WO2002079326A1

WO2002079326A1 - Asymmetric azo-based metal complex dye, preparation thereof and acidic black dye composition containing the same

Info

Publication number: WO2002079326A1
Application number: PCT/KR2001/000515
Authority: WO
Inventors: Jong-Joo Na
Original assignee: DAEKWANG CHEMICAL IND Co Ltd
Current assignee: DAEKWANG CHEMICAL IND Co Ltd
Priority date: 2001-03-29
Filing date: 2001-03-29
Publication date: 2002-10-10
Anticipated expiration: 2003-09-29
Also published as: CN1204203C; CN1406266A; TW570960B

Abstract

Disclosed are a novel asymmetric azo-based metal complex dye which exhibits superior high color depth and excellent fatness, preparation thereof, and an acidic black dye composition comprising the same.

Description

ASYMMETRIC AZO-BASED METAL COMPLEX DYE, PREPARATION THEREOF AND ACIDIC BLACK DYE COMPOSITION CONTAINING THE

SAME

TECHNICAL FIELD

The present invention relates to a novel asymmetric azo-based metal complex dyes. More particularly, the present invention relates to a novel asymmetric azo-based metal complex dyes having very deep colors as well as superior fastness, and a process for preparing such a novel asymmetric azo-based metal complex dye. Further, the present invention is concerned with an acidic black dye composition comprising the novel asymmetric azo-based metal complex dyes as a main component.

BACKGROUND ART

There have been developed various black dyes for dyeing polyamide fibers, such as nylon 6 and 66. Representative of the black dyes for dyeing polyamide fibers, an acidic black dye is represented by the following Formula 13:

Formula 13

However, when the dye as above is used in an amount of 5-7 % o.w.f, much thereof remains unfixed, which results in exhibiting inferior properties in terms of washing fastness, water fastness, sweat fastness and so forth. Another problem with the dye is that, because the dye is required to be rinsed many times in order to improve their fastness, much time and expense are required for treating the waste water. Particularly, the above conventional acidic black dye suffers from the disadvantage of being poor in dyeing levelness and buildup effect and inadequate color expression with cellulose fibers, natural wool fibers, and synthetic polyester fibers. Furthermore, in order to express deep colors, the conventional acidic black dye requires to be used in combination with another dye.

EP 0 384 893 Al (corresponding to U. S. Patent No. 5,229,502) discloses a process for the preparation of at least 85% pure, asymmetric 1 :2 chromium complex azo dyes and/or azomethine dyes containing at least two groups which impart solubility in water. The dyes are represented by the following Formula 14:

Formula 14

Although described to be applied to various fibers, including silk, woolen knitting yarns, leather, synthetic polyamide fibers, etc., and be superior in fastness, the dyes in accordance with the above patent are not applicable to clothing or articles which require higher qualities of dyes. In addition, the dyes are limited mainly to the expression of reddish or orange colors. Nowhere are mentioned black dyes capable of expressing various colors. In general, black dyes may be used in mixture with shades of red, orange, and/or yellow dyes in order to enhance their black build-up effect. Dye mixtures comprising black dyes and dyes of other colors are well known from the prior arts, for example, Japanese Patent Laid-Open Nos. Sho. 58-160362, Hei. 2-202956 and

Hei 2-73870, and U. S. Patent Nos. 5,445,654, 5,092,905 and 6,126,700, which are incorporated herein by reference of the present invention. Because properties of the dye mixtures disclosed in the references are greatly dependent on the black dye component, other properties than color expression cannot be expected to improve without improvement in properties of the black dyes used as bases.

Accordingly, there remains a need for an improved acidic black dye that can solve the fastness problems of the conventional acidic black dyes and the economical disadvantage attributable to the additional rinsing process, and that can afford the expression of various colors in combination with other dyes, thereby having high value-added effect.

DISCLOSURE OF THE INVENTION

Leading to the present invention, the intensive and thorough research on acidic black dyes, conducted by the present inventor, resulted in the finding asymmetric metal complex of an acidic black azo dye, in which a disazo compound is coupled with chromium complex, capable of imparting vaiious fibers to a very deep color and exhibiting an improved fastness, and an acidic black dye composition containing the same.

Therefore, it is an object of the present invention to provide asymmetric metal complex of acidic black dyes, which can produce deep color dyeing and are superior in fastness.

It is another object of the present invention to provide a process for preparing the asymmetric metal complex of acidic black dyes with ease.

It is a further object of the present invention to provide a black dye composition based on the acidic black dye.

