HK1068364B - Method disperse dye mixtures - Google Patents

Description

Disperse dye mixtures

Technical Field

The present invention relates to non-azo disperse dye mixtures.

Background

The dyeing of polyester fiber products of different deniers, including polyester fibers of fine denier such as 0.1 denier to 0.7 denier and polyester fibers of ordinary denier such as 1 denier to 5 denier, is generally carried out by a conventional dyeing method using known disperse dyes. However, due to the different specific surface areas of the structural fibers, polyester fibers of different deniers exhibit certain application drawbacks, such as, for example, relatively poor level or migration properties, an excessive dependence of the color yield on the different dyeing parameters in the dyeing process or an insufficient dye accumulation on the polyester, or unsatisfactory fastness properties.

In many respects, efforts to extend or supplement the dye range by modern disperse dyes have reached limits which, if some can be overcome, can only be insufficiently overcome by the individual dye components.

The requirement for the dyes used in the mixture is that the dyes exhibit the same dyeing behavior. Furthermore, the dyeing behaviour of the dye should be kept constant throughout the dyeing process to ensure that the same hue is not obtained at the beginning of the dyeing process only.

According to subtractive color mixing theory, relatively definite hues can only be obtained by using distinctly different dyes, of which three are required with the desired color: cyan, yellow and magenta (trichromatic dyes) to produce all hues.

Accordingly, there is a need for disperse dye mixtures which provide improved fastness properties and improved build-up behaviour on polyester fibres of fine denier, such as from 0.1 to 0.7 denier, and on polyester fibres of ordinary denier, such as from 1 to 5 denier, particularly where it is desired to produce a defined hue.

Disclosure of Invention

According to the present invention, it has been found that a dye mixture of non-azo disperse dyes of formulae (1) to (9) given and defined below can satisfy the requirements for trichromatic dyeing, which is capable of forming very uniform dyeings having excellent light fastness properties on polyester fibers of fine denier, such as 0.1 denier to 0.7 denier, and polyester fibers of ordinary denier, such as 1 denier to 5 denier, or synthetic textile materials and fiber mixtures thereof by exhaust dyeing, and can form dispersions therefor. The interesting characteristic of the inventive dye mixture is that the inventive dye mixture has good same-color shade and light color gradient performance between common polyester and fine denier polyester in the dyeing process.

Accordingly, the present invention provides a non-azo disperse dye mixture comprising a blue dye mixture, a yellow dye mixture and a red dye mixture:

the blue dye mixture includes a compound of formula (1), at least one compound of formula (2), and a compound of formula (3) below:

wherein the substituents at positions 5 and 8 may be 5-hydroxy-8-amino or 5-amino-8-hydroxy, respectively;

wherein R is¹Is C₁-C₄Alkyl, 3-methoxypropyl, 3-ethoxypropyl and 3-methoxyethoxypropyl;

the yellow dye mixture comprises the following compounds of formula (4), formula (5) and formula (6):

wherein R is²Are methyl and ethyl;

and

the red dye mixture includes compounds of formula (7), formula (8), and formula (9) below:

alkyl radical R¹It may be linear or branched, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Methyl and ethyl are preferred.

In the blue mixture, the ratio of the dyes (1) to (2) to (3) is: 40-80% by weight of a compound of formula (1), 10-40% by weight of a compound of formula (2) and 10-30% by weight of a compound of formula (3). The preferred blue mixtures of the invention have the ratio of the dye of formula (1) to the dye of formula (2) to the dye of formula (3): 50-70% by weight of a dye of formula (1): 15-35% by weight of a dye of formula (2): 10-20% by weight of a dye of formula (3).

These blue compounds are novel and are thus part of the present invention.

In the yellow mixture, the ratio of the dyes (4) to (5) to (6) is: 30 to 70% by weight of formula (4), 30 to 60% by weight of formula (5) and 10 to 40% by weight of formula (6). The preferred yellow mixture of the invention has a ratio of dye of formula (4) to dye of formula (5) to dye of formula (6) of 40 to 60% by weight: 30-50 wt%: 10-30 wt%.

