KR20030094982A - Blue Dye Mixture Of Metal Complex Formazan Derivatives - Google Patents

Abstract

PURPOSE: A blue dye mixture of metal complex formazan is provided, to improve the dyeing efficiency (color yield) and the fastness compared with those of individual dye. CONSTITUTION: The blue dye mixture comprises two different compounds represented by the formula 1 in the molar ratio of 1:99 to 99:1, wherein A is H, Cl, a methoxy group or a sulfo group; M is H or a monovalent metal; R is H, a substituted or unsubstituted linear or branched alkyl group of C1-C4 or an optionally substituted aryl group; X is a halogen atom, OH, an alkoxy group of C1-C4, an alkylthio group of C1-C4, a substituted or unsubstituted amino group, or an N-heterocyclo group containing no or at least one hetero atom; Y is a vinyl group or -CH2-CH2-Q (wherein Q is an inorganic or organic radical capable of removed under the alkali condition); and -SO2Y comprises -o, -m and -p positions.

Description

Blue Dye Mixture Of Metal Complex Formazan Derivatives

The present invention relates to a blue dye mixture of dicyclic metal complex salt formazan, and more particularly, a blue dye mixture combining two or more different dicyclic metal complex salt formazan dye compounds, each of which is a dye. Compared with the compound to provide a dye mixture having a more excellent effect, such as dyeing properties.

The dicyclic metal complex salt formazan dye compound is disclosed in Korean Patent No. 135648 of the present applicant, and its representative chemical formula is as follows.

Wherein A is benzene or naphthalene having a sulfo group (-SO ₃ M) at the ortho position relative to the N atom of the hydrazone compound and having 1 to 3 substituents, B is a straight or branched chain alkyl group, a phenyl group , A naphthyl group or a heterocyclic substituent, C is benzene or naphthalene having 1 to 3 substituents, D is benzene or naphthalene, M is a hydrogen atom or an alkali metal or an alkaline earth metal, Me is an atomic number 27 to 29 is a metal ion, Y is a halogen, X is a sulfo group, a carboxy group, a phosphonic acid group that provides solubility in hydrogen atoms or water, R is a straight or branched alkyl group, and Q is -SO ₂ CH = CH ₂ , -SO ₂ CH ₂ CH ₂ L, L is a group which may be substituted by alkali, and l, m and n are each an integer of 0 to 3)

Although the dicyclic metal complex salt formazan dye compound has excellent dyeing property and color fastness, the recent development of various kinds of fibers and its quality improvement require more physical properties such as better dyeing rate, color fastness, and laundry removal property. And the demand for it is gradually increasing.

Therefore, an object of the present invention is to provide a blue dye composition which solves these technical problems at once.

The inventors have conducted a series of studies and comparative analysis of the applicant's continuous Korean patent, and through a number of experiments and comparative analysis, a dye mixture combining different kinds of metal complex salt formazan compounds selected from the following general formula (1), individual dyes of the general formula (1) The present invention has been found to provide surprisingly higher color yields than the average of the color yields ("dyeing rates") of dyes obtained from the compounds, and also to achieve good overall fastnesses. This totally unexpected synergy results in excellent improved properties of the dye mixtures of the invention when compared to the individual dyes in the mixture.

The present invention relates to a dye mixture of 1:99 to 99: 1 (molar ratio) of two different kinds of compounds (component a and component b) selected from the following formula (1).

Where

A is hydrogen, chloro, methoxy or sulfo;

M is hydrogen or an equivalent metal;

R is hydrogen, a substituted or unsubstituted straight or branched alkyl group of 1 to 4 carbon atoms, or an optionally substituted aryl radical;

X is halogen, hydroxyl, alkoxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted amino group, or N-heterocyclo group with or without a hetero atom;

Y is a vinyl group or the general formula -CH ₂ -CH ₂ -Q, where Q is an inorganic or organic radical which can be removed under alkaline conditions (-SO ₂ Y comprises -o, -m, -p positions box).

