DE1469732C - Process for printing fully synthetic and semi-synthetic fiber materials - Google Patents

Description

30th

It is known to print hydrophobic fiber materials, in particular aromatic polyesters, triacetate fibers, 27 ₂ acetate fibers and polypropylene fibers and also polymers and copolymers of acrylonitrile, the latter in light shades, with disperse dyes. Although textile prints with excellent fastness properties can be achieved in this way, this procedure has the disadvantage that it requires a formation of the dyestuffs, which is often costly and laborious. In principle, it is therefore preferable to use aqueous solutions of dyes for printing, as is customary when dyeing hydrophilic fibers such as cotton and wool and the like. In the area of the hydrophobic fiber materials mentioned, however, no processes have so far been able to establish themselves which make use of the advantageous use of aqueous dye solutions. It is also known to color or print fiber materials of a hydrophilic character with dyes containing carboxylic acid groups or their alkali salts from aqueous solution. However, applying this method to hydrophobic fibers gives useless results. So far, dyes containing carboxyl groups have only been applied to hydrophobic fibers in the form of dye dispersions, and the disadvantages outlined above have to be accepted in their production.

It has now been found that fully synthetic and hylbsynthetic fiber materials, in particular those made from aromatic polyesters such as polyethylene terephthalates and polyesters made from terephthalic acid and 1,4 - bis - hydroxymethylcyclohexane, cellulose triacetate, Polyvinyl chloride, synthetic super polyamides and polyurethanes, with per se in water insoluble or sparingly water-soluble dyes by processes known per se in the simplest possible way Way and with the achievement of excellent fastness properties, if you print on the fiber materials a printing paste that has a free carboxyl group that is sparingly to insoluble in water containing dye, an amount of a volatile amine sufficient to dissolve that dye or ammonia or, together with an alkaline agent, such an amine or ammonia releasing salt of an acid which is able to convert the dye into the free carboxylic acid and optionally contains further auxiliaries, intermediate drying of the printed material and then heated to temperatures of 150 to 230 ° C (dry-set) or steamed with or without pressure. The received Finally, prints can be post-treated in the usual way, e.g. B. rewashed and equipped will.

The printing pastes are applied to the fiber materials using the customary practice Printing devices. The printing paste can be applied. by removing the carboxyl-containing Dye, which is said to be insoluble or sparingly soluble in water, is introduced into the aqueous medium and with the aid of a volatile amine, e.g. B. with ammonia or an oxalkylamine, stirred and on this Way in solution.

The amount of volatile amine required to dissolve the dye can be determined by experiments easily determine. It is naturally due to the type of dye used, i. H. the molecular size, the substituents and the number of free carboxyl groups of the dye. In many cases it is advantageous to use excess moisture -tiges amine. If one uses compounds, the required amount under the reaction conditions If a volatile amine is released, for which ammonium salts are primarily suitable, they become alkaline Agents such as alkali carbonates or bicarbonates are also used.

Particularly suitable usable volatile amines are ammonia and aüphatische amines such as methylamine, dimethylamine, trimethylamine, dimethyl - / - oxäthylamin, diethyl - ß oxäthylamin, Di - β - oxäthylamin, diethylamine. Triethylamine, alkylamine and tri-n-propylamine. Ammonia occupies a particularly preferred position among the amines. These amines can be used in the form of the bases or in the form of their salts with, for example, hydrochloric acid, nitric acid, tartaric acid, sulfuric acid. Suitable compounds which release volatile amines, in particular ammonia, are, for example, ammonium chloride, sulfate, nitrate, rhodanide and tartrate. Alkaline agents that can be used together with such compounds include, for example: sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, the corresponding potassium salts, trisodium phosphate, etc.

The dissolution of the water-insoluble or water-insoluble carboxylic acid present in the form of its free carboxylic acid sparingly soluble dye with the help of volatile amines or the compounds releasing such amines is probably based on a simple salt formation. The resulting ammonium salts of dyes containing carboxyl groups can be isolated in many cases; they are easily soluble or at least Much more readily soluble in water than the underlying dyes containing free carboxyl groups. The dyes can therefore also be added to the printing paste in the form of the ammonium salts, however, there is still another

Addition of a volatile amine, e.g. B. ammonia, recommends to prevent hydrolysis and thus refilling to counteract the dyes containing free carboxyl groups.

If volatile amine-releasing compounds, in particular ammonium salts, are used in conjunction with alkaline agents, such as alkali carbonates, an alkali salt is presumably formed first of the carboxyl group-containing dye, which then in the presence of ammonium salts in the Free carboxylic acid is converted, which in turn then dyes the fiber. However, these assumptions are not proven experimentally.

The treatment of the printed fabric at temperatures from 150 to 230 ° C (thermosol process) is preferably carried out with dry heat in suitable devices over a period of Carried out for 2 to 300 seconds.