In the red mixture, the ratio of dyes (7) to (8) to (9) is: 20-60 wt% of formula (7), 30-60 wt% of formula (8) and 10-50 wt% of formula (9). Preferably 30 to 50% by weight of formula (7), 50 to 30% by weight of formula (8) and 10 to 40% by weight of formula (9).

If the ratio of the dyes of the formulae (1): (2): (3), or of the dyes of the formulae (4): (5): (6), or of the dyes of the formulae (7): (8): (9) exceeds the abovementioned range, color differences between the fibers can occur in the application, which is undesirable.

Dye mixtures comprising dyes of the formulae (1) and (2) and (7) and (8) are known from JP 04173871 and JP 04173874, dye mixtures comprising dyes of the formulae (2) and (3) are known from DE03643752 and EP 601439, and dye mixtures comprising dyes of the formulae (7) and (9) are known from JP 05861154 and JP 04173875.

The ratio of the blue dye mixture comprising the dyes of formulae (1) to (3) and the yellow dye mixture comprising the dyes of formulae (4) to (6) and/or the red dye mixture comprising the dyes of formulae (7) to (9) is: the yellow dye mixture is 0.1 to 100,000 parts by weight, preferably 1 to 10,000 parts by weight, and the red dye mixture is 0.1 to 100,000 parts by weight, preferably 1 to 10,000 parts by weight, per 100 parts by weight of the blue dye mixture. The ratio is appropriately selected within these ranges to obtain a desired color.

The mixtures of the invention can be prepared, for example, by mixing the required amounts of the dye components. Suitable mixing methods include:

co-crystallization

Typically, the dye is dissolved in a hot solvent, for example by placing the dye in a suitable solvent and heating to the reflux temperature of the solvent until the dye is dissolved, then filtering to obtain a solution, and then allowing the solution to cool to form crystals. The resulting mixture may be subjected to further processing, such as milling or spray drying. Examples of suitable solvents for the process are organic solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, amides, sulfoxides, esters, ketones and ethers. Specific examples of the organic solvent are toluene, ethyl cellosolve, acetone, chlorobenzene, pyridine, dimethylformamide, dimethylsulfoxide, ethyl acetate, benzene, tetrahydrofuran and cyclohexane.

Co-grinding

(a) Mixing the dyes and then grinding them together to obtain a homogeneous blend, followed by spray drying to obtain a solid mixture; or

(b) Each dye was milled separately and then mixed in the required proportions before spray drying.

Dry blending

Each dye was spray dried separately and then mixed in the required proportions by a dry blending process.

The mixtures of the invention provide particularly useful disperse dyes which are of value in being able to dye polyester fibers of fine denier, for example from 0.1 to 0.7 denier, and polyester fibers of conventional denier, for example from 1 to 5 denier, or synthetic textile materials and fiber blends thereof by exhaust dyeing, pad dyeing or printing processes and to form dispersions therefor. They can also be used, for example, in inkjet printing, dye diffusion, thermal transfer printing and dyeing of plastics for textiles or non-textiles.

A particular aspect of the present invention provides a composition comprising a mixture of dyes (1) to (9), and additionally at least one other ingredient normally used in dyeing applications, such as a dispersant and optionally a surfactant or wetting agent. The composition typically comprises from 1% to 65%, preferably from 10 to 60%, more preferably from 20 to 55% of the total dye mixture in a solid medium.

Specific examples of dispersants are lignosulfonates, naphthalenesulfonic acid/formaldehyde condensates and phenol/cresol/p-aminobenzenesulfonic acid/formaldehyde condensates, typical examples of wetting agents are alkylaryl ethoxylates which can be sulfonated or phosphated, and typical examples of other ingredients which may be present are inorganic salts, defoamers such as mineral oil or nonanol, organic liquids and buffers. Dispersants may be present in amounts of from 10% to 200% by weight of the dye mixture. The wetting agent may be used in an amount of 0% to 20% by weight of the dye mixture.

