DE2634308A1 - REACTIVE DYES, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE FOR COLORING CELLULOSE TEXTILE MATERIALS - Google Patents

Description

PATENT LAWYERS

DR. -ING. H. FINCKE DIPL.-ING. H. BOHR DlPL-ING. S. STAEGER DR. Rer. nat. R. KNElSSL

8 MÖNCHEN S, Müllersiraße 31 Telephone: (089) '266060 Telegrams: Claims Munich Telex: 523903 cloim d

3 0. JUL11976

Folder 2406l ICI CASE Dd. 28086

IMPERIAL CHEMICAL INDUSTRIES LTD. London, UK

Reactive dyes, process for their production and their use for dyeing cellulose textile materials

Priority: 7/31/75 - Great Britain

The invention relates to new reactive dyes, in particular Reactive dyes which have a triazinyl group which has a quaternary substituent.

The invention relates to reactive dyes which, in the form of the free acid, have the formula:

709807/1 183

D-N'- C

I I

X (COOH)

where D is a chromophoric radical, R iHr is H or C ₁ , -alkyl, R is H, alkyl or substituted

2 1

Alkyl, R is substituted alkyl, or R and IT together are - _(CH2) ^ -, - (CHp) ₅ - or-CH ₂ CH ^ o.CH ₂ CH ₂ -, X a ~ below is a defined anion and η is 1 or 2.

The anion X ~ is any negatively charged entity, which serves to balance the positive charge on the Stickstoffaton in ¹ Formula (1). Thus X ~ can therefore be a separate anion, v / is eg Cl ", or be formed by an anionic group such as eg -GOO""or-SCu" which is bound to any part of the dye molecule.

The symbol D stands for a chromophoric residue of any of the dye series, such as the azo, anthraquinone, phthalocyanine, Formazan, nitroarylamine, oxazine, azine, triphenylmethane or xanthene series. The connecting nitrogen between the triazine nucleus and D itself is preferential to one Carbon atom bonded in D, which can form part of an aliphatic or cycloaliphatic radical, which but is preferably a carbon atom forming part of an aromatic ring. Preferred forms of D are chromophoric residues of the copper-plated monoazo or anthraquinone series.

R can be any Cj ^ -alkyl, such as η-butyl, n-propyl, Ethyl and especially methyl. However, R preferably represents H.

- 2 709807/118 3

Examples of alkyl groups R are n-octyl, n-hexyl, and in particular C / j _j, alkyl and especially methyl.

1 2

Examples of substituted alkyl groups R and R are hydroxyalkyl, such as β-hydroxyethyl and β-hydroxypropyl, sulfatoalkyl, such as, for example, β-sulfatoethyl, arylalkyl, such as benzyl, 4- or 3-sulfobenzyl, 3-carboxybenzyl, 2-phenylethyl, sulfoalkyl such as -CH ₂ .SCUH and -CH ₂ CH ₂ -SO _x H, carboxyalkyl, such as -CH ₂ CSH ₂ , COOH, cyanoalkyl, such as ß-cyanoethyl and ß-cyanopropyl, and alkoxyalkyl, such as y- Methoxypropyl, ß-lthoxyethyl uncj. ß-methoxyethyl.

1 2

In those cases where both R and R are substituted

Are alkyl, they can be the same or different.

Λ " 2
Preferred groups -KR R are those in which

(a) R ^{1 is} -H, -CH, or R ² and

R ^{2 is} hydroxypropyl or -CH ₂ CH ₂ Z, where Z is -OH,

-ClT, -COOH or -SO ₃ H;

R ^{1 represents} -H, -CH, or -CH ₂ CH ₅ and

R ^{2 is} - (CH ₀ ) - // ~% , where ρ is 1 or 2

and q is 0 or 1; or

(c) the group -ITR ¹ R ^{2 represents} N-horpholino, N- (ß-hydroxyethyl) -ßcarboxyäthylamino, N-pyrrolidino or IT-piperidino.

Λ 2
Particularly preferred groups -KR R are ß-Hydroxyäthylamino., Di (ß-hydroxyethyl) amino, ß-Carboxyäthylamino, ß-sulfoäthylamino, K-methyl-ß-sulfoäthylamino, benzylamino, 3- "and 4 ^ SuIf benzylaiaino and K- Morpholino.

It is preferred that η be 1, and it becomes very special it is preferred that the one carboxy group is in the 4 or, in particular, in the 3 position of the pyridinium ring.

