DE2009390B2 - DYE AND ITS USE IN THE COLORING OF POLYESTERS - Google Patents

Description

The invention relates to novel dyes which are suitable for bulk coloring of synthetic polyesters are and their use for coloring such a material.

In order for a dye to be satisfactorily used for bulk coloring of polyesters, one must the dye generally meet the following conditions:

1. The dye must be at the polymerization temperature or at the temperature at which the Polymer is molded to the Formarti'cel, or in which such molded articles are processed be stable enough:

2. the volatility must be low enough under the above conditions, since the color, if the volatility is high, may be irregular or uneven and the neighboring one The object (e.g. a fabric) could become discolored;

3. The dye should have a high degree of fastness or resistance to light and the effects of it of cleaning solvents, sweat and bleach.

It has now been found that certain dyes condensed or fused with three to five Rings meet the above conditions.

In particular, the dye for bulk coloring of polyesters according to the invention by the general formula (I) reproduced:

CH ₂ -N-COR ₂

J »

(D

wherein A is the imino group or a sulfur atom, Z is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, and m and η each represent an integer from 1 to 4, A being different when π is 2 or greater , and D represents a dye residue consisting of 3 to 5 fused rings, each of which does not have a sulfonic acid group but has one or more hydroxyl, amino, nitro groups. Halogen atom / s, lower-alkyl, lower-alkoxy, N-lower-alkylamino, phenylamino, cyclohexylamine or carboxyl radical / s can be substituted, and R ₁ and R _{2 have} the meaning given below. The invention also relates to the use of one or more of these dyes. In the invention, the terms "lower alkyl" and "lower alkoxy" mean those alkyl and alkoxy groups having 1 to 5 carbon atoms.

From the Belgian patent specification 728 536 disperse dyes are known, which preferably together with other disperse dyes intended for coloring polyamides and polyesters are. Their use as disperse dyes does not suggest that they can also be used for bulk dyeing are useful. The chemical structure shows that they have no carboxyl group, which is essential for compatibility with polyesters and the good distribution in polyesters is essential and also the resistance to sublimation increased, moreover, the lack of a carboxyl group precludes incorporation of the dye in the polyester itself when used during its manufacture, which, however, results in particularly real colorations of polyesters.

The dye of the formula (I) can be prepared by one by the following general formula (II) reproduced connection:

D-

(Z) _n ,

in which A, Z, D, m and η have the meaning given above and in which, if η ^ 2, A can be different, with a compound which is represented by the following general formula (III):

T-CH ₂ -N-COR,

(III)

where T is a hydroxyl radical, a halogen atom, an alkoxy or alkylamino _{radical, R 1 is} a hydrogen atom, a lower-alkyl radical or —CO — R ₃ ,

R ₅ R ₆

—CH- CH,

COOH

HN-COR ₂

(IV)

wherein R ₁ and R _{2 have} the meanings given above, in the presence of formaldehyde. Reacts paraformaldehyde or di (halomethyl) ether, or with a compound represented by the general formula (V):

NC-R ₇

(V)

wherein R _{7 is} a saturated or unsaturated, with a carboxyl group, a carboxyphenyl group or their lower alkyl ester substituted lower alkyl radical or an aromatic, substituted with a carboxyl group, a carboxyalkyl group or their lower alkyl ester radical of the benzene series, in the presence of formaldehyde, parafonaldehyde or di (halomethyl) ether converts.

The solvent to be used in the above-mentioned condensation reaction may be 70 to 98% Sulfuric acid, 70 to 85% phosphoric acid or a lower fatty acids, e.g. formic acid or acetic acid, among these compounds is sulfuric acid particularly preferred

The reaction temperature is not critical. The reaction can be carried out at from 0 to 120 ^° C., usually at room temperature.

A catalyst can be used which is usually used in FriedeKks iteaktionen be used, e.g. S. anhydrous zinc chloride, anhydrous Aluminum chloride, boron trifluoride or phosphorus oxychlorite

and if R _{1 represents} a hydrogen atom or a lower alkyl radical, R _{2 represents} a saturated or unsaturated lower alkyl radical substituted with a carboxyl group, a carboxyphenyl group or their lower alkyl esters, an aromatic radical substituted with a carboxyl group, a carboxyalkyl group or their lower alkyl esters denotes the benzene series or an aniline radical which is substituted by a carboxyl group and which can additionally be substituted by a lower alkyl radical, a lower alkoxy radical or a halogen atom, and if R _{1 represents} the radical -CO-R ₃ , R ₂ and R ₃ interconnected R ₄ with the meaning