The compositions may be prepared by bead milling the dye mixture in an aqueous medium together with glass beads or sand. The composition may be further supplemented with dispersants, fillers, and other surfactants and may be dried, for example, by spray drying techniques to provide a solid composition comprising 5% to 65% dye.

In another aspect, the present invention provides a process for dyeing a synthetic textile material or a fiber blend thereof, comprising applying to the synthetic textile material or the fiber blend thereof a mixture comprising dyes of formulae (1) to (9).

The synthetic textile material may be selected from aromatic polyesters, in particular polyethylene terephthalate; polyamides, in particular polyhexamethylene adipamide, cellulose diacetate, cellulose triacetate; and natural textile materials, particularly cellulosic materials and wool. Particularly preferred textile materials are aromatic polyesters or blends thereof with fibers of any of the above-mentioned textile materials. Particularly preferred fiber blends include polyester-cellulose blends, such as polyester-cotton, and polyester-wool. The textile material or blend thereof may be in the form of a single fiber, loose fiber, yarn or woven or knitted fabric.

Mixtures of dyes of formulae (1) to (9) may be applied to synthetic textile materials or fibre blends by processes conventionally employed for the application of disperse dyes to such materials and fibre blends.

Suitable process conditions may be selected from the following:

(I) padding at a pH of 4 to 9.5, a temperature of 100 ℃ to 140 ℃ and a pressure of 1 to 2 bar for 10 to 120 minutes, optionally with addition of a sequestering agent;

(II) continuous dyeing at a pH of 4 to 6.5, at a temperature of 190 ℃ to 225 ℃ for 15 seconds to 5 minutes, optionally with the addition of a migration inhibiting group;

(III) carrier dyeing with a carrier such as methylnaphthalene, diphenylamine or 2-phenylphenol at a pH of 4 to 9.5 and a temperature of 95 ℃ to 100 ℃, optionally with the addition of a sequestering agent; and

(IV) atmospheric dyeing of acetate, triacetate and nylon at pH4 to 9.5 for 15 to 90 minutes, the temperature used for acetate being 85 ℃ or the temperature used for triacetate and nylon being 90 ℃, optionally with addition of a sequestering agent.

In all of the above processes, the dye mixture applied as a dispersion is a dye mixture comprising from 0.001% to 20%, preferably from 0.05 to 16%, of the dye mixture in an aqueous medium.

The dye mixture may also be applied to the textile material using supercritical carbon dioxide, in which case the dye formulating agent may optionally be omitted.

Detailed Description

Embodiments of the present invention will now be described in more detail with reference to the following examples, in which parts are by weight unless otherwise indicated. The relative CMC color Difference (DE) value of 0.5 denier polyester fibers was measured using 2 denier polyester as a standard to evaluate the same color depth light dyeing degree. According to ISO 105-B02: 1999 (xenon arc test, evaluated on the blue scale) the light fastness was measured.

Example 1

A blue dye mixture comprising 16.4 parts of the dye of the formula (1), 5.7 parts of the dye of the formula (3) and 10.6 parts of the dye of the formula (2-1) is prepared by: the three dyes were mixed together and then milled together as a 40% aqueous slurry with 20 parts of a high temperature stable dispersant until the dye particle size (average diameter) was 0.1-5 microns.

The dispersion was standardized to a solid form containing 32.7% of the mixture and 67.3% of the dispersant by adding 47.3 parts of a heat stable dispersant and drying in a spray dryer to a granular or powder form.