If, on the other hand, the dye is fixed by treatment with steam, the known steaming apparatus is used for this purpose.
Any type of dye can be used as a basis for the new process, provided that they have at least one carboxylic acid group and, in the form of the free acids, are sparingly or insoluble in water. The dyes to be used according to the process can, for. B. the series of metal-containing or metal-free mono- or polyazo dyes or (azo) methine dyes, the azaporphin dyes, in particular the series of copper or nickel phthalocyanines, the series of anthraquinone dyes and condensation products of the latter, which have more than three fused rings, belong to; Further suitable dyes are oxazine, nitro, diphenylamine, naphthalic acid, di- and triphenylmethane dyes. Naphtholactam - condensation dyes and dyes based on naphthoquinone and naphthoquinoneimine, and other condensation dyes. In addition to the carboxylic acid group (s) required according to the definition, the dyes can have other customary substituents, such as halogen, alkyl, cycloalkyl, aralkyl, aryl, alkoxy, aryloxy, nitro, sulfonic, optionally substituted sulfonic or substituted or unsubstituted} amide groups acylated amino groups, alkylthio and arylthio, hydroxy, hydroxyalkyloxy, aminoalkyloxy, cyano ,! Cyanoalkyl and other substituted alkyl, aryl, aralkyl radicals and the like.

The dyes contain one or more carbon! acid groups associated with the aromatic nuclei of the basic dye structure themselves or with external aryl, aralkyl or aliphatic groups are linked. The number of carboxyl groups is generally 1 to 8 and preferably 1 to 4.

Dyes containing carboxyl groups are known in large numbers and are used in a conventional manner produced by using appropriate dye precursors, which are nucleus-bound or in an external position have one or more carboxyl groups, while maintaining the carboxyl groups to the desired ones Converts end products and optionally carries out further conversion reactions in these. In the case of azo dyes, the usual conversion reactions are diazotization and coupling as well as condensation and, in most other classes of dyes, condensation reactions. The following compounds may be mentioned as examples of suitable azo dyes containing carboxyl groups:

COOH

R ₁₅ R ₂₅ R ₃ = H ₅ CH ₃₅ C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , Cl, Br, OCH ₂ COOR, NO ₂ , COOH, OCH ₂ COOH, COOR (R = alkyl)

R ₄ = alkyl

R ₂ COOH R ₃ R ₄

R ₁₅ R ₂ = H, CH ₃ , Cl, Br, NO ₂ , OCH ₃ R ₃₅ R ₆ = H, CH ₃ , OCH ₃ , OC ₂ H ₅

R ₄ , R ₅ = H, CH ₃ , C ₂ H ₅ , CH ₂ CH ₂ OH ₅ CH ₂ CH ₂ OR ₇ (R ₇ = acyl radical)

OH COOH

N = N

R ₁ , R ₂ , R3 = H, CH3, C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , Cl, Br, NO ₂ , COOH

R ₂

N = N

N OH

R ₁ = C ₂ H ₅₅ CH ₂ CH ₂ OH ₅ C ₆ H ₅ , C ₆ H ₄ Cl ₅ C ₆ H ₄ COOH

R ₂ = CH ₃₅ COOH

R ₃₅ R ₄₅ R ₅ = H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , OCH ₂ COOH ₅ COOH ₅ COOR ₅ OCH ₂ COOR ₅ NO ₂₅ Cl ₅ Br ₅ CN (R = alkyl)

HOOC R ₁

OR ₄

R ₁₅ R ₂ = H ₅ CH ₃ , C ₂ H ₅₅ OCH ₃ , OC ₂ H ₅ , NO ₂ , Cl ₅ Br

R ₄₅ R ₅ = CH ₃ , C ₂ H ₅ , CH ₂ CH ₂ OH

R ₂ R ₃

NH

O = C- _(CH2) "COOH

R ₁ , R ₂ , R ₃ = H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , OCH ₂ COOH, COOH, OCH ₂ COOR, COOR, NO ₂ , Cl, Br, CN

R ₄ , R ₅ = CH ₃ , C ₂ H ₅ , CH ₂ CH ₂ OH, CH ₂ CH ₂ OR (R = alkyl)

. η = 0,1,2,3

R ₂

R ₄

HOOC R ₁

R ₁₅ R ₂ = H, OH, OCH ₃ , Cl, NO ₂ , CH ₃ R ₃ , R ₄ = H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ R ₅ = H, CH ₃ , OCH ₃ , COOH

R ₁ R

"St-

-N = N

OH

OH

^R 5 H-N-OC- (CH ₂ J _n COOH

R ₁₅ R ₂₅ R ₃ = H ₅ CH ₃₅ C ₂ H ₅ , Cl, Br ₅ OCH ₂ COOH ₅ OCH ₃ COOR, COOH (R- alkyl) R ₄₅ R ₅ = H ₅ CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ π = 0.1 ₅