-C = C-

and R ₅ and R ₆ each linked to one another represent a radical which is a benzene ring substituted with a carboxyl group or its lower alkyl ester, reacts in a solvent and optionally in the presence of a catalyst, or with a compound represented by the general formula (IV) :

Examples of compounds of formula (II) which can be used in the preparation of the dyes of the invention can be used

1,4-, 1,5- or 1,8-dianilinoanthraquinone, 1,4-, 1,5- or 1,8-di (phenylthio) anthraquinone, 1,4-, 1,5- or 1,8-di (2-, 3- or 4-toluidino) -

anthraquinone,
1,4- 1,5- or 1,8-di (2-, 3- or 4-methylphenyl-

thio) anthraquinone,
1,4-, 1,5- or 1,8-di (2-, 3- or 4-anisidino) -

anthraquinone,
1,4-, 1,5- or 1,8-di (2-, 3- or 4-methoxy-

phenylthio) anthraquinone,
1,4-, 1,5- or 1,8-di (2-, 3- or 4-chloroanilino) -

anthraquinone,
1,4-, 1,5- or 1,8-di (2-, 3- or 4-chlorophenylthio) anthraquinone,

1,4-, 1,5- or 1,8-dimesidinoanthraquinone, 1,4-, 1,5- or 1,8-di (vic-m-xylidino) anthra-

chinone,
1,4-, 1,5- or 1,8-di (2,6-diethylanilino) -

anthraquinone,
1,4-, 1,5- or 1,8-di (2,6-dimethyl-4-t-butyl-

anilino) anthraquinone,
1,4-, 1,5- or 1,8-di (2,6-dimethyl-4-n-butyl-

anilino) anthraquinone,
1,4-, 1,5- or 1.8-di (2,3,5,6-tetramethylanilino) anthraquinone,

1,4,5,8-tetraanilinoanthraquinone, 1,4,5,8-tetra (phenylthio) anthraquinone, l-Amino ^ -phenylthio ^ -anilinoanthraquinone, l-Amino-2-phenylthio-4- (2-, 3- or 4-toluidinoJ anthraquinone,

l-amino-2,4-di (phenylthio) anthraquinone. 1-Amino-2,4-di (2-, 3- or 4-methylphenylthio) anthraquinone.

l-Amino-4- (4-methylphenylthio) anthraquinone, l-methylamino-4- (phenyIthio) anthraquinone, l-anilino-4-, 5- or 8-phenylthioanthraquinone, l ^ -dihydroxy-S-anilino-S-phenylthioanthraquinone,

!, S-dianilino-AS-dihydroxyanthraquinone,!, S-dianilino ^ .S-dihydroxyanthraquinone, l ^ -dianilino-S-nitro-S-hydroxyanthraquinone, l, 5-di (phenylthio) -4.8-dihydroxyanthraquinone, l, 8 -Di (phenylthio) -4,5-dihydroxyanthraquinone, l-cyclohexylamino ^ -toluidinoanthraquinone, l-methylamino ^ -anisidinoanthraquinone, 1-methylamino ^ toluidinoanthraquinone, l-cyclohexylamino-^ anisidinoanthraquinone,
1 - oxy-4-mesiounoanthraquinone, 1-oxy- ^ vic-m-xylidinojanthraquinone, 1,4-diamino-2,3-di (phenylthio) anthraquinone, 6-aniIino-3 '^' - phthaloylacridone, 6-phenylthio- 3 '^' - phtihaloxylacridone, 4-anflino-2-methyl-l '(N) ^' - anihrapyridine, ö- (4-toluidino) -3 ', 4'-phtiialoylacridone, 6- <4-chlorophenyltiiio) -3 ', 4'-phÜiaIoylacridon, 6-Aniüno-i, P'-anthrapyrimrdon,

yii ^

5-ailino-1 ', 9' {N) -isothiazelanthone, 7-phenyltfaio-1 '^' H
i

other

^ y
benzunidazoL

^ by the general formula {III) again geojsneVerbmdangen, soft in the production ae

dyes according to the invention can be used, are for example:

N-methylolmalonic acid monoamide,
N-methylol succinic acid monoamide, N-methylol tere (or iso) phthalic acid

monoamide,

N-MethyloM-carboxyphenylacetamide,
N-methylol-4-carboxymethylbenzamide,
N-methylol-3-methyl-terephthalic acid monoamide,

N-methylol trimellitimide,
N-methylol - ^ - carboxybenzyD-succinimide,
N- (chloro- or bromomethyl) -malonic acid-

monoamide,

N- (chloro- or bromo-methyl) succinic acid

monoamide,

N- (chloro- or bromomethyl) -trimellilinid,
N-methylol-N-methylterephthalic acid mono-

amide,

KN'-methylenebislcarboxyacetamide),
Bis (malonic acid monoamidomethyl) ether,
N-methylol-2-. 3- or 4-urcidobenzoic acid,
N-methylol-4-ureido-2-methylbenzoic acid,
N-methylol-3-ureido-benzoic acid,
N-Methylol-4-ureido-2-methoxybenzoic acid
and their lower alkyl esters.

The above-mentioned N-methyloleic acid amide compounds or N-methyloleimide compounds can be easily prepared by using the appropriate Acid amide or acid imide compound represented by the formula (IV) in one aqueous solution of formalin is heated.

As the compounds represented by the general formula (IV) which are used in the preparation of the invention Dyes can be used, the acid amides and acid imides are listed, which are the precursors of the above as examples of the compounds represented by the general formula (III) were called.

Examples of compounds represented by the general formula (V) which are used in the preparation of the dyes according to the invention can be used are: cyanoacetic acid, / ί-cyanopropionic acid, γ-cyanobutyric acid, 3- or 4-cyanobenzoic acid, or

4 - cyanomethylbenzoic acid. 4 - cyanophenylacetic acid, / i - (4 - cyanophenyl) - propionic acid. 4 - Cyanstilbene-4 ' - carboxylic acid, 2 - methyl - 4 - cyano benzoic acid, 4-chloro- or 4-methoxy-3-cyanobenzoic acid and their lower alkyl esters.

The dye residue represented by D in the general formula (I) includes the following two Groups:

1. Anthraquinone or derivatives thereof, which are represented by the following formula and contains sulfur atom, and more precisely the radicals represented by the following formulas:

N-CH ₃

N N

N —S

N-NH

or by the formula

2. Naphihaline derivatives represented by the following formulas:

wherein X is a residue of a heterocyclic ring which is a nitrogen atom or a nitrogen atom The anthraquinone and naphthalene nuclei can be substituted for the above-mentioned dye residues with hydroxyl, amino, nitro, a halogen, lower-alkyl, Lower-alkoxy, N-lower-alkylamino, phenylamino, Cyclohexylamine or carboxyl.

The dye of the present invention can be used in a usual manner. So can / can a or more of the dye (s) represented by the above general formula (1) Polyester are added in a manner known for mass coloring and mixed therewith. For example can use a finely ground dye in a polishing drum to coat chips Polyester applied and the resulting colored mixture then melted and made into single threads or other

whose objects are deformed. If necessary, the above mixing or application can be used in the polishing drum using a dispersion of the dye in a volatile liquid such as water, alcohol or ethylene glycol ethers (Cellosolve), or such a liquid can be used to moisten the mixture of dye and polymer. It is also possible to produce the polymer in the presence of such dyes. So are z. B. Monomers such as terephthalic acid or dimethyl terephthalate, a glycol, e.g. B. ethylene glycol, and one or more of the above dyes mixed and heated to carry out the polymerization to obtain a colored polymerizate will. The colored polymer produced in this way can become objects such as threads or films in a known manner Way to be deformed. In addition, it is also possible to produce a prepolymer or a precondensate, and then add the dye. The mixture is then subjected to further polycondensation, until a desired degree of polymerization is reached.

Polyester which can be dyed according to the invention is, for. B. a through the polycondensation of Terephthalic acid and / or isophthalic acid or esters thereof with glycol of the formula

HO - (CH ₂ ) _W - OH

(wherein w is an integer from 2 to 10) or l ^ -dihydroxymethyocyclohexane obtained polyester. As used herein, the term "polyester" includes copolyesters. Such a copolyester can be obtained by replacing part of the above-mentioned dicarboxylic acid with another dicarboxylic acid or an oxycarboxylic acid and / or by replacing part of the above-mentioned glycol with another glycol. Since these polyesters and copolyesters and their production are well known per se, no further explanations are required.

The colored products obtained according to the invention have good resistance to Light, steaming under pressure, sweat, rubbing after steaming and heat treatments in the case of hangers. The color possesses a deep tint and the coloring can be done without damaging the desired properties of the polyester or the articles formed therefrom.

The invention is illustrated by means of the following examples. In the examples, the parts of the specification relate and percent always on weight.

example 1

4 parts of 1,5-dianilinoanthraquinone are in 60 parts Dissolved 95% sulfuric acid. 4.4 parts of cyanoacetic acid are added to the solution and complete dissolved. Then, while the solution is being cooled with water, 1.6 parts of paraformaldehyde are added added successively in small amounts to the solution. This reaction solution is at room temperature Stirred for 20 hours. The solution is poured into 600 parts of cold water. The generated Crystals are filtered off, washed with water until neutral and dried. The yield is 5.6 parts. This dye has the following formula

O NH

HOXCh ₂ CONHCH ₂

CH ₂ NHCOCH ₂ CO ₂ H

Example 2

100 parts of dimethyl terephthalate, 71 parts of ethylene glycol, 0.05 part of manganese acetate and 0.04 part of phosphoric acid are stirred together for 4 hours at 97 ° C. The methanol formed as a by-product is distilled off. 3 parts of a dye such as it was prepared in Example 1 and which had previously been moistened with 12 parts of ethylene glycol by grinding in a ball mill for about 30 minutes .. Then the temperature of the mixture is increased to 277 ^° C. and the pressure is increased to 0.3 mm Hg Under these conditions, the elevated temperature is maintained for 6 hours to distill off any excess ethylene glycol. The melt is formed into filaments, which are drawn. The drawn filaments thus obtained are dyed in a reddish-purple color, which has high lightfastness and heat resistance.

Example 3

4.7 parts of 1,4-dimesidinoanthraquinone are dissolved in 70 parts of 85% strength sulfuric acid. It will 7.5 parts of 4-chloro-3-cyanobenzoic acid are added to the solution and the mixture is added until complete Dissolution stirred. Then 5.7 parts of di (chloromethyl) ether are added dropwise to the solution one after the other. After dropping, the solution is at room temperature Stirred for 20 hours. The reaction solution is poured into 700 parts of cold water. the Crystals generated are filtered off and washed with water until neutral. When drying the 7.9 parts of blue crystals are obtained from the cake.

to

This dye has the formula shown below

ο
11th NH- - < Ϋ CH ₂ NHCO Λ CH ₃ V T CH ₃ V M.
O NH- - < O H ₃ C. -CH ₃ CH ₂ NHCO

CO ₂ H

Cl

CO ₂ H

Example 4

If chips of a copolyester of 75% ethy

is used together with 100 parts of polyethylene terephthalate 25 and 25% ethylene isophthalate to Stell ----- ■ - · _{made of} polyethylene terephthalate un

these are colored by the same process, we ·) transform them into a polyester film Obtained in the form of a colored product which has excellent fastness.

1 part of the dye prepared in Example 3

lat treated in the form of chips in the polishing mill. If the mixture produced in this way is melt-spun in a known manner, it becomes blue in color Obtained threads which have excellent lightfastness and heat resistance.

Example 5

4.2 parts of 1,5-di (phenylthio) anthraquinone are completely dissolved in 84 parts of 95% sulfuric acid, and while this solution is being cooled with water, 7.7 parts of N-methyloltrimelHtimide are successively added here in small portions. Then the solution is stirred for 15 hours while being kept at room temperature. The reaction solution is poured into 800 parts of cold water. The crystals produced are filtered off, washed well with water until neutral and dried. The yield is 11.3 parts.
This dye has the following formula

40

HO ₂ C

N-CH,

CO, H

If N-bromomethyl-trimellitimide instead of the N-methylol trimellitimide was used in this example and the treatment is carried out in the same way, the same compound as in get this example.

Example 6

1 part of the dye produced according to Example 5 and 3 parts of ethylene glycol monoethyl ether (ethyl cellosolve) are used together with 100 parts of granulate

60 shaped polyethylene terephthalate treated in a polishing mill until a uniform mixture is produced. When the colored mixture at 120 ⁰ C in a vacuum is dried and schmelzversponncn, yellow-colored yarns are obtained of good stability.

Example 7

4.5 parts of 1,4-di (4-toluidino) -5,8-dihydroxyanthraquinone are 85% in 70 parts of phosphoric acid

dissolved. There are 4.9 parts of 4-cyanobenzocic acid in entered the solution. While the solution is cooled with water, 1.5 parts of paraformaldehyde become added here in small quantities one after the other. The solution is stirred at 30 to 35 ° C. for 15 hours. This reaction solution will slowly split into 700 parts

Let ice water flow in. After stirring for 1 hour, the mixture is used to separate the Crystals are filtered, these are washed with water until neutral. After drying will be 7.0 parts of green crystals were obtained. They have the following formula

CO ₂ H

HO O NH

When 2-methyl-4-cyanobenzoic acid is used instead of 4-cyanobenzoic acid in the example, and the treatment is carried out in the same way, a compound will have a similar hue obtained with the following formula:

CH ₂ NHCO - <f> --CO ₂ H

HO O NH

CH, NHCO- <f V-CO, H

HO O NH

Example 8

100 parts of dimethyl terephthalate, 71 parts of ethylene glycol, 0.05 part of manganese acetate and 3 parts of the after the method of Example 7 dye obtained are stirred for 4 hours at 197 ° C, while as By-product generated methanol is removed. 0.5 part triphenyl phosphate and 0.05 part antimony triooxide are added. The temperature of the mixture is increased to 277 ° C and the pressure is increased 0.3 mm Hg reduced. The mixture is kept under these conditions for 6 hours. Meanwhile excess ethylene glycol is distilled off. Then the mixture is deformed into threads, which be stretched. The drawn filaments obtained are colored green and have excellent properties Authenticity.

Example 9

4.2 parts of 1-amino-2-phenylthio-4-anilinoan1: hrachinon are dissolved in 63 parts of 85% strength sulfuric acid. 8.0 parts of 4-cyanomethylbenzoic acid are added here and completely dissolved. While the solution is being cooled with water, 1.5 parts of paraformaldehyde are added here in small amounts. The solution is kept for 20 hours at 5O ⁰ C. The reaction solution is allowed to flow into 700 parts of water. The crystals produced are filtered off. washed with water and dried, 7.2 parts of blue crystals being obtained. The compound obtained has the structure shown by the following formula

CH ₂ NHCOCH ₂ <■

O NH

CH ₁ NHCOCH ₂ CO, H

21

example

22nd

Parts of dimethyl terephthalate, 25 parts of dimethyl isophthalate, 100 parts of ethylene glycol, 0.035 part of manganese acetate and 1 part of the dye obtained in Example 9 are heated quickly until the dL temperature rises to 105 ° C and 5 hours at this temperature held while methanol produced as a by-product is distilled off. It became 0.03 parts Antimony trioxide and 0.4 parts triphenyl phosphate are added here. The temperature of the mixture will increase about 285 ° C and its pressure is reduced to 0.3 mm Hg. Under these conditions the mixture becomes Held for 6 hours while removing excess ethylene glycol. If so received Polymer is deformed in a known manner, becomes a

green-colored polyester film obtained, which has excellent fastness

In the following table I are the after same procedure as in example 1,3,5. 7 or 9 synthesized Dyes listed in the second column.

and the hues of these dyes according to the dyeing process of Examples 2, 4, 6, 8 or colored polyesters are given in the third column:

Table I. example

12 13 14 15 16 17 18 19 20 21 22 23 24 25 26

28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43

dye

1 ^ -Difcarboxyacetamidomethj l-4-anilino) anthraquinone !, S-Difcarboxyacetamidomethylanilinojantbrachinon 1,4-Di (trimelIitimidomethyl-4-methoxyaniIino) anthraquinone lAS ^ -Tetraicarboxyacelamidomethylanilinolanthraquinone

M-Dilcarboxyacetamidomethylanilinol-S-nitro-S-hydroxyanthraquinone

1,4-Di (trimellitimidomethyl-2-toluidino) anthraquinone 1,4-Di (trimellitimidomethyl-4-toluidino) anthraquinone 1,8-di (trimellitimidomethylphenylthio) anthraquinone l-amino-2,4-di (trimellitimidomethylanilino) anthraquinone IAS.S-Tetra trimellitimidomethylphenylthiuJanthraquinone 1,4-Di [(4-carboxyacetamidomethyl) mesidino] anthraquinone 1,4-di (trimellitimidomethylphenylthio) anthraquinone 1,4-Di [(4-carboxybenzamidomethyl) anilino] anthraquinone 1,4-Di (carboxyacetamidomethyl-vic-rn-xylidino) anhraquinone

1,4-Di [(3-carbomethoxybenzamidomethyl) -2,6-diethylanilino] anthraquinone

1,8-Di [(3-methyl-4-carboxybenzamidomethyl) -4-toluidino] -4,5-dihydroxyanthraquinone

l-Amino-2- (trimellitimidomethylphenylthio) -4- (trimellitimidomethylanilino) anthraquinone

1-Amino-2,4-di [(4-carboxyphenylacetamidomelhyl) phenylthio] anthraquinone

1,5-Dif (3-carboxybenzamidomethyl) -3-toluidino] anthraquinone 1,5-di [(3-carboxybenzamidomelhyl) -4-chloroanilino] anthraquinone 1,4-di [(3-carboxybenzamidomelhyl) -4-toluidino] anthraquinone 1,5Di [(4-carboxybenz; amidomethy]) phenylthio] anthraquinone 1,8-Di [(4-carboxybenzamidomethyl) phenylthio] anthraquinone l-cyclohexylamino-4- (lrimellitimidomethyl-4-anisid 4-ino) anthraquinone l-methylamino-1 (4-cirboxybenzamidomethyl) -4-loluidino] anthraquinone 1,8-di [(4-carboethoxybenzamidomet! "Yl) -4-iin. ⁱ lhylphenyllhio] anthraquinone l, 5-di (carboxyacetamidomethyl-2-methylphenylthio) anthraquinone l, 5-di ((nmelliüiTndomeUiylmesidino) anthraquinone 1,4-di (carboxypropionamidomethyl-2, (> dime-anthryl-4-butyl l, 5-di (carboxypiOpionamidomelhyl-2,6-dimethyl ^ tn-butylanilino) anthraquinone!, S-difcarboxybulyramidomelhyl-vic-m-xylidinotanlhraquinone 1,4-di (4-lrimellitimidomelhyl-2,3,5,6-lelramelhylanilino) anthraquinone l-hydroxy-4- (carboxyacetamidomclhylmesidino) anthraquinone shade

greenish blue

puipur

green

green

green

greenish blue

green

yellow

green

Red

blue

bluish-rol

greenish blue

blue

blue

blue

bluish green

Red

purple

purple

green

yellow

yellow

blue

bluish green

yellow

yellow

bluish red

blue

bluish red

bluish red

blue

bluish-rol

continuation

/ 3

example dye hue 44 l-hydroxy-4- (carboxyacetamidomethyl-vic-m-xylidino) anthraquinone bluish red 45 l-hydroxy-4- (4-carboethoxybenzamidomethylmesidino) anthraquinone bluish red -ι. 46 !, S-DiP-carbomethoxybenzamidomethylmesidinojanthraquinone bluish red 47 1,4-Di (trimethylitimidomethyl-2,6-dimethyl-4-t-butylanilino) anthraquinone blue 48 1,5-di (trimellitimidomethyl-4-methylphenylthio) anthraquinone yellow 49 1,5-di (trimililimidomethyl-2-methy! phenylthio) aiithraquinone yellow 50 1,5-di (trimellitimidomethyl-4-toluidino) anthraquinone purple

Example 51

2 parts of 1,8-dianilinoanthraquinone are in Dissolved 30 parts of 95% igcr sulfuric acid. 3.5 parts (4-carboxybenzyl) succinimide are in small Quantities added to the solution. 0.45 parts of paraformaldehyde are used in small amounts in the solution given. The solution is stirred for 20 hours at 20 to 25 ° C. and then poured into 300 parts of cold water. The crystals produced are filtered off, washed with water until neutral and dried. the Yield is 3.3 parts.

This dye has the following formula and it colors according to the procedures of Examples 2, 4, 6, 8 or 10 Polyester in purple.

O NH

HO ₂ C-

/ ~ Vhn ο

N-CH ₂

CH ₂ -N

CH,

CO ₂ H

CH, O

Example 52

4.7 parts of 1,4-dimesidinoanthraquinone are / u 94 parts of glacial acetic acid were added. There are 1.5 parts of boron trifluoride ether admitted here. 6.6 parts of N-methylol trimellitimide are still attached. The mixture is stirred for 20 hours at 50 to 55 ° C and then poured into 600 parts of cold water. the

Crystals produced are filtered off until neutral washed with water and dried. The yield is 10.3 parts.

This dye has the formula below, and if polyester herewith according to the procedures mentioned in Examples 2, 4, 6, 8 or 10 are colored, the result is a blue color.

CO ₂ H

CO ₂ H

25th

Example 53

4.2 parts of 1,4-di (4-toluidino) anthraquinone are dissolved in 63 parts of 90% strength sulfuric acid. It will 5.4 parts of N-methylol-4-ureidobenzoic acid were added in small amounts to the solution. If the solution is Was stirred room temperature for 24 hours, 8.5 parts of 1,4-di (4-carboxyphenylcarbamidomethyl-4-toluidino) anthraquinone obtained by the formula given below. When coloring polyester with following the procedures shown in Examples 2, 4, 6, 8 or 10, these dye turn green colored.

CH ₂ NHCONH

// V

CO ₂ H

- CO ₂ H

V ^ -CH ₃

CH ₂ NHCONH

Example 54

4.2 parts of 1,5-di (4-toluidino) anthraquinone are dissolved in 63 parts in 95% sulfuric acid. It will 5.4 parts of 3-ureidobenzoic acid were added to this solution. 0.9 parts of paraformaldehyde are used in small amounts introduced into the solution. The solution is stirred at room temperature for 24 hours, with 9.3 parts of 1,5-di- [P-carboxyphenyl-carbamidomethylH-toluidinojanthraquinone can be obtained by the following formula. This dye turns polyester purple.

O NH / ~~ V-CH ₃ ^C ° ^2H

CH ₂ NHCON H ~ \ S

9-

CO ₂ H

NHCONHCH

CH ₃

HN O

In Table II below are the names of those synthesized by the same procedures as in Example 52 or 53 Dyes listed in the second column, and those with these according to the procedures of Examples 2 4, 6, 8 or 10 colored polyesters are listed in the third column.

Table II

example dye hue 55 1,5-di [(4-carboxyphenylcarbamidomethyl) -4-methoxyphenylthio] anthraquinone yellow 56 1,4-Di [(3-carboxyphenylcarbamidomethyl) -3-chlorophenylthio] anthraquinone yellow 57 1,5-di [(3-carboxyphenylcarbamidomethyl) -4-chloroanilino] anthraquinone purple 58 1,5-di [(4-carboxyphenylcarbamidomethyl) -vic-m-xylidino] anthraquinone reddish purple 59 1,4-di [(4-carboxy-3-methylphenylcarbamidomethyl) -2,6-dimethyl-4-t-butyl- blue anflino] anthraquinone 60 1,4-di [4- (4-carboethoxyphenylcarbamidomethyl) -2,3,5,6-tetramethylanilino] blue anthraquinone 61 l-Amino-2 - [(4-carboethoxyphenylcarbamidomethyl) phenylthio] -4 - [(4-carb- bluish purple oxyphenYlcarbamidomethy:) - 4- ^io 'Uidino] anthraquinor. 62 lAS ^ -Tetra ^ S-carboxy - ^ - chlorphenylcarbamidomethyOphenylthio]
anthraquinone Red 63 1,4-di [(3-carboxy-4-chlorophenylcarbamidomethyl) anilino] -5,8-dihydroxy-
anthraquinone green 64 l-Cyclohexylamino-4 - [(3-carboxyphenylcarbamidomethyl) -4-anisidino] -
anthraquinone blue 65 1-hydroxy-4 - [(4-carboxy-3-methoxyphenylcarbamidomethyl jmesidino] - bluish red anthraquinone

Example 66

4.5 parts of o-anilinoO '^' - phthaloylacridone will be completely dissolved in 63 parts of 95% sulfuric acid. There are 3.3 parts of N-methyloltrimellitimide in added small portions to the solution. If the

The solution is then stirred for 20 hours at room temperature, 7.0 parts of dye are obtained.

This dye has the following structure, and it colors according to the procedures of Examples 2, 4, 5 6, 8 or 10 polyester green.

CH, -N

O NH

CO ₂ H

Example 67 Solution then stored for 20 hours at room temperature

3.5 parts of 6-anilino-3-methyl-r (N), 9-anthrapyridone is stirred, 4.2 parts of a red dye

are dissolved in 50 parts of 95% sulfuric acid. obtain.

There are 3.3 parts of N, N'-methylenebis (carboxyacet- This dye has the following formula

amide) is gradually added to the solution. When the 25 mel reproduced structure and colors polyester red.

N-CH,

CH ₂ NHCOCH ₂ CO ₂ H

O NH

In the following Table III the names of the are given and the color shades of the herewith after the by the same procedure as in Example 65 or the same procedure as in Example 2, 4, 6, 8 or 10 66 synthesized dyes in the second column 40 colored polyesters in the third column.

