CH689980A5 - Mixtures of monoazopyridone dyes. - Google Patents

Description

The present invention relates to mixtures of monoazopyridone dyes, their preparation and their use for dyeing or printing textile fiber materials.

Monoazopyridone dyes and their use for dyeing synthetic fiber materials are e.g. known from EP-A 0 440 072. However, it has been shown that these dyes do not always fully meet the highest requirements. There is therefore a need for new dyes or dye combinations which, in particular, show better extraction, build-up or wash fastness properties.

It has now surprisingly been found that the mixtures according to the invention are absorbed to a high degree on the fibers, are distinguished by a very good structure and the resulting dyeings have good light, sublimation and wash fastness properties.

The present invention thus provides a dye mixture containing at least two structurally different dyes, each of the formula

correspond to where R1 C1-C4-alkyl and R2 isopropyl, n-butyl, isobutyl, sec. Butyl, tert. Butyl; or C1-C3-alkyl substituted by phenyl or phenoxy; or R1 is phenyl which is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen; C1-C4-alkoxy-C1-C3-alkylene, phenoxy-C1-C3-alkylene or C1-C3-alkyl which is substituted by unsubstituted phenyl or by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen, and R2 unsubstituted or substituted by hydroxy, OCOR3 or phenoxy, C1-C10-alkyl, the phenyl ring being unsubstituted in phenoxy or substituted by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen and the alkyl chain being C1-C10-alkyl from C3 can be interrupted by one or more oxygen atoms; phenyl which is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen; C5-C7 cycloalkyl; and R3 is C1-C4-alkyl. C1-C3-alkyl in formula (1) denotes methyl, ethyl, isopropyl or n-propyl. C1-C3-alkylene in formula (1) means e.g. Methylene, ethylene or propylene. C1-C4-alkyl in formula (1) denotes methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, sec. Butyl or tert. Butyl. In addition to the radicals given above for C1-C4-alkyl, C1-C10-alkyl in formula (1) can contain straight-chain or branched alkyl radicals, e.g. Pentyl, hexyl, octyl, nonyl or decyl. C1-C4-alkoxy in formula (1) denotes methoxy, ethoxy, isopropoxy, propoxy, n-butoxy, isobutoxy, sec. Butoxy or tert. Butoxy.

C5-C7 cycloalkyl in formula (1) means e.g. Cyclopentyl, cyclohexyl or cycloheptyl. Halogen in formula (1) means e.g. Fluorine, bromine or especially chlorine.

Dyestuff mixtures containing dyestuffs of the formula (1) in which R1 is a phenyl substituted by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen, or preferably methyl or unsubstituted phenyl are preferred.

The structurally different dyes in the dye mixtures according to the invention can each contain the same substituents R1 and different substituents R2, or the same substituents R2 and different substituents R, or different substituents R1 and R2.

Dyestuff mixtures which contain two structurally different dyestuffs of the formula (1) are preferred.

The ratio of the individual dyes in the dye mixtures according to the invention can vary within a wide range, e.g. from 1: 1 to 1: 5. Dyestuff mixtures which have a ratio of the two dyes of 1: 1 to 1: 3 are preferred. Dye mixtures which contain the dyes in a ratio of 1: 1 are particularly preferred.

