CN102964870B - Active black dye composition - Google Patents

Abstract

The invention provides a reactive black dye composition, mainly comprising 45-90 parts by mass of at least one component A shown in formula (I), and 1-30 parts by mass of at least one component A shown in formula (II) Component B component shown, and 1~40 parts by mass of at least one component C shown in formula (III) and/or 1~40 parts by mass of at least one group shown in formula (IV) Point D: The reactive black dye composition of the present invention, when used in fabric printing and dyeing, has good lifting properties, strong salt and alkali resistance, easy washing, and excellent wet fastness. It is a rare economical deep black dye.

Description

A kind of reactive black dye composition

(1) Technical field

The invention relates to a reactive dye composition, in particular to a reactive black dye composition with excellent lifting power, easy water washing and stable dyeing performance.

(2) Background technology

In cotton fiber dyeing, black accounts for almost 40-50%, and more direct dyes and sulfur dyes are banned and restricted due to environmental protection issues. Reactive black KN-B is used in a large amount because of its low price, good fastness, high color fixation rate and easy washing, and there is no environmental protection problem including AOX. But there are also defects such as poor lifting force and insufficient blackness, which limit its wide use.

The existing reactive black dye color matching products still have problems such as poor dyeing depth, low dyeing rate and color fixation rate, and difficult cleaning of dyed fabrics in the actual application process, such as patents CN102245712, CN1730566, etc. This is due to the high concentration of dyes used in deep-color dyeing, the amount of floating dyes increases, and the adsorption of dyes to fibers has a saturation value. Generally, the concentration of dyes should not exceed 10% of the saturation value of dyeing. Excessive dyes cannot be dyed and fixed. It will accumulate on the surface of the fabric. If the cleanability is not good, it will inevitably affect the wet fastness of the dyed fabric, resulting in poor dyeing performance.

(3) Contents of the invention

In order to solve the above problems, the object of the present invention is to provide a reactive black dye composition, which has good dyeing depth, excellent lifting power, high dye uptake rate, high color fixation rate, less dye consumption in the printing and dyeing process, easy washing, and no residue. Liquid clear, stable dyeing performance.

The technical scheme adopted in the present invention is:

A reactive black dye composition, mainly comprising 45 to 90 parts by mass of at least one component A shown in formula (I), and 1 to 30 parts by mass of at least one component shown in formula (II) B, and 1 to 40 parts by mass of at least one component C shown in formula (III) and/or 1 to 40 parts by mass of at least one component D shown in formula (IV);

In formula (I):

R ¹ and R ² are each independently H, C ₁ to C ₄ alkyl, C ₁ to C ₄ alkoxy or -SO ₃ M ¹ , preferably -H, -CH ₃ , -OCH ₃ or -SO ₃ M ¹ ; M ¹ is hydrogen or an alkali metal atom, preferably -H or -Na.

In formula (Ⅱ):

R ³ and R ⁴ are each independently -H, -C ₁ to C ₄ alkyl, -C ₁ to C ₄ alkoxy or -SO ₃ M ² , preferably -H, -CH ₃ , -OCH ₃ or - SO ₃ M ² ; R ⁵ is -H or -SO ₃ M ² ; Y ¹ is -CH=CH ₂ or -C ₂ H ₄ OSO ₃ M ² ; M ² is hydrogen or an alkali metal atom, preferably -H or -Na.

In formula (Ⅲ):

R ⁶ is -COOR ⁷ , -CN or -CONR ⁸ R ⁹ , wherein R ⁷ is M ³ or C ₁ to C ₄ alkyl, and R ⁸ and R ⁹ are each independently -H or C ₁ to C ₄ alkyl; Y ² is -CH=CH ₂ or -C ₂ H ₄ OSO ₃ M ³ ; M ³ is hydrogen or an alkali metal atom, preferably -H or -N _a .

In formula (Ⅳ):

R ¹⁰ is -SO ₃ M ⁴ ; R ¹¹ is -COOM ⁴ , -SO ₃ M ⁴ , -SO ₂ CH═CH ₂ or -SO ₂ C ₂ H ₄ OSO ₃ M ⁴ ; Y ³ and Y ⁴ are independently -CH=CH ₂ , -C ₂ H ₄ OSO ₃ M ⁴ ; M ⁴ is H or an alkali metal atom, preferably H or Na.