Table III

example dye hue Red 68 4 - [(N-methyl-4-carboxybenzamidomethyl) anilino] 2-methyl-l '(N), 9'-anthra-
pyridine purple 69 6 - [(4-carboxybenzamidomethyl) anilino] -r.9'-anthrapyrimidone Red 70 6- (Trimellitimidomethylanilino) -3-methyl-r (N), 9'-anthrapyridone yellow 71 5- (Trimellitimidomethylanilino) -1 ', 9' (N) -isothiazolan thron blue 72 o-CTrimellitimidomethylphenylthioJ-S '^' - phthaloylacridone green 73 6 - [(4-C £ rboxyphenylcarbamidomethyl) anilino] -3 \ 4'-phihaloylacridone green 74 6 - [(3-carboxyphenylcarbamidomethyl) -4-toluidino] -3 ', 4'-phthaloylacridone blue 75 6 - [(4-Carboxyphenylcarbamidomethyl) phenylthio] ^ 4'-phthaloylacridone Red 76 4 - [(3-Carboxyphenylcarbaniidoinethyl) anilino] -2-methyl-r, (N), 9'-anthra-
pyridine purple 77 6 - [(4-carboxyphenylcarbamidomethyl) aniiino] -1 ', 9' -anthrapyrimidone yellow 78 S - ^ - Carboxyphenylcarbamidomethynanilinoj-r ^ '^ Hsothiazol-anthron yellow . 79 4 ', 5'-di [(4-carboxyphenyJcarbamidomethyl) -4-methylphenylthio] -r, 8 ^/ -naph-
thoylenebenzimidazole

Claims (16)

Patent claims: 1. Dye of the general formula - NCOR, IO series or represents an aniline radical which is substituted by a carboxyl group and which is furthermore substituted with a lower alkyl radical, a lower alkoxy; radical or a halogen atom, and when R _{1 represents} the radical - CO - R ₃ , R ₂ and R ₃ , which are connected to one another, represent R, where R _{4 has the} following meaning: wherein D is a dye residue with 3 to 5 fused rings, none of which is a sulfonic acid group and each with a hydroxyl, amino, nitro, halogen, or Lower-alkyl, lower-alkoxy, N-lower-alkylamino, phenylamino, cyclohexylamino or carboxyl radical can be substituted, A represents an imino radical or a sulfur atom, Z represents a hydrogen atom, a lower alkyl radical, a lower alkoxy radical or represents a halogen atom, R _{1 represents} a hydrogen atom, a lower alkyl radical or the radical —CO - R ₃ , and when R _{1 represents} a hydrogen atom or a lower alkyl radical, R _{2 represents} a saturated or unsaturated, with a carboxyl group, a carboxyphenyl group or their lower alkyl ester-substituted lower alkyl radical, an aromatic radical substituted with a carboxyl group, a carboxylalkyl group or their lower alkyl ester, the benzene -C = C- R ₅ R ₆ —CH-CH ₂ - COOH and R ₅ and R ₆ , which are bonded to each other, represent a group forming a benzene ring substituted with a carboxyl group or its lower alkyl ester, and m and η each form. are an integer from 1 to 4, and when η ^ 2, A may be the same or different. 2. Dye of the formula HO ₂ C N-CH ₂ CH ₂ -N CO ₂ H S. 3. Dye of the formula HO ₂ CCh ₂ CONHCH CH ₂ NHCOCH ₂ CO ₂ H 4. Dye of the formula O NH CH ₂ N OCH ₃ -OCH ₃ CH ₂ N 5. Dye of the formula CH ₂ N NH- CO ₂ H CH ₃ NH CH ₂ N CH ₃ CO ₂ H 6. Dye of the formula O NH CH ₂ N CH, O NH CH ₂ N 7. Dye of the formula H ₃ C CK ₂ NHCOCH ₂ CO ₂ H H ₃ C CH ₂ NHCOCH ₂ CO ₂ H 8. Dye of the formula CH ₂ NHCO O NH C0, H CH ₂ NHCO O NH 9. Dye of the formula CONHCH, CO ₂ H _J CH ₂ NHCO- <> HN O CO ₂ H 10. Dye of the formula CH ₂ NIlCO O NH- / ■> CH, O NH -CH ₃
CH, NHCO CO, H CH, H 11. Dye of the formula H ₃ C CO ₂ H CO ₂ H 12. Dye of the formula O NH CH ₂ NHCONH CH ₂ NHCONH y v 13. Dye of the formula CH ₂ N O NH CO ₂ H 14. Dye of the formula O S 15. Dye of the formula HO ₂ C CO ₂ H 16. Use of the dyes according to any one of claims 1 to 15 for dyeing synthetic molded polyester bodies, characterized in that one or more of the dyes at or after Production of the polyester adds and shaped in the usual way.