prepared by combining the compound of Formula 14 and compound of Formula 19 in a weight ratio of 8: 2. The dye composition was used to dye wool fibers at concentrations of 1% and 5% based on the weight of the fiber (owf). As a result, the metal was a compound of Formula 2 (CI No. Acid Black 172, powder, manufactured by China BSI). Compared with the complex dyes, water fastness and washing fastness were excellent in grades 3 to 7, and the daylight fastness was improved by about 2 degrees compared to the conventional DKC Unisol dyes for wool fiber.

Example 7

The black dye composition was prepared by combining the compound of Formula 14 and compound of Formula 20 at a weight ratio of 8: 2.

Example 8

A black dye composition was prepared by combining the compound of Formula 14 and compound of Formula 21 at a weight ratio of 8: 2.

The dye compositions according to Examples 6 to 8 are respectively black at the time of dyeing.

Comparative Example 1

In order to confirm the superiority of the azo-based metal complex reactive dye according to the present invention, using a known compound of formula (2) and compound of formula (14) prepared using compound (2) as starting material in Example 3 of the present invention, nylon And dyeing the wool fibers to measure the fastness to wash, water, sweat, chlorine, daylight, respectively, are shown in Table 2 below. In the case of grades, the lowest level and the higher the number, the better the result.

Clean fastness (grade) Water fastness (grade) Sweat fastness (grade) Chlorine fastness (grade) Daylight Fastness (Rating) nylon fence nylon fence nylon fence nylon fence nylon fence Formula 2 3 3 4 4 4 4 4 4 3-4 3-4 Example 3 3 5 4 5 4 4 4 4 4 4

As can be seen from Table 2, since the dye according to the present invention is a reactive dye, it is confirmed that by binding strongly with the fiber, it is superior to the metal complex dye, which depends only on the dyeing of washing, water and the like. In addition, it can be seen that even though the reactor is combined, there is no change in daylight fastness, so that the properties of the metal complex dye are also maintained.

Comparative Example 2

Using the known compound of formula (2) and the mixed black dye compound prepared in Example 7 of the present invention, nylon and wool fibers were dyed to measure the fastness to washing, water, sweat, chlorine, and sunlight, respectively. It is shown in Table 3 below.

Clean fastness (grade) Water fastness (grade) Sweat fastness (grade) Chlorine fastness (grade) Daylight Fastness (Rating) nylon fence nylon fence nylon fence nylon fence nylon fence Formula 2 3 3 4 4 4 4 4 4 3-4 3-4 Example 7 4 5 4 5 4 5 4 4-5 4 4

As can be seen from Table 3, it can be seen that the same level of properties is maintained even in the case of a suitable ratio of the mixture, and some of the fastnesses were higher than the first grade.

All simple modifications and variations of the present invention shall fall within the scope of the present invention, and the specific protection scope of the present invention will become apparent by the appended claims.

As described above, according to the present invention, an azo-based metal complex reactive dye having excellent daylight fastness and general physical properties, a method for preparing the same, and a composition comprising the same are provided.

In the present invention, the daylight fastness problem of the reactive dye is solved by using the high daylight fastness of the azo-based metal complex dyes, and the metal complex salt-based bifunctional reactive dye having a high fixation rate by introducing an intermediate into the bifunctional reactor and its A method of preparation was provided.

The azo-based metal complex reactive dyes according to the present invention can obtain excellent fixation rate even when applied to acid dye dyeing.

Claims (15)

Azo-based metal complex reactive dye compounds represented by the following formula (6): [Formula 6]

Wherein M is a metal selected from the group consisting of Cr, Co, Fe, Cu and Ni, x and y are each 1 or 2, z is 1, 2 or 3, A is selected from tridentate ligands having the structures shown in Formulas 7-13, [Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

