CA1109061A

CA1109061A - Salts of 1:2-metal-complex dyes free from sulphonic acid groups

Info

Publication number: CA1109061A
Application number: CA299,199A
Authority: CA
Inventors: Paul Lienhard
Original assignee: Ciba Geigy Investments Ltd
Current assignee: BASF Schweiz AG
Priority date: 1977-03-21
Filing date: 1978-03-17
Publication date: 1981-09-15
Also published as: GB1599812A; FR2384825A1; DE2811752A1; FR2384825B1; JPS53117026A; IT7821368A0; CH624981A5

Abstract

Case 3-11044/+
Canada SALTS OF 1:2-METAL-COMPLEX DYES FREE FROM SULPHONIC ACID
GROUPS

Abstract of the Disclosure Salts of 1:2-chromium- or -cobalt-complex dyes free from sulphonic acid groups of the formula wherein V1 is methyl and V2 is a group of the formula W being hydrogen, halogen, alkyl or alkoxy, or the group forms a group of the formula Q being alkyl or alkoxycarbonyl, X is hydrogen or alkyl, Y is hydrogen, halogen, alkyl or nitro, Z is -O- or -COO-, B is a basic xanthene dye, A is a primary or secondary aliphatic or cycloaliphatic amine having 8-25 C-atoms, L is alkylsulphonyl or sulphamoyl, q is 0, 1 or 2, m + n = 1, wherein m = 0.2 - 0.8 and n = 0.8 - 0.2 which are excellently soluble in organic solvents and especially suitable for dyeing the solutions of polymers.

- 1a -

Description

l~9~L

The present invention relates to new salts of 1:2-metal-complex dyes free from sulphonic acid groups, which consist of the reaction product of 1 mol of a 1:2-metal-complex of a monoazo dye, free from sulphonic acid groups, with 0.2 to 0.8 mol of a basic xanthene dye and 0.8 to 0.2 mol of an aliphatic amine, which salts are excellently suitable for dyeing solutions of polymers.
; In the Swiss Patent Specification ~o. 316,749, there is described the production of transformation products of azo dyes '~ free from sulphonic acid groups, and containing metal bound in complex linkage, with nitrogen-containing bases to form base salts of the metal-complex acid.
The German Patent Specification No. 1,043,548 describes : . , the production of transformation products of monoazo dyes free c from sulphonic acid groups and contai~ning metal bound in complex linkage, and which contain a sulphone group or sulphonic scid smide group, with basic xanthene dyes. ~`
~ The salts obtained by both of these processes have good i solubility in organic solvents, such as esters, acetone and alcohol, and are suitable in particular for the dope dyeing ~` of acetate rayon.
It has been found that, surprisingly, dye salts having ~
properties very greatly improved compared with those of the ~.
aforementioned dye salts, such as fastness to light, washing, water, perspiration, fats, solvents, cross-dyeing, milling, dry heat, dry cleaning, rubbing and ironing, and also higher "
;, :. '' P~ 9~ 1 adhesion, purity, colouring strength, brilliancy and solubility in organic solvents, are obtained by combining the azo dye, free from sulphonic acid groups and containing metal bound in complex linkage, both with the basic xanthene dye and with an amine to form the dye salt having two different cationic radicals.
The salts, according to the invention, of 1:2-metal-complex dyes free from sulphonic acid groups are described by the formula (1) [ ] n [ ] m wherein the Vl's, V2's? X's, Y's and Z's have identical or different meanings, whereby Vl is methyl, and V2 is a group of the formula~
~CONH ~
W
in which W is hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms, ç~

or the radical ~ 1 forms a group of the formula :: ~ Q
~0 N,N

in which Q is alkyl having 1-4 C atoms or alkoxycarbonyl having 2-5 C atoms, and W has the aforesaid meaning, X is hydrogen, or alkyl having 1-12 C atoms, . Y is hydrogen, halogen, alkyl having 1-12 C atoms or nitro, Z is an O atom or a -COO group, M is a chromium or cobalt atom, B is a basic xanthene dye, A is a primary or secondary, aliphatic or cycloaliphatic . amine having 8 to 25 C atoms, L ~ is alkylsulphonyl which is bound to a benzene ring and which has 1-4 C atoms, or is sulphamoyl which is bound to a benzene ring and which has the formula -S02NV3V4, in which V3 is hydrogen, alkyl having 1-12 C atoms, hydroxy-. alkyl having 1-4 C atoms or alkoxyalkyl having 3-14 C atoms, ~ and V4 has the same meaning as V3 or is cyclohexyl, phenyl, :: or phenyl substituted by halogen, alkyl or alkoxy having 1-4 C atoms, q is naught or the number 1 or 2, and the sum of m + n is the number 1, with m being 0.2 to 0.8, and n being 0.8 to 0.2.
Of particular interest are dye salts of the formula CH3 ~3 ~~

¦ ~ ~ N=N ~ ¦ ~ W ¦ [ B ] [ AB
~ ~ ~ t ~1 ~ CH3 wherein the W's are identical or different, A, B, X + M have the given meanings, Y is hydrogen, alkyl having 1-4 C atoms or nitro, W is hydrogen, chlorine, or alkyl having 1-4 C atoms, ~- L is alkylsulphonyl which is bound to a benzene ring and which has 1-4 C atoms, or is sulphamoyl which is bound to a benzene ring and which has the formula S02NHV3, in which ~: V3 has the given meaning, q is the number 2, '~ and the sum of s ., , .

,, , m + n is the number 1, with m being 0.4 to 0.6, and n being 0.6 to 0.4 B is preferably a basic xanthene dye of the formula R~ ~ ~ R4 (3) wherein Rl, R2, R3, R5 and R6 are hydrogen or alkyl having 1-4 C atoms, R4 is alkyl having 1-4 C atoms, R7 is hydrogen, halogen, carboxyl, sulphamoyl or alkoxycarbonyl having 2-5 C atoms.
The metal complexes of the formula 1 are obtained for example by reaction of chromium- or cobalt-releasing agents with the corresponding metallisable azo dyes in an alkaline medium. Examples of such metallisable azo dyes are coupling products from the diazo components and coupling components given in the following:
Diazo components

2-amino-4-alkylphenol, 2-amino-4,5-dialkylphenols, 2-amino-4-or -5-halophenols, 2-amino-4- or -5-nitrophenol, 2-amino-4-alkyl-6-nitrophenols, 2-amino-4- or -S-alkylsulphonylphenols, 2-amino-phenol-4- or -5-sulphonic acid àmide, 2-aminophenol-4- or -5-sulphonic acid alkylamides, 2-aminophenol-4- or -5-sulphonic acid alkoxyalkylamides, 2-amino-4-alkylsulphonyl-5-nitrophenol, 2-aminophenol-4-sulph-N,N-dialkylamides, 2-aminophenol-4-sulph-N,N-dihydroxyalkylamides, 2-aminophenol-4-sulph-N-alkyl-N-cyclohexylamides, 2-aminophenol-4-sulph-N-alkyl^N-phenylamides, 2-aminobenzoic acid, 2-aminobenzoic acid-4- or -5-sulphonic acid amide and 2-aminbbenzoic acid-4- or -5-sulphonic acid alkylamides.
CouPlin~ comPonents:
l-phenyl-3-alkyl-5-hydroxy-pyrazoles, l-(halophenyl-, alkyl-phenyl-or alkylsulphonylphenyl)-3-alkyl-5-hydroxy-pyrazoles, 1-(sulphamoyl-phenyl)- or l-(N-alkylsulphamoylphenyl)-3-alkyl-5-hydroxy-pyrazoles, acetoacetylphenylamide, acetoacetal-halophenyl-amides, -alkylphenylamides or -alkylsulphonyl-phenylamides or acetoacetyl-(sulphamoyl-phenyl)-amides.
In the ~iven diazo components and coupling components, the alkyl groups contain 1-4 C atoms.
Examples which may be mentioned of amines of the formula A
are primary or secondary aliphatic amines having 8-Z5 C atoms, such as 2-ethylhexylamine, dodecylamine, stearylamine, 3-dodecyloxy-propylamine, 3-(2'-ethylhexoxy)-propylamine, N-butyl-N-(2-hydroxypropyl)-amine, bis-(2-ethylhexyl)-amine or diiso-butylamine. Of particular interest are the products obtainable from Rohm and Haas Co. under the trade-mark of Primene 81-R ~
and Primene JM-T ~ . These are a mixture of amines corresponding to the formula R8 - ~ -NH2 (4) wherein R8, Rg and Rlo are alkyl groups together having 7-24 C atoms.

~3 ' i.
, Examples which may be mentioned of cycloaliphatic amines are dicycl.ohexylamine, dehydroabietylamine and 4,4'-diamino-dicyclohexylmethane.
The following may be mentioned as examples of xanthene dyes:

Rhodamin B C.I. 45170 Rhodamin 2G C.I. 45165 Rhodamin 3G0 C.I. 45215 - Rhodamin 4G C.I. 45166 Rhodamin 6G C.I. 45160 Rhodamin S C.I. 45050 Rosamin C.I. 45090 Saccharein C.I. 45070 ; C.I. Basic Red 8 C.I. 4515Q
C.I. Basic Violett 11 C.I. 45175 Violamin 3G C.I. 45195 ~: . . Spirit Fast Violet R C.I. 45185 ,.:~ . .
: ' : The numbers relate to the 3rd Edition of the Color Index.
The salts are formed advantageously by reacting 1 mol of a 1:2-metal-complex f~ee from sulphonic acid groups and corresponding to the formula .~ V2 X

wherein "Alk" is an alkali atom, for example a sodium or potassium atom, or the ammonium group, and the remaining symbols have the aforesaid meanings, in an aqueous, aqueous-organic or organic medium, in any desired sequence, with 0.2 to 0.8 mol of a xanthene dye B~ An , wherein "An" is an anion, for example chloride, sulphate or nitrate, and 0.8 to 0.2 mol of a salt of a primary or secondary, aliphatic or cycloaliphatic amine A having 8 to 25 C atoms.
Preferably, 1 mol of a 1:2-chromium complex or 1:2-cobalt complex, free from sulphonic acid groups, of the dye of the formula _ _ : ¦ Y H0 ~ ~ q (6) . , ~W.
wherein L, X, Y and W have the given meanings, and q is the number 1, is reacted with 0.4 to o.6 mol of a xanthene dye of the formula Rl ~ ~ 3 ~al R ~ \ R4 (7) ~ R7 wherein Rl - R7 have the given meanings, and "Hal" denotes halogen, especially chlorine, and with 0.6 to 0.4 mol of a -primary aliphatic or cycloaliphatic amine having 8-25 C atoms.
_ 9 _ The reaction is advantageously performed at temperatures of between 40 and 80C and at a pH value of below 7.
Particularly interesting dye salts are the reaction product from 1 mol of the 1:2-cobalt complex of the monoazo dye of OH
the formula CH
~ r~ ~ 3 (8) .. S02NH ~5 (CH ) OC~I(CI:~3)2 with 0.5 mol of Rhodamin B (C.I. 45170) and 0.5 mol of the primary aliphatic amine of the formula 4, wherein R8, Rg and Rlo : ` are alkyl groups together having 17 to 21 C atoms; and also the reaction product from 1 mol of the 1:2-chromium complex of the monoazo dye of the formula OH

N - N ~ 3 ~,, , . , ~
with 0.5 mol of Rhodamin B (C.I. 45170) and 0.5 mol of the primary aliphatic amine of the formula 4, wherein R8, Rg and Rlo are alkyl groups together having 11 to 13 C atoms; and the reaction product from 1 mol of the 1:2-chromium complex of the monoazo dye of the formula .
,; ..
.,. - 10-.
;

~9~

OH

CH3 (10) 02CH3 ~
~.
with O.S mol of Rhodamin ~ (C.I. 45170) and 0.5 mol of the primary aliphatic amine of the formula 4, wherein R8, R9 and Rlo are alkyl groups together having 17 to 21 C atoms.
The dye salts have very good solubility in alcohols, especially in lower alkanols, such as methanol, ethanol, n-propanol or iso-propanol, in alkylene glycol monoalkyl ethers, e.g. in ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, in alkylene glycols such as in propylene glycols, or in araliphatic alcohols such as in benzyl alcohol, or in mixtures of such alcohols. They are excellently soluble also in lower aliphatic ketones, e.g. acetone, methyl ethyl ketone, methylisobutyl ketone, or in cyclohexanone; also in carboxylates, e.g. methyl acetate, ethyl acetate, butyl acetate or glycol-monoacetate; and also in halogenated hydrocarbons, such as chloroform, methylene chloride, ethylene chloride or carbon tetrachloride. With respect to their solubility, the dye salts according to the invention are superior to similarly formed dye salts known hitherto.
On account of their good solubility in the aforementioned ketones, particularly acetone, the dye salts obtainable according ,. - 11 -.

?

to the invention are suitable for dyeing cellulose-2 1/2-acetate in the spinning solution; by virtue of their good solubility in halogenated, lower aliphatic hydrocarbons, particularly chloroform, they can also be used for the mass dyeing of cellulose triacetate.
Because of their good solubility in organic solvents, the new dye salts are especially suitable for dyeing the solutions of polymers, such as polystyrene or polyamide, particularly solutions of film-forming polymers. By solutions, containing alcohols, ketones and/or esters, of film-forming polymers are meant in this case in particular those liquid lacquers which are suitable for use in printing pastes for flexographic printing.
T'nese solutions contain as polymers for example natural resins such as shellac or Manila copal; or cellulose derivatives, for example cellulose ethers, such as ethyl cellulose or cellulose esters, such as nitrocellulose, also maleic resins or phenol-formaldehyde resins, which are preferably modified with -colophonium, such as the products described in the U.S.A. Patent Specification No. 2,347,923; polyamide resins, i.e. poly-condensation products of polyamines with polycarboxyl compounds, which are described, for example, in the U.S.A. Patent Specifi-cation No. 2,663,649; also formaldehyde-resin condensation products and formaldehyde-melamine condensation products, ketone-formaldehyde condensation products, polyvinyl acetates or polyacrylic acid resins, e.g. polybutylacrylate resin, or mixtures thereof.

~1~39~1 Furthermore, the solutions of film-forming polymers can also contain auxiliaries customary in the lacquer industry, such as wetting agents, e.g. higher fatty acid-bis-hydroxy-alkylamides, such as coconut oil fatty acid-bis-(-~-hydroxy-ethyl)-amide.
These solutions of film-forming polymers containing dye salts according to the invention are suitable, for example, for printing various materials, such as metal sheets, e.g.
aluminium sheets, paper, glass, synthetic resin sheets and films, and so forth. They are stable in storage and give on the stated materials waterproof coatings having good ,: .
adhesion.

~' ' .

., .

Example 1 A solution of 12.0 g of Rhodamin B (C.I. 45170) in 150 ml of water at 50C is added dropwise to a suspension (at 40C) of 51 g (O.OS mol) of the 1:2-cobalt complex of the azo dye formed from a diazotised 2-aminophenol-4-sulph-(3'-isopropoxy-propyl)-amide coupled with l-phenyl-3-methyl-5-pyrazolone in 1000 ml of water. The mixture is stirred for 1 hour, and to it is then added dropwise the solution of 8.2 g of Primene JM-T
(primary branched aliphatic amine with 18-22 C atoms (Rohm ~ Haas)) in 90 ml of water and 1.5 ml of formic acid. The mixture is subsequently rendered acid with 2 ml of formic acid to the extent that litmus paper is turned red; the mixture is stirred for a j further 5 hours, then filtered, and the suction-filter residue ` is washed with water. After drying in vacuo, the product weighs 64 g. It is very readily soluble in alcohols and ketones.
If solutions of the colorant and nitrocellulose in ethanol are used to print paper or aluminium sheets, red dyeings of excellent purity and high colouring strength are obtained.
Example 2 To a suspension of 42.2 g (0.05 mol) of the sodium salt of the 1:2-chromium complex of the azo dye formed from a diazotised 2-amino-S-ethylsulphonyl-phenol coupled with l-phenyl-3-methyl-5-pyrazolone in 1000 ml of water at 80C are successively added dropwise the solutions of 12.0 g of Rhodamin B (C.I. 45170) in 150 ml of water at 50C, and of 4.85 g (0.025 mol) of Primene 81-R (primary ' branched aliphatic amine with 12-14 C atoms (Rohm ~ Haas)) in 100 ml of water and l.S ml of formic acid. The pH value of the mixture is adjusted with 2 ml of formic acid to 3-4, and the mixture is stirred at 50C for 6 hours. The dye is then filtered off, thoroughly washed with water, and dried to yield 58 g of a red powder which is excellently soluble in acetone and in the solvent mixture methylene chloride/methanol 9:1.
Brilliant red fibres having good fastness to light, washing, water, perspiration, solvents, cross-dyeing, milling and dry heat are obtained by spinning, in the dry spinning process, the solution obtained by adding to a solution of cellulose-2,5-acetate in acetone 0.5% of the above dye, relative to the cellulose acetate, and stirring to obtain a homogeneous dispersion.
r Example 3 45.3 g (0.05 mol) of the sodium salt of the 1:2-chromium complex of the monoazo dye formed from a diazotised 2-amino-4-methylsulphonyl-5-nitro-1-phenol coupled with 1-phenyl-3-methyl-5-pyrazolone and 12.0 g of Rhodamin B (C.I. 45170) are dissolved in 300 ml of methylisobutyl ketone. To the solution are added dropwise 9.85 g of Primene JM-T (Rohm ~ Haas) and 1.7 ml of formic acid, and the whole is stirred for 1 1/2 hours at room temperature; the salts which havé precipitated are filtered off, ~; and the dye is obtained from the filtrate by concentration and drying in vacuo. There is obtained 65 g of a reddish-brown powder which is excellently soluble in acetone, ethyl acetate, ethylene g~

glycol and ethylene glycol monoethyl ether.
If the process is carried out in a manner analogous to that of Examples 1-3 except that there are used 0.05 mol of the 1:2-metal complex given in column II of the following Table, 12 g of Rhodamin B (C.I. 45170) and 0.025 mol of the amine shown in column III of the Table, there are likewise obtained readily soluble dye salts which, incorporated into nitrocellulose solutions, yield brilliant red printings on paper.

~' .

, ';

Table I II III
Ex. 0.05 mol of 1:2-M-complex (Na salt) 0.025 mol of amine No. of monoazo dye DH2 A

~ _ 4 4-nitro-2-aminophenol -~ Co Primene 81-R
l-phenyl-3-methyl-5-pyrazolone ditto Cr ditto 6 2-aminophenol-4-sulphamide -~ Co ditto 1-(3'-chlorophenyl)-3-methyl-5-pyrazolone 7 ditto Cr ditto 8 ditto Cr dicyclohexylamine 9 ditto Cr dehydroabietylamine 2-amino-4-chloro-5-sulphamoyl- Cr Primene 81-R
phenol -~ l-phenyl-3-methyl-5-pyrazolone 11 2-aminophenol-4-sulph-(3'-isopro- Co ditto poxypropyl)-amide -~ l-phenyl-3-methyl-5-pyrazolone 12 ditto Co 3-(2'-ethyl-hexoxy)-propylamine 13 ditto Cr Primene 81-R
14 ditto Co 2-ethylhexylamine ditto Co n-ethylcyclohexyl-amine 16 ditto Co dodecylamine 17 ditto Co 3-dodecyloxypropyl-amine 18 ditto Co stearylamine 19 ditto Co 0.0125 mol of 4,4'-diamino-dicyclo-hexylmethane ~ ~39~

I II III
Ex. 0.05 mol of 1:2-M-complex (Na salt) 0.025 mol of amin~
No. o~ monoazo dye DH2 A
. . _ . __ I

. . . _ 2-aminophenol-4-sulph-(3'-isopro- Co diisobutylamine poxypropyl)-amide -i~ l-phenyl-3-methyl-5-pyrazolone 21 anthranilic acid -i~ 1-phenyl-3- Cr Primene 81-R
methyl-5-pyrazolone : 22 4-nitro-2-aminophenol -~ 1-(3'- Cr ditto : sulphamoylphenyl)-3-methyl-5-pyrazolone : 23 5-nitro-2-aminophenol -~ Cr ditto l-phenyl-3-methyl-5-pyrazolone 24 5-sulphamoyl-2-aminophenol -~- Cr ditto l-phenyl-3-methyl-5-pyrazolone 25 2-amino-4-methylsulphonyl-phenol Cr ditto -i~ l-phenyl-3-methyl-5-pyrazolone 26 ditto Cr Primene JM-T
27 2-aminophenol-4-sulphamide -~- Co ditto acetoacetic acid anilide 28 2-aminophenol-4-sulph-methylamide Co Primene 81-R
-~ acetoacetic acid-2-chloro-anilide 29 ditto Co dehydroabietylamine ~30 ditto Co 3-(2'-ethylhexoxy)-propylamine , 31 ditto Co dicyclohexylamine 32 2-amino-4-methylsulphonyl-phenol Co Primene 81-R
acetoacetic acid-2,5-dimethoxy-anilide 33 2-aminophenol-4-sulphamide -~- Co -ditto ~: l-phenyl-3-ethoxycarbonyl-5-pyrazolone , I II III
Ex. 0.05 mol of 1:2 M-complex (Na salt) of 0.025 mol of No. monoazo dye DH2 amine A
- 2 __ ___ M

34 2-aminophenol-4-sulph-N,N-diethyl- Cr Primene 81-R
amide -~ 1-(4'-methylphenyl)-

3-methyl-5-pyrazolone 2-aminophenol-4-sulph-N,N-di- Cr ditto (2'-hydroxyethyl)-amide -~-1-(2'-chlorophenyl)-3-methyl-5-pyrazolone 36 2-aminophenol-4-sulph-N-methyl- Cr ditto N-cyclohexylamide -~- 1-(2'-ethyl-phenyl)-3-methyl-5-pyrazolone 37 2-aminophenol-4-sulph-N-ethyl-N- Cr ditto phenylamide -~- l-phenyl-3-methyl-5-pyrazolone 38 2-aminophenol-4-sulph-(3',4'- Cr ditto dimethylphenyl)-amide -i~ l-phenyl-3-methyl-5-pyrazolone 39 1:2-Cr-mixed complex of 2-amino- Cr ditto

4-nitrophenol - 1-phenyl-3-methyl-5-pyrazolone and 2-aminophenol-4-sulphamide -~-: ¦ l-phenyl-3-methyl-5-pyrazolone .

.

Example 40 To a suspension of 136 g of the sodium salt of the 1:2-Cr-complex of the azo dye formed from a diazotised 2-amino-4-methyl-sulphonyl-5-nitro-1-phenol coupled with 1-phenyl-3-methyl-5-pyrazolone in 1500 ml of water at 50C is firstly added dropwise the solution of 36 g of Rhodamin B in 400 ml of water at 60C, and then the solution of 30 g of Primene JM-T (Rohm ~ Haas) in 210 ml of water and 5 ml of formic acid. The weakly acid solution is stirred for 1 hour at 75C; the dye salt is subsequently filtered off, thoroughly washed with water and dried to yield 184 g of a reddish-brown powder having excellent solubili~y in ketones and acetic esters.
Likewise valuable colorants are obtained by using, instead of 36 g, 28.8 g and 43.2 g, respectively, of Rhodamin B, and, instead of 30 g, 36 g and 24 g, respectively of Primene JM-T, ;.
with otherwise the same working procedure.

Example 41 To a suspension of 45.3 g (0.05 mol) of the sodium salt of the 1:2-chromium complex of the azo dye formed from a diazotised 2-a~ino-4-methylsulphonyl-5-nitro-phenol coupled with l-phenyl-3-methyl-5-pyrazolone in 500 ml`of water at 50C are added dropwise the solutions of 6.35 g (0.015 mol) of Rhodamin G
(C.I. 45150) in 100 ml of hot water, and of 6.8 g (0.035 mol) of Primene 81-R (Rohm ~ Haas) in 150 ml of water and 3 ml of formic acid. The mixture producing an acid reaction is stirred ~ ~ 9~ ~ 1 for 1 hour and filtered; the suction-filter residue is washed with water and then dried. The dye salt produced in this manner is a brownish-red powder which dissolves at high concentrations in alcohols, ketones and carboxylates.
t Likewise readily soluble dye salts are obtalned in an analogous manner by using, instead of 6.35 g (O.OlS mol) of Rhodamin G, O.OlS mol of any one of the following Rhodamin dyes:
C.I. 45160, 45165, 45175 and 45210.
Example 42 To a suspension of 89 g (0.1 mol) of the sodium salt of the 1:2-chromium complex of the azo dye formed from a diazotised 2-amino-4-t-amyl-6-nitro-phenol coupled with 1-phenyl-3-methyl-S-pyrazolone in 500 ml of methylisobutyl ketone are added the solutions of 14.4 g (0.03 mol) of Rhodamin B in 200 ml of hot water, and of 14.3 g (0.075 mol) of Primene 81-R (Rohm ~ Haas) in 300 ml of water and 4 ml of formic acid. The mixture is then ; rendered acid to litmus; it is subsequently stirred for 10 hours at 50C and filtered. The filtrate is separated in a separating funnel; the ketone solution is washed twice with water and then evaporated to dryness. The residue weighs 110 g. It is excellently soluble in chloroform, acetone,~ethyl acetate and ethanol.
s~ Example 43 To a suspension (at 50C) of 44.3 g (0.05 mol) of the sodium salt of the 1:2-chromium complex of the azo dye formed from a diazotised 2-aminophenol-4-sulphamide coupled with 1-(3'--~ - - 21 -~V9~6~

chlorophenyl)-3-methyl-5-pyrazolone are added dropwise the solution of 4.8 g (0.01 mol) of Rhodamin B in hot water and the solution of 13.1 g (0.04 mol) of Primene JM-T in dilute formic acid. The reaction mixture producing an acid reaction is stirred for 1 hour; it is then filtered and the residue is washed with water. After drying, the product weighs 58 g.
Brilliant scarlet dyeings are obtained when solutions of the above dye salt and nitrocellulose in ethanol/ethyl acetate mixtures are applied to paper.
There is likewise obtained a readily soluble dye salt, which yields brilliant bluish-red dyeings, by using 19.2 g (0.04 mol) of Rhodamin B instead of 4.8 g (0.01 mol) thereof, and 3.3 g (0.01 mol) of Primene JM-T instead of 13.1 g (0.04 mol) thereof, the working procedure otherwise being as described in the preceding Example.

Example 44 20 g of the dye salt obtained according to Example 1, 30 g of bleached shellac free of wax, 5 g of dibutylphthalate and 45 g of ethanol are mixed together. There is obtained in this way a printing paste which has good storage stability and which is applicable for flexographic printing on paper sheets and on aluminium sheets. Brilliant, deeply coloured red printings having good adhesion are obtained using this printing paste on the said materials.

Example 45 10 g of the dye salt obtainable according to Example 1 is stirred into 90 g of a solution consisting of 25% of a spirit-soluble polyamide resin modified with esters, produced according to Example 7 of the U.S.A. Patent Specification No.
2,663,649, 2% of water, 5% of ligroin of the fraction 80-100C, 48% of ethanol and 20% of isopropanol. There is obtained a printing paste which dyes, in flexographic printing, Cellophane in a red shade of colour having good adhesion and a high degree of purity.
Example 46 . .
- 1.3 g of the dye salt according to Example 40 is sprinkled into 1000 g of a solution of acetylcellulose in acetone having a solids content of 26%. There is then added 20 ml of acetone, and the mixture in a well sealed bottle is rolled on a rolling device until the dye is completely dissolved. The dyed spinning solution is subsequently extruded through nozzles. The formed filament passes through a fairly long heated tube, and can then be directlyspooled. The dyed material displays a red shade and has excellent fastness properties, particularly fully satisfactory fastness to washing, water, cross-dyeing, dry cleaning, rubbing, ironing and light.

.
~ - 23 -' ~

,

Claims

1. Salts of 1:2-metal-complex dyes free from sulphonic acid groups and corresponding to the formula (1) wherein the V1's, V2's, Y's and Z's have identical or different meanings, whereby V1 is methyl, and V2 is a group of the formula in which W is hydrogen, halogen, alkyl or alkoxy having 1-4 C atoms, or the radical forms a group of the formula in which Q is alkyl having 1-4 C atoms or alkoxycarbonyl having 2-5 C atoms, and W has the aforesaid meaning, X is hydrogen, or alkyl having 1-12 C atoms, Y is hydrogen, halogen, alkyl having 1-12 C atoms or nitro, Z is an O atom or a -COO group, M is a chromium or cobalt atom, B is a basic xanthene dye, A is a primary or secondary aliphatic or cycloaliphatic amine having 8 to 25 C atoms, L is alkylsulphonyl which is bound to a benzene ring and which has 1-4 C atoms, or is sulphamoyl which is bound to a benzene ring and which has the formula -SO2NV3V4 in which V3 is hydrogen, alkyl having 1-12 C atoms, hydroxy-alkyl having 1-4 C atoms or alkoxyalkyl having 3-14 C atoms, and V4 has the same meaning as V3 or is cyclohexyl, phenyl, or phenyl substituted by halogen, alkyl or alkoxy having 1-4 C atoms, q is naught or the number 1 or 2, and the sum of m + n is the number 1, with m being 0.2 to 0.8, and n being 0.8 to 0.2.

2. A dye salt according to Claim 1 of the formula wherein the W's are identical or different and have the meanings given in claim 1, A, B, X + M have the meanings given in claim 1, Y is hydrogen, alkyl having 1-4 C atoms or nitro, W is hydrogen, chlorine, or alkyl having 1-4 C atoms, L is alkylsulphonyl which is bound to a benzene ring and which has 1-4 C atoms, or is sulphamoyl which is bound to a benzene ring and which has the formula SO2NHV3 in which V3 has the meaning given in claim 1, q is the number 2, and the sum of m + n is the number 1, with m being 0.4 to 0.6, and n being 0.6 to 0.4.

3. A dye salt according to claim 1, containing a xanthene dye of the formula wherein R1, R2, R3, R5 and R6 are hydrogen or alkyl having 1-4 C atoms, R4 is alkyl having 1-4 C atoms, R7 is hydrogen or halogen, carboxyl, sulphamoyl or alkoxycarbonyl having 2-5 C atoms.

4. A dye salt according to Claim 1, wherein A in the formula 1 is a primary aliphatic amine of the formula (4) in which R8, R9 and R10 are alkyl groups together having 7 to 24 C atoms.

5. A dye salt according to claim 1 of the formula wherein B is Rhodamine B (C.I. 45170), AB denotes a primary aliphatic amine of the formula (4) wherein R8, R9 and R10 are alkyl groups together having 17 to 21 C-atoms, and m and n are each 0,5.

6. A dye salt according to Claim 1 of the formula wherein AH, B, m and n are as defined in Claim 5.

7. A dye salt according to Claim 1 of the formula wherein AH, B, m and n are as defined in Claim 5.