Indian Patents. 211282:ASYMMETRIC AZO-BASED METAL COMPLEX DYE, PREPARATION THEREOF AND ACIDIC BLACK DYE COMPOSITION CONTAINING THE SAME.

Title of Invention	ASYMMETRIC AZO-BASED METAL COMPLEX DYE, PREPARATION THEREOF AND ACIDIC BLACK DYE COMPOSITION CONTAINING THE SAME.
Abstract	DISCLOSED ARE A NOVEL ASYMMETRIC AZO-BASED METAL COMPLEX DYE WHICH EXHIBITS SUPERIOR HIGH COLOR DEPTH AND EXCELLENT FASTNESS, PREPARATION THEREOF, AND AN ACIDIC BLACK DYE COMPOSITION COMPRISING THE SAME.

Full Text	ASYMMETRIC AZO-DASED METAL COMPLEX DYE, PREPARATION THEREOF AND ACIDIC BLACK DYE COMPOSITION CONTAINING TIIE 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: 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. Although described to be applied to various fibers, including silk, woolen knitting yams, 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-,445,6S4, 5,092,905 and 6.126.700, which are incorporated herein by reference of the present invention. Because properties of 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 build- up 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: the dye mixtures disclosed in the references are greatly dependent on the blade d e 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 various 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 Formula 1: wherein R1, 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 (Cl), 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 (N02), a chlorine atom (Cl) and a sulfone group (SO3) , and all the individual compounds falling within the ambit of general Formula 1 are black dyes. In accordance with another aspect of the present invention, there is provided a process for preparing asymmetric metal comples black dyes of general Formula 1 as defined and claimed in Claim 1, which comprises - (a) reacting an aqueous solution of diazonium naphthalene compound of Formula 2 shown below with an aqueous solution of naphthol of Formula 3 in an equivalent ratio of 1:0.8-1.3 at a temperature varying between 20°C and 30°C at pH 10-11 for 5-6 hours with strring to produce a monoazo compound of Formula 4 shown below, in which R1 and R2 have the same significance as given above ; (b) dispersing the monoazo compound of Formula 4 in water and reacting with a chromium donor such as herein described in an equivalent molar ratio of 1:0.8-1.3 at an acidic pH under strring to produce a chromium complex of Formula 5 shown hereafter in which R1 and R2 are as defined in Claim 1; (c) dissolving an aminobenzene compound of Formula 6 in water and cooling the solution, which is mixed with an aqueous solution of a nitrite, preferably Sodium nitrite at O°-3O°C in presence of acid, followed by addition of an aqueous solution of phenylnaphthalene of Formula 7 with a base like NaOH to the aminobenzene solution in the equivalent ratio of aminobenzene : phenylnaphthalene :: 1.5-2.5:1, and conducting the coupling reaction to produce a bisazo compound of Formula 8 shown hereafter, in which R1 and R2 are as defined above, (d) dissolving 100-120 parts by weight of compound of Formula 5 and 60-70 parts by weight of compound of Formula 8 in water and reacting the solutions at a temperature varying between 50°C and 90°C and pH of 4.0-10.0, producing the desired black dyes as needle-shaped black crystals, which may be isolated by dialysis, suction-filtration and drying at around 40°C-60°C to produce highly pure black metal complex dye of Formula 1. 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 Formula 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:known in industry. The present invention pertains to novel asymmetric azo-based metal complex dyes represented by the Formula 1, which have an absorban at a wavelength of l max 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 Formula 2, is reacted with naphthol, represented by the following Formula 3, in the equivalent ratio of 1:0.8-1.3 to produce a monoazo compound, represented by the following Formula 4. wherein R1, 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 (C1), 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 (C1) 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 "0-30 °C. The naphthoi 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-l .3 at pH 1.0-5.0 at 125-135 °C with stirring. wherein R1 and R2 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. acidic black dye, and 1-20 % by weight of at least one dye selected from the group consisting of compounds represented by the following Formulas 9-12: 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 construed 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 (ZnC l2) 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 (CH3G0ONa) in 100 parts of water. After 15 parts of 2-naphthol (b-naphthol) was added to 150 parts of water of 80 °C and completely dissolved with 1ON 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 stirring. 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 C1O3 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 chromium 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 10 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 parts 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. 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 Formula 16c, was prepared finally. Application of this dye on nylon or polyamide fibers resulted in bluish black coloring. 