KR100686978B1 - Composition of reactive dyestuffs and methods for dyeing fiber using the same - Google Patents

Abstract

Provided are a reactive dyestuff composition which is excellent in overall fastness and leveling property, and expresses deeper color with little contamination onto other fibers, and a method for dyeing fiber, particularly cellulose based fiber using the same. The reactive dyestuff composition comprises 30-90 wt% of at least one dyestuff component having a structure represented by the formula (1) and 1-50 wt% of at least one dyestuff component having a structure represented by the formula (2). In the formulae (1) and (2), each of R1, R2, R3, R4 and R5 is hydrogen, a C1-C4 alkyl, a C1-C4 alkoxy, -SO3H or acetylamino; each of Y1, Y2 and Y3 is vinyl or a radical of the formula -CH2-CH2-Q (where, Q is -Cl, -Br, -F, -OSO3H, -SSO3H, -OCO-CH3, -OPO3H2, -OCO-C6H5, -OSO2-(C1-C4 alkyl) or -OSO2-N(C1-C4 alkyl)2); and A is a C1-C6 alkyl.

Description

Composition of Reactive Dyestuffs and Methods for Dyeing Fiber Using the Same

The present invention relates to a reactive dye composition, and more particularly, when dyed to cellulose fibers such as cotton, hemp, viscose rayon, expresses a deep black color even with a small amount of dye to obtain a high color intensity As a result, it is possible to obtain a cost reduction, and excellent in water fastness and daylight fastness compared to the conventional black dye composition, in particular, it can improve the fastness of wet friction, good fastness, uniformity and no other fiber contamination In addition, the present invention relates to a black dye composition having a high depth of color and excellent accumulation after dyeing.

As a conventional dark black reactive dye composition, C.I. which is a dye component of the following general formula having a vinyl sulfone group as a reactor is generally used. The dye composition which mixed the orange dye component with C.I.Reactive Black 5, or the orange dye component, the yellow dye component, etc. has been used.

Where X is an esterifiable reactor (typically -SO ₂ Cl) by substitution reaction, R ₁ , R ₂ are each independently hydrogen, methyl or methoxy group, M is hydrogen atom, sodium, lithium, potassium Alkali metal atoms, such as these.

Other prior arts for dye compositions used as dark black reactive dye compositions are as follows.

Japanese Patent Application Laid-Open No. 1-289868 discloses C.I. The black reactive dye composition which mixed the dye component of following formula with Reactive Black 5 is shown. However, with these two components, it is difficult to express dark black with strong red rice and there is also a problem in accumulation.

Where M is a hydrogen atom, an alkali metal atom such as sodium, lithium or potassium, R ₁ and R ₂ are each independently hydrogen, methyl or methoxy, X is an esterifiable reactor by substitution reaction, Y and Z is hydrogen or a sulfonic acid group and is not a hydrogen atom at the same time, and either is a sulfonic acid group.

In addition, in addition to the dye components, compositions containing other reactive yellow dye components for color control have been proposed, but C.I. Mixing of the yellow dye components of the pyrazolone family such as Reactive Yellow 15 does not produce a deep black color and is not satisfactory in accumulation.

Korean Patent Application Publication Nos. 194-24006 and 1992-19883 disclose the above-mentioned C.I. Reactive Black 5 in the vinyl sulfone type orange dye component of the formula

(Where M represents an alkali metal such as a hydrogen atom, sodium, lithium or potassium)

Monoazo yellow dye component of the formula

Where M is a hydrogen atom, an alkali metal such as sodium, lithium or potassium, and R ₁ And R ₂ Are each independently hydrogen, methyl or methoxy and X is an esterifiable reactor by substitution reaction)

Or a double coupling disazo yellow dye component of the formula

　　

Where R ₁ And R ₂ Are each independently hydrogen, methyl or methoxy, X is an esterifiable reactor by substitution reaction, n is an integer from 0 to 3)

Such a dye composition has a merit of being able to express deep black and be used in various dyeing methods such as dyeing, but due to the orange dye component, contamination with other fibers is severe, and there is a problem in washing fastness.

In addition, Korean Patent Application Publication No. 1989-2348, European Patent No. 0974621, etc., shows a black dye, which has a slightly improved accumulating ability with a compound of the following formula, but has a disadvantage of poor chlorine water and oxidative bleaching fastness.

Where R is hydrogen, methyl or methoxy and X is an esterifiable reactor by substitution.

In addition, Korean Patent No. 03046148 discloses a black dye having the disadvantage of improving the accumulator and increasing the chlorine fastness but having the disadvantage of poor light fastness.

Wherein R ₁ and R ₂ are each independently hydrogen, methyl or methoxy, X is a leaving group, and A is a substituted or unsubstituted benzene or naphthalene ring without a substituent.

As described above, the conventional dark black reactive dye composition is satisfactory in homogeneity, white dyeing, flame retardancy, etc., but there is a case in which deep black color is not expressed, other fibers are highly contaminated, or some fastnesses are problematic. Many.

Therefore, an object of the present invention is to solve the problems of the prior art and the technical problems that have been requested from the past.

The present inventors continue to conduct in-depth studies and various experiments, and the dye composition described later, in particular, when dyed textile materials such as cellulose can not only express a deeper black than conventional compounds, It can be applied to various dyeing methods, has good fastness to washing, daylight, sweat, chlorine water, good leveling, low contamination with other fibers, and especially the same color with a small amount of dye. By expressing it is excellent in economic efficiency, and relatively small amount of unfixed dyes, it was confirmed that the above-mentioned object can be solved for the most part, such as being able to obtain a result of excellent wet friction and water fastness, thereby completing the present invention.

Accordingly, the reactive dye composition of the present invention is composed of 30 to 99% by weight of at least one dye component having the structure of Formula 1 and 1 to 50% by weight of at least one dye component having the structure of Formula 2 .

[Formula 1]

[Formula 2]

In the above formulas,

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, C ₁ to C ₄ Alkyl, C ₁ -C ₄ alkoxy, —SO ₃ H or acetylamino;

Y ₁ , Y ₂ and Y ₃ are each independently vinyl or the formula —CH ₂ —CH ₂ —Q; Here, Q is _{-Cl, -Br, -F, -OSO 3} H, -SSO 3 H, -OCO-CH 3, -OPO 3 H 2, -OCO-C 6 H 5, -OSO 2 - (C 1 ˜C ₄ alkyl) or —OSO ₂ —N (C ₁ -C ₄ alkyl) ₂ ;

A is C ₁ ~ C ₆ Alkyl is preferable, especially methyl.

The dye composition according to the present invention, by the combination of the blue or indigo dye component represented by the formula (1) and the orange or yellow component represented by the formula (2), provides a deeper black and overall fastness compared to the conventional dye composition, It is excellent in preventing contamination with other fibers and homogenization, and can be applied to almost all dyeing fields.

In some cases, the reactive dye composition according to the present invention is 1 to 25% by weight, more preferably 5 to 20% by weight based on the total weight of the composition of one or more compounds selected from the group consisting of It may further include.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In the above formulas,

R ₁ to R ₄ , Y ₁ and Y ₂ are the same as defined in Formulas 1 and 2;

R ₉ is hydrogen or a sulfo group;

R ₁₂ , R ₁₃ , R ₁₄ , R ₁₆ , R ₁₈ and R ₁₉ are each independently hydrogen, sulfo, acetylamino, methyl or methoxy;

X ₃ is halogen or hydroxy;

Y ₅ , Y ₆ , Y ₇ and Y ₈ are the same as defined for Y ₁ and Y ₂ ;

A ₁ is a substituent selected from Formula 3a or 3b:

[Formula 3a]

[Formula 3b]

In the above formulas

R ₁₇ is phenyl or substituted or unsubstituted C ₁ -C ₆ alkyl;

X ₁ and X ₂ are each independently halogen or hydroxy,

D is a substituent selected from Formula 7a or 7b:

[Formula 7a]

[Formula 7b]

In the above formulas.

Y ₉ and Y ₁₀ are the same as defined for Y ₁ ;

R ₂₀ and R ₂₁ are each independently hydrogen, sulfo, acetylamino, methyl or methoxy.

The reactive dye mixture according to the present invention, as defined above, consists of a ratio of 30 to 99% by weight of the dye component of Formula 1 and 1 to 50% by weight of the dye component of Formula 2, more preferably the dye component of Formula 1 It consists of 50 to 80% by weight and 20 to 50% by weight of the dye component of formula (2). Too little dye component of formula (1) prevents oxidative bleaching fastness and relative dyeing strength at a desired level; on the contrary, too little dye component of formula (2) yields light fastness and water fastness to a desired level. It is not preferable, because it can not be.

Other components, such as a solubilizer, a buffer, an antifreezing agent, can be added to the composition of this invention within the range which does not impair the objective and effect of this invention. Such other additives may be added in the range of approximately 1 to 20 weight percent based on the total weight of the composition.

The solubilizer is an additive component that prevents agglomeration of dyes and helps dissolution, and typical examples thereof include urea, thiourea, and caprolactam. The buffer is a component that buffers the pH to prevent degradation of the dye during storage and storage, and representative examples thereof include sodium phosphate, potassium phosphate, sodium acetate and the like. The freezing inhibitor lowers the freezing point during liquid freezing and serves as a component that does not freeze the liquid dye. Representative examples include ethylene glycol, polyethylene glycol, and polyalcohol compounds.

The compound of Formula 2 may preferably be selected from one or more dye components consisting of the following Formula 8 and Formula 9.

[Formula 8]

[Formula 9]

In the above formulas, R ₂₂ and R ₂₃ are each independently hydrogen, sulfo, methyl or methoxy.

In addition, the compound of Formula 1 is a compound containing one or two mono azo ring, preferably may be selected from one or more dye components selected from the group consisting of the following formula (10 to 13).

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

Compounds of Formula 1 and Formulas 3 to 7 may be prepared by known methods, and the reactive dyes of Formula 2 may be prepared through various stages of diazo coupling reactions. same.

For convenience of description, the following Chemical Formula 14, Chemical Formula 15 and Chemical Formula 16 will be described first. R ₁ , A, Y _1, and the like in the following Chemical Formulas 14, 15, and 16 are the same as defined in Chemical Formula 2.

[Formula 14]

[Formula 15]

[Formula 16]

First, the compound of formula 14 is diazotized by a known method, and the first compound is reacted with 2,4-diaminobenzenesulfonic acid to prepare a compound of formula 16. On the other hand, after the diazotization of the compound of Formula 15 by a known method, it can be subjected to a second coupling reaction with the compound of Formula 16 to obtain a compound of Formula 2.

The first and second coupling reactions in this step can be carried out in an organic medium, an aqueous medium or an aqueous-organic medium, preferably in the presence of an acid-binder in the aqueous medium. Preferred examples of the acid-binding agent include carbonates, bicarbonates, hydroxides of alkali metals, carbonates of bicarbonate, bicarbonates, hydroxides, alkali metal acetates or mixtures of two or more selected from these, or tertiary amines. Can be mentioned. Preferred examples of the alkali metal and alkaline earth metal include lithium, sodium, potassium, calcium, and the like, and preferred examples of the tertiary amine include pyridine, triethylamine, quinoline, and the like. The coupling reaction can be carried out at -10 to 40 ℃, preferably at 0 to 20 ℃ and pH 1.0 to 8.0.

Various methods for preparing the dye compound of Formula 2 in addition to the above-described method is possible, and even if there is no separate description, those skilled in the art to which the present invention pertains to such methods through the method described above You will be able to recognize it.

The present invention also provides a method of dyeing a fiber material using a fiber reactive dye mixture.

The reactive dye compositions according to the invention are suitable as dyes for dyeing or printing fiber materials, preferably inter alia cellulose fiber materials. Such cellulose fiber materials include, for example, natural cellulose fibers such as cotton, flax, and hemp, pulp and regenerated cellulose, and are particularly suitable for dyeing cotton. The dye mixtures according to the invention are also suitable for dyeing or printing cellulose blend fabrics, for example cotton / polyester, cotton / nylon, cotton / wool blend fabrics and the like.

In the dye liquor, the amount of the fiber reactive dye mixture may vary depending on the desired degree of coloring, for example, it may be used at 0.01 to 10% by weight, preferably 0.01 to 6% by weight, based on the fabric to be dyed.

The reactive dye composition according to the present invention can be dyed by various methods, for example, cold pad placement, continuous dyeing, dyeing, printing, printing. It can be used, and these staining method is outlined as follows.

As a cold pad batch dyeing method, after neutralized (e.g., anhydrous sodium sulfate, salt, etc.) and an acid binder (e.g., caustic soda, sodium silicate, etc.), padding is performed and left in a sealed packaging material at a constant temperature. Dyeing methods can be used.

As the continuous dyeing method, an acid binder (e.g., sodium carbonate, sodium bicarbonate, etc.) is mixed with a padding liquid, padded by a known method and dyed by dry heat or steaming, and an inorganic neutral salt after dye padding ( For example, an anhydrous padding method in which anhydrous sodium sulfate, salt, etc.) and an acid binder (e.g., caustic soda, sodium silicate, etc.) are mixed and padded with a padding solution, and dyeing by dry heat or steaming by a known method is used. Can be.

The dip salt method is absorbed at about 40 DEG C in the presence of neutral salts (e.g. sodium sulfate, sodium chloride, etc.), and an alkali, which is an acid binder (e.g., sodium carbonate, caustic soda, trisodium phosphate, etc.) is added. After fixing for 1 hour at 50 ~ 60 ℃, it is fixed, washed with water and soap-dried at 95 ~ 100 ℃ with a nonionic surfactant and dried.

In the printing method, after printing a printing arc containing an acid binder (sodium bicarbonate) or the like, the printing method is printed by dry heat or steaming, or after printing the printing foil, an inorganic neutral salt (for example, salt) and the like. An ideal printing method such as printing by putting in a high temperature solution of 80 ° C. or higher containing an acid binder (eg, sodium hydroxide, sodium silicate, etc.) may be used.

In the case of white flame retardant or flame retardant, it is possible to obtain a good flame retardant and pressure suppression effect by forming a fired arc with long garret or the like, or by creating a fire extinguishing arc with Crintex PWC.

The dyeings and printings obtained according to the present invention are excellent in build-up and leveling. In addition, it is excellent in coloration, high fiber-dye bonding stability, and excellent in all fastnesses such as daylight fastness, and also excellent in preventing contamination with other fibers.

Although the content of the present invention will be described in detail with reference to the following Examples, the scope of the present invention is not limited thereto.

Production Example  One

After cooling by adding 32 g of ice to 23.7 g of 4-sulfatoethylsulfone-1-aminobenzene, 7.6 g of sodium nitrite and 31.3 g of hydrochloric acid (35%) were stirred and mixed at 0-5 ° C. and about pH 2 The mixture was stirred for 3 hours to diazotize. After dissolving 15.0 g of 2,4-diaminobenzenesulfonic acid under neutral conditions, the diazonium salt solution was added dropwise at 5 to 10 ° C. at about pH 6 for about 1 hour. The resulting solution is stirred at 5-10 ° C., about pH 6 for 2 hours to prepare a coupling. 36 g of ice was added to 14.3 g of 6-amino metatoluene sulfonic acid, and then cooled. After cooling, 8.2 g of sodium nitrite and 21.3 g of hydrochloric acid (35%) were mixed and stirred at 5 ° C. and pH 2 for 3 hours to diazotize. The coupling reaction mixture and the diazo body of 6-amino metatoluenesulfonic acid were stirred at 5 to 20 ° C. and pH 6.5 for 2 hours to complete the coupling reaction. The product was dried to give 88.0 g of a compound of formula 17 showing λ _max = 411 nm.

[Formula 17]

Example  One

A dye composition was prepared by mixing the compound of Formula 12 synthesized by a known method, the compound of Formula 18 below, and the compound of Formula 17 synthesized in Preparation Example 1 in a ratio of 65:10:25, respectively.

[Formula 18]

The dye composition prepared above was dyed to cellulose fibers by dyeing, printing, cold pad placement and continuous dyeing, respectively, and as a result, a deep black color was obtained.

(One) In salivation  By dyeing

To a solution in which 5 g of neutral salt (sodium sulfate) was dissolved in 100 l of water, 5 g of cotton with 0.15 g of dye composition was added and absorbed at about 30 ° C. for 20 minutes, and then slowly to 60 ° C. at a rate of 1.5 ° C./min. It heated up. When it reached 60 degreeC, 2 g of alkali (soda carbonate) was added, it stained and fixed at about 60 degreeC for 1 hour, and the dyed cloth was washed with cold water. After washing with water, in order to remove the dyeing residue, a solution containing 1 ml of a soaping agent in 250 ml of water was soaped at 95-97 ° C. for about 10 minutes and dried.

(2) Dyeing by Printing

10 g of urea, 10 g of sodium metanitrobenzenesulfonic acid, 20 g of sodium bicarbonate and 55 g of sodium alginate were mixed in 815 L of water to make a paste, of which 46 g were taken and 4 g of the mixture was added and mixed well. Then, the 100-mash print screen was used to print rayon and cellulose. In order to fix the printed dyestuff, the dried cloth was dried at 100 ° C. for 2 minutes and 30 seconds, and the dried cloth was steamed at 102 to 105 ° C. for 10 minutes using steam. The fixed dyes were washed three times or more alternately with cold water and hot water, and dried by soaping.

(3) Cold pad placement method  By dyeing

A salt solution was prepared at a ratio of 80:20 to a dye solution and an alkali solution. The dye solution was made using a dye composition and 100 g / l of urea, and the alkali solution was made by mixing 39 g of water with 7 g of sodium silicate and 2 g of sodium hydroxide (32.5% solution). Batch time was 6-12 hours, and it dried after maintaining 20-25 degreeC.

Example  2

Each component prepared in Example 1 was mixed in the liquid phase in the mixing ratio of Example 1, and then 955 g of a desalted and concentrated solution using a reverse osmosis membrane apparatus or the like, 10 g of urea as a solubilizer, and sodium phosphate 20 as a buffer. 15 g of ethylene glycol was added as g and an antifreezing agent, and it mixed well, and obtained 1000 g of liquid black dye compositions. This dye composition was dyed on cellulose fibers as in Example 1 by dipping, printing, cold pad placement and continuous dyeing to obtain a deep black color.

Example  3 to 25

The dye composition was prepared by changing the type and content of the dye components as shown in Tables 1 and 2, and then, respectively, these were applied to the cellulose based fibers by dipping, printing, cold pad placement, and continuous dyeing, respectively. Dyeing yielded a deep black color.

For convenience of description, the compounds included in Examples 3 to 25 are represented by Chemical Formulas 19 to 28.

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

TABLE 1

Comparative example  1 to 5

In order to identify the difference in physical properties between the dye composition according to the present invention and the conventional dye composition, the dye components of the following formula 29 to 32, the indigo blue component of the formula 12, and the formula 22 and formula 18 Vermilion components were mixed and compared.

For convenience of description, the compounds included in Comparative Examples 1 to 5 are represented by the chemical formulas 29 to 32.

[Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

TABLE 2

Dyeing power and various fastnesses of the dye compositions from the respective comparative examples and the dye composition of Example 1 according to the present invention were measured and shown in Tables 3 and 4 below. First, the dyeing power is dried by changing the concentration by the dyeing method, and then completely dried, and then average the values measured evenly eight times or more on the front and back of the cloth using a Macbeth 7000A colorimeter, based on Comparative Example 1 100 and converted to a relative value.

TABLE 3

TABLE 4

As can be seen in Table 3 and Table 4, the dye composition (Example 1) according to the present invention is excellent in dyeing power and fastness in all ranges compared to the conventional dye composition (Comparative Examples 1 to 5) It can be seen that it is superior to the comparative examples.

As the dye composition of the present invention, when dyeing cellulose-based fiber material, the deep black color can be expressed, and it can be used for various dyeing methods such as dyeing, printing, cold pad placement, continuous dyeing, anti-dyeing, dyeing, etc. Not only is it excellent in salting and low in other fiber contaminants, it is also excellent in compatibility between the components constituting the composition.

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.

Claims (7)

A reactive dye composition comprising 30 to 99% by weight of at least one dye component having a structure of Formula 1, and 1 to 50% by weight of at least one dye component having a structure of Formula 2:

(One)

(2) In the above formulas, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, C ₁ to C ₄ Alkyl, C ₁ -C ₄ alkoxy, —SO ₃ H or acetylamino; Y ₁ , Y ₂ and Y ₃ are each independently vinyl or the formula —CH ₂ —CH ₂ —Q; Here, Q is _{-Cl, -Br, -F, -OSO 3} H, -SSO 3 H, -OCO-CH 3, -OPO 3 H 2, -OCO-C 6 H 5, -OSO 2 - (C 1 ˜C ₄ alkyl) or —OSO ₂ —N (C ₁ -C ₄ alkyl) ₂ ; A is C ₁ ~ C ₆ Alkyl. The reactive dye composition of claim 1, wherein A is methyl. The reactive dye composition of claim 1, further comprising 1 to 25% by weight of one or more compounds selected from the group consisting of Formulas 3 to 7 based on the total weight of the composition:

(3)

(4)

(5)

(6)

(7) In the above formulas, R ₁ to R ₄ , Y ₁ and Y ₂ are the same as defined in Formulas 1 and 2; R ₉ is hydrogen or a sulfo group; R ₁₂ , R ₁₃ , R ₁₄ , R ₁₆ , R ₁₈ and R ₁₉ are each independently hydrogen, sulfo, acetylamino, methyl or methoxy; X ₃ is halogen or hydroxy; Y ₅ , Y ₆ , Y ₇ and Y ₈ are the same as defined for Y ₁ and Y ₂ ; A ₁ is a substituent selected from Formula 3a or 3b:

(3a)

(3b) In the above formulas R ₁₇ is phenyl or substituted or unsubstituted C ₁ -C ₆ alkyl; X ₁ and X ₂ are each independently halogen or hydroxy, D is a substituent selected from Formula 7a or 7b:

(7a)

(7b) In the above formulas. Y ₉ and Y ₁₀ are the same as defined for Y ₁ ; R ₂₀ and R ₂₁ are each independently hydrogen, sulfo, acetylamino, methyl or methoxy. The reactive dye composition of claim 1, further comprising other components such as solubilizers, buffers, freezing agents, etc. in the range of about 1 to 20% by weight based on the total weight of the composition. The method of claim 1, wherein the compound of formula 2 is a reactive dye composition, characterized in that at least one compound selected from the group consisting of

(8)

(9) In the above formulas, R ₂₂ and R ₂₃ are each independently hydrogen, sulfo, acetylamino, methyl or methoxy. The reactive dye composition of claim 1, wherein the compound of Formula 1 comprises at least one compound selected from the group consisting of Formulas 10-13:

10

(11)

(12)

(13) A method of dyeing a fiber material comprising nitrogen or a hydroxy group using the reactive dye composition according to any one of claims 1 to 6.