In the above M, the equivalent metal is preferably an alkali metal or an alkaline earth metal as a monovalent or divalent metal, and particularly preferably sodium, lithium, potassium or calcium.

R is preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms.

Y is preferably -CH ₂ -CH ₂ -Q, wherein the inorganic or organic radicals (Q) which can be removed under alkaline conditions are preferably chlorine or acetyloxy groups, benzoyloxy groups, benzenesulfonyloxy Organic carboxylic acid containing a group and a lower alkoxyoxy group, or an ester group of sulfonic acid, -OPO ₃ H, -OSO ₃ H and the like, and particularly preferably -OSO ₃ H.

In X, preferred examples of the halogen include fluorine and chlorine, and preferred examples of the N-heterocyclo are morpholine, thiomorpholine, piperazine or piperidine radical, and the like. Preferred examples of the amino group are alkylamino, and examples of such alkylamino are N-mono- (C ₁ -C ₄ ) straight or branched alkyl in which unsubstituted or substituted alkyl residues are substituted with hydroxyl, sulfato or sulfur. Amino or N, N-di- (C ₁ -C ₄ ) straight or branched alkylamino and the like, and the like.

Wherein R and Y are the same as in Formula 1 (-SO ₂ Y comprises the -o, -m, -p positions).

Preferably, in Formula 2, R is hydrogen or ethyl, and Y is a vinyl group or β-sulfatoethyl.

The dye mixtures according to the invention exhibit excellent dyeing rates, overall fastnesses and the like compared to the individual dye compounds of formula 1, for example, the dyeing rates of dyes obtained from the dye mixtures are obtained from each dye compound. It is higher than the mean of the sum of the staining rate, and this is an unexpected result at all.

When the content (molar ratio) of one component of the different dye compounds is less than 1%, there is a problem that the solubility is lowered. If the content of the component a is more than 99%, there is a problem that the synergistic effect of the dyeing rate and color fastness is lowered have. The mixing molar ratio of component a and component b which are different dye compounds is preferably 20:80 to 80:20, more preferably 40:60 to 60:40. In some cases, another type of dye compound (component c) selected from Chemical Formula 1 may be added to 1% or more based on the total molar ratio of the dye mixture.

Preferred examples of the dye mixture according to the present invention include a mixture of 20:80 to 80:20 (molar ratio) of the dye compound of formula 1a and the dye compound of formula 1b.

Each formazan dye compound of Formula 1 may be prepared by various methods, for example, as follows.

Exemplary first method is a first condensation reaction of the formazan derivative of Formula 3 with 1,3,5-trihalogeno-S-triazine to prepare a formazan derivative of Formula 4 below, The second condensation reaction with the amine compound of 5 to prepare a compound of formula (1).

Wherein A and M are the same as in formula (1).

Wherein A, M and X are the same as in formula (1).

Wherein R and Y are the same as in Formula 1 (-SO ₂ Y comprises the -o, -m, -p positions).

Exemplary second method, the first condensation reaction of 1,3,5-trihalogeno-S-triazine and the amine compound of Formula 5 to prepare a compound of Formula 6, and then formazan of Formula 3 A second condensation reaction with a derivative to prepare a compound of formula (1).

Wherein R, X and Y are the same as in Formula 1 (-SO ₂ Y comprises the -o, -m, -p positions).

The reaction conditions and the reaction sequence are not particularly limited, but in general, the condensation reaction is performed in the range of pH 2 to pH 8 and 5 ° C. to 70 ° C., preferably at pH 3 to 6 and 0 ° C. to 60 ° C. Perform within range.

The dye mixtures according to the invention can be prepared, for example, in the form of dye powders or granules, their synthesized solutions, or aqueous solutions of the individual dye compounds, and generally also in the form which may comprise conventional auxiliaries. It can be prepared by mechanical mixing of individual dye compounds or chemical synthesis in one pot reaction, for example by using condensation components of individual dye compounds in the same reaction batch.

For example, the powder mixture contains an electrolyte salt and a buffer salt in the range of 20 to 30% by weight based on the total weight of the dye mixture. Preferably, 15-20% by weight of the electrolyte salt and 5-10% of the buffer salt are contained based on the total weight of the dye mixture. Representative examples of the electrolyte salt include sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, and the like, and the buffer salt is a salt for adjusting the pH of the aqueous solution in which the mixture is dissolved as 3 to 7, and representative examples thereof include sodium carbonate, sodium bicarbonate, and acetic acid. Sodium, sodium borate, sodium citrate, sodium hydrogen phosphate and the like.

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

The dye mixtures according to the invention have useful application properties. They are suitable as dyes for dyeing all types of cellulose fiber materials. For example, natural cellulose fibers such as cotton, flax, and hemp, pulp and regenerated cellulose, and the like, are preferably used for dyeing cotton.

The dye mixtures according to the invention can be used in a variety of known ways, in particular in the form of an aqueous dye solution which can be applied to the fiber material or fixed to the fiber. These dye mixtures can be impregnated with an aqueous dye solution, which may contain salts, by an adsorption method and a pad dyeing method, which are stored after the alkali treatment or in the presence of alkali and stored and fixed for several hours at room temperature. Suitable for both dyeing and more. After fixation, the dyeings can be washed thoroughly with cold or hot water and, if appropriate, a formulation can be added which has a dispersing action and promotes the diffusion of the unfixed portion.

The dye mixtures according to the invention have advantages in terms of solubility and dyeing rate over individual dyes. The dyeing rate of the dyes obtained with the dye mixture is higher than the mean of the sum of the dyeing rates of the dyes obtained with each dye.

In addition, the dye mixtures according to the invention are characterized by high fixing strength when used in dyeing processes on cellulose fiber materials. After conventional post-treatment by washing to remove unfixed dye moieties, the dyeings on cellulose show good wet fastness, in particular the unfixed dye parts have good solubility in cold water and can be easily washed. Because there is. In particular, it has very good wet fastnesses such as good light fastness and washing, fastness to chlorine water and acid and alkaline sweat.

Hereinafter, the present invention will be described in more detail with reference to Examples, which are only intended to illustrate the present invention, but do not limit the scope of the present invention.

Example 1

80 g of the blue electrolyte salt containing the dye compound of formula 1a at 80% ratio and 20 g of the blue electrolyte salt containing the dye compound of formula 1b at 80% ratio were mixed in a mechanical mixer to obtain 100 g of the dye mixture. Sodium chloride was used as each of the electrolyte salts.

The resulting dye mixture was dyed cellulose fibers according to the following dyeing and fixing method, which was then dyed red-tone blue.

(Dyeing and fixing method)

Two parts of the obtained reactive dye were dissolved in 400 parts of water, and a saline solution was prepared by adding 1500 parts of a solution containing 53 g of sodium chloride per liter. 100 parts of cotton were introduced into the salt solution at 35 ° C. After 20 minutes, 100 parts of a solution containing 16 g of sodium hydroxide and 20 g of sodium carbonate were added per liter. The temperature of the salt bath was kept at 35 ° C. for an additional 15 minutes. The temperature was then raised to 60 ° C. over 20 minutes. The temperature was kept at 60 ° C. for an additional 35 minutes. The product was then rinsed and soaped at boiling point with a nonionic detergent for 30 minutes, washed again and dried.

Example 2

70 g of the blue electrolyte salt containing the dye compound of formula 1a at 80% ratio and 30 g of the blue electrolyte salt containing the dye compound of formula 1b at 80% ratio were mixed in a mechanical mixer to obtain 100 g of the dye mixture. As a result of dyeing in the same manner as in Example 1, the cellulose fabric was dyed red-tone blue.