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. These dyes obtained in these examples were measured to show almost the same fastness as the dyes prepared in Examples 1 and 2. EXAMPLE 26 The dye represented by the chemical formula 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 Formula 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 Formula 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. The dye represented by the Formula 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 in 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°Cx2 hrs. Materials were immersed in a solution having sodium perchkoate effective chlorine 0.5 g/1 of H2O, at pH 8.0±0.2 at 27.2±2 °C for 4 hours. 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. I claim : 1. Asymmetric metal complex black dyes represented by the general Formula 1 shown hereinbelow, wherein R1 may be same or different, selected from the group consisting of hydrogen (H), nitro (N02), chlorine (Cl), sulfonamide (-SO,NH2) and sulfone (-SO3); and R2, which may be same or different, each being selected from the group consisting of hydrogen, nitro, chlorine and sulfone, and all the individual compounds falling within the ambit of general Formula 1 are black dyes. 2. A process for preparing asymmetric metal complex black dyes of general Formula 1 as defined and claimed in Claim 1, which comprises - (a) reacting an aqueous solution of diazonium naphthalene compound of Formula 2 shown below with an aqueous solution of naphthol of Formula 3 in an equivalent ratio of 1:0.8-1.3 at a temperature varying between 20°C and 30°C at pH 10-11 for 5-6 hours with strring to produce a monoazo compound of Formula 4 shown below, in which R1 and R2 have the same significance as given in Claim 1 ; (b) dispersing the monoazo compound of Formula 4 in water and reacting with a chromium donor such as herein described in an equivalent molar ratio of 1:0.8-1.3 at an acidic pH under strring to produce a chromium complex of Formula 5 shown hereafter in which R1 and R2 are as defined in Claim 1; (c) dissolving an aminobenzene compound of Formula 6 in water and cooling the solution, which is mixed with an aqueous solution of a nitrite, preferably Sodium nitrite at 0°-30°C in presence of acid, followed by addition of an aqueous solution of phenylnaphthalene of Formula 7 with a base like NaOH to the aminobenzene solution in the equivalent ratio of aminobenzene : phenylnaphthalene :: 1.5-2.5:1, and conducting the coupling reaction to produce a bisazo compound of Formula 8 shown hereafter, in which R1 and R2 are as defined in Claim 1, (d) dissolving 100-120 parts by weight of compound of Formula 5 and 60-70 parts by weight of compound of Formula 8 in water and reacting the solutions at a temperature varying between 50°C and 90°C and pH of 4.0-10.0, producing the desired black dyes as needle-shaped black crystals, which may be isolated by dialysis, suction-filtration and drying at around 40°C-60°C to produce highly pure black metal complex dye of Formula 1. 3. The method as claimed in Claim 2, wherein the chromium donor is selected from the group consisting of chromium formate, chromium chloride and chromium oxide. 4. The method as claimed in Claim 2, wherein the step a) comprises : dissolving the diazonium napthalene compound in water at 0° to 10°C with strring ; adjusting the solution to pH 3 to 5 and adding a naphthol solution thereto so as to perform 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°C to 135°C. 5. The method as claimed in Claim 2, wherein the step b) comprises : dissolving the aminobenzene compound at 0°C to 30°C in water with strring ; 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. A process for preparing asymmetric metal complex black dyes of general formula 1 depicted hereinbefore, wherein R1 and R2 have the same significance as defined in Claim 1, substantially as hereinbefore described with particular reference to the illustrative Examples given herein. 7. An acidic black dye composition comprising - (i) 80-99% by weight of the asymmetric azo-based, acidic black metal complex dye of general Formula 1 as shown earlier, wherein substituents R1 and R2 have the same significance as given in Claim 1, and (ii) 1-20% by weight of at least one conventional cobalt or chromium complex dye selected from the group consisting of compounds represented by Formulae 9, 10, 11 and 12 shown hereafter : 8. An acidic black dye composition substantially as herein described with particular reference to the illustrative Examples given hereinbefore. 9. Asymmetric metal complex black dyes of general Formula 1 shown above, wherein Ra and R2 are as defined in Claim 1, substantially as hereinbefore described. Conventional dyeing with acidic black dyes suffered from the fastness problems and economical disadvantages attributable to the additional rinsing process of the conventional acidic black dyes, not to speak of pollution problems resulting from the disposal of higher volume of rinsing effluents. The present invention attempts to overcome the above drawbacks and provides a novel asymmetric azo-based metal complex dye which exhibits superior high colour depth and excellent fastness, along with a process for preparing such novel compounds. This invention also relates to an acidic black dye composition which uses conventional acidic black dyes with the compounds of this invention, resulting in expression of various colours of varying shades and tints, thereby producing high value-added effect.