Preferably, based on the sum of the mass of components A to D, the mass percentage of component A is 50-85%, the mass percentage of component B is 1-25%, and the mass percentage of component C The content is 0-35%, and the mass percentage of component D is 0-35% (the mass percentages of components C and D are not equal to 0 at the same time).

Preferably, the reactive black dye composition is composed of component A, component B and component C, wherein the mass percentage of component A is 50-85%, and the mass percentage of component B is 5% ~20%, the mass percentage of component C is 10~35%.

Preferably, the reactive black dye composition is composed of component A, component B and component D, wherein the mass percentage of component A is 55-85%, and the mass percentage of component B is 1 ~20%, the mass percentage of component D is 10~35%.

Preferably, the reactive black dye composition is composed of component A, component B, component C and component D, wherein the mass percentage of component A is 50-85%, and the mass percentage of component B is The component content is 1-25%, the mass percentage content of component C is 5-35%, and the mass percentage content of component D is 1-25%.

The component A is preferably one of the following or a mixture of two or more thereof:

The component B is preferably one of the following or a mixture of two or more thereof:

The component C is preferably one of the following or a mixture of two or more thereof:

The component D is preferably one of the following or a mixture of two or more thereof:

Preferably, the reactive black dye composition of the present invention consists of at least one component A represented by formula (I-1) to formula (I-7), at least one component A represented by formula (II-1) to (II) Component B shown in -7) consists of at least one component C shown in formulas (III-1) to (III-9), wherein the mass percentage of component A is 50 to 85%, and the composition The mass percentage of component B is 5-20%, and the mass percentage of component C is 10-35%.

Or the reactive black dye composition of the present invention is composed of at least one component A shown in formula (I-1) to formula (I-7), at least one component A shown in formula (II-1) to (II-7) ), component B shown in ), at least one component D shown in formula (IV-1)～(IV～12), wherein, the mass percentage of component A is 55～85%, component B The mass percentage of component D is 1-20%, and the mass percentage of component D is 10-35%.

Or the composition of the present invention is composed of at least one component A shown in formula (I-1) to formula (I-9), at least one component B shown in formula (II-1) to (II-7) , at least one component C shown in formulas (Ⅲ-1)～(Ⅲ-9) and at least one component D shown in formulas (Ⅳ-1)～(Ⅳ～12), the composition of component A The mass percentage is 50-85%, the mass percentage of component B is 1-25%, the mass percentage of component C is 5-35%, and the mass percentage of component D is 1-25% %.

The reactive black dye composition of the present invention is particularly preferably made up of component A, component B and component C shown below, wherein:

Component A: at least one dye selected from formulas (I-1) to (I-3);

Component B: at least one dye selected from formulas (II-1) to (II-3);

Component C: at least one dye selected from formulas (III-1), (III-2), (III-7) and (III-8);

Based on the sum of the mass of the above-mentioned components A, B and C, the mass percentage of component A is 50-85%, the mass percentage of component B is 5-20%, and the mass percentage of component C is 10-35%;

Or, the reactive black dye composition of the present invention is particularly preferably made up of component A, component B and component D as shown below, wherein:

Component A: at least one dye selected from formulas (I-1) to (I-3);

Component B: at least one dye selected from formulas (II-1) to (II-3);

Component D: at least one dye selected from formulas (IV-1) to (IV-3), (IV-7), and (IV-8);

Based on the sum of the above-mentioned components A, B and D mass, the mass percentage of component A is 55-85%, the mass percentage of component B is 1-20%, and the mass percentage of component D is 10-35%;

Or, the reactive black dye composition of the present invention is particularly preferably made up of component A, component B, component C and component D as shown below, wherein:

Component A: at least one dye selected from formulas (I-1) to (I-3);

Component B: at least one dye selected from formulas (II-1) to (II-3);

Component C: at least one dye selected from formulas (III-1)-(III-2), (III-7)-(III-8);

Component D: at least one dye selected from formulas (IV-1) to (IV-3), (IV-7) to (IV-8).