Example 3

60 g of the blue electrolyte salt containing the dye compound of formula 1a at 80% ratio and 40 g of the blue electrolyte salt containing the dye compound of formula 1b at 80% ratio were mixed in a mechanical mixer to obtain 100 g of the dye mixture. As a result of dyeing in the same manner as in Example 1, the cellulose fabric was dyed red-tone blue.

[Examples 4 to 13]

In Example 1, a dye mixture in which A is hydrogen, M is sodium, and X, R, and Y, respectively, is a combination of two different compounds (components a and b) as defined in Table 1 below. As a result of manufacturing and dyeing in the same manner as in the following, the cellulose fabric was dyed red-tone blue.

Example Dye compound of component a Dye compounds of component b MR X R Y X R Y 4 Cl H 3- (β-sulfatoethyl) Cl ethyl 3- (β-sulfatoethyl) 80:20 5 Cl H 3- (β-sulfatoethyl) Cl ethyl 3- (β-sulfatoethyl) 60:40 6 Cl H 3- (β-sulfatoethyl) Cl ethyl 4- (β-sulfatoethyl) 80:20 7 Cl H 3- (β-sulfatoethyl) Cl ethyl 4- (β-sulfatoethyl) 60:40 8 Cl H 4- (β-sulfatoethyl) Cl ethyl 3- (β-sulfatoethyl) 80:20 9 Cl H 4- (β-sulfatoethyl) Cl ethyl 3- (β-sulfatoethyl) 60:40 10 Cl H 4- (β-sulfatoethyl) Cl ethyl 4- (β-sulfatoethyl) 80:20 11 Cl H 4- (β-sulfatoethyl) Cl ethyl 4- (β-sulfatoethyl) 60:40 12 Cl ethyl 3- (β-sulfatoethyl) Cl ethyl 4- (β-sulfatoethyl) 80:20 13 Cl ethyl 3- (β-sulfatoethyl) Cl ethyl 4- (β-sulfatoethyl) 60:40

MR in Table 1 means a mixing molar ratio of component a and component b.

Comparative Example 1

In order to compare the dyeing rate of the dye compound selected from Formula 1 alone with the dyeing ratio of the dye mixture according to the present invention, the results of dyeing the dye compound of Formula 1a in the same manner as in Example 1 and the results in Example 1 3 is shown.

Comparative Example 2

In order to compare the dyeing rate of the dye compound selected from Formula 1 alone with the dyeing ratio of the dye mixture according to the present invention, the results of dyeing the dye compound of Formula 1b in the same manner as in Example 1 and the results in Example 1 3 is shown. First, the method of measuring the dyeing rate and various fastnesses will be described.

How to measure dyeing rate and various fastnesses

1. Dyeing rate: When the cloth dyed by the dyeing method ("dyed cloth") is completely dried, the front and back sides of the dyed cloth are averaged at least eight times using a Macbeth 7000 A colorimeter. The relative value which made the staining rate of Example 1 the reference | standard (100) was converted and displayed.

Various fastnesses were measured by the method described below.

2. Wash fastness: The dyeing cloth and the white cloth were put into the solution containing 5 g / L of soap solution and 2 g / L of soda ash, and it operated for 30 minutes at 60 degreeC using 10 steel balls. The measurement results were divided into 5 grades.

3. Chlorine water fastness: tested by ISO-E03. The measurement results were divided into 5 grades.

4. Acid sweat fastness: NaH ₂ PO ₄ and NaCl were mixed with 0.5 g / L of L-Histidine hydrochloride, adjusted to pH 5.5, and dyed cloth was inserted between glass plates. And it dried at 60 degrees C or less. The measurement results were divided into 5 grades.

5. Alkali sweat fastness: L-Histidine hydrochloride 0.5g / ℓ Na ₂ HPO ₄ and NaCl was adjusted to pH8, and the same experiment as the acid sweat fastness measurement. The measurement results were divided into 5 grades.