The following dye mixtures of structurally different dyes (A) and (B) of the formula (1) listed in Table 1 are particularly preferred: <TABLE> Columns = 5 Table 1 Head Col 2 AL = L: Dye (A) Head Col 4 AL = L: dye (B) Head Col 1: dye Mixture No. Head Col 2: R1 Head Col 3: R2 Head Col 4: R1 Head Col 5: R2 1 CH3 CH (CH3) 2 CH3 CH2CH (CH3) 2 2 <CEL AL = L> CH3 <CEL AL = L> CH (CH3) 2 CH3 (CH2) 3CH3 3 CH3 CH (CH3) 2 CH3 <CEL AL = L> CH (CH3) CH2CH3 4 CH3 CH (CH3) 2 CH3 C (CH3) 3 5 CH3 <CEL AL = L> (CH2) 3CH3 CH3 CH2CH (CH3) 2 6 CH3 (CH2) 3CH3 CH3 <CEL AL = L> CH (CH3) CH2CH3 7 CH3 (CH2) 3CH3 CH3 C (CH3) 3 8 CH3 <CEL AL = L> CH ( CH3) CH2CH3 CH3 CH2CH (CH3) 2 9 CH3 CH2CH (CH3) 2 CH3 <CEL AL = L> C (CH3) 3 10 CH3 CH (CH3) CH2CH3 CH3 C (CH3) 3 11 C6H5 <CEL AL = L> CH3 C6H5 (CH2) 2OCH3 12 C6H5 CH3 C6H5 (CH2) 3OCH3 <CEL AL = L> 13 C6H5 CH3 C6H5 (CH2) 3OCH2CH3 14 C6H5 CH3 <CEL AL = L> C6H5 (CH2) 3OCH (CH3) 2 15 C6H5 CH2 ( CH2) 2OCH3 <CEL AL = L> 16 C6H5 CH2CH3 C6H5 (CH2) 3OCH3 17 C6H5 CH2CH3 <CEL AL = L> C6H5 (CH2) 3OCH2CH3 18 C6H5 CH2CH3 C6H5 (CH2) 3OCH (CH3) 2 <CEL AL = L> 19 CH3 (CH2) 3CH3 C6H5 CH3 20 CH3 CH (CH3) CH2CH3 <CEL AL = L> C6H5 CH3 21 CH3 CH2CH (CH3) 2 C6H5 CH3 22 <CEL AL = L> CH3 C (CH3) 3 C6H5 CH3 23 CH3 CH ( CH3) 2 C6H5 CH3 24 CH3 (CH2) 3CH3 C6H5 CH2CH3 25 CH3 <CEL AL = L> CH (CH3) CH2CH3 C6H5 CH2CH 3 26 CH3 CH2CH (CH3) 2 C6H5 <CEL AL = L> CH2CH3 27 CH3 C (CH3) 3 C6H5 CH2CH3 28 CH3 <CEL AL = L> CH (CH3) 2 C6H5 CH2CH3 </TABLE>

Also particularly preferred is the mixture containing the dye of the formula (1) in which R1 is methyl and R2 is n-butyl, the dye of the formula (1) in which R1 is methyl and R2 sec. Butyl and the dye of the formula (1) in which R1 is methyl and R2 are isopropyl.

The present invention also provides a process for the preparation of the dye mixtures of the formula (1). The mixtures according to the invention can e.g. be prepared by mixing at least two structurally different individual dyes of the general formula (1) known per se with one another in the desired ratio, or by using a diazo component of the formula

in which R1 has the meaning given under formula (1), diazotized and based on a mixture of at least two coupling components of the formula

which differ from one another in the substituent R2 and in which R2 has the meaning given under the formula (1), couples.

The dye mixtures of the formula (1) according to the invention can be used as dyes for dyeing and printing semisynthetic and, in particular, synthetic hydrophobic fiber materials, especially textile materials. Textile materials made from mixed fabrics which contain such semi-synthetic or synthetic hydrophobic textile materials can likewise be dyed or printed with the aid of the dye mixtures according to the invention.

Cellulose 21/4 acetate and cellulose triacetate are particularly suitable as semi-synthetic textile materials.

Synthetic hydrophobic textile materials mainly consist of linear, aromatic polyesters, for example those made from terephthalic acid and glycols, especially ethylene glycol, or condensation products from terephthalic acid and 1,4-bis (hydroxymethyl) cyclohexane; made of polycarbonates, e.g. those made from alpha, alpha-dimethyl-4,4 min -dihydroxy-diphenylmethane and phosgene, from fibers based on polyvinyl chloride and polyamide.

The dye mixtures according to the invention are applied to the textile materials by known dyeing processes. For example, polyester fiber materials are dyed in the exhaust process from aqueous dispersion in the presence of customary anionic or nonionic dispersants and, if appropriate, customary swelling agents (carriers) at temperatures between 80 and 140 ° C. Cellulose 21/4 acetate is preferably dyed at between about 65 to 85 ° C. and cellulose triacetate at temperatures up to 115 ° C.

The dye mixtures according to the invention do not or only slightly dye wool and cotton that are simultaneously present in the dyebath (very good reserve), so that they can also be used well for dyeing polyester / wool and polyester / cellulose fiber blended fabrics.

The dye mixtures according to the invention are suitable for dyeing by the thermosol process, by the exhaust process and for printing processes. The exhaust method is preferred. The liquor ratio depends on the equipment, the substrate and the form of presentation. However, it can be chosen within a wide range, e.g. 1: 4 to 1: 100, but is preferably between 1: 6 to 1:25.

The textile material mentioned can be present in various processing forms, e.g. as fibers, threads or fleece, as woven or knitted fabrics.

It is advantageous to convert the dye mixtures according to the invention into a dye preparation before they are used. For this purpose, the dye mixture is ground so that its average particle size is between 0.1 and 10 microns. Milling can take place in the presence of dispersants. For example, the dried dye mixture is ground with a dispersant or kneaded in paste form with a dispersant and then dried in vacuo or by atomization. The preparations obtained in this way can be used to produce printing pastes and dye baths after adding water.

The usual thickening agents will be used for printing, e.g. modified or unmodified natural products, for example alginates, British gum, gum arabic, crystal gum, locust bean gum, tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starch or synthetic products, for example polyacrylamides, polyacrylic acid or their copolymers, or polyvinyl alcohols.

The dye mixtures according to the invention give the materials mentioned, especially the polyester material, level yellow or golden-yellow shades of very good fastness to use, such as above all good lightfastness and good fastness to sublimation. The very good wash fastness should be emphasized. The dyes according to the invention are also distinguished by good extract and structure.

The dye mixtures according to the invention can also be used well for producing mixed shades together with other dyes or together with a suitable red and blue dye for trichromatic dyeing.

The above-mentioned uses of the dye mixtures of the formula (1) according to the invention are also an object of the present invention, as is a process for dyeing or printing semi-synthetic or synthetic hydrophobic fiber material, in particular textile material, which consists of the dye mixture of the formula (1) according to the invention to apply said material or to incorporate it into it. Said hydrophobic fiber material is preferably a textile polyester material. Further substrates which can be treated by the process according to the invention and preferred process conditions can be found above in the more detailed explanation of the use of the dye mixtures according to the invention.

The invention also relates to the hydrophobic fiber material, preferably polyester textile material, which is dyed or printed by the process mentioned.

The following examples serve to illustrate the invention. Unless otherwise stated, the parts therein are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius. The relationship between parts by weight and parts by volume is the same as that between grams and cubic centimeters.

example 1

A suspension of 33.6 parts of 2-nitro-4-methoxyaniline in 220 parts of water is cooled to about 10-15 ° C. and 60 parts of 32% hydrochloric acid are added dropwise. Then 55 parts of a 4N sodium nitrite solution are added over the course of 15 minutes with thorough stirring, the temperature of the reaction mixture being kept at about 15.degree. After the addition has ended, the mixture is stirred for a further hour and the excess nitrite is destroyed with a little sulfamic acid. The resulting diazotization mixture is slowly poured into a solution, cooled to about 5-10 ° C., of 20.4 parts of N-isopropyl-3-cyano-4-methyl-5-hydroxypyridone and 21.8 parts of N-butyl-3-cyano Pour -4-methyl-5-hydroxypyridone and 18 parts of a 30% strength aqueous sodium hydroxide solution in 200 parts of water. During the addition of the diazotization mixture, the pH is kept constant between 5 and 6 with a 30% strength aqueous sodium hydroxide solution. The orange-red suspension is stirred at 15-20 ° C. for a further 1 hour. The precipitate is filtered off with suction, washed with water and dried at 70 ° C. in vacuo. 75.5 parts of dye mixture no. 1 are obtained. The dye mixture dyes polyester in brilliant golden yellow shades with good fastness properties, in particular very good wash fastness properties.

Example 2

A suspension of 11.5 parts of 2-nitro-4-phenoxyaniline in 100 parts of water and 20 parts of 32% hydrochloric acid is stirred at 40-50 ° C. for 30 minutes. The mixture is then cooled to 15-20 ° C. and 15 parts of a 4N sodium nitrite solution are added with thorough stirring. After the addition has ended, the reaction mixture is stirred at about 20 ° C. for a further two hours. The excess nitrite is destroyed with sulfamic acid and the diazotization mixture is clarified by filtration. The clear solution of the diazonium salt thus produced is slowly poured into a solution, cooled to about 10-15 ° C., of 5.2 parts of N-ethyl-3-cyano-4-methyl-5-hydroxypyridone and 6.1 parts of N-isopropoxypropyl Pour -3-cyano-4-methyl-5-hydroxypyridone and 4.2 parts of a 30% strength aqueous sodium hydroxide solution in 100 parts of water. During the addition of the diazonium salt solution, the pH is kept constant between 5 and 6 with a 30% strength aqueous sodium hydroxide solution. The orange-red suspension is stirred at 15-20 ° C. for a further 1 hour. The precipitate is then filtered off with suction, washed with water and dried at 70 ° C. in vacuo. 22 parts of dye mixture No. 14 are obtained. The dye mixture dyes polyester in brilliant golden yellow shades with good fastness properties, in particular very good wash fastness properties.