709807/1 1 83

Particularly preferred dyes combine in sicii the above

1 2
added groups -IiS E and 3-Carb> oxypyridinium as substituents-

ten of the triazine nucleus.

Examples of the anion Σ "are halide, such as bromide and especially chloride. Ii" can also form part of an anion with more than one negative charge, such as 2.B. Sulfate. Such multiply charged anions will be associated with more than one positively charged pyridine group, at least in terms of their formula. X ~ will of course not exist as a separate atom or as a separate group if the positive charge on the pyridinium group is balanced by an anionic group on the same or a different part of the dye molecule, i.e. the dye molecule has a hybrid structure. For example, the -GOOH on the pyridinium nucleus could be ionized in -C00 ~, where it acts to compensate for the positive charge on nitrogen.

It is usually preferred that the dye form (1) is water soluble. The chronotshore rest D or any of the substituted alk2 / l groups R and / or 3 'are water-soluble containing making groups, especially carboxy and sulfonic acid groups,

It is clear that in order to further improve the solubility of the dye, the acid groups can be converted into their salts, in particular into alkali metal salts, especially sodium salts.

It should be further emphasized that, as with most ionic structures, it is usually not very useful to to assign any anionic group to any cationic group and that in solution the ions either essentially exist independently of one another or form aggregates that are determined by external factors, such as the pH-

709807/1183 ORIGINAL BATHROOM

Value of a solution containing the ionic material such as dyes of formula (1). Of course, the dyes in the solid form must contain groups that are necessary to ensure overall electrical neutrality. The anionic group, which is necessary to balance the positively charged pyridinium residue, can be formed by any of the acid groups of the dye or a salt thereof, ie that the molecule is in the form of a cvitterion _o This means that a separate anion X ~ in the formula (1) does not necessarily have to be present5 although the entire dye composition can contain anions. For example, the dyes of the same overall composition can be present as dyes in zwitterion form in admixture with sodium chloride or as the sodium salt of an acid group in the dye with the chloride of the pyridinium group. For the practical application of these dyes it is usually not necessary to know the exact ionic structure of the molecule.,

The invention further relates to a process for the preparation of reactive dyes of formula (1), which is carried out by using a triazinyl dye of the formula:

D-N- (Τ C - N "

RNN . .

with a pyridinearboxylic acid of the formula:

/ Tλ— (COOH) K

- 5 709807/1183

BAD ORlGlNAU;

"" Which converts its salt, v / whether ei D, R, R, K ~ and η have the above ■ ϊϋ5 · 3 (3-level meanings and Y stands for a substituent that can form an anion.

The above process can expediently be carried out by eating the triazinyl dye (2), usually in the form of a salt, if it contains acidic groups, and the pyridinecarbic acid (3) or its salt in an aqueous solution at 50 to 150 ⁰ G _1, preferably 80 to IQO ⁰ C, mixes. It is usually desirable to use the pyridinecarboxylic acid in the form of a 3 salt, in particular in the form of its sodium salt, and to keep the reaction mixture at a pH of M to 9, in particular 6 to Z c .

The sea active dye can usually be in the form of a salt, like ζe3. of a sodium salt, by any suitable one Process * such as spray drying or precipitation and filtration, to be isolated. The aqueous reaction mixture, soft iea. Containing dye of formula (1) can in some cases can be conveniently used for the preparation of dye liquids without prior isolation of the solid dye.

It is usually appropriate to use triazinyl dyes of the formula (2) in which X is -Br, -F, -SO ^ H and very particularly -Cl stands, whereby dyes of the formula (1) are formed, _ at least? form-wise _

where X / is Br, F ", HSO ^ or Cl. Other values for X "can be achieved by known metathesis reactions. However, since the ionic group X ~ usually exists independently in aqueous solutions, it is rarely worthwhile to to produce solid dyes in which X "is a special "v / ert on v / e, since it usually does not have the coloring properties and there also when a concentration of any particular anion in the dyeing liquid is desired is, this can usually be achieved more conveniently by

709807/1 183 BADORTG (NAl

2634301

that a suitable inorganic salt is added.

The triazinyl dye of the formula (2) for use in the above processes can be conveniently obtained by known processes, in particular by reacting cyanuric chloride in any order with a dye of the formula D-IT-H and with an amine of the formula HUE E, where D, R ₅

1 · 2
R and R have the meanings given above.

