MXPA00010142A - Disperse dye mixture - Google Patents

Abstract

A dye mixture comprises (A) at least one dye of formula (I) wherein X is Cl, Br or I;Q is C1-4alkyl;and each of R1 and R2 independently, is C1-4alkyl or C1-4alkenyl;and (B) at least one dye of formula (II) wherein Q1 is C1-4alkyl;and each of R1 and R2 independently, is C1-4alkyl or C1-4alkenyl.

Description

DISPERSED COLORING MIX DESCRIPTION OF THE INVENTION The present invention relates to mixtures of dispersed dyes, to compositions comprising such mixtures, and to processes for coloring plastics with blends. More particularly, the invention relates to a mixture comprising at least two monoazo dyes. The two monoazo dyes each have respective aromatic cores bonded via an azo group, one of the aromatic cores in each dye having a dialkyl or dialkenyl group for the azo group. In a first dye of the mixture the other aromatic nucleus is a benzene ring substituted by a nitro group (some of these dyes tend to be reddish blue), while in a second dye, the other aromatic nucleus is a nucleus of thiophene substituted by a nitro group (some of these dyes tend to be greenish in color). EP-A-0300626 discloses mixtures of dyes containing only colorants of the aforementioned first type having a nitrobenzene group, while each of EP-A-0347685 and WO-A-97/04030 disclose mixtures of dyes of the first and second types containing nitrobenzene and nitrothiophene groups respectively. However, it has been found that certain mixtures, even when they give bright reddish blue shades on the polyester when viewed in normal daylight, tend to exhibit a "red" flash at the. tungsten light, which represents a serious commercial disadvantage. Although the problem of "flash" is solved by at least one mixture described in EP-A-0300626, this is achieved at the expense of brilliance; such mixing provides a relatively opaque hue. Similarly, this "flash" problem can be solved by at least one of the blends described in EP-A-0347685, but that mixture is especially sensitive to reduction and has a relatively low firmness to heat. Likewise, the flash can be avoided by using a mixture of dyes in which the nitrothiophene contains an acetyl group. However, such dyes tend to be expensive. Surprisingly, we have found that a dye mixture, defined below, surprisingly not only allows reduction or even elimination of the "red" flash, but provides a brighter hue, is less sensitive to reduction and has a higher firmness heat than other known mixtures and at a lower cost. Thus, the invention provides a mixture of coloring materials containing at least: (A) at least one dye of the formula: (I) where X is Cl, Br or I; Q is alkyl of 1 to 4 carbon atoms; and each of R1 and R2, independently is alkyl of 1 to 4 carbon atoms or alkenyl of 2 to 4 carbon atoms; and (B) at least one dye of the formula (II) gave) wherein Q1 is alkyl of 1 to 4 carbon atoms, each of R1 and R2, independently is alkyl of 1 to 4 carbon atoms or alkenyl of 2 to 4 carbon atoms. An especially preferred value of X is Br, especially preferred values for Q and Q1 are methyl and ethyl, and especially preferred values of R1, R2, R3, and R4 are methyl, ethyl and allyl. Especially preferred mixtures contain respectively, (a) a dye of the formula (I), wherein X is Br, Q is methyl and each of R1 and R2 is ethyl [dye (1)] and a dye of the formula ( II), wherein Q1 is methyl and each of R3 and R4 is ethyl [dye (2)] (this dye is known as Green 9 Dispersed Cl), more preferably a mixture such that the ratio of dye (I) dye (II) is 91.5: 8.5, (b) a dye of the formula (I), wherein X is Br, Q is ethyl and each of R1 and R2 is ethyl [dye (3)] (this dye is known as Blue 183 Dispersed Cl) and a dye of the formula (II) which is the dye (2) mentioned above (Green 9 Dispersed Cl) and (c) a dye of the formula (I)wherein X is Br, Q is methyl and each of R1 and R2 is ethyl (dye (1) of mixture (a) above) and a dye of formula (II), wherein X is Br, Q1 is methyl and each R3 and R4 is allyl [dye (4)]. A preferred ratio of dye (I): dye (II) by weight is 98: 2 to 50:50, more preferably 95: 5 to 70:30, especially from 93: 7 to 85:15. The individual dyes can be prepared in a conventional manner by diazotization and coupling. More particularly, for the dye (I), an amine of the formula (III) wherein X is Cl, Br or I, is diazotized and coupled with a coupling component of the formula (V) (V) wherein Q, R1 and R2 are defined as in the above For the dye (11) / an amine of the formula (IV) (IV) It is diazotized and coupled with a coupling component of the formula (VI) (SAW ) Where Q1, R3 and R4 are as defined above. In the above diazotization and coupling reactions, the diazotization is carried out using a diazotization agent, which is preferably nitrosyl sulfuric acid, optionally diluted with glacial acetic acid or a mixture of phosphoric / acetic acid, and preferably at a temperature of 0-10 ° C, more preferably 0-5 ° C. The coupling reaction is preferably carried out at a temperature of 0-10 ° C, more preferably 0-5 ° C and preferably at a pH < 1 (ie 0.5) to 7, more preferably 0.5-1, followed by a subsequent increase in pH to 3-4 to isolate the dye. The mixture of at least one dye of the formula (I) and at least one dye of the formula (II) may additionally comprise at least one other dye, especially a yellow, orange, red or brown dye, capable of producing a marine hue or black Mixtures incorporating the invention can be prepared by a number of methods including: (1) Co-crystallization Typically, the colors are dissolved in a hot solvent, for example by placing the dyes in a suitable solvent and heating them to the reflux temperature of the solvent until the dyes are dissolved, then filtered to provide a solution, and then allow the solution to cool so that crystals form. The resulting mixture can then undergo an additional process, such as grinding and spray drying. Examples of solvents suitable for this process are organic solvents such as aromatic hydrocarbons, chlorinated hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, amides, sulfoxides, esters, ketones and ethers. Specific examples of organic solvents are toluene, ethylene glycol monoethyl ether, acetone, chlorobenzene, pyridine, dimethylformamide, dimethisulfoxide, ethyl acetate, benzene, tetrahydrofuran and cyclohexane. (2) Co-olid (a) The dyes are mixed and then milled together to give an intimate mixture which is then spray-dried to give