A yellow dye mixture comprising 5.9 parts of the dye of the formula (4), 4.4 parts of the dye of the formula (5) and 2.6 parts of the dye of the formula (6-1) is prepared by: the three dyes were mixed together and then milled together as a 40% aqueous slurry with 20 parts of a high temperature stable dispersant until the dye particle size (mean diameter) was 0.1-5 microns.

The dispersion was standardized to a solid form containing 12.9% dye mixture and 87.1% dispersant by adding 67.1 parts of a heat stable dispersant and drying to a granular or powder form in a spray dryer.

A red dye mixture comprising 8.0 parts of the dye of the formula (7), 8.5 parts of the dye of the formula (8) and 10.5 parts of the dye of the formula (9) is prepared by: the three dyes were mixed together and then milled together as a 40% aqueous slurry with 20 parts of a high temperature stable dispersant until the dye particle size (mean diameter) was 0.1-5 microns.

The dispersion was standardized to a solid form containing 27% of the mixture and 73% of the dispersant by adding 53 parts of a heat stable dispersant and drying in a spray dryer to a granular or powder form.

Preparation of the dyeing bath for dip-dyeing the polyester flakes: 1.5ml of an aqueous blue dye mixture dispersion (1 g of blue dye dispersed in 100ml of water at a temperature of 40-50 ℃) and 1.5ml of an aqueous yellow dye mixture dispersion (1 g of yellow dye dispersed in 100ml of water at a temperature of 40-50 ℃) and 1.5ml of an aqueous red dye mixture dispersion (1 g of red dye dispersed in 100ml of water at a temperature of 40-50 ℃) were added to 57ml of deionized water and 1.2ml of a buffer solution. To this bath were added one piece of 2.5g normal denier polyester and one piece of 2.5g fine denier polyester and the bath was held at 120 ℃ for 30 minutes in a high temperature dyeing machine. After rinsing the dyed materials with water and subsequent reductive cleaning treatment, each material was dyed in a gray tone with excellent light fastness.

Example 2

The preparation, dyeing and evaluation of the dye mixture were carried out in the same manner as in example 1, except that the formulation was changed as shown below:

the blue dye mixture comprises 18.2 parts of the dye of formula (1), 5.1 parts of the dye of formula (3) and 8.0 parts of the dye of formula (2-1);

the yellow dye mixture comprises 5.9 parts of the dye of the formula (4), 5.0 parts of the dye of the formula (5) and 2.0 parts of the dye of the formula (6-1); and

the red dye mixture comprises 9.1 parts of the dye of the formula (7), 8.45 parts of the dye of the formula (8) and 9.0 parts of the dye of the formula (9). The results are given in table 1.

Example 3

The preparation, dyeing and evaluation of the dye mixture were carried out in the same manner as in example 1, except that the formulation was changed as shown below:

the blue dye mixture comprises 13.0 parts of the dye of the formula (1), 6.5 parts of the dye of the formula (2-1), 8.4 parts of the dye of the formula (3) and 6.5 parts of the dye of the formula (2-2):

the yellow dye mixture comprises 4.6 parts of the dye of the formula (4), 5.7 parts of the dye of the formula (5) and 2.6 parts of the dye of the formula (6-1); and

the red dye mixture comprises 7.0 parts of the dye of the formula (7), 14.0 parts of the dye of the formula (8) and 7.0 parts of the dye of the formula (9). The results are given in table 1.

Comparative example 1

The preparation, dyeing and evaluation of the dye mixture were carried out in the same manner as in example 1, except that the formulation was changed as shown below:

26.0 parts of a blue dye of formula (1), 13.1 parts of a yellow dye of formula (4) and 23.0 parts of a red dye of formula (7).

TABLE 1

	Color Difference (DE) between the fibers used	Light fastness of fine fineness side	Light fastness of ordinary fineness side
				Example 1	2.5	5	5-6
Example 2	2.7	5	5-6
				Example 3	2.7	5	5-6
Comparative example 1	3.4	3-4 (turning red)	4-5 (turning red)

As shown in table 1, the color difference of DE of examples 1 to 3 is smaller than that of comparative example, showing that the disperse dye composition of the present invention can provide excellent dyed products having excellent light fastness and excellent shade of the same color between the fibers used even when used for fiber products of different deniers.