Examples of dyes of the formula D-IT-H are in particular

R dyes of the following classes:

wherein the anthraquinone nucleus can contain an additional sulfonic acid group in the 5- »6-, 7- or 8-position, V stands for a bridging group which is preferably a divalent radical of the benzene series, such as phenylene, diphenylene or 4,4 -'- divalent stilbene or a Azobenzolradikal is' and R is H or C ^ _-Z alkyl. It is preferred that V have one sulfonic acid group for each benzene ring present.

(II) monoazo compounds of the formula:

(5)

7 0 9 8 0 7/1183 '

wherein D- is a mono- or dicyclic aryl radical which is free from azo groups and groups of the formula -ITHS ^, where the group -MHR _{2 is} preferably bonded to the 6-, 7- or 8-position of the uaphthalene nucleus and wherein the monoazo compound can also contain a sulfonic acid group in the 5- or 6-position of the ifephthalene nucleus.

D ₂ can be a radical of the naphthalene or benzene series that is free of azo substituents, v; ie, for example, a stilbene, diphenyl, benzthiazolyphenyl or diphenylamine radical. This _s class also includes the related dyes in which the group of the formula -NER is not bound to the naphthalene nucleus but to a benzoylamino or anilino group which in turn is bound to the 6-, 7- or 8-position of the uaphthalene nucleus .

Particularly valuable dyes are obtained when Dp represents a sulfonated phenyl or ITaphthyiradical, and in particular one which contains a group of the formula -SC ^ H in the ortho position to the azo group. The Pheny! Radical can be further substituted, such as by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino radicals such as Acetylamino, and alkoxy radicals such as kethoxy.

(III) Disaz © compounds of the formula (5) »where B ^ is a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series and the ifephthalene nucleus is substituted by the group -ΙίΞΏ. ^ And optionally by sulfonic acid groups as in class (II) .

(IV) ΡΊοηο or disazo compounds of the formula:

D ₂ - N = N - D - NEH (6)

xtforin Dp stands for a radical, as it did above for the classes (II) and (III) was defined, and D, for a 1,4-phenylene-

709807/1183 ORIGINAL BATHROOM

or SuIfo-1,4-naphthylene or stilbene radical, it being possible for the benzene nuclei D ₂ ″ and D 1 to contain further substituents, such as halogen atoms or alkyl, alkoxy, carboxylic acid and acylamino groups.

(V) Kono or disazo compounds of the formula:

H - ν - D ₀ - N = N - ¹ K (7)

\ ²

where D ^ _{n stands} for an arylene radical, such as a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series, or preferably an at most dicyclic arylene radical of the benzene or pure eaphthalenes, and K stands for the radical of a naphtholsulfonic acid or the radical of an enolized or enolizable ketomethylene compound (such as for example an acetoacetarylide, 5-pyrazolone or 6-hydroxypyrid-2-one) which has the -OH group in the ortho position to the azo group. Dp preferably represents a benzene series radical which has a sulfonic acid group.

(VI)? Fono or disazo compounds of the formula:

D - N = N - K ₂ - NHR (8)

wherein D2 is a radical of such a kind as defined above for D ₂ in the classes (II) and (III), and E ₂ ^f ^ ^r is the radical of an enolisable ketomethylene compound (such as an acetoacetarylide or a 5-JPyr & .Zolon) which contains the group of the formula -OH in the er position to the azo group.

(VII) 1: 1 metal complex compounds, in particular 1: 1 copper complex compounds of dyes of the formulas 5i 7 "and 8 (in which D ₂ , K and K ₂ all have the meanings given), which have a metallizable group (for example a hydroxy,

- 9 709807/118 3

40

Lower alkoxy or carboxylic acid group) in the ortho position to Azo group contained in Dp.

(VIII) Phthalocyanine compounds of the formula:

Pc (9)

where Pc is the phthalocyanine nucleus, preferably a copper phthalocyanine nucleus, oo is a hydroxy and / or a substituted or unsubstituted amino group, V ^ j is a bridging group, preferably an aliphatic, cycloaliphatic or aromatic bridging group, and η is 1 , 2 or 3 stands.

(IX) Nitro dyes of the formula:

B _- - NH - B- - NHR.

where B ^. and Bp stand for monocyclic ^ aryl nuclei and the Nitro group in B ^, in ortho position to the group of For nel -UH- is located.

