KR0132300B1 - Mono-azodye composition and process for dyeing polyester containing fibers using the same - Google Patents

Abstract

The present invention is about monoazo dye composite and dying method textile containing polyester with excellent exhaustion, daylight fastness, sublimation fastness and pH stability.Monoazo dye composite of present invention comprise formula(4) of monoazo compound 10-90 weight% and formula(5) of monoazo compound 90-10 weight%.In said structural formula, X is chlorine or bromine; R5 is alkyl group of carbon number 1-4 each independently; R6 and R7 are alkenyl group of carbon number 2-4 each independently; R8 and R9 are alkyl group of carbon number 1-4 or alkenyl group of carbon number 2-4 each independently; R10 have methyl, ethyl, methoxyethyl group.

Description

Mono-azo dye composition and dyeing method of polyester-containing job using the same

1 is a graph of the pH stability of the dyeing results using the dye composition of the present invention and the conventional dye composition

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a dye composition which exhibits two or more dispersible monoazo dyes to show navy blue or black and a method for dyeing or printing a polyester fabric or a fabric containing polyester using the composition. will be.

BACKGROUND ART A method and a composition for dyeing or printing using an azo dye are known in the art.

Representative examples thereof include Japanese Patent Laid-Open No. 49-13479, Japanese Patent Laid-Open No. 60-26060, Japanese Patent Laid-Open No. 62-6592, European Patent Publication No. 0300626, and European Patent Publication No. 0563975. As a dye, the compound of following General formula (1) is used individually or in mixture of 2 or more.

In the case of Japanese Patent Laid-Open No. 49-13479, X is hydrogen, chlorine, cancellation, cyano group nitro group, Y is hydrogen, chlorine, cancellation, cyano group, trifluoromethyl group, lower alkyl group, lower alkoxy group, lower alkyl foam. Is an alkyl group, R ₁ is hydrogen, lower alkyl, lower alkoxy group, R ₂ is lower alkyl, lower alkoxy, furyl group, R ₃ is allyl group, and R ₄ is hydrogen or aryl group. A method for dyeing fabrics in color.

In the case of JP-A-60-26060, a water-insoluble black dye and a navy blue dye composition are prepared by blending two or more kinds of water-insoluble compounds having the general formula (1), and dyeing or printing the same. The azo compound constituting this composition is an azo compound in which X is a nitro group, Y is bromine, R ₁ is hydrogen, R ₂ is a methyl group, R ₃ and R ₄ are ethyl groups, and n is 1 And X and Y are cancelled, R ₁ is hydrogen, R ₃ is cyanoethyl group, R ₄ is ethyl group, n is 0, or a composition composed of an azo compound wherein X is nitro group Y is bromine, R 1 Is a methoxy group, R ₂ is a methyl group, R ₃ is an aryl group, R ₄ is a benzyl group, an azo compound of formula (1) wherein n is 1 or X is a nitro group, Y is cancelled, R ₁ is a methoxy group, R ₂ is a methyl group, R ₃ and R ₄ are an aryl group, and azo compounds of the general formula (1) wherein n is 1 The present invention provides a method of improving dyeing, coldness, sublimation resistance, washing resistance, and fastness by dyeing or printing polyester fibers by adding water.

In Japanese Patent Publication No. 62-6592, X is a nitro group, Y is chlorine or cancelled, R ₁ is hydrogen, R ₂ is an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ are 1 to 4 carbon atoms. An azo compound of the general formula (1) wherein n is 1, X is a nitro group, Y is chlorine or cancellation, R ₁ is an alkoxy group having 1 to 4 carbon atoms, R ₂ is an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ is an alkyl group having 1 to 4 carbon atoms and n is 1, the dye composition of the azo compound of the general formula (1) and the dyeing property, colorability, color fastness to a blend of polyester and cellulose using the composition Revealed technology that improved.

