KR100831600B1 - Fiber-reactive dyestuff composition and methods for dyeing fiber using the same - Google Patents

Abstract

A reactive dye composition, and a method for dyeing a fiber material containing a nitrogen atom or hydroxyl group by using the composition are provided to improve washing fastness, chlorine fastness and fixation. A reactive dye composition comprises at least one compound represented by the formula 1; and at least one compound represented by the formula 2, wherein D is a group represented by the formula 3. In the formula 3, R1 and R2 are independently H, a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C1-C4 alkoxy group or -SO3H; p is 0, 1 or 2; Z1 is a vinyl group or -CH2-CH2-Q; Q is a group capable of leaving under alkali condition; n is 0, 1, or 2; Z2 is a vinyl group or -CH2-CH2-Q; and R3 is H, a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C1-C4 alkoxy group or -SO3H.

Description

Reactive dye composition and fiber dyeing method using the same {Fiber-Reactive Dyestuff Composition and Methods for Dyeing Fiber Using the Same}

The present invention relates to a reactive dye composition and a method for dyeing fibers using the same, and more particularly, to realize red color, the color is vivid, dyeing with high color concentration, repeated washing and The present invention relates to a reactive red dye compound having excellent chlorine water fastness and useful for dyeing fibrous materials including nitrogen or hydroxy groups, particularly cellulose fibers, and a method of dyeing fibers using the same. In general, the reactive dye is composed of a combination of three primary colors of red, yellow, and blue, and dyes such as dark red, dark blue, and black are also used together.

In particular, a deep red dye such as Burgundy, Bordeaux, etc. is not easy to express the color concentration, and even in the dyeing, color defects frequently occur due to color defects.

Conventional reactive red dyes include C.I. CI Reactive Red 195 is a hetero-functional red dye that shows good fastness, but does not show sufficient build-up when deep color is implemented, and thus the fastness is reduced because unfixed dye is accumulated after dyeing. There was a problem. In addition, there is a problem that a defect occurs when the color difference appears.

[Formula A]

Thus, US Patent Nos. 4,485,041 and 6,090,164 propose compounds of formula B to impart directness.

[Formula B]

However, since the above dyes have low chlorine water and oxidative bleaching fastness, development of better dyes is desired.

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

The inventors of the present application, after continuing in-depth research and various experiments, not only can the new reactive dye composition described later not only express deep red color, but also repeat washing and dyeing at the time of dyeing as compared to conventional heterofunctional compounds. With excellent chlorine water fastness and sufficient build-up, it is possible to realize deep green color even with relatively small amount of dyes. It was confirmed that most of the above-mentioned objects can be solved, and the present invention has been completed.

The fiber reactive red dye composition of the present invention according to this object is composed of one or more compounds having the structure of formula (1) and at least one compound having the structure of formula (2).

[Formula 1]

[Formula 2]

Where

I) D is a substituent of formula (3);

(3)

(3)

Where

i) R ₁ and R ₂ Are each independently hydrogen, substituted or unsubstituted C ₁ -C ₄ alkyl, substituted or unsubstituted C ₁ -C ₄ alkoxy, or —SO ₃ H;

ii) p is 0 or an integer from 1 to 2;

iii) Z ₁ Is a vinyl group or a general formula -CH ₂ -CH ₂ -Q group; Where Q is a leaving group that can be removed under alkaline conditions.

II) n is 0 or 1 to 2;

III) Z ₂ is a vinyl group or a general formula —CH ₂ —CH ₂ —Q; Wherein Q is a leaving group that can be removed under alkaline conditions;

IV) R ₃ is hydrogen, substituted or unsubstituted C ₁ -C ₄ alkyl, substituted or unsubstituted C ₁ -C ₄ alkoxy, or —SO ₃ H;

V) Y is a substituent selected from Formulas 4 to 6 below;

(4)

(4)

(5)

(5)

(6)

(6)