(X) Formazan dyes of the formula:

N NH

a ι

L 7 09807/1183

- 10 -

where M stands for Cu or Ni, A and B for single or inehr nuclear Aryl groups in which the bonds shown are in the ortho position lead away carbon atoms that are in relation to one another,

2
the group R for an optionally substituted hydrocarbon

2 group and one of the groups A, B and R is a group of

Formula -NH carries.
R ..-

(XI) nitrous oxide dyes of the formula:

.CH = CH-

/ ΓΛ

(12)

(SO ₇ H)

^(S0 3 ^H) »

where η and m are each independently 1 or 2.

(XII) triphendioxazine dyes of the formula:

Cl

_ IiH

where m is 0 or 1 and η is 0 or 1. (XIII) Phenazine dyes of the formula:

- 11 709807/118 3

(13)

v / orin n stands for 1 or 2, lP stands for optionally substituted C 1, ..- alkyl R ° represents optionally substituted G ^ ._ ^ - alkyl, optionally substituted Aralkyl or optionally substituted aryl and the bensol ring A ^ can be further substituted, for example

se by -Cl, -CH-. or -OCH ₅ .

Specific examples of compounds of classes (I) to (XIII) are the following:

In class (I)

1- Aziino-4- (4- '-aminoanilino) anthraquinone-2,2'-disulphonic acid, i-alino-4- (4 ·' -methylaminoanilino) anthraquinone-2,3 '-disulphonic acid and

1-Αΐαίηο-4- (3 '-amino-2 ¹ , 4', 6'-trimethylanilino) anthraquinone-2,5-disulfonic acid.

In class (II)

6-amino-1-hydroxy-2- (2'-sulfophenylazo) naphthalene-3-sulfonic acid,

8-Asiino-i-hydroxy-2- (2'-sulfophenylazo) naphthalene-3,6-disulfonic acid,

7-aaino-2- (2 ', 5'-disulfophenylazo) -1-hydroxynaphthalene-3-s sulfonic acid, -

7-methylamino-2- (2'-sulfophenylazo) -1-hydroxynaphthalene-3-sulfonic acid,

7-diethyianiino-2- (4'-methoxy-2 '-sulfophenylazo) -1-hydro2cynaphthalene-3-sulfonic acid,

8- (3'-AminobenzoylaEiino) -1-hydroxy-2- (2'-sulfophenylazo) naphthalene-3,6-disulfonic acid,

8-Amino-1-hydroxy-2,2 * -azonaphthalene-1 ', 3,5'16-tetrasulfonic acid »

6-Amino-1-hydroxy-2- (4'-acetylamino-2'-sulfophenylazo) naphthalene-3-sulfone acid,

6-Kethylamino-1-hydroxy-2- (4'-methoxy-2'-sulfophenylazo) naphthalene-3-sulfonic acid,

- 12 - 709807/1 183

S-amino-1-hydroxy-2-phenylazonaphthalene ~ 3, 6-disulfonic acid, 8-Ainino-1-hydroxy-2,2 '-azonaphthalene-1', 3 »6-trisulfonic acid, 6-aniino-1-hydroxy-2- (4'-methoxy-2-sulfophenylazo) naphthalene 3-sulionic acid,

8-Amino-1-liydroxy-2,2 '-azonaphthalene-i', 3 * 5 '-trisulfonic acid, 6-amino-1-hydroxy-2,2'-azonaphthalene-1 ', 3 »5'-trisulfonic acid, 6-methylamino-1-hydroxy-2,2'-azonaphthalene-1 ', 3 »5'-trisulfone

acid

7-Aiaino-1-liydroxyT-2,2 '-azonaphthalin-i', 3-disulfonic acid, 8-Amino-1-hydroxy-2- (4'-hydroxy-3 '-carboxyplienylazo) naphth.alin-3,6-disulfonic acid and

6-Amino-1-hydroxy-2 - (^ -'-hydroxy-3'-carboxyphenylazo) naphthalene-3,5-disulfonic acid.

In class (III)

8-Amino-1-hydroxy-2- {ji- '- (2 "-sulfophenylazo) -2' -methoxy-5 '-

methylphenylazo] naphthalene-3,6-disulfonic acid,

4,4'-bis (8 "-amino-1 ⁿ -hydroxy-3", 6 "-disulfo-2" -naphthylazo) -

3,3'-dinethoxydiphenyl and

6-Amino-1-hydroxy-2- [4 '- (2 "-sulfophenylazo) -2' -niethoxy-5 '-

methylphenylazou naphthalene-3,5-disulfonic acid.