Evaluation standard of various fastnesses

Rating Evaluation standard One Very Poor 2 Poor 3 Fair 4 Good 5 Excel

Example 1 Comparative Example 1 Comparative Example 2 Dyeing rate 100 97 91 Color fastness 5 4 to 5 4 to 5 Chlorine Water Color Fastness 3 to 4 3 3 Acid sweat fastness 4 to 5 4 4 Alkali sweat fastness 4 to 5 4 4

As can be seen from the comparison results in Table 3, when one type of dye compound is used, the dyeing rate is 97 or 91, and when the dye mixture of Example 1 according to the present invention is used in the same amount, the dyeing rate is As 100, it can be seen that the dye mixtures according to the invention show better dyeing rates than the arithmetic mean of the single dye compounds. In addition, it was confirmed that the mixture of Example 1 according to the present invention was also excellent in chlorine water fastness, sweat fastness and washing fastness, etc., compared to one kind of dye compound.

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

The two or more different dye mixtures selected in formula (I) according to the present invention not only exhibit higher dyeing rates than the dyeing rates of their individual dye compounds, but also have excellent various fastnesses.

Claims (8)

A blue dye mixture of metal complex salt formazan, in which two different kinds of compounds (component a and component b) selected from Chemical Formula 1 are mixed in a molar ratio of 1:99 to 99: 1. (One) Where A is hydrogen, chloro, methoxy or sulfo; M is hydrogen or an equivalent metal; R is hydrogen, a substituted or unsubstituted straight or branched alkyl group of 1 to 4 carbon atoms, or an optionally substituted aryl radical; X is halogen, hydroxyl, alkoxy group having 1 to 4 carbon atoms, alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted amino group, or N-heterocyclo group with or without a hetero atom; Y is a vinyl group or the general formula -CH ₂ -CH ₂ -Q, where Q is an inorganic or organic radical which can be removed under alkaline conditions (-SO ₂ Y comprises -o, -m, -p positions box). The method of claim 1, In M, the equivalent metal is an alkali metal or an alkali earth metal as a monovalent or divalent metal; R is a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms; In X, the halogen is fluorine or chlorine, the N-heterocyclo is morpholine, thiomorpholine, piperazine or piperidine radical, and the amino group is unsubstituted or the alkyl residue is hydroxyl, sulfate or substituted N-, sulfur mono - (C ₁ -C ₄₎ straight or branched alkylamino or N, N- di - (C ₁ -C ₄₎ alkyl amino group, a straight or branched; Wherein Y is —CH ₂ —CH ₂ —Q, wherein the inorganic or organic radicals (Q) which may be removed under alkaline conditions are chlorine or acetyloxy groups, benzoyloxy groups, benzenesulfonyloxy groups and lower alkanoxy groups An organic carboxylic acid, or an ester group of sulfonic acid, -OPO ₃ H, -OSO ₃ H, and the like. The blue dye mixture of claim 2, wherein X is a group represented by the following Chemical Formula 2. (2) Wherein R and Y are the same as in Formula 1 (-SO ₂ Y comprises the -o, -m, -p positions). 2. A blue dye mixture according to claim 1, wherein the mixing molar ratio of component a and component b is 20:80 to 80:20. 2. A blue dye mixture according to claim 1, wherein the mixing molar ratio of component a and component b is 40:60 to 60:40. The blue dye mixture according to claim 1, wherein another dye compound (component c) selected from Chemical Formula 1 is further added at 1% or more based on the total molar ratio of the mixture. 2. The blue dye mixture of claim 1, wherein component a is a dye compound of formula 1a and component b is a dye compound of formula 1b. (1a) (1b) 8. The dye mixture according to any one of the preceding claims, further comprising 15 to 20% by weight of electrolyte salt and 5 to 10% by weight of buffer salt, based on the total weight of the dye mixture.