Where

i) R ₄ , R ₅ , R ₆ , R ₇ and R ₈ Are each independently hydrogen, substituted or unsubstituted C ₁ - C ₄ alkyl, substituted or unsubstituted C ₁ -C ₄ alkoxy, carboxy, or -SO ₃ H, and;

ii) Z ₃ And Z ₄ Are each independently Z ₁ And chemical definitions are the same;

iii) q and r are each independently 0 or an integer from 1 to 2;

iv) X ₁ and X ₂ Are each independently selected from the following substituents;

a) halogen, hydroxy;

b) 3-carboxypyridin-1-yl, 3-carbamoylpyridin-1-yl;

c) N-heterocycle, which may further contain hetero atoms;

d) substituted or unsubstituted C ₁ -C ₄ alkoxy, a substituted or unsubstituted C ₁ -C ₄ al skill alkylthio, substituted or unsubstituted amino; And

(7)e)

(7)

Where

R ₉ Is hydrogen, methyl, ethyl or phenyl;

K is a _{phenyl, -C 6 H 4 - CONH- (} CH 2) m -, -C 6 H 4 - SO 2 NH- (CH 2) m -, -CH 2 CH 2 -, or -CH ₂ CH ₂ - O-CH ₂ CH _2- , where m is an integer from 1 to 6;

Z ₅ Z ₁ And chemical definitions are the same.

In the dye composition according to the invention, the R ₁ and R ₂ Are each independently hydrogen, -SO ₃ H, methyl or methoxy, and particularly preferably hydrogen.

Also, the Q is a leaving group which can be removed under alkaline conditions, preferably _{halogen, -OSO 3 H, -SSO 3 H} , -OCO-CH 3, -OPO 3 H 2, -OCO-C 6 H ₅ , -OSO ₂ -R 'and -OSO ₂ N-R' ₂ It may be selected from the group consisting of, more preferably -OSO ₃ H It may be. Wherein R 'is hydrogen or substituted or unsubstituted C ₁ -C ₄ Alkyl.

In one preferred embodiment, 10 to 95% by weight of the compound having the structure of Formula 1, and 5 to 90% by weight of the compound having the structure of Formula 2, and more preferably, Formula 1 30 to 90% by weight of the compound having the structure of, may be to include 10 to 70% by weight of the compound having the structure of formula (2).

The reactive dye composition according to the present invention has high reproducibility, excellent fixing ability, and good fastness at the time of dyeing as compared to the conventional heterofunctional compound and the vinyl sulfone compound.

The reactive dye composition according to the present invention may include one or more compounds having the structure of Formula 1 and / or Formula 2.

When two or more compounds having the structure of Formula 2 are included, at least one of these substituents Y preferably has the structure of Formula 4, wherein any one of R ₄ or R ₅ groups is hydrogen, Oxy or —SO ₃ H, particularly preferably —SO ₃ H.

In one preferred embodiment, the compound of Formula 1 is a formula (1a), and in addition to the compound of Formula 2 may further include one or more compounds having a structure of the formula (2a).

[Formula 1a]

[Formula 2a]

Where

n is 0 or 1 to 2;

Z ₆ , Z ₇ , and Z ₈ are each independently Z ₁ And chemical definitions are the same;

R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently R ₃ And the chemical definition is the same, preferably hydrogen.

In one preferred embodiment, the dye composition is 10 to 95% by weight of the compound having the structure of Formula 1a, 5 to 90% by weight of the compound having the structure of Formula 2, and 1 to 50% by weight of the compound having the structure of Formula 2a It may be configured to include, more preferably 30 to 95% by weight of the compound having the structure of Formula 1a, 5 to 40% by weight of the compound having the structure of Formula 2, and Compound 1 to 1 with the structure of Formula 2a It may be 30% by weight.

The dye compositions according to the invention can be prepared in solid or (dissolved) liquid form, in which the compositions in solid form are generally combined with electrolyte salts such as sodium chloride, potassium chloride and sodium sulfate, which are conventional in water-soluble and especially fiber-reactive dyes. Commercial dyes contain auxiliaries together with buffering agents such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogen phosphate and disodium hydrogen phosphate, which can form a pH of 3-7 in aqueous solution, and a small amount of a drying agent or dye composition. When present in this liquid aqueous solution (including thickeners of the usual form in the printing arc), it may contain substances such as anti-molds which give the formulation its durability.

Generally, the dye composition is a colorless concentration-standardizing diluent of 10 to 80% by weight, based on the dye powder or formulation, in the form of a dye powder containing an electrolyte salt, which dye powder is further based on the dye powder. In total, up to 5% of the aforementioned buffer materials.

Thus, when the dye composition is present in an aqueous solution, the total dye content may be up to about 50% by weight, for example 5 to 50% by weight, based on the total aqueous solution, and the content of the electrolyte salt is preferably 10 It may contain less than% by weight, such an aqueous solution (liquid formulation) may contain up to 5% by weight, preferably up to 2% by weight of the buffer material.

The present invention also provides a method of dyeing a fiber material using the dye composition. The fiber reactive dyes according to the present invention can be used for dyeing fiber materials containing nitrogen or hydroxy groups, and representative examples of such fiber materials include cellulose fibers.

The dye compositions according to the invention are suitable as dyes for dyeing or printing all types of 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 compositions according to the invention are also suitable for dyeing or printing cellulose blend fabrics, for example cotton / polyester, cotton / nylon blend fabrics and the like.

In the dye solution, the content of the dye composition may vary depending on the desired degree of coloring. The dye compounds according to the invention can be used at 0.01 to 10% by weight, preferably 0.01 to 6% by weight, based on the fabric to be dyed.

The fiber reactive compounds according to the invention are particularly suitable for dyeing by the absorption method.

The dyeing by the adsorption method is generally carried out in an aqueous medium, in which the weight ratio of water to dye is 1: 2 to 1:60, preferably 1: 5 to 1:20, 20 to 105 ° C, preferably 30 to 90 ° C, more Preferably it is performed at the temperature of 40-80 degreeC.

Other suitable dyeing methods include pad dyeing, in which the fabric is generally immersed in an aqueous solution, saline solution, saline solution or the like. In this case, the pick-up is 20 to 150%, in particular 40 to 120%, preferably 50 to 100% by weight of the fiber material to be dyed. In some cases, the aqueous liquid already contains a fixed alkali, or after impregnation, the fiber material is treated with a fixed alkali. Suitable alkali metals are, for example, mixtures of sodium carbonate, sodium bicarbonate, sodium hydroxide, disodium phosphate, trisodium phosphate, sodium borate, aqueous ammonia, sodium trichloroacetate or sodium silicate solution, among others alkali hydroxides and alkali carbonates. This is preferred, with sodium hydroxide and sodium carbonate being particularly preferred.

Fixation can be carried out, for example, by means of steaming the impregnated fibrous material at a temperature of 100 to 120 ° C., in particular through thermal action such as saturated steam. Alternatively, the dye can be placed in a padder with alkali and stored at room temperature for several hours, for example 3 to 40 hours, in accordance with a cold pad-batch method. After fixing, a dispersant is added to the dyeing or printing as necessary and thoroughly washed.

The dyeings and printings obtained according to the present invention not only have excellent accumulation and levelness, but also have high fixing properties, and non-fixed dyes can be easily washed off, and the difference between adsorption and fixing properties, That means less soap loss. Moreover, the obtained dyeings and printings have excellent colorability, high fiber-dye binding stability, excellent repetitive washing fastness and chlorine water fastness.

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

Example  One

After dissolving 34.9 g of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid with 200 g of water and dissolving the same, a diazotized compound corresponding to 23.3 g of 1-sulfonic acid-2-aminonaphthalene was added thereto. 55.6 g of compound of 8a was obtained. 270 g of ice was added to the compound of Formula 8a, and cooled. 20.0 g of chlorocyanuls were added to the solution, and the reaction was completed by stirring at 10 ° C. and pH 4.0 for 4 hours, and then 34.9 g of 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid was added thereto. Stirring at 30 ° C. and pH 5.0 for 4 hours afforded a compound of formula 8b. Then, using a known method, a diazolated compound corresponding to 28.8 g of 4-sulfatoethylsulfone-1-aminobenzene was added and stirred at 12 ° C. and pH 5.0 for 2 hours to complete the coupling reaction. The reaction product was dried to obtain 130.9 g of a compound represented by Chemical Formula 8.

[Formula 8a]

[Formula 8b]

[Formula 8]

On the other hand, 54 g of 1-aminobenzene-2-sulfonic acid-4-β-sulfatoethylsulfone, 15 g of sodium nitrite, and 47 g of hydrochloric acid (35%) were stirred and mixed in 110 g of water. The diazonium salt was prepared by diazolating this mixed liquid at 0-5 degreeC and about pH 2 for 3 hours by stirring. After dissolving 15.0 g of 3-amino 8-hydroxynaphthalene 6-disulfonic acid under neutral conditions, the diazonium salt solution was added dropwise at 5-10 ° C., about pH 2, for about 1 hour. The resulting solution was stirred at 5 to 10 ° C. for about 2 hours to prepare a compound of formula 9a. 36 g of ice was added to 14.3 g of 4-sulfatoethylsulfone-1-aminobenzene, and cooled. After cooling, 8.2 g of sodium nitrite and 21.3 g of hydrochloric acid (35%) were stirred and mixed, and the mixture was stirred at 5 ° C. and pH 2 for 3 hours. Was stirred to diazotize. The prepared diazo of the compound of formula 9a and 4-sulfatoethylsulfone-1-aminobenzene was stirred at 5 to 20 ° C. and pH 6.5 for 2 hours to complete the coupling reaction. To obtain 88.0 g of the compound represented by formula 9 having a lambda max = 492nm.

 [Formula 9a]

 [Formula 9]

The dye of the compound of Formula 8 and the compound of Formula 9 was prepared in a ratio of 90:10 to prepare a red dye having a λ _max = 514 nm.

Example  2 to 42

According to the same method as in Example 1, the compound of Formula 10 and Formula 11 were mixed in a specific ratio to prepare a dye, and the color of the dye was confirmed thereby. For convenience of explanation, D ₁ and Y ₁ are represented in any of Formulas 10 and 11 shown below, and the results are shown together with the experimental results in Table 1 below.

 [Formula 10]

[Formula 11]

Example 43

The compound of Formula 8 and Formula 9 and the compound of Formula 12 were mixed at a ratio of 80:10:10 to prepare a dye, and a red color of λ _max = 512 nm was confirmed.

[Formula 12]

Example  44 to 89

According to the same method as in Example 43, the compound of Formula 10, Formula 11 and Formula 13 were mixed in a specific ratio to prepare a dye, thereby confirming the color of the dye. For convenience of description, D ₁ , Y _1, and Y ₂ are represented in any of Chemical Formulas 10, 11, and Chemical Formula 13 below, and each is shown together with the experimental results in Table 2 below.

 [Formula 13]

Experimental Example 1

The dye compositions of Examples 44 and 55, dyes of formula A (CI Reactive Red 195), and dyes of formula B were compared by dyeing under the same conditions using the dyeing method, and the dyes stained under the above conditions. Relative staining intensity was measured using a color difference meter from Gretag Macbeth, and repeated washing fastness and chlorine water fastness were measured and compared with the dye stained under the above conditions. Indicated.

As can be seen from Table 3, the dye compositions of Examples 44 and 55 according to the present invention showed better fixation and relative dye strength than the dyes of Formula A (CI Reactive Red 195) and Formula B dyes. Repeated washing, it was confirmed that the chlorine water fastness.

Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above contents.

As described above, the reactive dye composition according to the present invention is a dye having excellent fiber reactivity properties, and is effective for dyeing and printing fiber materials, particularly cellulose fiber materials by a fixing method commonly used in the field of fiber reactive dyes. It has an excellent adsorption / fixation rate and is excellent in color fastness to repeated washing and chlorine water.

Claims (10)

Reactive dye composition comprising at least one compound having the structure of Formula 1 and at least one compound having the structure of Formula 2 [Formula 1]

[Formula 2]

Where I) D is a substituent of formula (3);

(3) Where i) R ₁ and R ₂ Are each independently hydrogen, substituted or unsubstituted C ₁ -C ₄ alkyl, substituted or unsubstituted C ₁ -C ₄ alkoxy, or —SO ₃ H; ii) p is 0 or 1 to 2; iii) Z ₁ Is a vinyl group or a general formula -CH ₂ -CH ₂ -Q group; Wherein Q is a leaving group that can be removed under alkaline conditions; II) n is 0 or 1 to 2; III) Z ₂ is a vinyl group or a general formula —CH ₂ —CH ₂ —Q; Wherein Q is a leaving group that can be removed under alkaline conditions; IV) R ₃ is hydrogen, substituted or unsubstituted C ₁ -C ₄ alkyl, substituted or unsubstituted C ₁ -C ₄ alkoxy, or —SO ₃ H; V) Y is a substituent selected from Formulas 4 to 6 below;

(4)

(5)

(6) Where i) R₄, R₅, R₆, R₇ And R₈ Are each independently hydrogen, substituted or unsubstituted C_One-C₄ Alkyl, substituted or unsubstituted C_One-C₄ Alkoxy, carboxy, or -SO₃H; ii) Z ₃ And Z ₄ Are each independently Z ₁ And chemical definitions are the same; iii) q and r are each independently 0 or an integer from 1 to 2; iv) X ₁ and X ₂ Are each independently selected from the following substituents; a) halogen, hydroxy; b) 3-carboxypyridin-1-yl, 3-carbamoylpyridin-1-yl; c) N-heterocycle, which may further contain hetero atoms; d) substituted or unsubstituted C ₁ -C ₄ alkoxy, substituted or unsubstituted C ₁ -C ₄ al skill alkylthio, substituted or unsubstituted amino; And e)

(7) Where R ₉ Is hydrogen, methyl, ethyl or phenyl; K is a _{phenyl, -C 6 H 4 - CONH- (} CH 2) m -, -C 6 H 4 - SO 2 NH- (CH 2) m -, -CH 2 CH 2 -, or -CH ₂ CH ₂ - O-CH ₂ CH _2- , where m is an integer from 1 to 6; Z ₅ Z ₁ And chemical definitions are the same. 2. The method of claim 1, wherein Q is _{halogen, -OSO 3 H, -SSO 3 H} , -OCO-CH 3, -OPO 3 H 2, -OCO-C 6 H 5, -OSO 2 -R ' and R' It is selected from the group consisting of wherein R 'is hydrogen or substituted or unsubstituted C ₁ -C ₄ Dye composition, characterized in that alkyl. The dye composition of claim 2, wherein Q is -OSO ₃ H. The reactive dye composition of claim 1, wherein the reactive dye composition comprises 10 to 95 wt% of the compound having the structure of Formula 1, and 5 to 90 wt% of the compound having the structure of Formula 2. The reactive dye composition according to claim 4, wherein the reactive dye composition comprises 30 to 90 wt% of the compound having the structure of Formula 1, and 10 to 70 wt% of the compound having the structure of Formula 2. The dye composition of claim 1, wherein the compound of Formula 1 is represented by Formula 1a, and further includes one or more compounds having the structure of Formula 2a in addition to the compound of Formula 2. [Formula 1a]

[Formula 2a]

Where n is 0 or 1 to 2; Z ₆ , Z ₇ , and Z ₈ are each independently Z ₁ And chemical definitions are the same; R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently R ₃ And chemical definitions are the same. The dye composition according to claim 6, wherein R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen. The method according to claim 6, comprising 10 to 90% by weight of the compound having the structure of Formula 1a, 5 to 70% by weight of the compound having the structure of Formula 2, and 1 to 50% by weight of the compound having the structure of Formula 2a. Reactive dye composition, characterized in that. The method of claim 8, wherein the dye composition is 30 to 90% by weight of the compound having the structure of Formula 1a, 5 to 40% by weight of the compound having the structure of Formula 2, and 1 to 30% by weight of the compound having the structure of Formula 2a Reactive dye composition, characterized in that comprising a. A method of dyeing a nitrogen or hydroxy-containing fiber material using the reactive dye composition according to any one of claims 1 to 9.