Based on the sum of the mass of the above-mentioned components A, B, C and D, the mass percentage of component A is 50-85%, the mass percentage of component B is 1-25%, and the mass percentage of component C The content is 5-35%, and the mass percentage of component D is 1-25%.

The dye compounds of formula (I) to formula (IV) described in the present invention can exist in the form of free acid (M ¹ to M ⁴ is -H) or salt, preferably in the form of salt, and the salt can be Alkali metal salts (M ¹ to M ⁴ are alkali metals), particularly preferably sodium salts (M ¹ to M ⁴ are -Na).

In the reactive black dye composition of the present invention, the used component A, component B, component C and component D can be easily synthesized in a manner well known to those skilled in the art, wherein (I) of the present invention ), (II), (III) and (IV) compounds can be prepared respectively according to the methods described in patents CN101580649, KR100686977, CN102245712, CN1569969 or similar methods.

The reactive black dye composition of the present invention, its preparation method comprises mixing formula (I)～formula (IV) dyestuff according to aforesaid proportion, and mixing can adopt conventional mechanical means to carry out, as in grinder, kneader or It is carried out in a homogenizer. During the mixing process, individual dyes (I), (II), (III) and (IV) can exist in the form of powder, granular, aqueous solution or synthetic solution. When individual dyes (I), (II) , (Ⅲ) and (Ⅳ) when blending together with the form of synthetic solution, from synthetic solution separation complex reactive black dyestuff of the present invention can carry out generally known method, for example with electrolyte (such as sodium chloride or potassium chloride ) salting out and filtering out the dyestuff from the reaction medium, or evaporating and spray-drying the mixed solution, at this time, a commercially available auxiliary agent can be added, and the auxiliary agent is one of the following or a mixture of any proportion thereof: auxiliary solvent, Dispersants, alkali-resistant additives, dustproof agents, surfactants, buffers and dyeing accelerators, etc., preferably naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), Diffusion agent CNF (benzyl naphthalene sulfonate formaldehyde condensate), Yuanming powder (industrial sodium sulfate), etc. The above auxiliary agents are commercially available conventional varieties. Usually, depending on the actual needs, the addition amount of the auxiliary agent is 0-45%, preferably 0-40% (accounting for the weight of the total composition of the dye).

The reactive black dye composition of the present invention is suitable for printing and dyeing of cellulose fibers, polyamide fibers and fabrics thereof, wherein the cellulose fibers are preferably cotton fibers and regenerated fibers, and of course other vegetable fibers, such as hemp Polyamide fibers are preferably animal fiber materials including fur, wool or silk, and synthetic fiber materials such as nylon 6 and nylon 66. When adopting the reactive black dye composition of the present invention to print and dye the above-mentioned fiber materials, it can be carried out in accordance with known reactive dye dyeing methods, such as the commonly used reactive dye exhaust dyeing method and pad dyeing method, and the described exhaust dyeing method is to fabricate The method of dipping in the dyeing solution to gradually dye the fabric with the dye usually needs to go through dyeing-fixation-washing-soaping-washing-dehydration-drying and other processes.

The pad dyeing is a dyeing method in which the fabric is dipped in the dye solution first, and then the fabric is passed through a roller, and the dye solution is evenly rolled into the inside of the fabric, and then steamed or hot-melted. Liquid-drying-(padding fixing solution)-steaming or baking-washing-soaping-washing-drying and other processes.

Usually, due to the different color requirements on the fabric, the amount of dye used will also be different. When dyeing by exhaust dyeing, the depth of dyeing (owf) is generally 0.1% to 10% (the dye accounts for the weight percentage of the fabric), and the liquor ratio is 1: 2～1:60 (fabric to dye liquor weight ratio, preferably 1:10～1:30, initial dyeing temperature control 30～60℃, dyeing time 10～30 minutes, soaping temperature 85～95℃, soaping time 10 ～15 minutes, color fixing temperature 60～100℃, color fixing time 10～50 minutes, color fixing pH value 9～11. When dyeing by pad dyeing method, the excess rate of cellulose fiber is generally 60～80%. The steaming temperature is 100-103°C, and the steaming time is 1-3 minutes. Among the pad dyeing methods, the cold pad-batch dyeing method is mostly used at present. Rolls are stacked for 2 to 30 hours to fix, followed by a thorough rinse.