Example 3

Analogously to the processes described in Examples 1 and 2 or by mixing two structurally different dyes of the formula (1), the dye mixtures 2-13 and 15-28 listed primarily in Table 1, which also contain polyester in brilliant golden yellow tones dye good fastness properties, especially very good wash fastness properties.

Example 4

100 g of polyester fabric are in a liquor containing a liquor ratio of 1:20 1 g of the dye mixture No. 5, 1 g / l ammonium sulfate and 0.5 g / l of a commercially available leveling agent, which is adjusted to pH 4.5-5 with 80% formic acid, immersed at room temperature. The liquor is then heated first at a rate of 3 ° C./min to 60 ° C. and then at a rate of 2 ° C. to 130 ° C. Dyeing is carried out at 130 ° C. for 60 minutes. The liquor is then cooled to 40 ° C., the dyed polyester fabric is washed with water and rinsed in a bath containing 5 ml / l of 30% sodium hydroxide solution, 2 g / l of 85% sodium dithionite solution and 1 g / l of a commercially available detergent for 20 minutes purified reductively at 70-80 ° C. The finished dyeing is then washed with water and dried. A brilliant golden yellow dyeing with excellent wash fastnesses is obtained.

Claims (10)

1. Dyestuff mixture containing at least two structurally different dyestuffs, each of the formula correspond to where R1 C1-C4-alkyl and R2 isopropyl, n-butyl, isobutyl, sec. Butyl, tert. Butyl; or C1-C3-alkyl substituted by phenyl or phenoxy; or R1 is phenyl which is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen; C1-C4-alkoxy-C1-C3-alkylene, phenoxy-C1-C3-alkylene or C1-C3-alkyl which is substituted by unsubstituted phenyl or by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen, and R2 unsubstituted or substituted by hydroxy, OCOR3 or phenoxy, C1-C10-alkyl, the phenyl ring being unsubstituted in phenoxy or substituted by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen and the alkyl chain being C1-C10-alkyl from C3 can be interrupted by one or more oxygen atoms; phenyl which is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen; C5-C7 cycloalkyl; and R3 is C1-C4-alkyl. 2. Dyestuff mixture according to claim 1 containing at least two dyestuffs of the formula (1) which contain the same substituent R2 and different substituents R1. 3. Dyestuff mixture according to claim 1 containing at least two dyestuffs of the formula (1) which contain the same substituent R1 and different substituents R2. 4. Dyestuff mixture according to claim 1 containing at least two dyestuffs of the formula (1) which contain different substituents R1 and R2. 5. Dye mixture according to claim 3, wherein R1 is methyl. 6. Dyestuff mixture according to claim 3, wherein R1 is phenyl which is unsubstituted or substituted by C1-C4-alkyl, C1-C4-alkoxy, hydroxy or halogen 7. Dye mixture according to claim 3, wherein R1 is phenyl. 8. Dyestuff mixture according to claim 4, containing two dyestuffs of the formula (1), where one dyestuff is methyl as R1 and isopropyl, n-butyl, isobutyl, sec. Butyl or tert as R2. Contains butyl and the other dye as R1 contains phenyl and as R2 contains methyl or ethyl. 9. Process for the preparation of the dye mixtures according to claim 1, characterized in that a diazo component of the formula in which R1 has the meaning given under formula (1), diazotized and based on a mixture of at least two coupling components of the formula which differ from one another in the substituent R2 and in which R2 has the meaning given under the formula (1), couples. 10. A process for dyeing or printing semisynthetic or synthetic hydrophobic fiber material, in particular textile material, characterized in that the dye mixture of the formula (1) according to claim 1 is applied to said material or incorporated into it.