CN101173113B - A kind of reactive dye composition - Google Patents

Abstract

The present invention relates to a reactive dye composition, in particular to a disazo reactive dye composition, mainly containing one or more components A with structures such as formula (I) and one or more structures such as formula The composition of component B shown in (II) is based on the components A and B, the weight fraction of the component A is 1-99%, and the weight fraction of the component B is 1-99%. The product of the invention has high solubility, high color fixing rate, excellent dyeing fastness, environmental protection and does not contain carcinogenic aromatic amine components, can replace most imported dyes, can dye fabrics into bright orange to bright red colors, and is suitable for fabric materials such as fibers Printing and dyeing of plain fiber, cotton fiber, synthetic fiber, etc.

Description

A reactive dye composition

(1) Technical field

The invention relates to a reactive dye composition, in particular to a disazo reactive dye composition. the

(2) Background technology

Reactive dyes are generally used in the dyeing of cellulose fibers, protein fibers and polyamide fibers and materials containing cellulose fibers, protein fibers and polyamide fibers; it has the characteristics of bright color, excellent application performance, convenient use and strong adaptability. The specific dyeing mechanism is that when it diffuses in cellulose, it chemically reacts with the fiber to form a covalent bond, so its soaping and rubbing fastness are better, while the light fastness varies with the structure of the dye matrix. In the application of reactive dye patents, the application of new dyes with a single chemical structure is rare. The research direction of reactive dyes in various countries has shifted from the development of a single dye chemical structure to the compounding of multi-component dyes. The synergistic effect of different parts can achieve better dyeing performance and effect. the

So far, the published patents related to the compounding of red reactive dyes include CN1112947, CN1590469, CN1594445, CN1810893, US6090163 and US6090164, etc., but the red dyes obtained by compounding these reactive dyes are still lacking in brilliance. When the three primary colors are dyed, the compatibility is not good enough. the

(3) Contents of the invention

The object of the present invention is to provide a reactive dye composition with excellent color fastness, high lift and high color fixation rate, bright hue, capable of dyeing fabrics into bright orange to bright red. They have a disazo structure with two to three different active groups, whose synergistic effect greatly improves the brilliance of the dye and has excellent compatibility. the

To achieve the purpose of the invention, the present invention adopts the following technical solutions:

The composition of the present invention mainly contains one or more components A as shown in formula (I) and one or more components B as shown in formula (II), based on the components A and Component B, the weight fraction of the component A is 1 to 99%, and the weight fraction of the component B is 1 to 99%,

In formula (I), M ¹ , M ² , M ³ are each independently -H or an alkaline earth metal; R ₁ , R ₂ are each independently -H, -SO ₃ M ⁴ , C ₁ ~C ₄ alkyl or C ₁ ~C ₄ alkoxy group, wherein M ⁴ is -H or alkaline earth metal; in formula (I), M ¹ , M ² , M ³ and M ⁴ are preferably simultaneously -H or alkaline earth metal; in formula (II), M ⁵ , M ⁶ , M ⁷ , M ⁸ are each independently -H or an alkaline earth metal; R ₃ , R ₄ , R ₅ , and R ₆ are each independently -H, -SO ₃ M ⁹ , C ₁ -C ₄ alkane group, C ₁ to C ₄ alkoxy group or halogen, wherein, M ⁹ is -H or alkaline earth metal; X ¹ and X ² are each independently -CH=CH ₂ or -CH ₂ CH ₂ OSO ₃ M ¹⁰ , M ¹⁰ is -H or alkaline earth metal; Y is halogen; in formula (II), M ⁵ , M ⁶ , M ⁷ , M ⁸ M ⁹ , and M ¹⁰ are preferably -H or alkaline earth metal at the same time.

Each of M ¹ , M ² , M ³ and M ⁴ in the formula (I) of the present invention is preferably -H or -Na.

M ⁵ , M ⁶ , M ⁷ , M ⁸ , M ⁹ , and M ¹⁰ in the formula (II) of the present invention are each preferably -H or Na, and the halogen is preferably -Cl or -Br.

The composition of the present invention is composed of one or more components A with structures such as formula (I) and one or more components B with structures such as formula (II) and auxiliary agents, based on the Component A and component B, the component A weight fraction is 1 to 99%, and the component B weight fraction is 1 to 99%; preferably the component A weight fraction is 1 to 45%, so The weight fraction of component B is 55-99%; more preferably, the weight fraction of component A is 1-15%, and the weight fraction of component B is 85-99%. the

Component A of the present invention is preferably one or a mixture of any of the compounds shown in formula (I-1) to (I-10):

Component B of the present invention is one or any mixture of compounds shown in formulas (II-1) to (II-17):

The reactive dye composition of the present invention consists of one or more of the compounds shown in formula (I-1), (I-2), (I-5), (I-6), (I-7) A mixture of component A and one or any mixture of compounds shown in formula (II-1), (II-11), (II-12), (II-16), (II-17) Component B and additive composition, based on the component A and component B, the weight fraction of the component A is 1-15%, the weight fraction of the component B is 85-99%, the auxiliary The ratio of the agent to the total weight of the components A and B is 0.8-5:1. the

The active dye auxiliary agent described in the present invention is one of naphthalenesulfonic acid formaldehyde condensate, alkylnaphthalenesulfonic acid formaldehyde condensate, benzylnaphthalenesulfonic acid formaldehyde condensate, lignin sulfonate or sodium sulfate, or any combination thereof. mixture of species. the

To prepare the reactive dye composition of the present invention, the dye A and dye B used can be easily synthesized in a manner well known to those skilled in the art, such as preparing according to the method described in the published patent KR9004223B, US4485041A or similar methods respectively, Commercially available items can also be used. the

The auxiliary agent described in the present invention is specifically, naphthalenesulfonic acid formaldehyde condensate such as diffusion agent NNO, alkylnaphthalenesulfonic acid formaldehyde condensate such as dispersant MF (methylnaphthalenesulfonic acid formaldehyde condensate), benzyl naphthalenesulfonic acid formaldehyde Condensate such as diffusion agent CNF etc., lignosulfonate such as sodium lignosulfonate (as commercially available dispersant Reax 83A, Reax 85A) etc.; The recommended agent is industrial sodium sulfate. the

The reactive dye composition of the present invention, said composition mainly contains one or more components A with structures such as formula (I) and one or more components with structures such as formula (II) Part B can also contain some other dye components or auxiliaries and some impurities, because in the conventional synthesis of dyes, there is a process of adding acid first, then adding alkali or salting out, so the synthesized dyes are generally unavoidable It is a dye powder with electrolyte, such as the electrolyte salt can be sodium sulfate, sodium chloride and sodium acetate, prepared according to the content of the A or B component compound in the batching, the addition of these substances does not affect the present invention technical effect. the

The reactive dye composition of the present invention can be made into a liquid dye product as required, or a solid product can be obtained by spray-drying the liquid dye product, or can be obtained by directly mixing the solid dye powder of each component. the

The reactive dye composition of the present invention, because its component contains active groups such as s-triazine group, vinyl sulfone group, makes this compound dyestuff have following excellent properties: the one, solubility is high; The 2nd, fixation rate height, because The synergistic effect between the multiple active groups of the composite dye increases the probability of dye and fiber bonding, improves the utilization rate of the dye, enhances the reactivity, and has good dyeing stability, and the dye has high strength and high solubility, effectively ensuring Third, the dyeing fastness is excellent, the acid resistance of vinyl sulfone and the alkali resistance of s-triazine and the high color fixation rate of the dye make the dye have good acid and alkali resistance and stability, and can be hydrolyzed Less dyes; Fourth, it is environmentally friendly, does not contain carcinogenic aromatic amine components, and can replace most imported dyes. the

The reactive dye composition of the present invention is suitable for the printing and dyeing of fabric materials such as cellulose fibers, cotton fibers, synthetic fibers, etc., and can dye the fabric into a bright orange to bright red color, preferably dyeing the fabric into a red hue. In addition, the reactive dye composition of the present invention has excellent lifting power, excellent compatibility, and bright shade, and is suitable for compounding with components such as navy blue and orange to form a reactive black dye composition with a full hue. the

(4) Specific implementation methods

The present invention will be further described below in conjunction with the examples, but the protection scope of the present invention is not limited thereto. the

Example 1

90 parts of dye powders with electrolytes containing 65% of the compound of formula (I-1) and 10 parts of dye powders with electrolytes containing 70% of compounds of formula (II-1) were mixed with 400 parts of water, adjusted The pH value of the dye solution is 5.5-6.5, and the dye solution is dried to prepare the reactive dye composition. According to the conventional dyeing method of the reactive dye, orange tone dyeing and printing can be obtained on the cotton fabric. the

Dye powder with electrolyte is a customary saying in the dye industry, because dyes have the process of adding acid first, then adding alkali and salting out in the conventional synthesis, so generally the synthesized dye filter cake contains inorganic salts. Salt is the so-called electrolyte, so the raw material dyes usually used are all dye powders with electrolytes, and the ingredients are prepared according to the content of the compounds therein, which will not affect the effect of the present invention. the

The composite reactive dye that embodiment 1 is made is applied to fabric dyeing:

Take 2g of the composite reactive dye prepared in Example 1 and place it in a 500ml volumetric flask to prepare a uniform solution, draw 40ml in the dye vat, add 50ml of 20% sodium sulfate solution, and add 100ml of distilled water, and immerse 8g of cotton cloth in the dye , heated to 60°C under normal temperature and pressure, dyed for 30 minutes, then added 10ml of 20% sodium carbonate solution into the dye vat to fix the cotton cloth, fixed it in the dyeing machine at 60°C for 45 minutes, and took it out after dyeing. Fully wash with water and wring dry, boil in 3g/L soap solution containing soap flakes for 15min, wash and wring dry, dry and sample at 60-70°C to obtain dyed fabric with orange hue. The color fastness to rubbing, color fastness to washing and color fastness to perspiration are tested by the methods determined in GB/T3920, GB/T3921 and GB/T3922. the

Example 2

80 parts of dye powders with electrolytes containing 70% of the compound of formula (I-2), 20 parts of dye powders with electrolytes of compounds of formula (II-2) containing 75%, 80 parts of sodium sulfate, plus 500 parts The water is stirred and mixed, the pH value of the dye solution is adjusted to 5.5 to 6.5, and the dye solution is dried to obtain the reactive dye composition. According to the conventional dyeing method of the reactive dye described in Application Example 1, it can be obtained on cotton fabrics. Dyeing and printing in deep orange shades with excellent color fastness. the

Embodiment 3～20

According to the preparation method of Example 2, the difference is that the compound structure and proportioning of component A and component B are changed to prepare the reactive dye composition of the present invention, and the cotton fabric can be dyed orange with the conventional dyeing method of reactive dye to red hues, as shown in Table 1 below:

The reactive dye composition of table 1 different components and content

Example name Component A Component A Contains Electrolyte Mass Weight Parts A component content Converted to A in parts by weight Component B Component B contains electrolyte by weight Component B content Converted B parts by weight Parts by weight of additives and relative components Hue Example 3 (I-3) 7.5 67% 5 (II-3) 155.7 61% 95 Yuan Mingfen 90 bright red Example 4 (I-4) 15.9 63% 10 (II-4) 132.4 68% 90 NNO 80 Brilliant red Example 5 (I-5) 24.6 61% 15 (II-5) 134.9 63% 85 MF 100 Brilliant red Example 6 (I-6) 33.9 59% 20 (II-6) 111.1 72% 80 CNF 100 Brilliant red Example 7 (I-7) 39.1 64% 25 (II-7) 101.4 74% 75   Yuan Mingfen NNO 40 60 Brilliant red Example 8 (I-8) 52.6 57% 30 (II-8) 109.4 64% 70   Yuan Mingfen MF 70 25 bright red Example 9 (I-9) 51.5 68% 35 (II-9) 97.0 67% 65 Yuan Mingfen 90 bright red Example 10 (I-10) 75.5 53% 40 (II-10) 95.2 63% 60 NNO 100 red Example 11 (I-1) 7.7 65% 5 (II-1) 135.7 70% 95 MF 80 Brilliant red Example 12 (I-1) 15.4 65% 10 (II-11) 134.3 67% 90 CNF 95 Brilliant red Example 13 (I-1) 76.9 65% 50 (II-16) 72.5 69% 50   Yuan Mingfen NNO 40 60 red Example 14 (I-4) 87.3 63% 55 (II-1) 64.3 70% 45   Yuan Mingfen MF 50 50 red Example 15 (I-5) 98.4 61% 60 (II-1) 57.1 70% 40 Yuan Mingfen 90 red Example 16 (I-6) 118.6 59% 70 (II-1) 42.9 70% 30 NNO 105 dark orange Example 17 (I-9) 117.6 68% 80 (II-11) 29.9 67% 20 MF 100 dark orange