The beneficial effects of the present invention are mainly reflected in: the reactive black dye composition of the present invention, when used for fabric printing and dyeing, has good lifting properties, high color fixation rate, high dye uptake rate, easy washing, clear dyeing residue, and salt-alkaline resistance Stable, excellent wet fastness, is a rare economical deep black dye.

(4) Specific implementation methods

The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:

The compounds described in the examples can be similarly synthesized in the form of free acid or its salt by using known methods. Unless otherwise specified, the following "parts" are hundreds of weight parts.

Example 1:

Mechanically mix 60 parts of the dye of formula (I-1), 13 parts of the dye of formula (II-1), 23 parts of the dye of formula (III-8) and 4 parts of sodium sulfate, and the obtained composite dye dyed cotton is dark black.

Example 2

57 parts of dyestuffs of formula (I-3), 16 parts of dyestuffs of formula (II-2), 27 parts of dyestuffs of formula (III-7) and 2.5 parts of sodium sulfate are mechanically mixed, and the composite dyed cotton obtained is dark black.

Example 3

56 parts of dyes of formula (I-3), 17 parts of dyes of formula (II-2), 12 parts of dyes of formula (III-7), and 15 parts of dyes of formula (IV-1) were mechanically mixed to obtain The complex dye dyes cotton in dark black.

Embodiment 4～28:

Mechanically mix the dyes listed in Table 1 to dye cotton in dark black.

Table 1

Application example:

Take the reactive black dyes prepared in Examples 1-28 of the present invention, dissolve them in water respectively, and add 50 g/L of sodium sulfate to prepare a dye solution. Dyeing concentration 4% (dye to cloth weight), liquor ratio 1:10 (cloth weight in grams to dye liquor volume in milliliters), put in cotton cloth at 60°C for 30 minutes, add alkali (sodium hydroxide 15g/L, carbonic acid Sodium 10g/L) color fixing for 45 minutes, the dyed fabric was washed with water, soaped and dried to obtain a black dyed fabric.

(1) Color fastness

Test its washing fastness according to ISO105-C03, 60°C:

Original discoloration≧4-5 level; staining≧4 level

Test its perspiration fastness according to ISO105-E04:

Acid sweat: discoloration ≧ grade 4; staining ≧ grade 3-4

Alkaline sweat: discoloration≧4 grades; staining≧3-4 grades

Test its rubbing fastness according to ISO105-X12:

Dry friction: ≧4-5 level; Wet friction: ≧2-3 level

According to ISO105-E01 test its water immersion fastness ≧ 4-5 grade.

According to ISO105-X11 test its ironing fastness, discoloration ≧ 4-5 level.

(2) Salt-alkaline resistance: when the above-mentioned dyes are dyed, the strength increases with the increase of salt consumption and pH value respectively, and basically has no effect on shade, which shows that the reactive black dyes of the present invention are stable in salt-alkali resistance.

Contrast dyeing experiment:

Comparative example 1, according to the embodiment 31 in the patent CN102245712, prepare the reactive black dye of following three components:

Comparative example 2, according to embodiment 6 among the patent CN1730566, prepare the reactive black dye of following three components:

According to the method described in the above-mentioned application examples, select the closest embodiment 22, embodiment 5, and embodiment 21 of the present invention with comparative examples 1 and 2 to compare the dyeing properties, and the results are as follows:

(1) Lifting power comparison, K/S value under different dyeing depths

staining depth 2.0% 4.0% 6.0% 8.0% 10.0% 12.0% Example 5 18.59 27.06 34.12 37.10 39.78 40.61 Example 21 17.69 26.12 32.85 35.32 37.83 39.80 Example 22 17.03 24.97 30.17 35.19 37.26 39.63 Comparative example 1 12.92 20.64 26.11 29.11 31.63 32.94 Comparative example 2 15.24 23.00 27.91 33.73 34.13 34.24

It can be seen from the above table that with the increase of the dyeing depth, the dyeing depth of the present invention is obviously better than that of the comparative examples.

