DE4329761A1 - Method of dyeing polyester and polyester-containing textile materials - Google Patents

Abstract

The invention relates to a method of dyeing polyester or polyester-containing textile materials at a pH of from 8 to 11, characterised in that one or more monoazo dyes are employed of the general formula I <IMAGE> in which X is (C1-C3)-alkyl, R is (C2-C6)-alkyl, and R<1> and R<2> independently of one another are linear (C2-C4)-alkyl.

Description

The present invention relates to a method for dyeing of textile polyester or polyester-containing textile materials with red dicyanazo dyes.

As a rule, textile polyester or polyesterhal term textile materials with disperse dyes aqueous dye bath under HT conditions in one temperature range from 120 to 140 ° C at pH values from 4 to 6 ge colors because the disperse dyes at higher pH values partially or completely destroyed. At higher pH values Thus, there is a loss of color strength and color tone softening when dyeing and the dyeings are not right producible. Now usually the polyester fiber in a separate step before staining an alkali subjected to rinsing treatment to aids that have been used in weaving or spinning the fiber, to remove. These tools are e.g. B. oiling or Sizing agents that, when available, are level Dyeing the polyester fiber difficult or impossible would do. The alkaline treatment is also through led to oligomers of polyester fiber used in dyeing process have emerged from the inside of the fiber and the Color uneven, destroy and appear in the to keep aqueous dye liquor. The oligomers mentioned are particularly undesirable in yarn dyeing because they spinning the dyed yarn in the spinning apparatus at the points where the yarn is deflected by Ab settle in powdery form. So they pollute the appa and cause the yarn to tear.

This alkaline rinsing treatment is convenient performed at elevated temperature. For time and energy  to save and the number of for both processes, alka pretreatment and dyeing, required equipment reduce, it has always been the goal of both processes to form a one-bath rinsing and dyeing process. To achieve this goal, however, procedures ren are developed in an aqueous dyebath at pH 8 reproducible colorations up to pH 11.

Polyester-cellulose or polyester-polyamide blend are with disperse or reactive dyes from aq dyebath usually in two dyeing steps colors. As mentioned above, the dispersions dyes on the polyester portion at pH 4 to 6 appli adorns the reactive dyes on the cellulose or Polyamide content in the pH range between pH 11 and 13. Also the goal here in the past was a one-bath Application process for both dye classes wrap. They searched for reactive dyes who are already colored at pH values between 8 and 11 can, and procedures were also required here lich who ensure that under these conditions the Polyester content reproducible with disperse dyes can be colored.

To deal with the shortcomings of previous methods is in DE-A 39 38 631 describes a method in which Dis persion dyes in the pH range between pH 8 and 10 in Presence of at least one, optionally on nitrogen substituted amino acid and / or an alkali metal salt zes one optionally substituted on nitrogen Amino acid can be colored.

For example, using this method with the color substance of the formula

at pH 9.5 brilliant red colors in the color of the anthra quinoid C.I. Disperse Red 60 can be obtained (Appl Example 33 of DE-A 39 38 631). The alkali stabili This dye is sufficient for dyeing higher pH values or to carry out the above rinse treatment does not rule out. same for also for the commercial dye of the formula

the loss of color strength and hue at higher pH values shows deviations. The reason for this should be in the Acidi act as the sulfonamide hydrogen for example at R.O.C. Norman "Principles of Organic Synthesis ", Methnen and Co. Ltd. and Science Paperbacks, 1968, on page 66. After that the mentioned acidity when dyeing at higher pH values at least partial salt formation.

Red dicyanazo dye are already known from EP-A 501 238 fe known with which polyester or polyester-containing Fiber materials according to the HT process in the pH range between can be colored 8 and 11. These dyes have a high pH stability, but not the ge  wanted brilliance. In addition, they do not come in the shade close enough to C.I. Disperse Red 60 and have Defects with regard to their application and their ge fastness to use.

The object of the present invention is therefore, alka to provide listable dyes that are brilliant red deliver stains with sufficient fastness properties.

It has now surprisingly been found that out chose dicyanazo dyes to solve this task. These Dicyanazo dyes are partly already from DE-A 27 11 130 known, but without their special Suitability for alkali dyeing known or obvious would have been.

The invention thus relates to a method for dyeing Polyester or polyester-containing textile materials at pH 8 to pH 11, characterized in that one or several monoazo dyes of the general formula I

uses what
x (C₁-C₃) alkyl
R (C₂-C₆) alkyl and
R¹ and R² are independently linear (C₂-C₄) alkyl.

X represents (C₁-C₃) alkyl, for example Methyl, ethyl, i-propyl or n-propyl, with ethyl before trains and methyl is particularly preferred.  

R stands for (C₂-C₆) alkyl, for example Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, n-pentyl, i-pentyl and n-hexyl.

R is preferably (C₃-C₅) alkyl.

For R¹ and R² is linear (C₂-C₄) alkyl for example ethyl, n-propyl and n-butyl.

Preferably R1 and R2 are the same and are ethyl or n-propyl.

Preferred dyes to be used according to the invention general formula I are those in which the sum of the Carbon atoms in the radicals X, R, R¹ and R² 9 to 14, particularly preferably 9 to 12.

Particularly preferred dyes of the general formula I have several of the preferred features mentioned above on.

The present invention also relates to monoazo dyes of the general formula I

wherein
X (C₁-C₃) alkyl
R (C₅-C₆) alkyl and
R¹ and R² are independently linear (C₂-C₄) alkyl.

Preferred general dyes according to the invention Formula I are those that are preferred as above have written characteristics.

The dyes of the general formula I can according to the methods known to those skilled in the art for the preparation of Di cyanazo dyes are produced. In particular, by cyan exchange from compounds of general my formula II

wherein
Y cyan or hal,
Hal is a halogen atom, such as chlorine or, in particular, bromine, and X, R, R 1 and R 2, as defined above, is defined.

The cyan exchange process is, for example, in DE-A 27 11 130. Also the production of the verb The general formula II can be analogous to that of the formula Information is given.

The process according to the invention can be carried out using a dye of the general formula I are carried out. But it can also with two, three or four dyes of the general Formula I run, but two and three Dyes are preferred. The proportion of a dye in in these cases it is preferably 5 to 95% by weight, particularly preferably 20 to 70 wt .-%, each based on the Total amount of dye.  

If several dyes of the general formula I are used sets, they preferably differ only in the Meaning of the radicals R or only in the meaning of the radicals R¹ and R², which are the same within a dye.

The process according to the invention is preferably carried out under HT Conditions executed, d. H. in aqueous dye liquor Temperatures between 120 ° C and 140 ° C in a dyeing car slave. The pH value is preferably pH 9 to pH 10.

The dyes of the general formula I according to the invention can not according to the inventive method, son but also in other conventional processes for dyeing and Printing on hydrophobic synthetic textile materials lien, e.g. B. under HT conditions in the pH range between 4 and 11, in the so-called thermosol process or after be applied to the fiber in a printing process.

Those to be colored by the process according to the invention Polyesters are in particular those based on poly ethylene glycol terephthalates. Textile mat containing polyester rials are z. B. Mixtures of polyester and polyami the.

In the process according to the invention, the dyes or dye mixtures used in fine distribution. The fine distribution of the dyes takes place in itself known by the fact that in manufacturing falling dye together with dispersants in a liquid medium, preferably in water slurries and the mixture of exposure to shear forces exposes the original dye particles are mechanically crushed so far that a optimal specific surface is achieved and the Sedimentation of the dye is as low as possible. The  Particle sizes of the dyes are generally between 0.5 and 5 µm, preferably around 1 µm.

The dispersants used in the grinding process can be nonionic or anionic. Non-ionogenic Dispersants are e.g. B. reaction products of alky lenoxides, such as B. ethylene or propylene oxide with alky connectable compounds, such as. B. fatty alcohols, fat amines, fatty acids, phenols, alkylphenols and carbon acid amides. Anionic dispersants are an example as lignin sulfonates, alkyl or alkylaryl sulfonates or alkyl aryl polyglycol ether sulfonates.

The dye preparations thus obtained are intended for most applications are pourable. The dye and Dispersant content is therefore limited in these cases animals. In general, the dispersions are in one Dye content up to 25 wt .-% and a dispersant tel content adjusted up to about 25%. From economic Dye contents of 15% by weight are usually not the reason undershot.

The dispersions can also contain other auxiliaries ten, e.g. B. those that act as oxidizing agents, such as e.g. B. sodium m-nitrobenzenesulfonate or fungicidal agents, such as B. sodium o-phenyl phenolate.

For certain areas of application there are powder settings prefers. These powders contain the dye or that Dye mixture, dispersant and other auxiliaries tel, such as B. network, oxidation, preservation and Dedusting agent.

A preferred manufacturing method for powdery Dye preparations are that the above be  wrote liquid dye dispersions the liquid speed is withdrawn, e.g. B. by vacuum drying, freezing drying, by drying on drum dryers, preferred but by spray drying.

To produce the dyeing liquors, the required Chen amounts of dye settings made according to the were made with the coloring medium, preferably diluted with water to such an extent that for the dyeing a liquor ratio of 1: 5 to 1:50 results. In addition, the fleets are generally white tere dyeing aids, such as dispersing, wetting and Fixing aid added.

The required pH value of the dye liquor is checked before or also during dyeing by adding bases such as Alka lihydroxides, e.g. B. aqueous sodium hydroxide solution, alkali hydrogen carbonates, e.g. B. sodium bicarbonate or alkali bonaten z. B. Soda.

To minimize pH fluctuations, we prefer Buffer substances added, such as z. B. in JSDC 77 (1979), p. 47, or JSDC 79 (1981), p. 115 are. Particularly suitable buffer substances are those which is the largest buffer in the pH range between 9 and 11 own kung. Suitable buffer systems are e.g. B. Vinegar acid / sodium pyrophosphate, boric acid / borax, sodium dihyd drug phosphate / disodium hydrogen phosphate, phosphoric acid / Bern succinic acid / boric acid or combinations of organic Phosphorus compounds with polycarboxylic acids. The stake Amounts of buffer system are preferably between 0.5 and 10 g / l.

The buffer systems described in DE-A 39 38 631 described amino acids in the manner described there be used.

example 1

0.5 g of a 20% powder preparation of the dye Formula Ib

are in a dyeing autoclave from a dye liquor standing from 2 l of water, 2 g of a dyeing aid based on formaldehyde condensation product and 5 g one Buffer substance, which is a mixture of an organic Represents phosphorus compound and a polycarboxylic acid, 45 min at 130 ° C on 100 g of a fabric made of polyethylene terephthalate stained after the pH of the stain was set to 10 with aqueous sodium hydroxide solution. Then the coloring is rinsed, reductively cleaned, see above like rinsed and dried. This gives a red color exercise with brilliant hue.

Comparative experiment 1

The coloring is repeated, using as a buffer substance now added 4 g of sodium acetate and the pH of the Dyeing liquor is adjusted to 4.5 with acetic acid. The resulting coloring is almost color strength and color Same tone, the dye is practical at pH 10 not decomposed.

Comparative experiment 2

The colorations described above are at pH 10 and 4.5 repeated, but instead of the dye of Formula Ib the commercially available dye of the formula III

is used. A coloration is obtained at pH 10 Color depth is only approx. 45% of the color depth required at pH 4.5 is achieved.

Example 2

57.4 g of the intermediate of formula IV

are suspended in 250 ml of dimethylformamide and with 11.8 g of zinc cyanide and 1 g of copper I cyanide were added. To The dye is precipitated by heating to 100 ° C. for 30 minutes with 250 ml of water, sucks it off, washes it with 50% aqueous dimethylformamide and then with Water and dry it at 50 ° C. It dissolves in acetone with bluish red color and has in phthalic acid ester its absorption maximum at 524 nm and dyes polyester in clear bluish red shade even at pH values <9. The shade comes from that of C.I. Disperse Red 60 very much Near.

The table below shows other dyes performed, entered according to the inventive method can be set. They dye polyester in clear blue tinged red tones similar to the shade of C.I. Disperse Red 60.

The following table shows colors according to the invention fabrics listed.

Claims (9)

1. A process for dyeing polyester or polyesterhal term textile materials at pH 8 to pH 11, characterized in that one or more monoazo dyes of the general formula I uses what
X (C₁-C₃) alkyl
R (C₂-C₆) alkyl and
R¹ and R² are independently linear (C₂-C₄) alkyl. 2. The method according to claim 1, characterized in that that X means methyl. 3. The method according to claim 1 and / or 2, characterized records that R means (C₃-C₅) alkyl. 4. The method according to one or more of claims 1 to 3, characterized in that R¹ and R² are the same and mean ethyl or n-propyl. 5. The method according to one or more of claims 1 to 4, characterized in that it is under HT conditions gene in aqueous dye liquor at temperatures between 120 ° C and 140 ° C in a staining autoclave.   6. The method according to one or more of claims 1 to 5, characterized in that it is at pH 9 to pH 10 is performed. 7. Monoazo dyes of the general formula I wherein
X (C₁-C₃) alkyl
R (C₅-C₆) alkyl and
R¹ and R² are independently linear (C₂-C₄) alkyl. 8. A process for the preparation of monoazo dyes of the general formula I according to claim 7, by cyan exchange from compounds of the general formula II wherein
Y cyan or hal
Hal is a halogen atom, such as chlorine or especially bromine, and
X, R, R¹ and R² are as defined in claim 7. 9. Use of monoazo dyes of the general Formula I according to claim 7 for dyeing and printing hydrophobic textile materials.