= CHCOOH

H ₅ CH ₃ , C ₂ H ₅ , Cl, Br, OCH ₂ COOH, OCH ₃ COOR, COOH (R = alkyl) H ₅ CH ₃₅ C ₂ H ₅₅ OCH ₃₁ OC ₂ H ₅

R ₂ R ₄ . - R ₅

/ K ^/

-N = N- / VN (HOOC (CH ₂ ) _n CO) HN R ₁ R ₃ R ₆

H ₅ CH ₃₅ Cl ₅ Br ₅ NO ₂₅ OCH ₃ H ₅ CH ₃₅ OCH ₃ , OC ₂ H ₅ , NHCO (CH ₂ ) _B COOH, NHCOCH = CHCOOH,

C = O

N χ (CH ₂ ) _n

R ₅₅ R ₆ = H ₅ CH ₃ , C ₂ H ₅₅ CH ₂ CH ₂ OH ₅ CH ₂ CH ₂ OR ₇ (R ₇ = aryl radical) η = 0, 1, 2,

HOOCH ₂ CO <^ ·. R ₁ ^ N = N - <^ A. H, CH ₃ , C ₂ H ₅ , R ₁ , R ₂ , R ₃ , R ₄ . R ₃ = OCH ₃ C = O
/ 0
Il , ι? -N = N-CH
\ Il /
CN
\ V
R ₄ \ HOOCH ₂ CO R ₁ /
CN
Il ^ 0

-N = N

R ₁ , R ₂ = H, CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , NO ₂ , Cl, Br

R ₄₉ R ₅ = CH ₃ , C ₂ H ₅ , CH ₂ CH ₂ OH

For the construction of such and other azo dyes can, for. B. used the following diazo components will:

1-amino-4-methyl-benzene,., L-amino-4-chlorobenzene, l-amino-4-bromobenzene, 1-amino-4-nitrobenzene, 1-amino-4-cyanobenzene, 1-amino-4-methylsulfonylbenzene, 4-aminobenzoic acid methyl ester, 1-amino ^ -dichlorobenzene, 1-amino ^ -methyM-chlorobenzene, l-amino-2-trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4-chlorobenzene, l-amino ^ -chlor ^ -cyanbenzene, 1 -Amino ^ -chloM-nitrobenzene, l-amino ^ -chloro ^ -methylsulfonylbenzene, l-Amino ^ -chloM-methylsulfonylbenzene, 1-Amino ^^ - dicyanobenzene, l-amino-2-cyano-4-methylsulfonylbenzene, 1 -Amino ^ -cyan - ^ - methylsulfonylbenzene, l-amino-2,4-bis (methylsulfonyl) -benzene, l-amino-2,6-dichloro-4-nitrobenzene, l-amino-2,6-dibromo-4-methylsulfonylbenzene, 1-amino ^ -methyM-nitrobenzene, l-amino-2-trifluoromethyl-4-nitrobenzene, 1-amino-2-chloro-4-nitrobenzene, 1 -Amino ^ -cyan - ^ - nitrobenzene, 1-amino-2-methylsulfonyl-4-nitrobenzene, 1-amino-2,4-dinitrobenzene, l-amino-2,4-dinitro-6-chlorobenzene, l-amino-2,4-dinitro-6-bromobenzene, l-amino-2,4-dinitro-6-cyanobenzene, 1-amino-4-acetylaminobenzene, 2-Amino-6-cyanobenzothiazole-l, 3, l-Amino-4-methylsulfonyloxäthylsulfonylmethylbenzene,

1-amino-2,6-dichloro-4-cyanobenzene, 1-Amino-2-cyano-6-bromobenzene, 1-amino ^ -bromo ^ -acetobenzene, 2-amino-5-nitrothiazole

as well as those in the 4-position by ethyl, cyano, trifluoromethyl, Phenyl or substituted phenyl substituted derivatives:

OH

1-amino ^ -nitro ^ -acetobenzene,
2-aminothiophene,
5-aminobenzothiadiazole-1,2,3,
5-aminothiadiazole-1,2,4,
5-aminobenzothiazole-1,3,.

S-Amino-S-benzylmercapto-thiadiazol-l ^^,

2-aminothiazole,

2-amino-4-phenylthiadiazole-1,3,5

■ as well as their nonionic substituted in the phenyl nucleus Derivatives:

Aminoazobenzene,

Aminoazotoluene,

l-acetylamino-3-aminobenzene,

l-aminobenzene-2-carboxylic acid, ■

l-aminobenzene-3-carboxylic acid,

1-aminobenzene-4-carboxylic acid,

1-amino-4-nitrobenzene-2-carboxylic acid,

1-amino-S-chlorobenzoM-carboxylic acid,

l-Amino ^ -chlorbenzoM-carboxylic acid,

1-amino-4-phenoxyacetic acid,

1-amino-3-phenoxyacetic acid,

1-amino-S-chTor ^ -phenoxyacetic acid,

l-amino ^ -oxybenzene-S-carboxylic acid,

Coupling components suitable for the construction of the azo dyes to be used according to the process are, for. B. those of the benzene, naphthalene ^ pyrazolone, acylacetic acid amide, aminopyrazole and oxy or aminoquinoline series. From the large number of usable components the following may be mentioned in extracts: 1-phenyl-S-methyl-S-pyrazolone and those in the phenyl nucleus z. B. by the substituents mentioned on page 5 substituted derivatives, 1-phenyl - 5 - pyrazolone - 3 - carboxylic acid and their esters, especially the esters with lower aliphatic alcohols, and the derivatives further substituted in the phenyl nucleus, eg. B. the 3'- or 4'-carboxyphenyl compounds, 1 - phenyl - 3 - methyl - 5 - aminopyrazole and the derivatives further substituted in the phenyl nucleus, z. B. 3'- or 4'-carboxyphenyl compounds, acetoacetic acid alkyl, aralkyl and arylamides, as well as those on the aralkyl and aryl radicals z. B. by - COOH groups further substituted derivatives, a- and / J-naphthylamine and those in the naphthyl nucleus

z. B. by —COOH further substituted derivatives, a- and / 9-naphthol and the derivatives further substituted in the aryl nucleus, such as in particular 2,3-oxynaphthoic acid and its core substitution products, 8-oxyquinoline, aniline derivatives such as alkyl, aralkyl and / or aryl substituted anilines or their core substitution products, e.g. B .:

1 -HN-dimethylamino-S-aminobenzene,
1 -N ^ -Diethylamino-S-aminobenzene,
lN, N-Di - ^ - cyanäthylamino-3-aminobenzene, 'l- ^ N-Di-zS-oxyathylamino-S-aminobenzene,
lN, N-di- / 3-oxyethylamino-2-methoxy or
-2-ethoxy-5-amino benzene,

209 547/475

lN-methyl-N-ethylamino-3-aminobenzene,
1 -N - ^ - cyanoethyl-N-jS-oxyäthylamino-3-amino-

benzene,

lN-ß-cyanoethyl-N-methyl- or
-N-ethylamino-3-aminobenzene,
lN-ethyl-N-ßy-dioxypropylamino - ^ - methoxy-5-aminobenzene,

lN.N-Di-jS-oxypropylamino-S-aminobenzene,
lN-, 5-cyano- / 3- (trifluoromethyl) -ethylamino-

3-aminobenzene,
lN - /? - Hydroxy- / S- (trifluoromethyl) -ethylamino-

3-aminobenzene,

1-amino-l ^ -dimethoxybenzene,
l-amino-2-methyl-5-methoxybenzene,
l-amino-2,5-dimethylbenzene,
1-aminobenzene,
1-amino-2-methoxybenzene,
1-amino-2-methylbenzene,
1-amino-3-methoxybenzene,
l-amino-3-methylbenzene,

also the coupling components of the formula

alkylene-COOH

NHAc

the French patents 791 119, 847 706, 1 213 082, 1255 348 and 1262 441 and the USA patents 2 195 974, 2 051 004 and 2 921 945.

Suitable anthraquinone dyes are, for. B. those in which one or more carboxyl groups in the Anthraquinone molecule itself or in aryl or alkyl radicals that are linked to the anthraquinone molecule via bridges such as amino, ether, thioether, Sulfonamide or sulfonylamino groups are linked. The anthraquinone compounds can, for. B. who have the constitutions shown in the following table:

O NH,

COOH

O NH ₂
O OH

COOH

Ac = OCCH ₃ , OCCH ₂ CH ₃ , OC (CH ₂ ) "COOH,

OCCH = CH-COOH
η = integer

where R _{6 is} hydrogen, alkyl or alkoxy and R _{4 is} hydrogen or a substituent, such as 1- (N-methyl- or -ethyl- or -propyl- or - isopropyl - N - β - carboxy -, - carboethoxy - ethyl) -amino-3-aminobenzene and the derivatives further substituted in the 6-position by methyl or methoxy, 1 - N, N - di - (ß - carboxyethyl) - amino - 3 - aminobenzene ^ ₀ and those in the 6-position by methyl, Methoxy or ethoxy further substituted derivatives, 1- (N- / S-cyanoethyl or - / 3-chloroethyl-N- / S-carboxyethyl) -amino-3-aminobenzene and the derivatives further substituted in the 6-position by methyl or methoxy, furthermore 1- (N -β -Methoxy- or -ethoxy- or -propoxycarbonyloxyethyl) -amino-3-aminobenzene and the derivatives further substituted in the 6-position by methyl or methoxy, lN, N-di - (/? - methoxy- or - ethoxy or -propoxy-carbonyloxyethyl) -amino-3-aminobenzene and the derivatives further substituted in the 6-position by methyl or methoxy, 1- (N- £ -cyanoethyl- or - / I-chlorine ethyl-N-iS-methoxy- or - ethoxy - carbonyloxyethyl) - amino - 3 - aminobenzene and the derivatives further substituted in the 6-position by methyl or methoxy.

Azo dyes containing carboxyl groups of these constitutions and other structures as well as carboxyl group-containing dyes Anthraquinone dyes and condensation products of the latter and those containing carboxyl groups Dyes of other classes are described in numerous patents. Excerpts please refer to the following patents: German patents 261 885, 433 848, 455 823, 502 554, 638 835, 654 615, 677 860, 695 033, German patents

1048 374, 1117 233, German publications

1049 821, 1143481 and 1156525, the Swiss Patent 154,707, British Patent 794,177, -COOH

Cl Y VcOOH

-COOH

O NH,

NH

COOH

O NH ₂
O NH,

COOH

COOH

O NH,

9 NH ₂

O NH ₂ acylation products of aminoanthraquinone with ίο

COOH

^C1

Cl (OH, NH ₂ , NH-alkyl)

b) HOOC - \ "^>

SO ₂ -Cl

c) HOOC — X — COOH X = aryl, alkyl, heterocyclic.

O NH ₂

Alkyl (aryl)

O NH ₂ HO O OH

H ₂ NO NH ₂ O NH ₂

H ₂ NO OH O NH ₂

20th

35

40

45

55

6o

HO O NH -CH, ■ CH, ■ OH

HO O NH-CH ₂ • CH ₂ • OH H ₂ NO NH ₂

HO O NH ₂

HO O NH ₂

H ₂ NO NH ₂ H ₂ NO NH ₂

H ₂ NO NH ₂ O OH

O NH ₂ O OH

NH,

Q oh;

O NH,

O NH

NH ₂ / or NI

ο NH,

O OCH ₃

^Alk y!

O NH,

HOOD · MlV - S - I ^ V - HN

HOOD · MlV - l ^ V - HN

HOOD · MlV - O -1 ^ JV - HN

HOOD-I ^ V-HN

HOOD-I ^ V -S

HOOD - ^ - ¹ VO

HOOD-MlV-HN

X.

XX

HOOD-MlV-S

HOOD-MlV - O

HOOD-MlV

continuation

Among the anthraquinone condensation products containing carboxyl groups, which have more than three fused-on 45 rings, for example, the following be mentioned:

N-S '

Pyrazole anthrones, such as

N-NH

X O

55

- ■ ■ ■ ■■ '' (NH ₂ ) O ₂ NO OH
ι υ ι ■. yl ■ COOH Jkyl-COOH lkyl • COOH Ukyl ■ COOH _t ryl · COOH ryi · COOH Aryl COOH X X
O X ί ty- -AIk - ^.
I. I. X I. I. I.
X O O
υ O i T
HO ( I. O Z O m Z O
υ <
< COi / 6 ilkyl lkyl IT ■■. . ■
3 X X X X Aryl - 0 - A >>
t Aryl-S-A HO O OH
I Ρ ι I.
X C. I.
EC (X Z Z X X X X X ■ ■%. ' lii
H ₂ NO NH ₂ H ₂ NO OH
1 P ι X X X (Y X X X V- XH III
HO O NH ₂

S-alkyl-COOH, NH-alkyl-COOH, X S-aryl-COOH, NH-aryl-COOH

X O

S —alkyl —COOH, NH-alkyl —COOH, S-aryl-COOH, NH-aryl-COOH

N-S

COOH

60

65

N-N

CO NH

COOH

209 547/475

also the dyes of the type

HOC

N-CH,

X O

O = C

C = O

3 °

O X

S - alkyl - COOH, NH-alkyl - COOH, S-aryl-COOH, NH-aryl-COOH

O O

/ Cv-CX O NH

X = NH - alkyl - COOH, O - aryl - COOH, NH-aryl-COOH

COOH

Anthraquinone dyes of the formulas given are made according to those known in anthraquinone chemistry Construction principles shown. For this purpose, condensation reactions are primarily used suitable starting products in question. So you can z. B. amino-containing anthraquinone compounds, in which the amino groups are either in ^

external, but preferably in the nucleus-bound position, with suitable carboxyaryl acid halides or anhydrides, e.g. B. carboxyphenyl or carboxynaphthyl sulfonic acid or carboxylic acid chlorides or condense bromides to the corresponding acid amides or z. B. Anthraquinone compounds with mobile halogen atoms, such as 1-amino or 1-subst. Amino-4-bromoanthraquinone-2-sulfonic acids, with carboxyarylamines, such as carboxyphenyl or carboxynaphthylamines to the ι implement corresponding carboxyarylamino-anthraquinone derivatives. According to similar construction principles one can produce anthraquinone ether and thioether derivatives in which carboxy groups are contained in alkyl, aralkyl or aryl radicals of the ether or thioether component. Another Possibility of building up carboxyl group-containing anthraquinone dyes to be used according to the process is also due to the fact that anthraquinonic acid

halide, such as carboxylic acid and sulfonic acid chlorides or bromides, with suitable amino or oxy compounds, which additionally have at least one carboxylic acid group into the corresponding Amides or esters converted. Of course, such anthraquinone compounds can also be used for the The present processes are used in which one or more carboxyl groups are bonded to the nucleus or in which both core and externally bonded carboxyl groups are present.

Suitable azaporphine dyes containing carboxyl groups are synthesized, for example, by condensation of metal phthalocyaninesulfonic acid halides, in particular copper and nickel-Pc-sulfonic acid halides, or of chloromethyl-substituted phthalocyanine dyes with aminoaryl carbon acids, aminoaralkylcarboxylic acids or aminoalkylcarboxylic acids.

Diarylamine dyes containing carboxyl groups are also produced by condensation of suitable starting compounds, such as carboxyarylamines.

As mentioned earlier, the printing paste can be next Dye and volatile amine or a compound releasing such an amine in connection with alkaline agents, if necessary, also contain other auxiliaries, such as highly condensed sodium salts Naphthalenesulfonic acid - formaldehyde - resins, sulfite cellulose waste liquor products, condensation products from higher alcohols with ethylene oxide, polyglycol ethers from fatty acid amides and alkylphenols, Sulfosuccinic acid ester or turkey red oil.

Fully synthetic and semi-synthetic fiber materials can be produced by the method according to the invention various types of printing. The process is gaining particular interest for printing of fiber fabrics made from aromatic polyesters, in particular polyethylene terephthalates and polyesters from terephthalic acid and 1,4-bis-hydroxymethyl-cyclohexane as well as cellulose triacetate. Particularly favorable results will be obtained on these materials achieved. The prints obtained are distinguished by good general fastness properties and are im

ίο Comparison with prints made using the dispersion printing method with the carboxyl group-containing dyes in the form of the free acid or its sodium salts are performed, distinguished by better levelness, sublimation and rubbing fastness of the

Coloring. example 1

A printing paste is made from the following components set:

20 parts by weight of the monoazo dye
^ Nitro - ^ - chloro-1 -aminobenzene - »N, N-Di- £ -carboxyäthylaminobenzol,
30 parts by weight of diethylene glycol,
20 parts by weight of soda,
40 parts by weight of ammonium chloride,
400 parts by weight of crystal rubber thickening,
490 parts by weight of water.

1000 parts by weight

This printing paste is used to create a fabric made of polyethylene terephthalate printed in the usual way on a film printing or roller printing machine and Steamed for 30 minutes at 1.5 atmospheres. An excellent wet and sublimation fast red print is obtained.

Example 2 With a printing paste made from the following components

20 parts by weight of monoazo dye

(HOOC-CH ₂ -CH ₂ ) ₂ -

= N-C C -C COOCH ₃

HO-C

20 parts by weight of soda,

40 parts by weight of ammonium nitrate,
400 parts by weight of locust bean gum ester,

30 parts by weight of thiodiethylene glycol,
490 parts by weight of water.

1000 parts by weight

a triacetate fabric is printed in the usual way and treated (fixed) for 40 seconds at 200 to 220 ° C. A wet, sublimation and lightfast yellow print is obtained.

Using the dyes shown in the following table in the procedure of this example a, the azo dyes each obtained by coupling a diazo component of column 1 with a coupling component of column 2 and optionally renewed diazotization and coupling with an azo component from the 3rd column, valuable prints are likewise obtained on aromatic ones Polyesters in the specified colors.

Diazo component 1. Coupling component 2. Coupling
component hue l-amino-5-nitro-
benzene-2-carbon
acid l-phenyl-S-pyrazolone-S-carboxylic acid - yellow

continuation

Diazo component 1. Coupling component * ·. 2. Coupling
component hue 1 -amino-2-chloro- ^ -Oxynaphthalene-S-carboxylic acid . Red benzene-5-carbon acid 1-amino-3-methylbenzene 4-chloro-3-amino- N, N-pi - (/ S-oxyethyl) -3-methylaminobenzene - Reddish benzoic acid ■ - - yellow S-chlorine ^ -amino- N, N-di- (| S-oxyethyl) -3-methylaminobenzene 3-methyl-N, N-di- / S-oxyethylaminobenzene - Red benzoic acid 4-chloro-3-amino- N, N-di (/ S-oxyethyl) aminobenzene - Reddish benzoic acid 1 -! ^, N-di-iS-oxyethylamino-S-methylbenzene yellow 3-nitro-amino N, N-di (/ 3-carboxymethyl) aminobenzene ■ -; Reddish benzoi yellow 5-chloro-2-amino- N, N-di- (jS-oxyethyl) aminobenzene scarlet benzoic acid 4-nitro-2-carboxy-
1 -aminoben7ol N, N-Di - (/ 5-oxyethyl) -3-methyl-1-aminobenzene ■ - violet X> U.JIXXJLAJIV1 / LZvIl ^ V /!
4-nitro-2-carboxy- l-phenyl-S-pyrazolone-S-carboxylic acid - Reddish 1-aminobenzene yellow 4-nitro-2-carboxy- N ^ -Di - ^ - cyanäthyty-aminobenzol . - - Red 1-aminobenzene ¹ chlorine a nitro- · - ■ '■■' OCH ^ CH ^ OOCCH = GHCOOH Red 1-aminobenzene v_ / \. ,
OCH ₂ CH ₂ OOCCH = CHCOOh 4-chloro-3-amino-
hen 7oe *? äiirfi 1- (3'-carboxy) phenyl-3-methyl-5-pyrazolone - yellow UwllbvwOCl VtX ^
4-aminobenzoic 1- (3'-carboxy) phenyl-3-methyl-5-pyrazolone yellow acid methyl ester 4-aminobenzoe-. 1- (3'-carboxy) phenyl-3-methyl-5-pyrazolone - yellow acid 4-aminobenzoic 1 - (S'-Carboxy ^ '- chlorJ-phenyl-S-methyl- ■ yellow acid methyl ester 5-pyrazolone 5-amino-1,2,4-tri- N, N-di (/ cyanethyl) aminobenzene - yellow azole-3-carbon acid 3-aminobenzoic 1-amino-2,5-dimethoxybenzene 1-carboxy Brown acid 2-oxybenzene 4-nitro-2-cyano N, N-Di - (/ 3-carboxyethyl) -2-ethoxy-5-acetamino- - Navy blue 1-aminobenzene 1-aminobenzene 2,4-dinitro-6-bromo N, N-Di - (^ - carboxyethyl) -2-ethoxy-5-acetamino- - Greenish 1-aminobenzene 1-aminobenzene blue 4-aminophenoxy 1-amino-3-methylbenzene Oxybenzene Yellowish tinge acetic acid orange 4-nitro-2-carboxy- N, N-di (/ 3-oxyethyl) aminobenzene - violet 1-aminobenzene 1 -amino-3-carboxy- Aminobenzene N, N-Di- / 3- Red-brown 4-oxybenzene oxyethyl aminobic zol 1 -amino-4-phen- 1-oxybenzene orange oxyacetic acid 2-carbon acid l-amino-2,4-di- - ■ Reddish nitrobenzene blue 6-carboxylic acid l-amino-2-chloro Reddish benzene-5-carbon orange acid

23

24

Diazo component Coupling component hue 3-phenyl-5-amino-thiediazole- (1,2,4) l-dimethylamino-3-glutaraminobenzene Red-brown 4-aminoazobenzenesalicylic acid Dioxethyl-m-toluidine Red-brown 2-amino-3,5-dinitrobenzoic acid Dioxethyl-m-toluidine Blue violet 4-aminobenzoic acid Phenyl-methyl-pyrazolone yellow 2-Amino-5-nitro-benzonitrile ■ 3,3'-aniline dipropionic acid Red 2,4-dinitraniline 3,3'-aniline dipropionic acid Red-brown 2-amino-5-nitro-benzoic acid l-diethylamino-3-acetaminobenzene violet 2-amino-5-nitro-benzonitrile l-methoxy-2-dioxyethylamino-4-glutar-
flmiTiobiT! 7nl blue 2-amino-5-nitro-benzonitrile Dioxyethylaniline bis-glutaric acid half-ester Bluish red 3-aminobenzoic acid Phenyl-methyl-pyrazolone yellow 3-amino-4-methoxy-benzoic acid Phenyl-methyl-pyrazolone yellow 4-aminobenzoic acid 3-aminophenyl-methylpyrazolone yellow 2-chloro-4-nitroaniline 3,3'-anilino-dipropionic acid Red 2-amino-5-nitro-benzonitrile l-methoxy-2-amino-bis-propionic acid violet 4-methylbenzene 2-chloro-4-nitroaniline .3,3'-m-Toluido-dipropionic acid Red 2,6-dichloro-4-nitroaniline 3,3'-anilino-dipropionic acid Brown orange 4-aminobenzoic acid p-cresol Reddish yellow 2-chloro-5-trifluoromethylaniline. 3,3'-anilino-dipropionic acid orange 2-chloro-5-trifluoromethylaniline 3,3'-m-toluido-dipropionic acid orange 2,6-dichloro-4-nitroaniline 3,3'-m-toluido-dipropionic acid Red-brown 2,5-dichloro-4-nitroaniline 3,3'-m-toluido-dipropionic acid Red 2-chloro-4-nitroaniline N-ethyl-anilino-3'-propionic acid Red 2-amino-5-nitro-benzoic acid N-atrryl-anilino-3'-propionic acid violet 2-amino-5-nitro-benzoic acid N-cyanoethyl-N-propionic acid aniline Red S-Amino-l ^ -triazole-S-carboxylic acid-azo- Dioxyethyl-m-toluidine Bordo 1 -methyl-i-amino ^ -methoxybenzene S-Amino-l ^^ - triazole-S-carboxylic acid-azo- Dioxethyl-m-toluidine Bordo amino hydroquinone dimethyl ether 2-amino _r 5-nitro-benzoic acid N-cyanoethyl-N-propionic acid-m-toluidine Red-violet 2-amino-5-nitro-benzonitrile l-ethoxy ^ -amino ^ -glutaraminobenzene violet 2-amino-5-nitro-phenoxyacetic acid N-cyanoethyl-N-propionic acid aniline Red 2-chloro-4-nitroaniline 3-anilino-mono-propionic acid Red 2-amino-5-nitro-benzonitrile 3-anilino-mono-propionic acid Red-brown 2-amino-4-chlorobenzonitrile 3,3'-m-toluido-dipropionic acid orange 2-amino-5-nitro-benzonitrile Dioxethyl-aniline-bis-phthalic acid half-ester violet 2-chloro-4-nitroaniline Dioxethyl-aniline-bis-phthalic acid half-ester Red 2-chloro-4-nitroaniline Dioxethyl-aniline-bis-glutaric acid half-ester Red-brown 2-chloro-4-nitroaniline Methyl-oxäthyl-aniline-glutaric acid half- Red ester 2-amino-4-chlorobenzonitrile Methyl-oxäthyl-aniline-glutaric acid half- orange ester 2-chloro-4-nitroaniline Methyl-oxäthyl-aniline-succinic acid half- Red ester 2-amino-5-nitro-benzonitrile 1-ethoxy-2-dioxäthyl-amino-4-acetamino-. blue benzene-bis-glutaric acid half-esters 2,4-dinitro-6-bromoaniline l-ethoxy-2-dioxäthylamino-4-acetamino- blue benzene-bis-glutaric acid half-esters

O OH

N — N — CH,

COOH

COOH

COOH

O OH

Greenish yellow

209 547/475

25th

H ₃ CO

C-COOH

Yellowish brown

0 O

NHCH ₇ CH ₇ COOH

O NHCH ₂ CH ₂ COOH

Prepared from the following paste:

Parts by weight

Parts by weight parts by weight parts by weight

Parts by weight

Parts by weight

ei s ρ i el 3

Components becomes a print

of the monoazo dye

2-amino-5-nitrobenzonitrile

-> aniline dipropionic acid,

Diethylene glycol,

30% ammonia water,

Ammonium chloride,

Crystal rubber thickening,

Water.

This printing paste is used to create a fabric made of polyethylene terephthalate printed in the usual way on a film printing or roller printing machine and Steamed for 30 minutes at 1.5 atmospheres. An excellent wet and sublimation fast red print is obtained.

B e4 s ρ i e 1 4

A printing paste is made from the following components:

20 parts by weight of the dye

O NHCH ₂ CH ₂ COOH

O NHCH ₂ CH ₂ COOH

20 parts by weight of 30% aqueous methylamine solution,

40 parts by weight of ammonium tartrate,
400 parts by weight of locust bean gum,

30 parts by weight of thiodiethylene glycol,
490 parts by weight of water.

1000 parts by weight

A triacetate fabric is printed with this printing paste in a known manner and treated (fixed) ^{at 200 to 220 ° C. for 40 seconds.} A wet-fast and sublimation-fast print is obtained.

Claims (2)

Patent claims: , 1. A method for printing fully synthetic and semi-synthetic fiber materials, characterized in that an aqueous printing paste is applied to the fiber materials containing a sparingly to insoluble free carboxyl groups in water and a sufficient amount of a volatile amine or ammonia to dissolve this dye or together with an alcoholic agent of such an amine or ammonia-releasing salt of an acid, which is able to convert the dye into the free carboxylic acid and optionally contains further auxiliaries, the printed material is temporarily dried and then ^{heated to temperatures of 150 to 230 0} C or with or without pressure dampens. 2. The method according to claim 1, characterized in that the printing paste on aromatic Polyesters, in particular polyethylene terephthalates or polyesters made from terephthalic acid and 1,4-bishydroxymethyl-cyclohexane, or applies to cellulose triacetate. ·