In class (IV)

2- (4'-Ainino-2 '-methylphenylazo) naphthalene-4,8-disulfonic acid, 2- (4'-Ainino-2 ^l -acetylaminophenyla2o) naphthalene-5,7- ^> disulfonic acid,

2- (4'-Amino-2'-ureidophenylazo) naphthalene-3,6,8-trisulfonic acid ,

4-nitro-4 · - (4 "-inethylaminophenylazo) stilbene-2,2 · -disulphone acid,

4-nitro-4 '- (4 "-amino-2" -methyl-5 ⁿ - methoxyphenylazo) stiltene-2,2-disulfonic acid,

2- (4'-amino-2'-acetylaminophenylazo) naphthalene-4,8-disulfonic acid,

- 13 - 709807/1183

4-amino-2-methylazobenzene-2 ^! , 5'-disulfonic acid,

4- [4 '- (2 ^M , 5 "-Disulfophenylazo) -2', 5'-dimethylphenylazoj -1-

naphthylamine-8-5ulfonic acid,

4- Dl · '- (2 ", 5", 7 "-Trisulfonaphth-1" -ylazo) -2 ·, 5 · -dimethylphenyl-

aso] -i-naphthylamine-6-sulfonic acid,

4- [4 · - (2 ", 5", 7 "-TrISuIf onaphtn-1 ^{! I} -ylazo) -2 ·, 5 '-dimethylphenyl-

azoj -1-naphthylamine-7-sulfonic acid,

^ i- [4 '- (2 ", 5", 7 "-Trisulf onaphth-1" -ylazo) napnth-1 «-ylazo] -1 -

napiithylamin-e-sulfonic acid,

4_ [4 «- (2", 5 "-Disulfophenylazo) -6 ^f -sulfonaphtn-1-ylazo] -1-

naphthyl-amine-8-sulfonic acid and

4- Ri- '- (4 "-Sulfophenylazo) -2' -sulfophenylazo] -i-naphthylamine-6-

sulfonic acid.

In class (V)

1 - (2 ', 5'-Dicliloro - ^ -'- sulfophenyl) -3-methyl-4- (3 "-amino-4 ^{! 1} -

sulfophenylazo) -5-pyrazolone,

1- (4 ^l -Sulfophenyl) -3-carboxy-4- (4 - "- amino-3" -sulfoplienylazo) -5-

pyrazolone,

1- (2 · -Methyl-5'-sulfophenyl) -3-methyl-4- (4 "-amino-3" -sulfo-

phenylazo) -5-pyrazolone,

1- (2'-sulfophenyl) -3-methyl-4- (3 "-aiaino-4" -sulfophenylazo) -

5-pyrazolone,

4-Amino-4 '- (3 ^lt -iaetliyl-1 "-phenyl-4 -" - pyrazole-5 "-onylazo) stilbene-

2,2'-disulfonic acid,

^ -Arnino- ^ '- (2 "-hydroxy-3", 6 "-disulf O-I" -naphtliylazo) style>) en-

2,2'-disulfonic acid,

8-acetylamino-1-hydroxy-2- (3'-amino-4'-sulfophenylazo) naph-

thalin-3 »6-disulfonic acid,

7- (3-sulfophenylamino) -1-hydroxy-2- (4 '-amino-2' -carb oxyphenyl-

azo) naphthalene-3-sulfonic acid,

8-phenylamino-1-hydroxy-2- (4 '-amino-2' -sulfophenylazo) naph-

thalin-316-disulfonic acid,

- 14 - 709807/118 3

6-acetylamino-1-hydroxy-2- (5 '-amino-2' -sulfophenylazo) naphthalene-5-sulfonic acid,

6-ureido-1-hydroxy-2- (5 '-amino-2' -sulfophenylazo) naphthalene-3-sulfonic acid,

8-Benzoylamino-1-hydroxy-2- (5 '-amino-2' -sulfophenylazoNaphthalene ^ »6-disulfonic acid,

1 - (4 ', 8' -disulfonapiith-2 '-yl) -5-methyl-4- (5 "-amino-2" -sulfophenylazo) -5-pyrazolone,

1- (2 ^l -Sulfoplienyl) -3-carboxy-4- (5 "-amino-2 ' ^t -sulfophenylazo) -5-pyrazolone _t

1- (2 ', 5'v-Dicliloro-4 ¹ -sulfophenyl) -3-methyl-4- (5 "-amino-2" -sulfophenylazo) -5-pyrazolone,

5- (3'-amino- ^ '-sulfophenylazo) -4-2net] ayl-5-cyano-6-liydroxypyrid-2-one,

5- (3 '-amino-4' -sulf op! Ienylazo) -4-methyl-5-carbonamido-6-nydr oxy-IT-ethylpyrid-2-one ,.

5- (3 '-Amino-4-' -sulfophenylazo) - ⁱ l-methyl-6-hydroxypyrid-2-one, 5- (3 '-amino-4' -sulfophenylazo) -4-methyllyl-5- cyano-6-llydroxy-lί-iae tliylpyridon,

5- (4'-Amino-3 '-sulfophenylazo) -4-methyl-5-cyano-6-hydroxy-IT-ethylpyridone and

5_ (4 · -Amino-2 ', 5'-disulfophenylazo) -A- methyl-5-cyano-6-hydroxy-N-ethylpyridone.

In class (VI)

1- (3-aminophenyl) -3-methyl-4- (2, 5 -disulfophenylazo) -5- '

pyrazolone,

1- (3'-Aminophenyl) -3-carboxy-4- (2 · -carboxy-4- '-sulfophenylazo) -

5-pyrazolone,

4-Amino-4 '- [3 ^f1 -methyl-4 "- (2"', 5 " ^! -Disulfophenylazo) -1" -

pyrazol-5 "-onyl] stilbene-2,2'-disulfonic acid and

1- (3'-aminophenyl) -3-carboxy-4- [4 ^u - (2 "·, 5"'- disulfophenylazo) -

2 "-methoxy-5" -methylphenylazo] -5-pyi ⁱ azolon «

- 15 709807/118 3

In class (VII)

The copper complex of 8-alino ~ '1-hydroxy-2- (2 ^l -hydroxy-5' -

sulfophenylazo) naphthalene-3,6-disulfonic acid,

the copper complex of 6-amino-1-hydrox7-2- (2 ^l -hydroxy-5'-sul-

fophenylazo) naphthalene-3-sulfonic acid,

the copper complex of 6-amino-1-hydroxy-2- (2'-hydroxy- ^ ¹ -sul-

fophenyiazo) naphthalene-3,5-aisulphonic acid,

the copper complex of 8-amino-1, 1 '-dihydroxy-2,2'-azcnap3itlia-

lin-3, ^ ¹ , 6,6'-tetrasulfonic acid,

the copper complex of 8-ijnino-1-liydroxy-2-L ^z i- ^l - (2 ^!! -sulfophenyl- £ zo) ~ 2 '- "" nietlioxy- ^' -methylplienylazol naptithalin-3 »6-aisuli on-

acid,

the copper complex of 6-amino-1-hydroxy-2- [4 -'- (2 ", 5" - "USuI-f ophenylazo) -2 '-aiethoxy.-5' -nethylphenylazo] naphthalene-3,5-

disulfonic acid,

the copper complex of 1 - (3 '-amino-4 ·' -sulfophenyl) -3-2iethyl-4 - [4 "- (2" ', 5 "' -disulfophenylazo) -2" -2.et; hoxy-5 "-methylphenyla2o} -

5-pyrazolone,

the Eupfer complex of 7- ( ^/ <- ^l -aiaino-3 '-sulfoanilino) -1-h3rdrcxy-2- [4 ^t! - (2 "', 5'" - disulf ophenylazo) -2 "-methoxy-5" -methyIphenyl-

azojnaphthalene-3-sulfonic acid and

the copper complex of 6 - (- 4 -'- Aiaino-3 ^l -sulfoanilino) -1-hydroxy-

2- (2 "-carboxyphenylazo) naphthalene-3-sulfonic acid.

In class (VIII)

3- (3 '-Aittino-4-' -sulfophenyl) sulf aiayl-copper-phthalocyanine-

tri-3-sulfonic acid,

4- (3 '-amino-4' -sulfophenyl) sulfainyl-copper-phthalocyanine-

tri-4 ~ sulfonic acid and

3- (3'- or -4 -'- aminophenyl) sulfaiayl-copper-phthalocyanine-

3-sulfonamide-di-3-sulfonic acid.

- 16 - 09807/1 1 83

4-Amino-2'-nitro-diphenylamine-3,4 · '-disulfonic acid.

In class (X)

The copper complex of N- (2-hydroxy-5-sulfo-3-aminophenyl) -

N - (2'-carboxy-4'-sulfophenyl) -ms-phenylformazan,

the copper complex of IT- (2-hydroxy-5-sulfo-3-aininoph.enyl) -N (2'-carboxy-4 -'-sulfoph.enyl) -ins- (4 "-sulfophenyl) formazan, the copper complex of N- (2-IIydroxy-5-sulfophenyl) -N - (2 ¹ -

carboxy ~ V-aminophenyl-ms- (2 '' - sulfopnenyl) formazan,

the copper complex of N- (2-hydroxy-5-sulfophenyl) -N - (2'-carboxy-4'-aiiiinoph.enyl) -ms- (2 ^I! -chloro-5 "-sulfoplienyl) formazan, the copper complex of N- (2-hydroxy-5-sulfoplienyl) -N - (2'-

carbon oxy ^J 4 '- sul fophenyl) -ms - (4 · "- aminophenyl) f ο r ma ζ an,

the copper complex of N- (2-hydroxy-5-sulfophenyl) -N '- (2 ¹ -carboxy-4'-sulfophenyl) -ms- (4 "-amino-2" -sulfophenyl) formazan and the copper complex of 2T- (2-Carboxy ~ ⁱ f-aminophenyl) -N - (2 ^f hydroxy-4'-sulfonaphth-1'-yl) -ms- (2 "-sulfophenyl) formazan.

In class (XI)

4 ~ Amino-4 -'-nitrostilbene-2,2'-disulfonic acid

In class (XII)

2,9-diamino-6,1J-dichlorotriphenodioxazine-J t ^ O-disulfonic acid

and -1,3 »ΊO-trisulfonic acid,

2,9-2i- (4- ^l -aiainoanilino) -6,13-i.e., chlorotriphenodioxazine-3,3 ', 3 "» 5,1O-pentasulfonic acid and -3,3', 3 ", 5 ', 5 ", 1O-hexasul-

fonsäure,

2,9-di (2 '-amino ethylamino) -6,13-dichlorotripb.enodioxazine-

1,8-disulfonic acid and

2,9-Di- (5 '-aminoanilino) -6,13-dichlorotriplienodioxazin-2 ^f , 2 ", 3> 4 -', iO-pentasulfonic acid and -2 ', 2", 3,4', 4 ", 1O-hexa-

sulfonic acid.

In class (XIII)

Anhydro-9- (4— amino-3-sulfoanilino) -5-anilino-7-phenyl-4— sulfo- or -2,4- or 4,11-disulfobenz [a] phenazinium hydroxide,

709807/118 3 - 17 -

Anhydro-9- (4 ~ amino-3-sulfoanilirio) -5-p-toluidino ~ 7-p-tolyl-2 _t 4-disulfobenz [a] phenazine hydroxide, anhydro-9- (4 · -amino-3- 3ulfoanilino) -5-P-'boluidino-7-p- ^ e'blioxypheny 1-2,4-di sulfob enz [a] phenanolium hydroxide, anhydro-3- (4-amino-3-sulfoanilino ) -7-N-ethyl-N- (3-sulfobenzyl) -amino-5- (2 -, - 3- or -4- sulfoplienyl) plienaziniuiii-hydroxide, aiihydro-3- (4 • -amino-3-sulf oanilino) -7-N-ätilyl-N- (3-sulfobenzyl) -amino-1-methyl- or -methoxy-5- (2-sulfopheri.yl) p3ienazini "Uiiihydroxid,

Anhydro-3- ( ² I-amino-3-sulfoanilino) -7 ~ N-ethyl-Ii- (3-sulfobenzyl) amino-5 - * ( ² * -chloro-, -methoxy- or -metliyl-3 -sulfophenyl) -phenazinitim-liydroxid and

Anhydro-5- (4-amino-2,5-d.isulfoanilino) -S-phenyl-10-sulf whether enz [a] phena zinium hydr oxide.

1 Examples of amines of the formula ENS S are:

Ethano lamin, diethanolamine, Isopropanolamine, diisopropanolamine, taurine,

IT methyl taurine, ß-alanine,

Benzylamine, 3- and 4-sulfobenzylamine, ß-Oyano-ethylamine, Di- (ß-cyanoethyl) amine, ß-phenylethylamine, R-Kethyl-benzylamine, N-ethyl-b enzy lamin, N-ethylethanolamine and N- (2-hydroxyethyl) -ß-alanine.

- 18 -

709807/1183

Examples of pyridinearboxylic acids of the formula (3) which can be used in the process according to the invention are: picolinic acid,
Nicotinic acid,
Isonicotinic acid,
Quinolinic acid,
Lutidic acid,
Cinchomeronic acid,
Dinicotinic acid,
Dipicolonic acid and
Isocinctiomeronic acid.