In the case of EP 0300626, X is a cyano group, Y is chlorine, cancellation, oxo, R ₁ is hydrogen, R ₂ is an alkyl group having 1 to 4 carbon atoms, and R ₃ and R ₄ are each having 1 to 4 carbon atoms. An azo compound of the general formula (1) having an alkyl group or an akenyl group having 2 to 4 carbon atoms and n is 1, X is a nitro group, Y is chlorine, cancellation, oxo and R ₁ is an alkoxy group having 1 to 4 carbon atoms, R ₂ Is an alkyl group having 1 to 4 carbon atoms, R ₃ and R ₄ are an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and a composition composed of the azo compound of the general formula (1) wherein n is 1 It discloses a technique for improving the fastness and the like by dyeing the polyester or polyester blend fabric.

In the case of European Patent Publication No. 0563975, X is a nitro group or a halogen, Y is a halogen, R ₁ is a lower alkoxy, R ₂ is a lower alkyl group, R ₃ and R ₄ are each an independent alkyl group, cyanoalkyl group, alkyl carbonyl come alkyl group, n azo compound and X of the person above general formula (1) is a nitro group, Y is halogen and R1 is hydrogen, R ₂ is methyl, R ₃ and R ₄ are each an independent group, n is 1 Wherein the azo compound of formula (1) and X and Y are halogen, R ₁ is hydrogen, R ₃ is cyanoethyl, R ₄ is ethyl group, and general formula (1) wherein n is 0 is composed of azo compound It discloses a technique for improving the fastness and the like by dyeing the polyester or polyester blend fabric using the composition.

The azo compounds enumerated above can be easily prepared by carrying out a coupling reaction between the already known diazohydrates of the following general formula (2) and the compound of (3).

X, Y, R ₁ , R ₂ , R ₃ , R ₄ and n in the general formulas (2) and (3) are the same as the definitions in the general formula (1).

In the case of dyeing polyester or polyester-containing fibers in black or navy blue, dye compositions containing a suitable amount of disperse dyes such as blue, yellow, red, and brown are generally used.

However, dyes that can be dyed deep black should be strictly selected and blended with a single dye to obtain the desired satisfactory dyeing.

In general, a deep color is required for the dyeing of black and navy blue color, and the dyeing to the deep color has a significant meaning in the selection and combination of dyes that enable the deep dyeing in absorbance.

Therefore, when Navy Blue or black blended fuel is mixed with dyes with poor dyeability, it is difficult to obtain dyes with excellent dyeability due to different dyeing speeds or incompatibility between dyes, and COD of wastewater disposed after dyeing. It has become a problem of water pollution, and efforts have been made to improve dyeing property, color fastness, and the like.

The present invention is to solve the above problems, good dust absorption, having a practical fastness and high pH safety, to obtain satisfactory dyeing results.

The present invention is a fabric containing a polyester or polyester in a navy blue or black by mixing two or more components of a compound that can solve the above problems well in the mono-zo dyes can be defined by the general formula (1) Dye composition used for dyeing or printing and to provide a method for dyeing or printing the fabric using the same.

The composition of the present invention is a compound defined by the following general formula (4) used as a blue dye of the compound defined by the general formula (1) and the general formula (5) used as a purple dye as a base compound It is constructed.

In the above formula, X is chlorine or cancellation, R ₅ is each independently an alkyl group having 1 to 4 carbon atoms, R ₆ and R ₇ are each an independent alkenyl group of 2 to 4 carbohydrates, and R ₈ and R ₉ are each independently carbon Hydrogen is an alkyl group of 1 to 4 or an alkenyl group of 2 to 4 independently of each other, and R ₁₀ has a methyl, ethyl or methoxyethyl group.

The composition ratio of the basic monoazo compound (4) and the monoazo compound (5) is blended in a ratio of 90:10 parts by weight to 10:90 parts by weight, and shows a black or navy blue color within the compounding ratio. In this way, the dye composition of the present invention is highly intended for the present invention, the COD of the wastewater after dyeing is significantly lowered, resulting in excellent results in dyeing, fastness and the like.

In particular, the compound for obtaining the most satisfactory result by dyeing in navy blue or black color is the case of compounds defined by the following general formula (4 ') and (5').

(Where X is chlorine or cancellation).

However, there are many difficulties in producing a desired color with only the composition in which the dye is mixed.