Example 18 (I-1) (I-6) 15.4 8.5 65% 59% 10 5 (II-1) 121.4 70% 85 CNF 100 Brilliant red Example 19 (I-1) (I-9) 7.7 7.4 65% 68% 5 5 (II-1) (II-12) 64.3 70.3 70% 64% 45 45 Yuan Mingfen NNO 55 45 red Example 20 (I-1) 15.4 65% 10 (II-13) (II-14) 58.8 74.6 68% 67% 40 50 Yuan Mingfen MF 50 65 red Example 21 (I-1) (I-4) 15.4 15.9 65% 63% 10 10 (II-13) (II-14) 44.1 74.6 68% 67% 30 50 Yuan Mingfen 90 red Example 22 (I-1) (I-4) 15.4 7.9 65% 63% 10 5 (II-15) (II-16) 53.8 72.5 65% 69% 35 50 NNO 100 red Example 23 (I-4) 15.9 63% 10 (II-17) 134.3 67% 90 MF 95 red Example 24 (I-6) 15.3 59% 9 (II-15) 140.0 65% 91 CNF 95 red Example 25 (I-6) 20.3 59% 12 (II-13) 129.4 68% 88 Yuan Mingfen NNO 50 60 red Example 26 (I-2) 14.3 70% 10 (II-2) 120.0 75% 90 Yuan Mingfen 120 red Example 27 (I-2) (I-6) 7.1 13.6 70% 59% 5 8 (II-2) 116.0 75% 87 Yuan Mingfen MF 70 30 red Example 28 (I-2) 21.4 70% 15 (II-1) (II-12) 60.0 65.6 70% 64% 42 42 Yuan Mingfen NNO 45 60 red Example 29 (I-1) (I-4) (I-2) 7.7 7.9 7.1 65% 63% 70% 5 5 5 (II-13) (II-14) (II-2) 44.1 52.2 26.7 68% 67% 75% 30 35 20 CNF MF 30 65 Brilliant red Example 30 (I-1) (I-9) (I-6) (I-8) 3.1 4.4 6.8 10.5 65% 68% 59% 57% 2 3 4 6 (II-1) (II-5) (II-8) (II-13) 28.6 31.7 31.3 36.8 70% 63% 64% 68% 20 20 20 25 Yuan Mingfen MF 70 30 Bright red

the Example 31 (I-1)(I-3) (I-6)(I-8) 3.1 6.0 5.1 10.5 65% 67% 59% 57% 2 4 3 6 (II-5) (II-9) 71.4 59.7 63% 67% 45 40 Yuanmingfen CNF 80 25   Deep Orange Example 32 (I-1)(I-4) (I-6)(I-10) 7.7 3.2 5.1 9.4 65% 63% 59% 53% 5 2 3 5 (II-5) 134.9 63% 85 Yuan Mingfen MF 30 80 red Example 33 (I-7) 132.8 64% 85 (II-1) (II-7) (II-8) (II-17) 5.7 5.4 6.3 4.5 70% 74% 64% 67% 4 4 4 4 3 Yuanmingfen MF 55 50 red

Claims (7)

1. reactive dye compositions, it is characterized in that described composition mainly contain one or more structures suc as formula the component A shown in (I) and one or more structures suc as formula the B component shown in (II), based on described component A and B component, described component A weight fraction is 1～99%, and described B component weight fraction is 1～99%

In the formula (I), M ¹, M ², M ³Independently separately be-H or-Na; R ₁, R ₂Independently be separately-H ,-SO ₃M ⁴, C ₁～C ₄Alkyl or C ₁～C ₄Alkoxyl group, M wherein ⁴For-H or-Na;

In the formula (II), M ⁵, M ⁶, M ⁷, M ⁸Independently separately be-H or-Na; R ₃, R ₄, R ₅, R ₆Independently be separately-H ,-SO ₃M ⁹, C ₁～C ₄Alkyl, C ₁～C ₄Alkoxy or halogen, wherein, M ⁹For-H or-Na; X ¹, X ²Independently be-CH=CH separately ₂Or-CH ₂CH ₂OSO ₃M ¹⁰, M ¹⁰For-H or-Na; Y is a halogen.

2. reactive dye compositions as claimed in claim 1, it is characterized in that halogen described in the formula (II) for-Cl or-Br.

3. reactive dye compositions as claimed in claim 1, it is characterized in that described composition is made up of suc as formula B component and auxiliary agent shown in (II) suc as formula the component A shown in (I) and one or more structures one or more structures, based on described component A and B component, described component A weight fraction is 1～99%, and described B component weight fraction is 1～99%.

4. as claim 1 or 3 described reactive dye compositionss, it is characterized in that based on component A and B component that the parts by weight of described component A are 1～45%, the parts by weight of B component are 55～99%.

5. as claim 1 or 3 described reactive dye compositionss, it is characterized in that based on component A and B component that the parts by weight of described component A are 1～15%, the parts by weight of B component are 85～99%.

6. reactive dye compositions as claimed in claim 1 is characterized in that component A is suc as formula a kind of or any several mixture in the compound shown in (I-1) to (I-10):

7. reactive dye compositions as claimed in claim 1 is characterized in that B component is suc as formula a kind of or any several mixture in the compound shown in (II-1) to (II-17):