B is H ₂ O or selected from tridentate ligands having the structure shown in Formulas 7 to 13, R ₁ and R ₂ are each selected from the group consisting of -OH, -NH ₂ , -COOH, -NHCOCH ₂ COCH ₃ and -NH- (C ₆ H ₅ ), R ₃ to R ₉ substituent during -NHCOCHBrCH or ₂ Br -NHCOCBr = CH ₂ that is contained at least one, or -NHCOCHBrCH ₂ Br -NHCOCBr = CH ₂ R ₃ to the rest of the R ₉ substituent is not -H, -NH ₂ , -SO ₃ H, -OH, -COOH, -CH ₃ , -OCH ₃ , -NH- (C ₆ H ₅ ), -NH- (C ₆ H ₅ ) CH ₃ , -NHSO _2- (C ₆ H ₅ ), -NHSO _2- (C ₆ H ₅ ) Cl, -NHSO _2- (C ₆ H ₅ ) COOH, -NHCOCH ₃ , -NH ₂ CH ₃ , -SO ₂ NH ₂ , -NHSO ₂ CH ₃ , _{-N (CH 3) 2, -N} (C 2 H 5) 2, -NO 2, -NHCONH 2, -CONH 2, -N (C 2 H 4 OH) 2 , and -OC ₂ H ₅ in the group consisting of It is chosen. The azo-based metal complex reactivity of claim 1, wherein x = y = 1, z = 3, A is selected from tridentate ligands having the structures represented by Formulas 7-13, and B is H ₂ O. Dye compounds. The azo-based metal complex reactive dye compound according to claim 1, wherein x = y = z = 1, and A and B are the same tridentate ligands each selected from those having the structures represented by Formulas 7 to 13. The azo-based metal complex reactive dye compound according to claim 3, which has a structure represented by the following formula (14), (19) or (21). [Formula 14]

[Formula 19]

[Formula 21]

The azo-based metal complex reactive dye compound according to claim 1, wherein x = y = z = 1, and A and B are tridentate ligands different from each other selected from those having the structures represented by Formulas 7 to 13. The azo-based metal complex reactive dye compound according to claim 5, which has a structure represented by the following Chemical Formula 20. [Formula 20]

The compound of claim 1, wherein x = y = z = 2, two A's are the same tridentate ligands selected from Formulas 7-13, and two B's are different tridentate ligands selected from Formulas 7-13. Azo metal complex reactive dye compound. (1) Azo-based metals in which one, two or four tridentate ligands identical or different from each other represented by the following Chemical Formulas 7a to 13a are coordinated with a metal selected from the group consisting of Cr, Co, Fe, Cu and Ni Reducing the nitro group of the complex compound to an amine group to obtain an amine compound, (2) Propionyl chloride, propionyl bromide, wherein the product of step (1) is substituted with 2- and 3- positions of the same or different halogen atoms selected from the group consisting of fluorine, chlorine, bromine and iodine Or reacting with propionyl iodine, the process for preparing the azo-based metal complex reactive dye according to claim 1 [Formula 7a]

[Formula 8a]

[Formula 9a]

[Formula 10a]

[Formula 11a]

[Formula 12a]

[Formula 13a]

In Chemical Formulas 7a to 13a, R ₁ and R ₂ are each selected from the group consisting of -OH, -NH ₂ , -COOH, -NHCOCH ₂ COCH ₃ and -NH- (C ₆ H ₅ ), R ₃ to R ₉ substituent during nitro group may contain one or more, and the remaining R ₃ to R ₉ substituent is not nitro is _{-H, -NH 2, -SO 3 H} , -OH, -COOH, -CH 3, - OCH ₃ , -NH- (C ₆ H ₅ ), -NH- (C ₆ H ₅ ) CH ₃ , -NHSO _2- (C ₆ H ₅ ), -NHSO _2- (C ₆ H ₅ ) Cl, -NHSO _2- (C ₆ H ₅ ) COOH, -NHCOCH ₃ , -NH ₂ CH ₃ , -SO ₂ NH ₂ , -NHSO ₂ CH ₃ , -N (CH ₃ ) ₂ , -N (C ₂ H ₅ ) ₂ , -NO ₂ , -NHCONH ₂ , -CONH ₂ , -N (C ₂ H ₄ OH) ₂ and -OC ₂ H ₅ . The process according to claim 8, wherein the reduction reaction of step (1) is carried out using hydrazine hydrate as reducing agent and iron or copper ions as catalyst. The process according to claim 8, wherein the reduction reaction of step (1) is carried out using Na ₂ S or NaSH as reducing agent. The production method according to claim 8, wherein the compound having a halogenated acrylic reactor is a 2,3-dihalogenated propionyl halide. The method according to claim 8, further comprising the step of treating the compound obtained in the step (2) with a base to dehydrohalogenate to obtain a compound having a vinyl group. 12. The process of claim 11 wherein said 2,3-dihalogenated propionyl halide is 2,3-dibromopropionyl chloride. (a) 80-90% by weight of one compound selected from azo-based metal complex reactive dye compounds according to any one of claims 1 to 7, and (b) according to any one of claims 1 to 7. A dye composition comprising 1-20% by weight of a dye compound which is not the same as the above (a) as one compound selected from azo-based metal complex reactive dye compounds. The dye composition according to claim 14, wherein the component (a) is a compound of Formula 14, and the component (b) is a compound of Formula 19, 20 or 21. [Formula 14]

[Formula 19]

[Formula 20]

[Formula 21]