The present inventors have repeatedly studied in view of the above problems, and by adding the monoazo compound represented by the following general formula (6) below to the total amount of the dye including the composition, by adding up to 60% by weight, As in the present invention, excellent dyestuffs were obtained in absorbent pH stability, dyeability, color fastness, etc., and a free choice of desired color was obtained.

In the above formula (6), W is chlorine or cancellation, R ₁₁ , and R ₁₂ are each an independent alkyl or cyano alkyl group.

In a salt bath having the compound of the formula (6) 20 wt% or less, the color is close to navy blue, but in a salt bath having 20 wt% or more and 60 wt% or less, the dye is dyed to a color close to black.

When dyeing to black, the composition of the dye is 20 to 50% by weight of the monoazo compound of the general formula (4), 10 to 30% by weight of the monoazo compound of the general formula (5), and the monoazo compound of the general formula (6) 20 to 60% by weight is preferable, in particular 25 to 35% by weight of the monozo compound of the general formula (4), 15 to 25% by weight of the monoazo compound of the general formula (5), mono of the general formula (6) More preferably, the azo compound is composed of 45 to 55% by weight.

In the case of dyeing with the color of navy blue, the composition of the dye is 30 to 65% by weight of the monoazo compound of Formula (4), 30 to 60% by weight of the monoazo compound of Formula (5), (6) The monoazo compound of 20% by weight or less, preferably 45 to 55% by weight of the monoa combination of the general formula (4), 40 to 50% by weight of the monoazo compound of the formula (5), (6) More preferably, the monoazo compound in the composition is 15% by weight or less.

In the case of this General formula (6), the most preferable compound is a compound represented by following General formula (6 ').

(W in the general formula above is chlorine or cancellation.)

The monoazo compound of the general formula used in the present invention is a known compound and can be easily prepared by coupling the compounds of the formulas (2) and (3) as described above.

Example 1

100 g of (2,4-dinitro-6-bromophenylazo) -4 '-(N, N-diarylamino-5'-methoxyacetanilide) defined by the above general formula (4') As a dispersing agent, 150 g of naphthalene sulfonic acid formaldehyde condensate is dispersed in fine particles in 300 g of water, followed by drying to obtain a compound component (A), which is defined by the general formula (5 ') (2,4-dinitro-6-bro). 100 g of phenyl azo) -4 '-(N, N-diarylaminoacetanilide) was dispersed as fine particles in 300 g of water together with 150 g of naphthalene sulfonic acid formaldehyde condensate as a dispersant, followed by drying to disperse the blending component (B). 100 g of each of (2, 6-dichloro-4-nitrophenylazo) -4- [N- (cyanoethyl) -N-ethyl)] aminobenzene, as defined by the general formula (6 '), was used as a dispersant. 150 g of naphthalene sulfonic acid formaldehyde condensate is dispersed as fine particles in 300 g of water, followed by drying to obtain a compounding component (C).

15 g, 10 g, and 25 g of each of the compounding components (A), (B) and (C) produced by the above method were blended to obtain 50 g of a dye composition.

0.5 g of the dye composition was taken and dissolved in 250 g of water to prepare an aqueous solution of 0.2%, and a salt bath ratio of 2 g of polyester fiber was adjusted to a salt solution having a concentration to be dyed within a range of 1:15 to 1:30. After adding the surfactant and adjusting the pH of the salt bath to 5 with glacial acetic acid, the dye was dyed at 130 ° C. for 1 hour using a high pressure dye, followed by reduction washing at 80 ° C. and drying to obtain a black colored chlorine.

Example 2

In the same manner as in Example 1 above, the pH was adjusted to 3 to obtain a black-colored salt solution.

Example 3

In the same manner as in Example 1 above, the pH was adjusted to 7 to obtain a black colored chloride.

Example 4

In the same manner as in Example 1 above, the pH was adjusted to 9 to obtain a black-colored salt solution.

Example 5

In the same manner as in Example 1, the pH was adjusted to 11.

[Comparative Examples 1 to 5]

Commercially available Resolin Black BLS (manufactured by Bayer) was dyed to the same polyester fiber under the conditions of Examples 1 to 5, and five dyes were obtained to obtain the results together with Examples 1 to 5. 1 degree.

As can be seen from the results shown in FIG. 1, the dye composition according to the present invention shows stability up to pH 9 which is alkaline, but in the conventional product, it can be seen that a downward curve is drawn at pH 7.

That is, the composition according to the present invention has stability in a wider pH range than conventional products.

Color fastness test

The light fastness test method of the dyeing product of JIS L 0842 (1971) and the dyeing product of the dye composition of the present invention obtained from the above Examples 1 to 5 and the dyes obtained from Comparative Examples 1 to 5 and JIS L 0879 ( The fastness test was performed according to the test method of sublimation fastness of the dye of 1975) and the results are shown in Table 1.

[Absorption test]

The polyester white cloth was added to the dye solution dyed polyester fiber according to Example 1 and Comparative Example 1, and the dye was dyed at 130 ° C. for 1 hour with a high-pressure dyeing machine, followed by reducing washing and drying at 80 ° C. from the residual bath. The staining state was observed and the results are shown in Table 1.

Example 6

25 g, 22.5 g, and 2.5 g of the compounding components (A), (B) and (C) used in Examples 1 to 6 were combined, respectively, to obtain 50 g of a dye composition.

0.5 g of this dye composition was taken and dyed in the same manner as in Example 1 to obtain a navy blue colored dye solution, and the results are shown in Table 2.

[Examples 7 to 10]

Using the composition mixed in the blending ratio of Example 6 to dye the polyester in the same manner as in Examples 2 to 5 to obtain a navy blue color dye.

[Comparative Examples 6 to 10]

Commercially available resolin navy blue GLS (manufactured by Bayer) was obtained under the same conditions as in Comparative Examples 6 to 10 to obtain polyester dyes.

The light fastness and sublimation fastness were tested for the examples and the comparative examples in the same manner as usual, and in the case of the absorbent properties, the test was carried out for Example 6 and Comparative Example 6 and the results are shown in Table 2 below. .

The color of the dye in Table 1 and Table 2 shows the dyeing state according to the pH change, as can be seen from Table 1 and Table 2, the dyeing results by the composition of the present invention is black or navy blue color Except for Examples 5 and 10, where the liquid composition was prepared at pH 11, the result was well dyed with black sand. However, in the case of commercially available products, pH 9 of Comparative Example 4 and Comparative Example 9 It can be seen from the case that the color of the polyester, which is a dye, is not preferable, and even in the absorbency test, even though the dyeing result from the residual bath is the same condition, the composition of the present invention is almost white and has a slight color. In the case of a commercial item, the mono of the present invention is considered to have a slightly darker color than the case of the composition of the present invention. It can be seen that the azo dye composition is excellent in the absorption and pH stability.

Claims (19)