In accordance with one aspect of the present invention, there is provided asymmetric azo-based, acidic black metal complex dyes, represented by the following F ^■ ormula 1 :

Formula 1

wherein Ri, which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a nitro group (NO₂), a chlorine atom (CI), a sulfoneamide group (SO NH ) and a sulfone group (SO₃); and R₂, which may be the same or different, each is selected from the group consisting of a hydrogen atom

(H), a nitro group (NO₂), a chlorine atom (CI) and a sulfone group (SO₃).

In accordance with another aspect of the present invention, there is provided a process for preparing the asymmetric azo-based, acidic black metal complex dyes, represented by the Formula 1 , comprising the steps of: a) reacting a diazonium naphthalene compound, represented by the following Formula 2, with naphthol, represented by the following Formula 3, in an equivalent ratio of 1:0.8-1.3 to give a monoazo compound, represented by the following Formula 4, and then reacting the monoazo compound with a chromium donor in an equivalent ratio of 1 : 0.8-1.3 to produce a chromium complex, represented by the following Formula 5 ; b) reacting an aminobenzene compound, represented by the following Formula 6, with a phenyl naphthalene compound, represented by the following Formula 7, in an equivalent ratio of 1.5-2.5:1 in the presence of a nitrite to produce a disazo compound, represented by the following Formula 8; and c) reacting 100-120 pails by weight of the chrominum complex resulting from the step a) with 60-70 parts by weight of the disazo compound resulting from the step b):

Formula 2

Formula 3

Formula 4

Formula 5

Formula 6

Formula 7

Foπnula 8

wherein Ri and R are as defined above.

In accordance with a further aspect of the present invention, there is provided an acidic black dye composition comprising 80-99 % by weight of the asymmetric azo-based metal complex dye represented by the Foπnula 1, and 1-20 % by weight of at least one dye selected from the group consisting of compounds represented by the following Formulas 9-12:

Formula 9

Formula 10

Formula 11

Formula 12

BEST MODES FOR CARRYING OUT THE INVENTION The present invention pertains to novel asymmetric azo-based metal complex dyes represented by the Fomiula 1, which have an absorbance at a wavelength of λ_maχ 576 nm with a solubility of 100 g/1 at 90 °C. In addition, the novel dyes of the present invention may exhibit almost the same color irrespective of fiber materials. Further, the novel dyes are far superior in washing fastness, water fastness and sweat fastness over the conventional acidic black dyes when being used at the same o.w.f. rate.

A description will be given of the preparation of the asymmetric azo-based metal complex of the acidic black dye, below.

First, a diazonium naphthalene compound, represented by the following Fomiula 2, is reacted with naphthol, represented by the following Fomiula 3, in the equivalent ratio of 1:0.8-1.3 to produce a monoazo compound, represented by the following Formula 4.

Formula 2

Formula 3

Formula 4

wherein Ri, which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a nitro group (NO ), a chlorine atom (CI), a sulfoneamide group (SO₂NH₂) and a sulfone group (SO₃); and R₂, which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a nitro group (NO₂), a chlorine atom (CI) and a sulfone group (SO₃).

In detail, the diazonium naphthalene compound is dissolved in water at 0- 10 °C with stirring and controlled to pH 3-5. For the pH control, sodium acetate, sodium bicarbonate, or soda ash may be used with preference for sodium acetate.

Separately, naphthol is added to water and controlled to pH 10-11 at 70-90 °C with a base such as sodium hydroxide, followed by cooling the solution to 20-30 °C. The naphthol solution was added to the diazonium naphthalene solution and subjected to coupling reaction at pH 10-11 for 5-6 hours with stirring, to produce the monoazo compound of the Formula 4. Then, impurities can be removed by well- known methods, for example, dialysis, suction-filtration and washing to increase the purity of the monoazo compound.

To prepare a 1 : 1 chromium complex, represented by the following Formula 5, the monoazo compound is dispersed in water and reacted with a chromium donor in an equivalent molar ratio of 1:0.8-1.3 at pH 1.0-5.0 at 125-135 °C with stirring.

wherein R*_. and R are as defined above.

Suitable in the present invention is a chromium donor selected from the group consisting of chromium formate, chromium chloride and chromium oxide.

Removal of impurities from the product may be achieved by a well-known method, for example, dialysis, suction-filtration and washing.