Full Text

ASYMMETRIC AZO-DASED METAL COMPLEX DYE, PREPARATION
THEREOF AND ACIDIC BLACK DYE COMPOSITION CONTAINING TIIE
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:
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.
Although described to be applied to various fibers, including silk, woolen
knitting yams, 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-,445,6S4, 5,092,905 and 6.126.700, which are
incorporated herein by reference of the present invention. Because properties of
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 build-
up 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:
the dye mixtures disclosed in the references are greatly dependent on the blade d e
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 various 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 Formula 1:
wherein R1, 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 (Cl), 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 (N02), a chlorine atom (Cl) and
a sulfone group (SO3) , and all the individual compounds falling
within the ambit of general Formula 1 are black dyes.
In accordance with another aspect of the present invention,
there is provided a process for preparing asymmetric metal comples
black dyes of general Formula 1 as defined and claimed in Claim
1, which comprises -
(a) reacting an aqueous solution of diazonium naphthalene
compound of Formula 2 shown below with an aqueous solution
of naphthol of Formula 3 in an equivalent ratio of 1:0.8-1.3
at a temperature varying between 20°C and 30°C at pH 10-11
for 5-6 hours with strring to produce a monoazo compound of
Formula 4 shown below, in which R1 and R2 have the same
significance as given above ;
(b) dispersing the monoazo compound of Formula 4 in water
and reacting with a chromium donor such as herein described
in an equivalent molar ratio of 1:0.8-1.3 at an acidic pH
under strring to produce a chromium complex of Formula 5
shown hereafter in which R1 and R2 are as defined in Claim 1;
(c) dissolving an aminobenzene compound of Formula 6 in
water and cooling the solution, which is mixed with an
aqueous solution of a nitrite, preferably Sodium nitrite
at O°-3O°C in presence of acid, followed by addition of an
aqueous solution of phenylnaphthalene of Formula 7 with a
base like NaOH to the aminobenzene solution in the equivalent
ratio of aminobenzene : phenylnaphthalene :: 1.5-2.5:1, and
conducting the coupling reaction to produce a bisazo compound
of Formula 8 shown hereafter, in which R1 and R2 are as
defined above,
(d) dissolving 100-120 parts by weight of compound of
Formula 5 and 60-70 parts by weight of compound of
Formula 8 in water and reacting the solutions at a temperature
varying between 50°C and 90°C and pH of 4.0-10.0, producing
the desired black dyes as needle-shaped black crystals,
which may be isolated by dialysis, suction-filtration and
drying at around 40°C-60°C to produce highly pure black metal
complex dye of Formula 1.
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 Formula 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:known in industry.
The present invention pertains to novel asymmetric azo-based metal
complex dyes represented by the Formula 1, which have an absorban at a
wavelength of l max 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
Formula 2, is reacted with naphthol, represented by the following Formula 3, in the
equivalent ratio of 1:0.8-1.3 to produce a monoazo compound, represented by the
following Formula 4.
wherein R1, 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 (C1),
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 (C1) 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 "0-30
°C. The naphthoi 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-l .3 at pH 1.0-5.0 at 125-135 °C with stirring.
wherein R1 and R2 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.
acidic black dye, and 1-20 % by weight of at least one dye selected from the group
consisting of compounds represented by the following Formulas 9-12:
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 construed
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 (ZnC l2) 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 (CH3G0ONa) in 100
parts of water.
After 15 parts of 2-naphthol (b-naphthol) was added to 150 parts of water
of 80 °C and completely dissolved with 1ON 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 stirring. 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 C1O3 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 chromium 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 10 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 parts 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.
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 Formula 16c, was prepared finally.
Application of this dye on nylon or polyamide fibers resulted in bluish black
coloring.
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.
These dyes obtained in these examples were measured to show almost the
same fastness as the dyes prepared in Examples 1 and 2.
EXAMPLE 26
The dye represented by the chemical formula 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 Formula 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 Formula 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.
The dye represented by the Formula 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 in 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°Cx2 hrs.
Materials were immersed in a solution having sodium perchkoate
effective chlorine 0.5 g/1 of H2O, at pH 8.0±0.2 at 27.2±2 °C for 4 hours.
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.
I claim :
1. Asymmetric metal complex black dyes represented by the general
Formula 1 shown hereinbelow, wherein R1 may be same or different,
selected from the group consisting of hydrogen (H), nitro (N02),
chlorine (Cl), sulfonamide (-SO,NH2) and sulfone (-SO3); and R2,
which may be same or different, each being selected from the
group consisting of hydrogen, nitro, chlorine and sulfone, and
all the individual compounds falling within the ambit of general
Formula 1 are black dyes.
2. A process for preparing asymmetric metal complex black dyes
of general Formula 1 as defined and claimed in Claim 1, which
comprises -
(a) reacting an aqueous solution of diazonium naphthalene
compound of Formula 2 shown below with an aqueous solution
of naphthol of Formula 3 in an equivalent ratio of 1:0.8-1.3
at a temperature varying between 20°C and 30°C at pH 10-11
for 5-6 hours with strring to produce a monoazo compound of
Formula 4 shown below, in which R1 and R2 have the same
significance as given in Claim 1 ;
(b) dispersing the monoazo compound of Formula 4 in water
and reacting with a chromium donor such as herein described
in an equivalent molar ratio of 1:0.8-1.3 at an acidic pH
under strring to produce a chromium complex of Formula 5
shown hereafter in which R1 and R2 are as defined in Claim 1;
(c) dissolving an aminobenzene compound of Formula 6 in
water and cooling the solution, which is mixed with an
aqueous solution of a nitrite, preferably Sodium nitrite
at 0°-30°C in presence of acid, followed by addition of an
aqueous solution of phenylnaphthalene of Formula 7 with a
base like NaOH to the aminobenzene solution in the equivalent
ratio of aminobenzene : phenylnaphthalene :: 1.5-2.5:1, and
conducting the coupling reaction to produce a bisazo compound
of Formula 8 shown hereafter, in which R1 and R2 are as
defined in Claim 1,
(d) dissolving 100-120 parts by weight of compound of
Formula 5 and 60-70 parts by weight of compound of
Formula 8 in water and reacting the solutions at a temperature
varying between 50°C and 90°C and pH of 4.0-10.0, producing
the desired black dyes as needle-shaped black crystals,
which may be isolated by dialysis, suction-filtration and
drying at around 40°C-60°C to produce highly pure black metal
complex dye of Formula 1.
3. The method as claimed in Claim 2, wherein the chromium donor
is selected from the group consisting of chromium formate, chromium
chloride and chromium oxide.
4. The method as claimed in Claim 2, wherein the step a)
comprises :
dissolving the diazonium napthalene compound in water at
0° to 10°C with strring ;
adjusting the solution to pH 3 to 5 and adding a naphthol
solution thereto so as to perform 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°C
to 135°C.
5. The method as claimed in Claim 2, wherein the step b)
comprises :
dissolving the aminobenzene compound at 0°C to 30°C in water
with strring ; 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. A process for preparing asymmetric metal complex black dyes
of general formula 1 depicted hereinbefore, wherein R1 and R2 have
the same significance as defined in Claim 1, substantially as
hereinbefore described with particular reference to the
illustrative Examples given herein.
7. An acidic black dye composition comprising -
(i) 80-99% by weight of the asymmetric azo-based, acidic
black metal complex dye of general Formula 1 as shown earlier,
wherein substituents R1 and R2 have the same significance as
given in Claim 1, and
(ii) 1-20% by weight of at least one conventional cobalt or
chromium complex dye selected from the group consisting of
compounds represented by Formulae 9, 10, 11 and 12 shown
hereafter :
8. An acidic black dye composition substantially as herein
described with particular reference to the illustrative Examples
given hereinbefore.
9. Asymmetric metal complex black dyes of general Formula 1
shown above, wherein Ra and R2 are as defined in Claim 1,
substantially as hereinbefore described.
Conventional dyeing with acidic black dyes suffered
from the fastness problems and economical disadvantages
attributable to the additional rinsing process of the conventional
acidic black dyes, not to speak of pollution problems resulting
from the disposal of higher volume of rinsing effluents.
The present invention attempts to overcome the above
drawbacks and provides a novel asymmetric azo-based metal complex
dye which exhibits superior high colour depth and excellent
fastness, along with a process for preparing such novel compounds.
This invention also relates to an acidic black dye
composition which uses conventional acidic black dyes with the
compounds of this invention, resulting in expression of various
colours of varying shades and tints, thereby producing high
value-added effect.