a solid mixture; or (b) each dye is ground separately and then mixed in the required ratio before spray drying. (3) Dry Mixing Each dye is spray-dried separately and then mixed in the required ratio by a dry mixing process. The mixtures give an especially bright shade without exhibiting a red flash in tungsten light. Mixtures incorporating the invention provide especially useful dispersed colorants, valuable for coloring synthetic fabrics and fiber blends thereof, and can be formed into a dispersion for this purpose. According to other aspects, the invention provides a composition comprising at least the dye mixture and a dispersing agent, surfactant or wetting agent, suitable for providing such dispersion, and also a process for coloring a synthetic textile or blend of fibers thereof, which comprises applying to the synthetic textile or fiber mixture a mixture comprising at least one dye of the formula (I) and at least one dye of the formula (II). The synthetic textile material can be selected from aromatic polyester, especially polyethylene terephthalate, polyamide, especially polyhexamethylene adipamide, secondary cellulose acetate, cellulose triacetate and natural textile materials, especially cellulose and wool materials. An especially preferred textile material is an aromatic polyester or blend of fibers thereof with fibers of any of the aforementioned textile materials. Especially preferred fiber blends include those of polyester-cellulose, such as polyester-cotton, and polyester-wool. The textile materials or mixtures thereof may be in the form of filaments, loose fibers, spun or woven or knitted fabrics. The dye mixtures of the formulas (I) and (II) optionally, together with other dispersed dyes can be applied to the synthetic textiles or fiber blends by processes that are conventionally employed in the application of disperse dyes to such materials and fiber blends. Suitable conditions can be selected from the following: (i) exhaustive dyeing at a pH of 4 to 6.5, at a temperature from 125 ° C to 140 ° C for 10 to 120 minutes and under a pressure of 1019 to 2. 038 kg / cm2 (1 bar) being optionally added a sequestrant; (ii) continuous dyeing at a pH from 4 to 6.5, at a temperature from 190 ° C to 225 ° C, for from 15 seconds to 5 minutes, an optional migration inhibitor being added, (iii) direct printing at a pH of 4 to 6.5, at a temperature from 160 ° C to 185 ° C for from 4 to 15 minutes for high temperature vaporization, or at a temperature from 190 ° C to 225 ° C for from 15 seconds to 5 minutes for heat setting dry or at a temperature from 120 ° C to 140 ° C and 1,019 to 2,038 kg / cm2 (1 to 2 bars), for from 10 to 45 minutes for vaporization under pressure, optionally adding wetting agents and thickeners (such as alginates) from 5 to 100% by weight of the colorant; (iv) discharge printing (by impregnation of the dye on the textile material, drying and over printing) at a pH from 4 to 6.5, with migration inhibitors and thickeners being optionally added; (v) dyeing by carrier at a pH from 4 to 6.5, at a temperature from 95 ° C to 100 ° C, using a carrier such as methanaphthalene, diphenylamine or 2- phenyl phenol, optionally being sequestrants; and (vi) atmospheric dyeing of acetate, triacetate and nylon at a pH from 4 to 6.5, at a temperature of 85 ° C for acetate or at a temperature of 90 ° C for triacetate and nylon for from 15 to 90 minutes, sequestrants of optional way In all the above processes, the dye mixture is applied as a dispersion comprising from 0.001% to 6, and preferably from 0.005 to 4%, of the dye mixture in an aqueous medium. A particular aspect of the invention provides a composition comprising a mixture of dyes (I) and (II), optionally at least one other disperse dye and additionally, optionally at least one additional ingredient used in a conventional manner in coloring applications such as an agent of dispersion, surfactant or a 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 liquid, preferably an aqueous medium, or solid. The liquid compositions are preferably adjusted to a pH of 2 to 7, more preferably to a pH of 4 to 6. Typical examples of dispersing agents are lignosulfonates, naphthalen sulphonic acid / formaldehyde condensates and phenol / cresol / acid condensates. sulphonic / formaldehyde, typical examples of wetting agents are alkyl aryl ethoxylates, which may be sulphonated or phosphated, and typical examples of other ingredients that may be present are inorganic salts, defoamers such as mineral oil or nonanol, organic liquids and shock absorbers. The dispersing agents can be present in from 10% to 200% by weight of the dye mixtures. The wetting agents can be used in from 0% to 20% by weight of the dye mixtures. The compositions can be prepared by grinding the dye mixture in a ball mill with glass beads or sand in an aqueous medium. The compositions may further have additions of dispersing agents, fillers and other surfactants and may be dried, by means of a technique such as spray drying, to give a solid composition comprising from 5% to 65% of coloring matter. In addition to the aforementioned application processes, the dye mixtures can be applied to synthetic textiles and fiber blends by ink jet printing, optionally the substrates have been previously treated to assist printing. For inkjet applications, the application medium may comprise water and a water soluble organic solvent, preferably in a weight ratio of 1:99 to 99: 1, more preferably 1:95 to 50:50 and especially in a interval from 10:90 to 40:60. The water-soluble organic solvent preferably comprises an alkanol of 1 to 4 carbon atoms, especially methanol or ethanol, a ketone, especially acetone, methyl ethyl ketone, 2-pyrrolidone or N-methylpyrrolidone, a glycol, especially ethylene glycol, propylene glycol, trimethylene glycol, 2,3-butanediol, thiodiglycol or diethylene glycol, a glycol ether, especially ethylene glycol monomethyl ether, propylene glycol monomethyl ether or diethylene glycol monomethyl ether, urea, a sulfone, especially bis- (2-hydroxyethyl) sulfone or mixtures thereof. The dye mixtures can also be applied to textile materials using supercritical carbon dioxide, in which case the dye formulation agents can optionally be omitted. The embodiments of the present invention will now be described in more detail with reference to the following Examples, in which the parts are by weight unless otherwise specified.

Examples 1-2: Preparation for individual dyes Example 1 2-Bromo-4-ni tro-6-c-anoaniline (24 parts) was stirred at 0-5 ° C with a mixture of acetic / propionic acid (100 parts, 96:14). Nitrosyl sulfuric acid (35 parts, 40% solution in H2SO4) was added gradually at 0-5 ° C and the mixture was stirred at that temperature for 60 minutes. The diazo solution was added to a coupling mixture of N, N-diethyl-n-aminoacetanilide (21.6 parts), water (100 parts), concentrated sulfuric acid (20 parts) and sulfamic acid (7 parts), stirring at 0 ° C. -5 ° C. After stirring for a further 2 hours, the product was isolated by filtration, washed with cold water and dried at 50 ° C. Performance: 39 parts. Example 2 2-Amino-3, 5-dini t rot iofen (19 parts) at 0-5 ° C was stirred with a mixture of acetic / propionic acids (100 parts, 86:14) Nitrosyl sulfuric acid was added gradually (35 parts, solution at 40% in H S04) at 0-5 ° C and the mixture was stirred at that temperature for 30 minutes.The diazo solution was added to a coupling mixture of N, N-jdiethyl-m-aminoacetanilide (21 parts) , water (100 parpes), concentrated sulfuric acid (20 parts) and sulphamic acid (7 parts), stirring at 0-5 ° C. After turning for an additional hour, the product was isolated by filtration, washed with Cold water and drying at 50 ° C. Yield: 30 parts Examples 3-4 Preparation of Mixtures Example 3 A mixture of 33.5 parts of dye (I) and 3.2 parts of dye (II) was prepared by mixing the two dyes together and grinding them as a 40% aqueous slurry with 20 parts of a dispersion agent stable at high temperature until the particle size of the colorant (average diameter) was in the range of 0.1-5 microns.