Aside from the preparation of the 1 :1 chromium complex, an aminobenzene compound, represented by the following Formula 6, is reacted with a phenyl naphthalene compound, represented by the following Formula 7, in the presence of a nitrite to give a disazo compound, represented by the following Formula 8. For instance, the aminobenzene compound is dissolved in water and the liquid preparation is cooled. The liquid preparation is mixed with an aqueous solution of nitrite, preferably sodium nitrite, at 0-30 °C after addition of an acid, preferably hydrochloric acid and more preferably concentrated hydrochloric acid in order to remove excess nitrite. Afterwards, an aqueous solution of phenylnaphthalene added with a base such as sodium hydroxide is added to the aminobenzene solution at such an amount that the equivalent ratio of the aminobenzene to the phenyl naphthalene ranges within 1.5-2.5:1, followed by conducting a coupling reaction at pH 9-11 for 5-6 hours. The resulting solution may be further purified by dialysis, suction-filtration and washing.

Fomiula 6

Formula 7

Fomiula 8

wherein R- and R? are as defined above.

Along with 60-70 parts by weight of the disazo compound, 100-120 parts by weight of the 1 : 1 chromium complex thus obtained is dissolved in water, after which the solution is reacted under the condition of 50-90 °C and pH 4.0-10.0 to afford an asymmetric metal complex of acidic black azo dye, represented by the Formula 1, as black crystals of needle-shape. They are isolated by dialysis, suction-filtration, followed by drying at 40-60 °C to obtain a highly pure metal complex.

In accordance with the present invention, the asymmetric metal complex of acidic black azo dye as above may be mixed with other dyes to express various colors. In this case, the dye composition comprising 80 to 99 % by weight of the acidic black dye, and 1 -20 % by weight of at least one dye selected from the group consisting of compounds represented by the following Fomiulas 9-12:

Fomiula 9

Formula 10

Formula 11

Formula 12

Less than 1 % by weight of the auxiliary dye is too small to have any effect on bathochromicity and color change. On the other hand, when the auxiliary dye is used in an amount larger than 20 % by weight, the color fastness of the black dye itself is deteriorated.

A better understanding of the present invention may be obtained in light of the following examples which are set forth to illustrate, but are not to be constmed to limit the present invention. In the following examples, the term "parts", unless otherwise described, means weight parts.

EXAMPLE 1

29.5 parts of l-diazo-2-naphthol-6-nitro-4-sulfonic acid, 100 parts of water and 100 parts of ice were mixed and stirred at 10 °C for 30 min. 2 parts of zinc chloride (ZnCl₂) was added to the mixture, after which the pH of the mixture was adjusted to 3.0 with a solution of 20 parts of sodium acetate (CH COONa) in 100 parts of water.

After 15 parts of 2-naphthol (β-naphthol) was added to 150 parts of water of 80 °C and completely dissolved with 10 N NaOH, the solution was cooled to 30 °C by addition of 150 parts of ice. The mixture as prepared earlier was added thereto, mixed, and adjusted to pH 10, and then was subjected to coupling reaction at 40 °C for 5 hours with Stirling. Dialysis of the product solution in a saturated saline solution afforded a monoazo compound, represented by the following Formula 15a, in the form of black crystals of needle shape, which were suction- filtered, washed with a 5 % sodium chloride solution, and dried at about 50 °C in vacuo. 43.9 parts of the monoazo compound was dissolved in 300 parts of water in the presence of 10 N NaOH and mixed with a solution of 10 parts of CrO₃ in 20 parts of water. The monoazo compound was reacted with the CrO₃ at pH 3.0 at 130 °C for 5 hours to produce a cliromium complex represented by the following Formula 15b. After being cooled to 50 °C, the resulting solution was dialyzed in a saturated saline to obtain crystals, which were then sunction-filtered, washed with a 5 % sodium chloride solution, and dried in vacuo.

Separately, 30.8 parts of 4-nitro-2-aminophenol was mixed, along with 150 parts of ice, with 150 parts of water for 30 min with stirring. Following addition of 40 parts of concentrated hydrochloric acid, a solution of 14 parts of sodium nitrite in

40 parts of water was added to the 4-nitro-2-aminophenol solution and stirred at 10 °C for 30 min. After removal of excess nitrite, the resulting solution was added with a solution (about 10 °C) of 31.5 parts of 6-amino-N-phenyl-3-sulfone-naphthol in IO N NaOH, 200 parts of water and 100 parts of ice, and then subjected to a coupling reaction for 5 hours with stirring to give a disazo compound represented by the following Formula 15c, which was then isolated by dialysis, suction-filtration, washing with a saturated saline, and drying in vacuo.

108.6 parts of the chromium complex was reacted with 64.5 pails of the disazo compound in 500 parts of water at 80 °C at pH 9 for 4 hours, followed by dialysis in NaCl to afford a dye, represented by the following Formula 15d, in the form of black crystals of needle shape, which were isolated by suction-filtration and concentration to dryness at 50 °C in vacuo. The dye was applied to nylon or polyamide fibers to give a greenish black color.

Fomiula 15a

Formula 15b

Formula 15c

Formula 15d

EXAMPLE 2

The same procedure as in Example 1 was conducted with exception of using 25 parts of l-diazo-2-naphthol-4-sulfonic acid, instead of l-diazo-2-naphthol- 6-nitro-4-sulfonic acid, to give compound represented by the following Formula 16a and chromium complex represented by the following Formula 16b, from which a complex, represented by the following Fomiula 16c, was prepared finally. Application of this dye on nylon or polyamide fibers resulted in bluish black coloring.

Fomiula 16a

Formula 16b

Formula 16c

EXAMPLES 3 to 25

The same procedure as in Example 1 was conducted with exception of using monoazo compounds and disazo compounds listed in Table 1, below. The dyes thus obtained were applied to nylon or polyamide fibers and the results are given in Table 1.

TABLE 1

These dyes obtained in these examples were measured to show almost the same fastness as the dyes prepared hi Examples 1 and 2. EXAMPLE 26

The dye represented by the chemical fomiula 15d was mixed in a weight ratio of 97:3 with the dye represented by the Formula 9. The dye composition had a solubility of 100 g/1 (190 °C). Dyeings obtained by applying the resulting dye composition to polyamide fibers at an amount of 5 % o.w.f. were found to be improved in water fastness, washing fastness and sweat fastness by 2 to 2.5 grades over the conventional acidic black dye represented by the Formula 13.

EXAMPLE 27

The dye represented by the Fonnula 16c was mixed in a weight ratio of 96.5:3.5 with the dye represented by the Formula 10. Dyeings obtained by applying the resulting dye composition to polyamide fibers at an amount of 5 % o.w.f. were found to be improved in the fastness to water, washing and sweat by about 2 grades over the conventional acidic black dye represented by the Formula 13, and showed a bluish black color.

EXAMPLE 28

The dye prepared in Example 3 was mixed in a weight ratio of 94:6 with the dye represented by the Formula 9. Dyeings obtained by applying the resulting dye composition to polyamide fibers an amount of 5 % o.w.f. were found to be improved in the fastness to water, washing and sweat by about 2.5 grades over the conventional acidic black dye represented by the Fomiula 13, and showed a greenish black color.

EXAMPLE 29

The dye prepared in Example 17 was mixed in a weight ratio of 98:2 with the dye represented by the Formula 11. Dyeings obtained by applying the resulting dye composition to polyamide fibers at an amount of 5 % o.w.f. were found to be improved in the fastness to water, washing and sweat by about 2 grades over the conventional acidic black dye represented by the Formula 13, and showed a bluish black color.

EXAMPLE 30 The dye represented by the Fomiula 15d was mixed in a weight ratio of 96:4 with the dye represented by the Formula 12. Dyeings obtained by applying the resulting dye composition to polyamide fibers at an amount of 5 % o.w.f. were found to be improved in the fastness to water, washing and sweat by about 2 grades over the conventional acidic black dye represented by the Formula 13, and showed a bluish black color.

EXAMPLE 31

The dye prepared in Example 4 was mixed in a weight ratio of 97.5:2.5 with the dye represented by the Formula 9. Dyeings obtained by applying the resulting dye composition to polyamide fibers at an amount of 5 % o.w.f. were found to be improved in the fastness to water, washing and sweat by about 2.5 grades over the conventional acidic black dye represented by the Formula 13, and showed a bluish black color.

COMPARATIVE EXAMPLES 1 TO 5

Dyeings obtained using the conventional acidic black dyes 52, 222, 107, and 172, respectively on nylon, cotton, and wool fibers were measured for fastness to washing, water, sweat and chlorine, and the results are given Table 2, below.

In this regard, the fastness properties were determined according to the following standards: - Fastness to Washing (ISO 105/C03 60 °)

Equipment: Launder-o-meter Temp.: 60±2 °C x 30 min Detergent (5g/l)/Na₂CO₃ (2 g/1) Ratio to Liquid: 50:1 - Fastness to Water (ISO 105/E01 )

Equipment: Perspirometer (4.5 kg pressure) Temp.: 37±2 °C x 4 hrs

- Fastness to Sweat (Salt) (ISO 105/E04)

Equipment: Perspiration tester Temp.: 30±2 °C x 4 hrs.

0.5 g of L-histidine hydrochloride monohydrate, 5 g of sodium phosphate, dibasic, 5 g of sodium chloride were dissolved in 1 liter of water.

- Fastness to Chlorine (KS K 0725)

Equipment: Perspiration tester Temp.: 38+2 °C x 2 hrs. Materials were immersed in a solution having sodium perchlorate effective chlorine 0.5 g/1 of H₂O, at pH 8.0±0.2 at 27.2±2 °C for 4 hours.

TABLE 2

As apparent from the data of Table 2, when the dyes of Comparative Examples 1 to 5 are used in an amount of 5 to 7 % o.w.f, the dyeings are in the second or third grade in fastness to washing, water, and sweat owing to the dye residues remaining unfixed. In the dyeing industry, the conventional dyeings are washed three or four times with water to remove the unfixed dyes, thereby improving their fastness, which causes to generate a great quantity of waste water. Further, much time and expense are required for treating the waste water, thus lowering the productivity.

In contrast, the dye of the present invention allows the dyeing to have superior fastness without washing in addition to imparting high dye concentrations of the dyeings. Thanks to its high dye concentration and superior fastness, the acidic black dye of the present invention can solve the pollution and economic problems from which conventional black dyes suffer. Additionally, the dye of the present invention can express various and deep colors in combination with other dyes.

The present invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of description rather than of limitation. Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, it is to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

?

Claims

1. An asymmetric azo-based, acidic black metal complex dyes, represented by the following Fonnula 1 :

Fomiula 1

wherein Ri, which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a nitro group (NO ), a chlorine atom (CI), a sulfoneamide group (SO₂NH ) and a sulfone group (SO₃); and R , which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a nitro group (NO₂), a chlorine atom (CI) and a sulfone group (SO₃).

2. A process for preparing the asymmetric azo-based, acidic black metal complex dyes, represented by the following Formula 1 , comprising the steps of: a) reacting a diazonium naphthalene compound, represented by the following Fomiula 2, with naphthol, represented by the following Formula 3, in an equivalent ratio of 1 :0.8-1.3 to give a monoazo compound, represented by the following Formula 4, and then reacting the monoazo compound with a chromium donor in an equivalent ratio of 1 : 0.8-1.3 to produce a chromium complex, represented by the following Formula 5; b) reacting an aminobenzene compound, represented by the following

Formula 6, with a phenyl naphthalene compound, represented by the following Foπnula 7, in an equivalent ratio of 1.5-2.5:1 in the presence of a nitrite to produce a disazo compound, represented by the following Formula 8; and c) reacting 100-120 parts by weight of the chrominum complex resulting from the step a) with 60-70 pails by weight of the disazo compound resulting from the step b): Formula 1

Fomiula 2

Fomiula 3

Foπnula 4

Foπnula 5

Formula 6

Foπriula 7

Formula 8

wherein R_1} which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a nitro group (NO₂), a chlorine atom (CI), a sulfoneamide group (SO NH ) and a sulfone group (SO₃); and R_2> which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a nitro group (NO₂), a chlorine atom (CI) and a sulfone group (SO₃).

3. The method as set forth in claim 2, wherein the chromium donor is selected from the group consisting of chrome formate, chrome chloride and chrome oxide.

4. The method as set forth in claim 2, wherein the step a) comprises: dissolving the diazonium naphthalene compound in water at 0 to 10 °C with stiπing; adjusting the solution to pH 3 to 5 and adding a naphthol solution thereto so as to perfomi a coupling reaction between the diazonium naphthalene and the naphthol to produce the monoazo compound; and dispersing the monoazo compound in water and coupling the monoazo compound with the chromium donor at pH 1.0 to 5.0 at 125 to 135 °C.

5. The method as set forth in claim 2, wherein the step b) comprises: dissolving the aminobenzene compound at 0 to 30 °C in water with stiπing; and adding a solution of the phenyl naphthalene compound in water thereto so as to perform a coupling reaction between the aminobenzene compound and the phenyl naphthalene compound at pH 9 to 11.

6. The method as set forth in claim 2, wherein the c) step is caπied out under the condition of 50 to 90 °C and pH 4.0 to 10.0.

7. An acidic black dye composition, comprising

80 to 99 % by weight of the asymmetric azo-based, acidic black metal complex dye, represented by the following Foπnula 1 ; and

1-20 % by weight of at least one dye selected from the group consisting of compounds represented by the following Formulas 9-12:

Formula 1

Fomiula 9

Formula 10

Fomiula 11

Formula 12

wherein R-, which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a nitro group (NO₂), a chlorine atom (CI), a sulfoneamide group (SO₂NH₂) and a sulfone group (SO₃); and R₂, which may be the same or different, each is selected from the group consisting of a hydrogen atom (H), a mtro group (NO₂), a chlorine atom (CI) and a sulfone group (SO₃).