Documents:

00550-cal-2002-abstract.pdf

00550-cal-2002-assignment.pdf

00550-cal-2002-claims.pdf

00550-cal-2002-correspondence.pdf

00550-cal-2002-description (complete).pdf

00550-cal-2002-form 1.pdf

00550-cal-2002-form 18.pdf

00550-cal-2002-form 2.pdf

00550-cal-2002-form 3.pdf

00550-cal-2002-form 5.pdf

00550-cal-2002-letter patent.pdf

00550-cal-2002-others.pdf

00550-cal-2002-pa.pdf

« Previous Patent

Next Patent »

Patent Number

211282

Indian Patent Application Number

550/CAL/2002

PG Journal Number

43/2007

Publication Date

26-Oct-2007

Grant Date

24-Oct-2007

Date of Filing

20-Sep-2002

Name of Patentee

DAEKWANG CHEMICAL IND. CO. LTD.

Applicant Address

123BL 3LT. 693-2, GOJAN-DONG, NAMDONG-KU, INCHON 405-820, KOREA.

Inventors:

#	Inventor's Name	Inventor's Address
1	NA, JONG-JOO	123BL 3LT, 693-2, GOJAN-DONG, NAMDONG-KU, INCHON, 405-820, KOREA.

PCT International Classification Number

C09B 7/22

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA