DE2009221A1 - Process for dyeing synthetic fibers - Google Patents

Description

The present invention relates to a method for dyeing synthetic fibers by applying a dye dispersion.

It is already known that 1,4-dianilidoanthraquinone and indeed every alkyl-aryl derivative symmetrically substituted in the 1,4-position such as 1,4-di-p-toluidinoanthraquinone as a disperse dye shows little or no affinity for polyester fibers.

It has now been found that certain asymmetrically substituted 1,4-diarylaminoanthraquinone dyes have greatly improved coloring and absorption properties compared to the corresponding symmetrical parent compounds. The dyes can be applied to the synthetic fibers by the carrier dyeing process, the "pressure dyeing process" or the thermosol dyeing process.

The present invention accordingly provides a method for dyeing synthetic fibers by applying a

Dye dispersion on the fibers, the method according to the invention being characterized in that the dye dispersion comprises a dye of the general formula wherein the symbols R and R [deep] 1, which have the same meaning but are in different positions, and / or have different meanings from one another, each represent hydrogen, lower alkyl, lower alkoxy, acyl, acyloxy or halogen and the symbols X and X [deep] 1, which are identical to or different from one another, denote hydrogen, hydroxy or halogen.

Accordingly, if, for example, in the above formula R = H and R [deep] 1 = para-methyl, this dye has considerably better dyeing and absorption properties than the dye in which R = R [deep] 1 = hydrogen or R = R [deep] 1 = para-methyl.

The compounds used according to the present invention can be prepared by the methods for unsymmetrical substitution of the amino groups in 1,4-diaminoanthraquinone. Such a process generally comprises the reaction of a 1-amino-4-arylaminoanthraquinone with a halobenzene (which may have further substituents), which leads to condensation with the 1-amino group, and the subsequent removal of the hydrogen halide. The condensation is due to the presence of a copper catalyst and an acid-binding one

Funded by.

Examples of synthetic fibers which can be dyed according to the method of the present invention are, in particular, polyester fibers and acetate fibers such as triacetate and diacetate, polyamide fibers such as nylon 6 and nylon 66 and polypropylene fibers such as nickel-modified polypropylene and other modified polypropylenes, e.g. Meraklon "(registered trademark of the Montecatini Edison Group).

The following examples illustrate the invention:

example 1

A mixture of 15.7 parts of 1-amino-4-phenyl-aminoanthraquinone, 11.5 parts of anhydrous potassium acetate, 80 parts of 4-chlorotoluene and 0.8 part of copper acetate is refluxed for 24 hours. Then another 0.8 part of copper acetate is added and refluxing is continued for an additional 8 hours. The hot green solution is then filtered to remove inorganic compounds and then cooled. The crystalline product 1-p-toluidino-4-anilinoanthraquinone is filtered off, washed with toluene and dried. It has a melting point of 175-176 ° C.

This dye can be applied to polyester fibers from a dispersion, bluish-green shades being obtained which have excellent fastness properties to heat and light.

A number of other compounds were prepared according to the procedure described in Example 1. These compounds are listed in the table below. In each case, the 1-amino-4-arylaminoanthraquinone compound mentioned in column 1 was reacted with the halogen compound mentioned in column 2. The melting points of the products obtained are given in column 3. The shades of those dyed with it

Polyester fibers are given in column 4.

Example 11

A mixture of 34.3 parts of 1-p-toluidino-4-methoxyanthraquinone, 21.2 parts of 1,3-diaminobenzene and 80 parts of diethylene glycol is stirred and heated to 130 ° C. until the reaction has ended. The mixture is then cooled to 80 ° C. The crude 1-p-toluidino-4-m-aminophenylaminoanthraquinone is isolated by slowly adding 80 parts of ethyl alcohol. The mixture is then cooled to room temperature, filtered, washed free of impurities with ethyl alcohol and dried. A product with a melting point of 174 ° C. is obtained by recrystallization from toluene. The shade when dyeing of polyester fiber is deep green.

Further compounds, which are listed in the table below, were prepared by the process described in Example 11. In each case, the 1-methoxy-4-aryl-amino-anthraquinone compound mentioned in column 1 was reacted with the arylamine mentioned in column 2. The melting points of the products obtained are given in column 3. The color shades of the polyester fibers dyed with it are given in column 4.

example

Example 17

A mixture of 5 parts of the product obtained according to Example 12 and 100 parts of acetic anhydride was refluxed for 21/2 hours. The acetylated product was precipitated by the dropwise addition of 50 parts of water and allowed to cool. By filtering off, washing with water and drying, 4.8 parts of the acetyl derivative with a melting point of 190 ° C. were obtained. A dispersion of this product gives bluish-green shades when dyeing polyester fibers.

Example 18

The dye described in Example 1 can be used to dye other non-polyester fibers. For this purpose, 5 g of a 10% aqueous dispersion of the dye are added to 250 cm [high] 3 of an aqueous solution containing 2 g / l Teepol (trademark of Shell) as a dispersant contains. This dispersion was used for dyeing in the following way:

(a) Dyeing Triacetate 50 cm [high] 3 of the dyebath are diluted to a total liquid volume of 150 cm [high] 3 with an aqueous solution containing 3 g / l Carrier DP 66 (trademark, Y.D.C.). A piece of triacetate material (5 g) is placed in the dyebath and this is then heated to 100 ° C. for one hour. The triacetate is colored in a green-blue shade and has excellent fastness.

(b) Dyeing of acetate The method described under (a) was used, but omitting the carrier and dyeing at 85 ° C. for one hour. The cellulose acetate is colored in a green-blue shade, which is weaker than the color of the triacetate.

(c) Nylon 6 and nylon 66 The procedure described under (a) was used, but the carrier was omitted. Green colorations were achieved on nylon 66 and green-blue colorations on nylon 6.

(d) Polypropylene (Meraklon and nickel-modified polypropylene) The procedure described under (c) was used. Green-blue shades were achieved.

When dyeing polyester fiber, one of the following methods can generally be used to apply the dye: the carrier method, the high temperature dyeing process (also known as "pressure dyeing") and the thermosol process. These three methods are described below.

(1) Carrier method The dye bath is mixed with a suitable carrier (ortho-phenylphenol gives good results) and dinaphthylmethanesulfonic acid in an amount of 1 g / l (Leveller T, trademark of LB Holliday & Co. Ltd.) and the required amount of the well-dispersed dye added

(pH 5 to 6). The dyestuff is introduced at 40 ° C (105 ° F) and the temperature increased to 100 ° C (212 ° F) over 45 minutes. This temperature is maintained for one hour. The material to be dyed is then rinsed well.

(2) High Temperature Dyeing Process 1 g / l of dinaphthyl methanesulfonic acid (Leveller T) and the desired proportion of the well-dispersed dye are added to the dyebath at a temperature of 50 ° C (120 ° F) at a pH of 6. The dyestuff is introduced and the temperature increased to 130 ° C (265 ° F) over 40 minutes. This temperature is maintained for 30 minutes to achieve pale shades and, if necessary, for up to 90 minutes for strong shades. When the dyeing is complete, the dyebath is removed and the material to be dyed is rinsed completely and thoroughly. In certain cases, dye particles can tend to form aggregates on the surface of the fiber, so that dyeings with poor rub resistance and consequently reduced strength (fastness) on wet treatment are achieved. These dyeings can be aftertreated with a reducing agent, which removes the loose dyes from the surface without attacking the dye that has penetrated the fiber. A suitable treatment for reducing and lightening can be carried out by soaking in a bath consisting of the following agents at 50 ° C for 30 minutes and then rinsing it thoroughly:

Hydrosulfite: 1 to 2 g / l sodium hydroxide solution (70 ° Tw, corresponding to a density d [deep] 15 ° of 1.35): 2 to 3 g / l Leveler LBH (trademark of LB Holliday & Co. Ltd.): 3 g / l

(3) Thermosol dyeing process The pretreated dyed material is in a suitable
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larding machine (for lack of) padded at 30 to 50 ° C (80 to 120 ° F) and then dried in a suitable device. The dye is fixed for 45 to 60 seconds at 200 to 210 ° C (380 to 410 ° F). The amount of dye used depends on the desired depth of the shade. For example, a lighter shade can be achieved by using 0.1 percent by weight of dye based on the weight of the fiber, while darker shades of color can be obtained by using 5 percent of the dye based on the weight of the fiber. Dye amounts from 0.1 to 5.0% result in different shades, depending on the exact amount used.

Any desired amount within this range can be used in the examples. It should also be emphasized that the invention is not limited to these staining methods described in more detail.

Claims (5)

1. A method for dyeing synthetic fibers by applying a dye dispersion to the fibers, characterized in that the dye dispersion is a dye of the general formula wherein the symbols R and R [deep] 1, which have the same meaning but are in different positions, and / or have different meanings from one another, each represent hydrogen, lower alkyl, lower alkoxy, acyl, acyloxy or halogen and the symbols X and X [deep] 1, which are identical to or different from one another, are hydrogen, hydroxy or halogen. 2. The method according to claim 1, characterized in that polyester fibers are dyed. 3. The method according to claim 1, characterized in that a synthetic fiber other than polyester is dyed. 4. The method according to claim 3, characterized in that an acetate fiber, a polyamide fiber or a polypropylene or modified polypropylene fiber is dyed. 5. The method according to claims 1-4, characterized in that dyeing is carried out according to the carrier dyeing method, the pressure dyeing method or the thermosol dyeing method.