This dispersion was "standardized" (ie adjusted to the desired nuance and strength) to provide a liquid composition containing 18. 35% of the mixture, by adding 6.5 parts of a humectant and water (to 100 parts). The same dispersion was standardized to provide a solid composition containing 36.7% of the mixture and 63.3% dispersion agent, by the addition of 43.3 parts of a stable dispersing agent at high temperature and drying it to either a form of granule or powder in a spray dye. Example 4 Example 3 was repeated, using exactly the same proportions and procedure but replacing the dye (1) with the dye (3). The liquid compositions of examples 3 and 4 are especially suitable for use in direct printing and continuous dyeing of polyester and polyester / cellulose blends, and can also be used for thorough dyeing. The solid compositions of Examples 3 and 4 are especially suitable for the exhaustive dyeing of polyester, polyester / cellulose and polyester / wool blends and can also be used for continuous dyeing and direct printing. Example 5 A dye bath was prepared for the exhaustive polyester dyeing in the form of a piece by adding 3 ml of an aqueous dispersion of the solid composition of Example 3 (1 g of dye in 100 ml of water at 40-50 ° C). 55.8 ml of deionized water and 1.2 ml of buffer solution. To this dyebath a 5g piece of polyester was added, and all was maintained for 45 minutes at 130 ° C in a Werner Mathis Labomat high temperature dyeing machine. After rinsing with water and a lightening reduction treatment, the material was dyed to a bright reddish blue hue that appeared almost identical when viewed under normal daylight and with tungsten light sources.

Claims (13)

1. A dye mixture comprising (A) at least one dye of the formula (I) where X is Cl, Br or I; Q is alkyl of 1 to 4 carbon atoms; and each of R1 and R2, independently is alkyl of 1 to 4 carbon atoms or alkenyl of 2 to 4 carbon atoms; and (B) at least one dye of the formula (II) wherein Q1 is alkyl of 1 to 4 carbon atoms; and each of R1 and R2, independently is alkyl of 1 to 4 carbon atoms or alkenyl of 2 to 4 carbon atoms.

2. A dye mixture according to claim 1, wherein the weight ratio of dye (I): dye (II) is from 98: 2 to 50:50.

3. A dye mixture according to claim 2, wherein the ratio is from 95: 5 to 70:30.

4. A dye mixture according to claim 3, wherein the ratio is from 93: 7 to 85:15.

5. A dye mixture according to any of the preceding claims, further comprising at least one additional dye.

6. A dye mixture according to any of the preceding claims comprising, as component (A), a dye (1) of the formula (I), wherein X is Br, Q is methyl and each of R1 and R2 is ethyl and, as component (B), a dye (2) of the formula (II), wherein Q1 is methyl and each of R3 and R4 is ethyl.

7. A dye mixture according to claim 6, wherein the weight ratio of dye (1): dye (2) is 91.5: 8.5.

8. A dye mixture according to any of claims 1 to 5, comprising, as component (A), a dye (3) of the formula (I), wherein X is Br, Q is ethyl and each of R1 and R2 is ethyl and, as component (B), a dye (2) of the formula (II), as defined in claim 6.

9. A mixture according to any of claims 1 to 5, comprising, as component (A), a dye (1) of the formula (I), as defined in claim 6 and, as component (B), a dye (4) of the formula (II) wherein Q1 is methyl and each of R3 and R4 is allyl.

10. A composition comprising a dye mixture according to any of the preceding claims and at least one dispersing agent, surfactant or wetting agent.

11. A process for coloring synthetic textile material or fiber mixture thereof, comprising applying thereto a dye mixture according to any of claims 1 to 9.

12. A process for coloring a synthetic textile or blend of fibers thereof, comprising applying thereto a composition according to claim 10, dispersed in an aqueous medium.

13. A process according to claim 11 or claim 12, wherein the synthetic textile or blend of fibers thereof is a polyester or polyester-cellulose or polyester-wool blend respectively.