In the dye composition composed of two or more monoazo compounds, the following general formula (4) is composed of 10 to 90% by weight of the monoazo compound and 90 to 10% by weight of the monoazo compound of the general formula (5) Dye composition. In the above structural formula, X is chlorine or cancellation and R ₅ is each independently an alkyl group having 1 to 4 carbon atoms, R ₆ and R ₇ are each independently an alkenyl group having 2 to 4 carbon atoms, and R ₈ and R ₉ are each independently 1 to 1 carbon atoms. An alkyl group of 4 or an alkenyl group having 2 to 4 carbon atoms each independently, and R ₁₀ has a methyl, ethyl or methoxyethyl group. The general formula (4) according to claim 1, wherein the compound Mur X of the general formula (4) is chlorine or cancellation, R ₅ is a methyl group, R ₆ and R ₇ are an aryl group, and R ₁₀ is a methyl group. A dye composition, characterized in that the mono azo compound of '). The compound of formula (5) according to claim 1 or 2, wherein in the compound of formula (5), X is chlorine or cancellation, R ₅ is methyl group, and R ₈ and R ₉ are ethyl groups A dye composition, characterized in that the monozoa compound. 95 to 40% by weight of the dye composition consisting of 10 to 90% by weight of the monoazo compound of the general formula (4) and 90 to 10% by weight of the monoazo compound of the general formula (5) and the general formula (6) The dye composition, characterized in that consisting of up to 60% by weight of the monoazo compound. In the above compounds, W is chlorine or cancellation, and R11 and R12 are each independently alkyl or cyano alkyl groups. 10 to 30% by weight of the monoazo compound of the general formula (5) of 20 to 50% by weight of the monozo compound of the general formula (4) according to claim 4, and the mono of the general formula (6) Dye composition comprising 20 to 60% by weight of the azo compound. The method according to claim 4, wherein 25 to 35% by weight of the monoazo compound of the general formula (4), 15 to 25% by weight of the monoazo compound of the general formula (5) below and the general formula (6) Thermal composition comprising a mono azo compound 45 to 55% by weight. The mono-compound according to claim 4, wherein 30 to 65 wt% of the monoazo compound of the general formula (4) and 30 to 60 wt% of the monozo compound of the general formula (5) A dye composition comprising 20% by weight or less of an azo compound. The mono-azo compound of the general formula (4) is 45 to 55% by weight and the mono-azo compound 40 to 50% by weight of the general formula (5) Dye composition, characterized in that composed of up to 15% by weight of the azo compound. The scope of claim 4, wherein X in the compound of formula (4) is chlorine or brittle. A dye composition, wherein R ₅ is a methyl group, R ₆ and R ₇ are an aryl group, and R 10 is a monoazo compound of the general formula (4 ′) wherein the methyl group is a methyl group. A compound according to any one of claims 4 to 8, wherein in the compound of formula (5), X is chlorine or cancellation, R ₅ is methyl group, and R ₈ and R ₉ are ethyl groups. A dye composition, characterized in that the monoazo compound of 5 '). The general formula below according to any one of claims 4 to 8, wherein the monoazo compound of formula (6) is W is chlorine or cancelled, R ₁₁ is cyanoethyl group, and R ₁₂ is ethyl group. (6 ') A dye composition characterized in that the monoazo compound. 10. The compound according to claim 9, wherein X in the compound of formula (5) is chlorine or cancelled, R ₅ is a methyl group and R ₈ and R ₉ are ethylis compounds of formula (5 ^) Dye composition characterized by The mono azo compound of formula (6) according to claim 9, wherein W is chlorine or cancelled, R ₁₁ is cyanoethyl group, and R ₁₂ is ethyl group, wherein mono Dye composition characterized in that the azo compound. The mono azo compound according to claim 10, wherein the monoazo compound of formula (6) is W is chlorine or cancelled, R ₁₁ is cyanoethyl group, and R ₁₂ is ethyl group Dye composition characterized in that the azo compound. The monoazo according to claim 12, wherein the monoazo compound of the general formula (6) is W is chlorine or cancellation, R ₁₁ is a cyanoethyl group, and R ₁₂ is an ethyl group. Dye composition characterized in that the compound. Dye consisting of 20 to 50% by weight of monoazo compound of formula (4), 10 to 30% by weight of monoazo compound of formula (5), and 20 to 60% by weight of monoazo compound of formula (6) Dyeing method characterized in that the dyeing or printing the polyester fiber in black using the composition. Claim 25 of Claim 16 WHEREIN: 25-35 weight% of mono azo compounds of General formula (4), 15-25 weight% of mono azo compounds of General formula (5), and of said General formula (6) A dyeing method comprising dyeing or printing polyester fiber in black using a dye composition, comprising a monoazo compound of 45 to 55% by weight or less. Using a dye composition comprising 30 to 65% by weight of the monoazo compound of formula (4), 30 to 60% by weight of the monoazo compound of formula (5) and 20% by weight or less of the monoazo compound of formula (6) The dyeing method characterized in that the dyeing or printing the polyester fiber in navy blue color. The method according to claim 18, wherein 45 to 55% by weight of the monoazo compound of the general formula (4) and 40 to 50% by weight of the monoazo compound of the following general formula (5), and the general formula (6) The dyeing method characterized in that the dyeing or printing the polyester fiber in a navy blue color using a dye composition, characterized in that the monoazo compound of 15% by weight or less.