Claims (12)

1. A non-azo disperse dye mixture comprises a blue dye mixture, a yellow dye mixture and a red dye mixture,

the blue dye mixture includes a compound of formula (1), at least one compound of formula (2), and a compound of formula (3) below:

wherein R is¹Is C₁-C₄Alkyl, 3-Methoxypropyl, 3-ethoxypropyl or 3-methoxyethoxypropyl;

the yellow dye mixture comprises the following compounds of formula (4), formula (5) and formula (6):

wherein R is²Is methyl or ethyl;

and

the red dye mixture includes compounds of formula (7), formula (8), and formula (9) below:

2. a disperse dye mixture as claimed in claim 1, wherein R is¹Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.

3. A blue dye mixture comprising 40 to 80% by weight of a compound of formula (1), and 10 to 40% by weight of at least one compound of formula (2), and 10 to 30% by weight of a compound of formula (3):

wherein R is¹Is C₁-C₄Alkyl, 3-methoxypropyl, 3-ethoxypropyl or 3-methoxyethoxypropyl.

4. A disperse dye mixture according to claim 1 wherein in the blue dye mixture the ratio of dyes (1) to (2) to (3) is: 40-80% by weight of a compound of formula (1), 10-40% by weight of a compound of formula (2) and 10-30% by weight of a compound of formula (3); in the yellow dye mixture, the ratio of dyes (4) to (5) to (6) is: 30 to 60% by weight of formula (4), 30 to 60% by weight of formula (5) and 10 to 40% by weight of formula (6); and in the red dye mixture, the ratio of dyes (7) to (8) to (9) is: 20-60 wt% of formula (7), 30-60 wt% of formula (8) and 10-50 wt% of formula (9).

5. A disperse dye mixture as claimed in claim 1, wherein in the blue dye mixture the ratio of dyes (1): (2): (3) is: 50-70% by weight of a dye of formula (1), 15-35% by weight of a dye of formula (2), 10-20% by weight of a dye of formula (3); the ratio of the dye of formula (4) to the dye of formula (5) to the dye of formula (6) in the yellow dye mixture of the invention is: 40-60 wt% of formula (4), 30-50 wt% of formula (5) and 10-30 wt% of formula (6); and in the red dye mixture, the ratio of the dyes of the formula (7) to (8) to (9) is: 30-50 wt% of dye (7), 30-50 wt% of formula (8) and 10-40 wt% of formula (9).

6. A dye mixture according to claim 1, wherein the ratio of the blue dye mixture comprising formulae (1) to (3) to the yellow dye mixture comprising formulae (4) to (6) and the red dye mixture comprising formulae (7) to (9) is: the yellow dye mixture is 0.1 to 100,000 parts by weight and the red dye mixture is 0.1 to 100,000 parts by weight per 100 parts by weight of the blue dye mixture.

7. The dye mixture according to claim 6, wherein the yellow dye mixture is 1 to 10,000 parts by weight.

8. The dye mixture according to claim 6, wherein the red dye mixture is 1 to 10,000 parts by weight.

9. A process for the preparation of a dye mixture as claimed in any one of claims 1 to 8, which comprises mixing the required amounts of the dye components.

10. A composition comprising the dye mixture of any one of claims 1 to 8 and at least one dispersant, surfactant or wetting agent.

11. A process for dyeing a synthetic textile material or a fibre blend thereof, which comprises applying to the synthetic textile material or fibre blend thereof a dye mixture according to any one of claims 1 to 8 by a padding process.

12. The method of claim 11, wherein the synthetic material or fiber blend thereof is fine denier polyester fibers, or regular denier polyester fibers, or synthetic textile material and fiber blend thereof.