(2) Contrast of dye uptake rate, %

dyeing time 0 15min 30min 40min 50min 70min 90min Example 5 0 45.98 49.32 70.23 77.15 79.38 80.75 Example 21 0 44.45 46.27 69.32 76.09 78.66 79.98 Example 22 0 43.37 45.61 69.56 75.81 78.47 79.76 Comparative example 1 0 32.90 37.16 64.47 70.45 71.64 72.00 Comparative example 2 0 30.46 36.09 65.52 71.26 73.06 73.32

(3) Comparison of color fixation rate, %

Fixing time 0 15min 30min 40min 50min 70min 90min Example 5 0 63.89 72.02 74.59 76.19 Example 21 0 64.10 71.73 74.08 75.57 Example 22 0 64.58 71.33 74.64 75.66 Comparative example 1 0 57.39 63.94 66.32 67.10 Comparative example 2 0 57.97 65.68 69.02 69.42

As can be seen from the above table, the dyestuff of the present invention is obviously better than the comparative examples, and for the industry, it has significant improvements in lifting power, dye uptake rate and color fixation rate.

Claims (6)

1. A reactive black dye composition, mainly comprising at least one component A of 45 to 90 parts by mass, at least one component B shown in formula (II) of 1 to 30 parts by mass, and 1 to 40 parts by mass Parts by mass of at least one component C shown in formula (III), or 1 to 40 parts by mass of at least one component C shown in formula (III) and at least one component C shown in 1 to 40 parts by mass Component D shown in formula (IV); The component A is one of the following or a mixture of two or more thereof: In formula (Ⅱ): R ³ and R ⁴ are each independently -H, -C ₁ ~C ₄ alkyl, -C ₁ ~C ₄ alkoxy or -SO ₃ M ² ; R ⁵ is -H or -SO ₃ M ² ; Y ¹ Be -CH=CH ₂ or -C ₂ H ₄ OSO ₃ M ² ; M ² is hydrogen or an alkali metal atom; In formula (Ⅲ): R ⁶ is -COOR ⁷ , -CN or -CONR ⁸ R ⁹ , wherein R ⁷ is M ³ or C ₁ to C ₄ alkyl, and R ⁸ and R ⁹ are each independently -H or C ₁ to C ₄ alkyl; Y ² is -CH=CH ₂ or -C ₂ H ₄ OSO ₃ M ³ ; M ³ is hydrogen or an alkali metal atom; In formula (Ⅳ): R ¹⁰ is -SO ₃ M ⁴ ; R ¹¹ is -COOM ⁴ , -SO ₃ M ⁴ , -SO ₂ CH═CH ₂ or -SO ₂ C ₂ H ₄ OSO ₃ M ⁴ ; Y ³ and Y ⁴ are independently -CH=CH ₂ , -C ₂ H ₄ OSO ₃ M ⁴ ; M ⁴ is H or an alkali metal atom. 2. reactive black dye composition as claimed in claim 1, is characterized in that described reactive black dye composition is made up of component A, component B and component C, and the mass percentage composition of component A is 50～ 85%, the mass percentage of component B is 5-20%, and the mass percentage of component C is 10-35%. 3. reactive black dye composition as claimed in claim 1, is characterized in that: described reactive black dye composition is made up of component A, component B, component C and component D, and the quality of component A is 100%. The component content is 50-85%, the mass percentage content of component B is 1-25%, the mass percentage content of component C is 5-35%, and the mass percentage content of component D is 1-25%. 4. The reactive black dye composition according to any one of claims 1 to 3, characterized in that said component B is one of the following or a mixture of two or more thereof: 5. The reactive black dye composition according to any one of claims 1 to 3, characterized in that said component C is one of the following or a mixture of two or more thereof: 6. The reactive black dye composition as claimed in claim 1 or 3, characterized in that said component D is one of the following or a mixture of two or more thereof: