CN106566281A - Reactive navy blue-to-black dye composition and dye product - Google Patents

Abstract

The invention discloses a reactive navy blue to black dye composition and dye products. The reactive navy blue to black dye composition includes component A and component B, wherein component A is selected from at least one compound shown in formula (I), and component B is selected from at least one compound shown in formula (II) The compound shown; wherein the mass ratio of component A to component B is 30-95:5-70. The reactive navy to black dye product contains the reactive navy to black dye composition. The reactive navy blue to black dye composition and dye products provided by the invention have the characteristics of good depth of dyeing, excellent lifting power and good fastness, and the dye consumption in the printing and dyeing process is small, easy to wash with water, and stable dyeing performance.

Description

A kind of reactive navy blue to black dye composition and dye product

(1) Technical field

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

(2) Background technology

Reactive black KNB has become the largest variety of black reactive dyes due to its low price, good fastness and easy washing. The disadvantage of KNB, dye researchers have done a lot of work in the research and development of reactive black dyes in recent years. The existing reactive black dye color matching products still have problems such as poor dyeing depth, poor color fastness, and difficult cleaning of dyed fabrics in the actual application process, such as patents CN102245712A, CN1730566A, CN1745147A, etc.

(3) Contents of the invention

In order to solve the above problems, the object of the present invention is to provide a reactive navy blue to black dye composition and dye products, which have the characteristics of good dyeing depth, excellent lifting power, and good fastness, and the dye consumption in the printing and dyeing process is small and easy to wash. , Dyeing performance is stable.

In order to realize the above-mentioned purpose of the invention, the present invention adopts following technical scheme:

A reactive navy blue to black dye composition, comprising component A and component B, wherein component A is selected from at least one compound shown in formula (I), and component B is selected from at least one compound shown in formula (II) ) shown in the compound; wherein the mass ratio of component A and component B is 30～95:5～70;

In formula (I):

R ¹ , R ² , and R ³ are each independently -H, -C ₁ ~C ₄ alkyl, -C ₁ ~C ₄ alkoxy or -SO ₃ M ¹ ;

Y ¹ and Y ² are each independently -CH=CH ₂ or -C ₂ H ₄ OSO ₃ M ¹ ;

M ¹ is hydrogen or an alkali metal;

In formula (Ⅱ):

R ⁴ is hydrogen, -SO ₃ M ² or -SO ₂ Y ⁴ ,

R ⁵ and R ⁶ are independently hydrogen, -SO ₃ M ² , -COOM ² ,

R ⁷ is -COOM ² , -SO ₂ Y ⁵ ,

Y ³ to Y ⁵ are each independently -CH=CH ₂ or -C ₂ H ₄ OSO ₃ M ² ,

^M2 is hydrogen or an alkali metal.

Further, the reactive black dye composition can also include component C, and component C is selected from at least one compound shown in formula (III)～(IV), and the mass of component C in the composition Accounting for 1-60% of the total mass of component A and component B, preferably 1-55%,

The definition of each substituent in formula (III) is the same as that of formula (I): the definition of each substituent in formula (IV) is the same as that of formula (II).

In the present invention, the C ₁ -C ₄ alkyl group may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl. The C ₁ -C ₄ alkoxy can be methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy .

In formulas (I) to (IV), whether M ¹ and M ² are H or alkali metal atoms has no effect on their dyeing performance, but for the convenience of preparation, they are usually prepared in the form of Na salt and K salt, and those skilled in the art will also It can be acidified to the free acid form.

Further, R ¹ , R ² , and R ³ are each independently preferably -H, -CH ₃ , -OCH ₃ or -SO ₃ M ¹ .

Specifically, the component A is preferably one of the following or a mixture of two or more thereof, wherein ^M is H (free acid form) or Na (salt form):

Component A is particularly preferably of formula (I-1), formula (I-3) or a combination thereof.

Specifically, the component B is preferably one of the following or a mixture of ^two or more thereof, wherein M is H (free acid form) or Na (salt form):

Component B is particularly preferably one or more of the formulas (II-1) to (II-3).

The component C is preferably one of the following or a mixture of two or more thereof, wherein M ¹ and M ² are H (free acid form) or Na (salt form):

Further, the dye composition is composed of component A and component B.

Further, the dye composition is composed of component A, component B and component C.

Further, based on the sum of the mass of component A and component B, the mass percentage of component A is 30-95%, and the mass percentage of component B is 5-70%.

Furthermore, the mass percentage of component A is 45-95%, and the mass percentage of component B is 5-55%.

Preferably, the reactive navy blue to black dye composition comprises component A, component B and component C, based on the sum of the mass of component A and component B, the mass percentage of component A is 30 ~95% (preferably 45 ~ 95%), the mass percentage of component B is 5 ~ 70% (preferably 5 ~ 55%), the quality of component C is 1 ~ 5% of the total mass of component A and component B 60% (preferably 1-55%). More preferably, the reactive navy blue to black dye composition is made up of component A, component B and component C, wherein, based on described component A and component B, the mass percentage of component A is 30 to 95% (preferably 45 to 95%), the mass percentage of component B is 5 to 70% (preferably 5 to 55%), and the mass of component C is 1% of the total mass of component A and component B -60% (preferably 1-55%).

Preferably, the reactive navy blue to black dye composition comprises component A, component B and component C, wherein component A is selected from at least one of formula (I-1) ~ formula (I-11) The compound shown, component B is selected from at least one compound shown in formula (II-1)～(II-17), component C is selected from at least one compound shown in formula (III-1)～(III-9), (IV-1)～(IV-4), based on the total weight of component A and component B, the mass percentage of component A is 30～95% (more preferably 45～95%) , the mass percentage of component B is 5～70% (more preferably 5～55%), the quality of component C is 1～60% (more preferably 1～60%) of the total mass of component A and component B 55%). More preferably, the reactive navy blue to black dye composition consists of component A, component B and component C.

Preferably, the reactive navy blue to black dye composition is composed of component A and component B, wherein the mass percentage of component A is 30-95%, and the mass percentage of component B is 5-70% %. More preferably, the reactive navy blue to black dye composition is composed of component A and component B, the mass percentage of component A is 45-95%, and the mass percentage of component B is 5-55%. %.

Preferably, the reactive navy blue to black dye composition comprises component A and component B, wherein component A is selected from at least one compound represented by formula (I-1) to formula (I-11), Component B is selected from at least one compound represented by formulas (II-1) to (II-17), based on component A and component B, the mass percentage of component A is 30 to 95% (more preferably 45-95%), and the mass percentage of component B is 5-70% (more preferably 5-55%). More preferably, the reactive navy blue to black dye composition consists of component A and component B.

In the active navy blue to black dye composition of the present invention, the dye compounds (I), (III), and (IV) used can be obtained by conventional methods, such as by using suitable components well known to those skilled in the art and using The necessary proportions are synthesized by means of the usual diazotization reaction and coupling reaction, or prepared by referring to the methods in patents CN101250334, CN 103897430, CN101255282 or similar methods. The preparation method of the compound of formula (II) is described in the subsequent examples.

The reactive navy blue to black dye composition of the present invention, its preparation method comprises dye component A, B, C are mixed 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 dye compounds (I) to (IV) can exist in the form of powder, granular, aqueous solution or synthetic solution. When the individual dye compounds are blended in the form of synthetic solution, they are separated from the synthetic solution. Composite reactive navy blue to black dyestuff of the present invention can carry out generally known method, for example with electrolyte (as sodium chloride or potassium chloride) dyestuff is salted out and filtered out from reaction medium, or mixed solution is evaporated, sprayed Drying, therefore, dye components A, B, C and their dye compositions usually contain conventional electrolyte salts (such as sodium chloride, sodium sulfate, etc.) in reactive dyes.

When the active navy blue to black dye composition of the present invention is sold as a commodity or applied to the coloring of textile materials, no auxiliary agent can be added, and conventional auxiliary agents in commercial dyes can also be added, such as auxiliary solvents, dispersants, alkali-resistant Sexual additives, dustproof agents, surfactants, buffers and dyeing accelerators, etc. Therefore, the present invention also provides a reactive navy blue to black dye product, which contains the reactive navy blue to black dye composition. Preferably, the reactive navy blue to black dye product mainly contains the reactive navy blue to black dye composition and auxiliary agents, and the weight ratio of the reactive navy blue to black dye composition to auxiliary agents is 100:0～ 45, preferably 100:0-40. Described auxiliary agent is preferably the following one or the combination of any several: naphthalenesulfonic acid formaldehyde condensate (NNO), methylnaphthalenesulfonic acid formaldehyde condensate (dispersant MF), diffusion agent CNF (benzylnaphthalenesulfonate formaldehyde condensate), Yuanming powder (industrial sodium sulfate). The auxiliary agents are commercially available conventional varieties.

The active navy blue to black dye product 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 or regenerated fibers, and of course other vegetable fibers can also be included, such as Hemp fibers or fabrics; 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 reactive navy blue to black dye product of the present invention to print and dye the above-mentioned fiber material, can follow known reactive dye dyeing method to carry out, as commonly used reactive dye exhaust dyeing method and pad dyeing method, described exhaust dyeing is the The method of dipping the fabric in the dye solution to make the dye gradually dye the fabric 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 (weight ratio of fabric to dye liquor, preferably 1:10～1:30), the initial dyeing temperature is controlled at 30～60°C, the dyeing time is 10～30 minutes, the soaping temperature is 85～95°C, and the soaping time 10-15 minutes, color-fixing temperature 60-100°C, color-fixing time 10-50 minutes, color-fixing pH 9-11. When dyed 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. The dyes and alkaline substances are introduced into the pad dyeing machine, and rolled up and stacked at room temperature for 2 to 30 hours to fix the color, and then thoroughly rinsed. .

The beneficial effects of the present invention are mainly reflected in that the active navy blue to black dye product of the present invention has the characteristics of good liftability, good compatibility, easy washing and excellent color fastness when used for fabric printing and dyeing.

(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:

It should be noted that, in order to make the characterization of dye compounds convenient and uniform, each monochromatic dye in the color-blocking component is presented in the form of free acid, but in actual production and processing, each monochromatic component is usually in the form of alkali metal They are present in the form of salts, preferably lithium, sodium or potassium, particularly preferably sodium, and used in the form of their salts for dyeing.

Embodiment 1: the preparation of formula (II-1) compound

(1) Diazotization: Add 17.3g of 2-aminobenzenesulfonic acid to 150mL of water and stir evenly, then cool to 0-5°C, add 12.5g of 31% (w/w) hydrochloric acid, maintain 0-5°C slowly Slowly add 24.5 g of 30% (w/w) sodium nitrite aqueous solution dropwise, stir at this temperature for 1 hour, eliminate excess sodium nitrite with sulfamic acid, and obtain the diazonium solution of 2-amino-benzenesulfonic acid;

(2) Diazotization: Add 56.2g of para-ester (i.e. p-(β-hydroxyethylsulfone sulfate) aniline) to 150mL of water and stir evenly, then cool to 0-5°C, maintain 0-5°C slowly Slowly add 21g of 31% hydrochloric acid and 48g of 30% sodium nitrite dropwise, stir at this temperature for 1 hour, use sulfamic acid to eliminate excess sodium nitrite, and obtain the diazonium solution of para-ester;

(3) Coupling: Add 15.2g of 5-(ethylsulfone group)-1,3-phenylenediamine into 100mL of water, after dissolving, add the diazonium salt of step (1) into the solution, adjust The pH value is 5.3-5.5 and the temperature is controlled at 5-8°C, and the coupling reaction is carried out for 3 hours to obtain a primary coupling solution for later use;

(4) Coupling: quickly drop the para-ester diazonium solution obtained in step (2) into the primary coupling solution obtained in step (3), adjust the pH value to 5.5-6.0 and control the temperature at 5-10°C, Coupling reaction was carried out for 3 hours to obtain a secondary coupling solution;

(5) Add 17.2g of p-aminobenzoic acid to 215mL of water and stir evenly, then add 25g of 30% (w/w) sodium nitrite aqueous solution to the above solution at 0°C, and slowly add it dropwise while maintaining 0-5°C 20g of 31% (w/w) hydrochloric acid was stirred at this temperature for 1 hour, and excess sodium nitrite was eliminated with sulfamic acid to obtain p-aminobenzoic acid diazo solution;

(6) Add the diazonium solution of step (5) into the secondary coupling solution of step (4), adjust the pH value to 6.0-7.0 and control the temperature at 5-10°C, perform coupling reaction for 2 hours, and dry to obtain the main formula: An orange dye with a hydrazone structure shown in (II-1), M ² is Na.

Embodiment 2: the preparation of formula (II-2) compound

(1) Diazotization: Add 17.2g of p-aminobenzoic acid to 215mL of water and stir evenly, then add 25g of 30% (w/w) sodium nitrite aqueous solution to the above solution at 0°C, and keep it at 0-5°C Slowly add 20 g of 31% (w/w) hydrochloric acid dropwise, stir at this temperature for 1 hour, eliminate excess sodium nitrite with sulfamic acid, and obtain p-aminobenzoic acid diazonium solution.

(2) Diazotization: Add 56.2g of para-ester (i.e. p-(β-hydroxyethylsulfone sulfate) aniline) to 150mL of water and stir evenly, then cool to 0-5°C, maintain 0-5°C slowly Slowly add 21g of 31% hydrochloric acid and 48g of 30% sodium nitrite dropwise, stir at this temperature for 1 hour, use sulfamic acid to eliminate excess sodium nitrite, and obtain the diazonium solution of the para-ester.

(3) Coupling: 20g of 3,5-diaminobenzenesulfonic acid is added to the hydrochloric acid solution of 100g0.05mol/L in the diazonium salt of step (1), the pH value is adjusted to 3.2, and then the mixture is mixed at 6～ Stir at 7°C for 30 minutes to obtain a primary coupling solution.

(4) Coupling: quickly drop the para-ester diazonium solution obtained in step (2) into the primary coupling solution obtained in step (3), adjust the pH value to 3.5, and control the temperature at 15-19°C. Stir at 25°C for 45 minutes, treat the resulting solution with 450 g of acetone, adjust the pH to 1.5, filter the precipitated dye, wash with acetone, and dry to obtain the orange dye of the hydrazone structure shown in formula (II-2) , ^M2 is Na.

Embodiment 3: the preparation of formula (II-3) compound

(1) Diazotization: Add 17g of 2-amino-5-sulfobenzoic acid to 150mL of water and stir evenly, then cool to 0-5°C, add 12.5g of 31% (w/w) hydrochloric acid to maintain 0-5°C Slowly add 24.5g of 30% (w/w) sodium nitrite aqueous solution dropwise at 5°C, stir at this temperature for 1 hour, and use sulfamic acid to eliminate excess sodium nitrite to obtain 2-amino-5-sulfobenzene Formic acid diazonium solution.

(2) Diazotization: Add 56g of para-ester (i.e. p-(β-hydroxyethylsulfone sulfate) aniline) to 150mL of water and stir evenly, then cool to 0-5°C, maintain 0-5°C and slowly 21g of 31% hydrochloric acid and 48g of 30% sodium nitrite were added dropwise, stirred at this temperature for 1 hour, and excess sodium nitrite was eliminated with sulfamic acid to obtain a diazonium solution of para-ester.

(3) Coupling: add 15g of m-phenylenediamine into 100mL of water, after dissolving, add the diazonium salt of step (1) into the solution, adjust the pH value to 5.3-5.5 and control the temperature at 5-8°C, and perform coupling React for 3 hours to obtain primary coupling solution.

(4) Coupling: quickly drop the para-ester diazonium solution obtained in step (2) into the primary coupling solution obtained in step (3), adjust the pH value to 6.0-7.0 and control the temperature to 5-10°C, After coupling reaction for 3 hours and drying, the orange dye with the hydrazone structure shown in formula (II-3) is mainly obtained, and M ² is Na.

Example 4:

According to the preparation method described in Example 1 or a similar method, the difference is that the p-(β-hydroxyethyl sulfone sulfate) aniline in the step (2) is replaced by an equimolar amount of p-(β-vinylsulfone)aniline After diazotization, the hydrazone dye of formula (II-4) can be obtained.

Example 5:

According to the preparation method described in Example 1 or a similar method, the difference is that the 5-(ethyl sulfate sulfone group in step (3) is replaced by an equimolar amount of 5-vinylsulfone-1,3-phenylenediamine )-1,3-phenylenediamine for coupling to obtain the hydrazone dye of formula (II-5).

Embodiment 6:

According to the preparation method described in Example 1 or a similar method, the difference is that 3-(β-hydroxyethylsulfone sulfate) aniline in an equimolar amount is used to replace the p-(β-hydroxyethylsulfone) in step (2) Sulfate) aniline is diazotized to obtain the hydrazone dye of formula (II-6).

Embodiment 7～12:

According to the preparation method described in Example 2 or a similar method, the difference is: respectively adopt diazo component 1 and diazo component 2 in Table 1 to replace the para-ester in step (2), then The hydrazone dyes shown in Table 2 were prepared, and the dyed fabric presented a bright orange color.

Table 1

Embodiment 13～17:

According to the preparation method described in Example 3 or a similar method, the difference is: respectively adopt diazo component 3 and diazo component 4 of equimolar amounts in Table 3 to replace the corresponding components in step (2), then The hydrazone dyes shown in Table 2 were prepared, and the dyed fabric presented a bright orange color.

Table 2

Example 18:

Mechanically mix 60 parts of the dye of the formula (I-1), 40 parts of the dye of the formula (II-1) and 10 parts of sodium anhydride, and the obtained composite dye dyed cotton is dark black (M ¹ to M ² are all H , that is, the dye compound is expressed in the form of free acid).

Example 19:

Mechanically mix 55 parts of the dye of formula (I-3), 25 parts of the dye of formula (II-2), 20 parts of the dye of formula (III-1) and 10 parts of sodium sulfate, and the obtained composite dyed cotton is Deep black (M ¹ ~ M ² are all H, that is, the dye compound is expressed in the form of free acid).

Example 20:

65 parts of the dyestuff of formula (I-3), 15 parts of dyestuff of formula (II-1), 10 parts of dyestuff of formula (III-3) and 10 parts of dyestuff of formula (IV-1) are mechanically mixed to obtain The composite dyes dyed cotton are dark black (M ¹ ~ M ⁴ are all H, that is, the dye compound is expressed in the form of free acid).

Examples 21-50

Mechanically mix the dyes listed in Table 3 to dye cotton from navy blue to black (M ¹ to M ² are all H, that is, the dye compound is expressed in the form of free acid).

table 3

Comparative example 1:

According to the method of embodiment 38 among CN1266869A, prepare following orange reactive dye compound:

Comparative example 2:

According to the method of embodiment 122 among CN101283054A, prepare following black reactive dye compound:

Comparative example 3: according to the method for embodiment 1 among CN1745147A, prepare following black reactive dye compound:

Dyeing example:

The active navy blue to the black dye dry product obtained by the reactive orange dye dry product that embodiment 1～3 and comparative example 1 (closest) obtain and embodiment 18～20 and comparative example 2,3 (closest) are dissolved in respectively In the water, add 50g/L of Yuanming powder to make 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) fixed color for 45 minutes, dyed fabrics were washed with water, soaped, dried to obtain navy blue to black dyed fabrics. According to the methods in ISO105-X12 and GB/T3921-2008, the color fastness to rubbing and soaping were compared, and the results are as follows:

Table 4: Fastness comparison

Table 5: Comparison of Lifting Power, K/S Values at Different Dyeing Depths

staining depth 2.0% 4.0% 6.0% 8.0% 10.0% 12.0% Example 18 18.03 28.37 35.22 36.93 38.36 39.69 Example 19 17.85 27.08 34.13 36.32 38.49 39.77 Example 20 18.12 28.26 35.29 36.74 38.32 39.49 Comparative example 2 15.72 24.72 33.36 34.11 34.28 34.80 Comparative example 3 15.98 25.01 33.87 34.45 35.29 35.66

In summary, the dyestuff of the present invention is obviously better than the comparative examples, and for the industry, it has significant improvements in color fastness and lifting power.

Claims (10)

1. a kind of reactive navy blue is to black dye composition, including component A and component B, and wherein component A is selected from least one such as formula (I) compound shown in, component B is selected from least one compound as shown in formula II；The wherein quality of component A and component B Than for 30～95:5～70；

In formula I：

R¹、R²、R³Each stand alone as-H ,-C₁～C₄Alkyl ,-C₁～C₄Alkoxyl or-SO₃M¹；

Y¹、Y²Each stand alone as-CH=CH₂Or-C₂H₄OSO₃M¹；

M¹For hydrogen or alkali metal；

In formula II：

R⁴For hydrogen ,-SO₃M²Or-SO₂Y⁴,

R⁵、R⁶It is each independently hydrogen ,-SO₃M²、-COOM²,

R⁷For-COOM²、-SO₂Y⁵,

Y³～Y⁵Each stand alone as-CH=CH₂Or-C₂H₄OSO₃M²,

M²For hydrogen or alkali metal.

2. reactive navy blue as claimed in claim 1 is to black dye composition, it is characterised in that：The reactive navy blue is to black Dye composite is made up of component A and component B.

3. reactive navy blue as claimed in claim 1 is to black dye composition, it is characterised in that：Described reactive black dye group Compound also includes component C, at least one of component C in the compound as shown in formula III and formula IV, the compositionss The quality of middle component C accounts for the 1～60% of component A and component B gross mass,

Each substituent group defines same formula I in formula III, and each substituent group defines same formula II in formula IV.

4. reactive navy blue as claimed in claim 3 is to black dye composition, it is characterised in that：Described reactive navy blue is to black Dye composition is made up of component A, component B and component C.

5. the reactive navy blue as described in one of Claims 1 to 4 is to black dye composition, it is characterised in that：R¹、R²、R³Each Stand alone as-H ,-CH₃、-OCH₃Or-SO₃M¹。

6. the reactive navy blue as described in one of Claims 1 to 4 is to black dye composition, it is characterised in that：Component A is Mixture more than one of following or two of which, wherein M¹For H or Na：

7. the reactive navy blue as described in one of Claims 1 to 4 or 6 is to black dye composition, it is characterised in that：The component B be one of following or two of which more than mixture, wherein M²For H or Na：

8. the reactive navy blue as described in claim 3 or 4 is to black dye composition, it is characterised in that：Component C is following One of or two of which more than mixture, wherein M¹、M²For H or Na：

9. reactive navy blue as claimed in claim 8 is to black dye composition, it is characterised in that：Component A for it is following it One or two of which more than mixture, wherein M¹For H or Na：

Component B be one of following or two of which more than mixture, wherein M²For H or Na：

10. to black dyes product, it contains reactive navy blue as claimed in claim 1 to black dyes group to a kind of reactive navy blue Compound.