DE2634169A1 - NEW DISPERSION DYES, PROCEDURES FOR THEIR MANUFACTURING AND APPLICATION - Google Patents

Description

CIBA-G ElGY AG, CH-4002 Basel \ j> g O / - \

Case 1-10016 / +

Germany dr.BERG DIPL-INQ STAPF DiPL-ING. SCHWABE DR. DR. SAND ^ *

PATENTANWÄLTE β MÖNCHEN 80 ■ M AUEBKinCHERSTft.4 *

Lawyer file 27 o7o . July 29, 1976

New disperse dyes, processes for their preparation and their application

The invention relates to new disperse dyes of formula (I)

• · 0 NHR

(D,

where R is optionally substituted alkyl, cycloalkyl or hydrogen, R ^{1 is} optionally substituted alkyl, cycloalkyl, aralkyl or phenyl and R "is a radical of the formulas -NR" ¹ R "" or -OX, in which X is optionally substituted alkyl, cycloalkyl, aralkyl or denotes phenyl and R ¹ ″ and R ^{! l! l are} each hydrogen or optionally substituted alkyl radicals which, together with the nitrogen atom, can also form a 5- or 6- ring, and η is 1 or 2.

The new dyes are obtained by adding anthraquinone-2-carboxylic acid esters of the formula

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Oh dear

(COHDR ')

^r 2-n O Hal

wherein R and R ^{1 are} the same as above and Hal is chlorine or bromine, with an aminobenzoic acid ester or amide of the formula

CO-R "

wherein R "is the same as above.

Preferred compounds are those of the formula

0 bra,

ry σο-0-R ¹

0 NH-

wherein R ¹ and X are the same as above.

In addition to hydrogen, the radicals R include cycloalkyl groups, such as cyclohexyl and cyclopentyl, and lower Alkyl groups in question, such as methyl, ethyl, propyl, butyl and penty! Groups, which are replaced by chlorine, bromine, Hydroxyl, cyano, lower alkoxy (methoxy, ethoxy, propyloxy, Butoxy), phenyl (e.g. nitrophenyl, chlorophenyl, bromophenyl, cyanophenyl, toluyl, cresyl, methoxyphenyl and ethoxyphenyl) or lower alkylcarbonyloxy (acetoxy, Formyloxy, propionyloxy) can be substituted.

Suitable groups R 'and X are lower alkyl radicals, such as Methyl, ethyl, propyl, butyl or pentyl, the substi-

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can be influenced, e.g. by chlorine, bromine, fluorine, hydroxyl, cyano, lower alkoxy (methoxy, ethoxy, propoxy, Butoxy), phenyl, cyanoethoxy and lower alkylcarbonyloxy (acetoxy, formyloxy, propionyloxy), lower alkoxycarbonyl (Carbomethoxy, carboethoxy, carbopropoxy); Phenyl group, by chlorine, bromine, fluorine, lower alkyl (methyl, ethyl, Propyl, butyl), lower alkoxy (methoxy, ethoxy, butoxy), nitro, cyano, lower alkoxycarbonyl (carbomethoxy, carboethoxy, Carbopropoxy), lower alkylcarbonyloxy (acetoxy, propionyloxy), formyloxy, phenyl, phenylazo substituted can be; Cycloalkyl groups such as cyclohexyl and cyclopentyl; as well as aralkyl groups such as benzyl, chlorobenzyl, Nitrobenzyl and phenylethyl.

Suitable radicals R ^f "and R ^mä are hydrogen, lower alkyl groups, such as methyl, ethyl, propyl, butyl and pentyl groups, which are replaced by chlorine, bromine, hydroxyl, cyano, lower alkoxy (methoxy, ethoxy, propyloxy, butoxy ) can be substituted, or together radicals of the formulas

₂ CH ₂ -S-CH ₂

CH ₂ CH ₂ -S-CH ₂ CH -, - ₂₂

CH

₂₂₂₂ or -CH CH ₂ -N-CH ₂ CH ₂ -. COCH ₃ HCO

The reaction according to the invention of 1-amino (or 1-alkylamino) -4- (chlorine or bromo) -anthraquinone-2-carboxylic acid esters or amides with aminobenzoic acid esters to give the dyes according to the invention is carried out at 50 to 250.degree. C., preferably 80.degree up to 180 ^G C in inert solvents such as nitrobenzene, Dia 'thylenglycolmonome thy lather, toluene, xylene, tetralin, etc. carried out.

The reaction of the aminobenzoic acid esters with the 4-chloro- or bromo-annthraquinones is advantageously carried out in Presence of acid-binding agents such as alkali hydroxides

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carbonates or acetates, such as sodium or potassium hydroxide, Sodium or potassium carbonate and sodium or potassium acetate, and of catalysts such as copper metal and copper (I) salts (e.g. copper (I) acetate or copper (I) chloride.

It is also possible to use the Dyes by reacting a 4-aminoanthraquinone

^Formula 0 ITHR

-CO-O-R

where R and R 'mean the same as above, obtained with a bromobenzoic acid ester, for which purpose in an inert solvent such as nitrobenzene, xylene, etc. is heated to 80 to 250 ° C.

A shorter route to the dyes according to the invention consists in reacting 1-amino-2,4-dichloro-anthraquinone in a first stage in the 4-position with aminobenzoic acid, then in the 2-position by treatment with potassium cyanide the chlorine atom against the _t exchanges the cyano group, the cyano group is saponified via the amide to form the carboxyl group and the free carboxyl groups are then esterified with an alcohol R'OH, where R 'is the same as in formula (I) .If the saponification of the amide is interrupted, compounds are obtained in where η = 1.

A particularly suitable starting material is bromamic acid, which is initially bonded to the bromine atom with aminobenzoic acids is implemented. Then the 2-sulfo group is with Cyanides (KCN) exchanged and hydrolyzed. The 1-amino-4-carboxyphenylamino-anthraquinone-2-carboxylic acid is obtained, which is then esterified.

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The new water-insoluble compounds are disperse dyes. They themselves, their mixtures or their mixtures with other disperse dyes are particularly suitable for dyeing and printing semi-synthetic and fully synthetic fibers, for example acrylic fibers or acrylonitrile fibers, polyacrylonitrile fibers and fibers made from copolymers of acrylonitrile and other vinyl compounds, such as acrylic esters, Acrylamides, vinyl pyridine, vinyl chloride or vinylidene chloride, fibers made from copolymers of dicyanomethylene and vinyl acetate and from acrylonitrile block copolymers, fibers made from polyurethanes, base-modified Polyolefins, for example polypropylene, cellulose triacetate and cellulose-2 ^ -acetate, polyamides, for example Nylon-6, nylon-6,6 or nylon-12, and in particular Aromatic polyester fibers, for example "

709807/1039 original inspected

wise those made from terephthalic acid and ethylene _{glycol or I 3} 4-Diinethylcyclohexan and fibers from copolymers of terephthalic acid _and isophthalic acid and ethylene glycol.

For dyeing from aqueous liquors, the compounds are advantageously in finely divided form used, the dyeing in the presence of dispersants, for example cellulose sulfite waste liquor or synthetic detergents or in the presence of a combination of various wetting agents and dispersing agents he follows. As a rule, it is advisable to transfer the dyes to be used into a dye preparation before dyeing, containing a dispersant and the finely divided dye in such a form that when the Dye preparations form a fine dispersion with water will. Such dye preparations can be used in known Ways to be prepared, for example, by grinding the dry or wet dye, which is the grinding with or without the addition of dispersants.

After wet milling, subsequent drying gives dye batches which contain textile auxiliaries and 5-95% dye. Examples which may be mentioned as advantageously usable dispersants of the non-ionic group are: addition products of 8 moles of ethylene oxide with 1 mole of p-tert.-octylphenol, of 15 or 6 moles of ethylene oxide with castor oil, of 20 moles of ethylene oxide with the alcohol CJ ₆ H- ^ OH, ethylene oxide addition products with di [a-phenylethyl] phenols, Polyä'thylenoxyd-tert. -dodecyithioa * ether, polyamine-polyglycol ether or addition products of 15 or 30 mol of ethylene oxide with 1 mol of amine or C, _O H "

The following may be mentioned as anionic dispersants: Sulfuric acid esters of alcohols of the fatty series with 8 to

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20 carbon atoms, from the ethylene oxide adducts from the corresponding fatty acid amides, or of alkylated phenols with 8 to 12 carbon atoms in the alkyl radical; Sulfonic acid esters with alkyl radicals having 8 to 20 carbon atoms; Sulphation products of unsaturated fats and oils; Phosphoric acid esters with alkyl radicals with 8 to 20 carbon atoms; Fatty acid soaps, also alkylarylsulfonates, Condensation products of formaldehyde with naphthalenesulfonic acid and ligninsulfonates.

Suitable cationic dispersants are quaternary Ammonium compounds which contain alkyl or aralkyl radicals with 8 to 20 carbon atoms.

The Färbstoffpräparate can, instead of the dispersants, organic solvents, in particular liber 100 ⁰ C boiling solvents which are miscible with water, preferably such as mono- and Dialkylglykoläther, dioxane, dimethylformamide or -acetamide, tetramethylene sulfone or DimethylsuIfoxyd included. The dye, dispersant and solvent can advantageously be ground together.

In order to obtain intense dyeings on PoIyäthylenterephthalatfasern from an aqueous dyebath, it is appropriate to enable the dyeing liquor with a swelling agent or to carry out the dyeing process under pressure at a temperature above 100 ⁰ C. Suitable swelling agents are aromatic carboxylic acids, phenols, aromatic halogen compounds or. Diphenyl.

For heat fixation of the dye the polyester fabric padded, advantageously heated, after drying, for example in steam or hot air to temperatures above 10O ⁰ C, for example to temperatures of 180-210 ⁰ C.

The dyeings achieved according to the invention can

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a caching treatment, for example by heating with an aqueous solution of a nonionic detergent. The specified connections can According to the invention, instead of by impregnation, also by printing be applied. For this purpose, for example, a printing paste is used that finely distributed the Dye and the auxiliary substances normally used in printing, e.g. wetting agents and thickeners and optionally an alkali.

According to the invention, strong prints with good fastness properties are obtained.

Cellulose 2 1/2 acetate fibers are preferably dyed at temperatures of 80-85 ° C., while cellulose triacetate fibers are advantageously dyed at the boiling point of the dye liquor. The use of dye carriers or swelling agent is superfluous when dyeing cellulose 2 1/2 acetate or polyamide fibers «

The dyeing of fully synthetic fibers, in particular polyester and polyamide fibers, can continue for example in an organic solvent bath, such as in perchlorethylene or a perchlorethylene-water emulsion or by means of the "Dybln process", as described below, for example, are carried out, but is not limited to the following procedure.

To produce a printing paste, 10 parts of dye paste of 5% concentration are stirred into a stock thickener which contains 80 parts of emulsion thickener and 10 parts of polyethylene glycol-400. The polyester-cotton blend (66:33) is printed with the above paste is dried at 70-8O ⁰ C and heat-set it for 30 seconds at 205 ⁰ C. It is then washed with cold water and subjected to soap treatment.

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The abovementioned processes give strong dyeings and prints with good color fastness properties, in particular against heat hardening, sublimation, heat setting, pleating, exhaust fumes, over-dyeing, Dry cleaning and chlorine and good wet fastness properties, for example to water, sea water, Wash and sweat.

The dyes show good fiber affinity and good exhaustiveness. The colors are resistant to peeling agents, ozone, smoke gas, rubbing and solvents and the reserve of wool and cotton, and the high temperature resistance are good. The etchability and the resistance to reduction (when dyeing wool) are good. The pH stability is also good.

It is still possible to use the new water-insoluble ones

Links to spin dyeing (dyeing in the mass) of To use polyamides, polyesters and polyolefins. The polymers intended for coloring are expediently in the form of powder, grains or flakes as they come out of the spinning solution, colored or in the molten state mixed with the dye, which is in the dry state or in the form of a dispersion or a solution in one Solvent, which may be volatile, is introduced. After the dye is uniform in the solution or Melt of the polymer is distributed, the mixture can in a known manner by casting, molding or extrusion can be processed into fibers, yarns, monofilaments, films and the like.

The following examples illustrate the invention. The temperatures are given in degrees Celsius, the parts and percentages are by weight unless otherwise stated.

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example 1

25.0 parts of ethyl p-aminobenzoate are melted at 100 and then 3.88 parts of n-propyl 1-amino-4-bromoanthraquinone-2-carboxylate, 1.33 parts of potassium acetate and 0.008 part of copper chloride are added. After the temperature has been increased to 135, the mixture is left to stir for 32 hours. After this time, the mixture is cooled to about 80 and 60 ml of methanol are added to the reaction mixture. The mixture is left to stir for a further 30 minutes while boiling and then filtered while hot. It is washed with 250 ml of methanol and 300 ml of hot water and , after drying, 3.5 parts of the dye with the following constitution are obtained:

-OOOC H

When applied as a bispersion dye to polyester fibers by the customary dyeing process, greenish blue dyeings with good fastness properties are obtained.

The procedure is analogous to that described in Example 1, but instead of the starting materials given there those listed in Table 1, the corresponding disperse dyes are obtained, vjelche all on polyester fabric greenish blue Nuances.

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- ii -

Table 1

O NH,

VCOOR _n

0 Br

O NH,

, i ^ VV ^ -cOOR

ν

O NH-

500R

Kr. ^R l ^R 2 1
2
3
4th CH ₃
Il
Il
It CH ₃
■ ^C 2 ^H 5
ⁿ " ^C 3 ^H 7 5
6th CH (CH ₃ ) CH ₂ OCH ₃
Il C ₂ H ₅ 7th Il XC ₄ H ₉ 8th XC ₃ H ₇ 11-C ₃ H ₇ 9 XC ₃ H ₇ XC ₃ H ₇ 10 iC ₄ H ₉ XC ₄ H ₉ 11 C ₂ H ₄ OH CH ₃ 12th
13th It
° 2 ^Η 5
CH ₂ CCH ₂ OH -C ₄ H ₉
CH ₃ 14th 4 9
Il HC ₄ H ₉ 15th Il ⁱ " ^C 4 ^H 9 16
17th ⁿ " ^C 3 ^H 7 C ₂ H ₅

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- 12 Example 2

In 40 ml of anthranilic acid ethyl ester, 7.48 g of l-amino ^ -bromoanthraquinone-2-carboxylic acid aryl ester, 2.66 g of potassium acetate and 0.012 g of copper chlorine slurried. The temperature is then set to 135 and left at this temperature for 90 hours react. During cooling, 50 ml of methanol and 50 ml of water are added to the reaction solution at 90. After the solution has cooled further to room temperature, it is filtered and mixed with 150 ml of methanol and 400 ml washed in hot water. After drying, 5.2 g of the dye are obtained with the following constitution:

COOC ₀ Iv 2

COOC _{0 tbsp}

In Table 2 further disperse dyes are compiled, which can be used in an analogous manner and Way is obtained as described in Example 2, using the appropriate starting materials. All The listed disperse dyes produce greenish blue dyeings with good fastness properties on polyester fabric.

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Table 2

O NH

rVcooR

O Br

+ ^H 2 ^

OOR

COOR,

O NH

COOR,

^R l R ₂ CH ₃ No. C ₂ H ₅ CH ₃ ^C 2 ^H 5 1 Il 11-C ₃ H ₇ ⁱ " ^C 4 ^H 9 2 It Ti-C ₄ H ₉ CH ₃ 3 It iC ₄ H ₉ Ti-C ₃ Ii ₇ 4th CH ₃ CH ₃ XC ₃ H ₇ 5 Il C ₂ H ₅ CH ₃ 6th ti egg. y ^C 2 ^H 5 7th 11-C ₃ H ₇ 8th Il 9 II 10 C ₂ H ₄ OH 11 It 12th It 13th XC ₄ H ₉ 14th Il 15th

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Example 3

A mixture of methyl p-aminobenzoate is used and butyl p-aminobenzoate, otherwise proceeding analogously to that described in Example 1, is obtained a dye mixture of the formula

0 NH.

0 EH

COOR R

(1: 1)

which dyes polyester fabric in greenish blue tones with good fastness properties.

Furthermore, amine mixtures were used, which resulted in dye mixtures which have the following
Data correspond to (numbers refer to table 1)

Dyes according to 16 and no. Table 1 Ratio (weight) 50 No. 16 and no. 17th 50: 60 No. 17 and no. 1 40: 30th No. 5 and no. 8th 70: 50 No. 5 and no. 1 50: 30th No. 8th 70:

With these dye mixtures, too, valuable, greenish blue tones are obtained on polyester fabric
Nuances.

Similar mixtures are obtained by mixing the dyes from Table 1 with those from Table 2, for example dye No. 5 (Table 2) with dye No. 1
(Table 1).

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Color instructions (Thermofix process)

20 parts of the dye according to Example 1 are ground with 140 parts of water and the 40 parts of sodium dinaphthylmethane disulfonate contains.

A padding liquor is prepared from 200 parts of the above dye preparation and 100 parts of carboxymethyl cellulose (in the form of a 4% aqueous solution) and 700 parts of hater by doing the above Stir the dye preparation into the prediluted thickener with the help of a fast-running stirrer and then the mixture with the help of 807oiger Acetic acid to a p "value of 6 adjusts. The polyester fiber fabric is padded with this liquor at 30 °, squeezes to an absorption of 60% and then dries the material at 70 to 80. The tissue will then heated to 210 on a stenter for 60 seconds and then washed hot and well rinsed with cold water. A greenish-tinged blue-dyed fabric with good fastness properties is obtained.

Staining instructions (HT process)

Is ground 1 part of the dye obtained according to Example 1 with 2 parts of a 507 _o aqueous solution of the sodium salt of dinaphthylmethanedisulfonic acid and dried. -. ·

This dye preparation is mixed with 40 parts of a lOXigen aqueous solution of the sodium salt of N-benzyl / ^J-heptadecyl benzimidazoldisulfonsäure stirred and mixed with 4 parts of a 40% acetic acid solution. 4000 parts of a dye liquor are then prepared by diluting with water.

70 9 807/1039

100 parts of a purified polyethylene terephthalate fiber material are then introduced into this liquor at 50 °, the temperature is increased in the course of half an hour to 120 to 130 ° and the dyeing is carried out for one hour at this temperature in a closed vessel. A ^% greenish blue coloration with excellent lightfastness and sublimation fastness is obtained.

Unless otherwise stated, the shades given in the examples are using the HT process been received.

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Claims (17)

-Yi- Claims
1. disperse dyes of the formula (I) n-l where R is optionally substituted alkyl, cycloalkyl or hydrogen, R 'is optionally substituted alkyl, cycloalkyl, aralkyl or phenyl and R "is a radical of the formulas -NR ¹¹¹ R ¹¹ " or -OX, where X is optionally substituted alkyl, cycloalkyl, aralkyl or Denotes phenyl and R ¹¹¹ and R ″ ″ are each hydrogen or optionally substituted alkyl radicals which, together with the nitrogen atom, can also form a 5- or 6-membered ring, and η is 1 or 2. 2. Dyestuff according to claim 1, characterized in that η = 1. 3. Dyestuff according to claim 2, characterized in that R is a hydrogen atom. 4. Dyestuff according to claim 3, characterized by the formula 5. Dyestuff according to claim 4, characterized in that R ¹ and X are optionally substituted alkyl radicals. 709807/1039 6. Process for the preparation of disperse dyes of formula (I) 'n-l UU ~ H. " / O NH- where R is optionally substituted alkyl, cycloalkyl or hydrogen, R ^{1 is} optionally substituted alkyl, cycloalkyl, aralkyl or phenyl and R "is a radical of the formulas -NR ¹¹¹ R""or -OX, where X is optionally substituted alkyl, cycloalkyl, aralkyl or Denotes phenyl and R "'and R""are each hydrogen or optionally substituted alkyl radicals which, together with the nitrogen atom, can also form a 5- or 6-membered ring, and η is 1 or 2, characterized in that anthraquinone-2- carboxylic acid ester of the formula 0 NHR R "; CO-OR ¹ ) -, (C0-N ^x 0 shark wherein R and R ^{1 are} the same as above and Hal is chlorine or preferably bromine, with an aminobenzoic acid ester or amide of the formula wherein R "means the same as above, converts, 709807/1039 7. The method according to claim 6, characterized in that one of anthraquinone-2-carboxylic acid esters goes out. 8. The method according to claim 7, characterized in that that one of l-aminoanthraquinone-2-carboxylic acid esters goes out. 9. The method according to claim 8, characterized in that it is reacted with p-aminobenzoic acid esters. 10. The method according to claim 9, characterized in that only alkyl esters are used as reactants used. 11. The method according to claims 6 to 10, characterized in that one of the 4-bromoanthraquinone derivatives goes out. 12. Dye preparations, which (A) disperse dyes of the formula (I) 0 NHR R " V (COOR ¹ ) (CON / \ (I), ^ - ^IJ - Vj it Ii CO-R " O NH- where R is optionally substituted alkyl, cycloalkyl or hydrogen, R ^{1 is} optionally substituted alkyl, cycloalkyl, aralkyl or phenyl and R "is a radical of the formulas -NR ¹¹¹ R""or -OX, in which X is optionally substituted alkyl, cycloalkyl, Aralkyl or phenyl and R "'and R""are each hydrogen or optionally substituted alkyl radicals, which together with the nitrogen atom can also form a 5- or 6-membered ring, and ή is 1 or 2, and 709807/1039 (b) contain a dispersant and / or an organic solvent. 13. Dyestuff preparations according to claim 12, characterized in that they contain finely ground dyestuff and contain at least one dispersant. 14. Dyestuff preparations according to claim 12, characterized in that they are an organic solvent
contain. 15. Process for dyeing semi- and fully synthetic Fibers, in particular fibers containing ester groups, characterized by the use of the dyes according to Claims Ibis 5. 16. The method according to claim 15, characterized in that cellulose 2% - or triacetate or
Dyes polyester fibers. 17. The according to claims 15 and 16 obtained
colored material. 709807/1039