The dyes of the invention can be used for coloring a large A variety of textile materials can be used which have hydroxyl or amino groups, such as wool, silk, synthetic Polyamides and natural or regenerated cellulose, such as cotton or viscose rayon materials. Here you can the conventional methods of dyeing such materials with water-soluble reactive dyes can be used. For example in the case of cellulose, they are preferably used together with a treatment with an acid-binding gown, such as sodium hydroxide, carbonate, phosphate, silicate or bicarbonate. The acid binding agent can on the cellulosic textile material before, during or after Applying the dye can be applied. The method, technique and conditions used to apply the dye applied to the textile material depend on various factors, such as the nature of those present Fiber or fibers and the physical form of the textile material. For example, the methods depend on whether the fiber is spun in a loose or in a thread Form is present, the threads in turn wound in strands or on bobbins or by knitting or weaving into a garment or cloth

- 19 709807/1183 '

could be. Any of the usual methods of dyeing or printing can be used to apply the dye to the textile material. Other dyes and / or pigments can also be used simultaneously or in succession with the dyes according to the invention, such combinations of conditions being used as dictated by the properties of the dyes and / or pigments. Such mixed dyeings are particularly valuable when the textile material containing E or ITH _P groups is mixed with other textile fibers that are free from. are such groups, as is the case with polyesters. The dyeings can be carried out in batches, using, for example, exhaustion techniques in a tub, reel, jet, paddle or jig device, in particular for strands or woven or knitted fabrics or garments. This subheading also includes the "pack" dyeing techniques for fibers wound onto cylindrical or conical packages, bobbins or warp beams, especially when these carriers are perforated. Finally, this subheading also includes the dyeing of loose fibers in permeable containers such as cages, where pressure and / or vacuum can be applied to facilitate penetration and circulation through the package. Alternatively, continuous or semi-continuous dyeing processes can also be used, such as padding techniques, for example pad mangles being used. In this process, the textile material is impregnated with a dye liquid and then passed between hollen to bring the amount of liquid retained to a certain value, which is followed by one or more different post-treatments, such as drying, jigging or reel development, baking, steaming, renewed Padding in other solutions, such as acid-binding agents, as mentioned above, store in a moist state at room temperature

- 20 709807/1 183

or elevated temperature, passing over heated rollers or passing through continuous or intermittent washing procedures. These post-treatments can also include finishing stages. For example, antistatic or anti-wrinkle agents can be incorporated. Textiles in web form can can also be colored by textile printing processes, e.g. by printing with engraved or embossed rollers or by screen or transfer printing techniques such as wet transfer printing techniques. Details of this and others suitable printing methods are described in "The Principles and Practice of Textile Printing" by E. Knecht, J.B. Fothergill and G. Hurst, 4th edition 1952, ed. von Griffin, or in "An Introduction to Textile Printing "by W. Clarke, 4th ed. 1974-, edited by Fewnes Butterworth.

The dyes of the invention exhibit several advantageous properties and combinations of properties. they react with cellulose at low temperatures and / or using less basic acid-binding agents or smaller amounts of acid-binding agents than is the case with many other known types of reactive dyes. They are free from the unpleasant odors often associated with other quaternary triazinyl reactive dyes. They show a good leveling of fixation and color yield. The dyed textiles have good fastness to Light, wash and bleach treatments, and they resist discoloration from contact with liquids, especially with acidic or alkaline solutions.

A particular advantage of the dyes according to the invention is that they are used together with disperse dyes Can be applied to blends of cellulose and polyester fibers to color. The low level of alkalinity required to fix the present dyes is often not so great that difficulties, such as an aggregate

- 21 709807/1183

tion, occur with the disperse dyes when the two types are applied from the same dye liquid. In this regard, the dyes of the invention cut when compared with most other reactive dyes, the degree of alkalinity required for their fixation on cellulose is already so large that flocculation of the disperse dye takes place from the liquid, which leads to uneven coloring of the polyester fabric.

Another advantage of the dyes according to the invention lies in that they are in spite of their high reactivity towards cellulose fibers are relatively stable to hydrolysis and that they have a surprisingly good shelf life in dyeing liquids and own printing pastes.

The invention is illustrated in more detail by the following examples, in which all parts and percentages are expressed by weight are.

example 1

A solution of 16.5 parts of the tetrasodium salt of the copper complex of 8-amino-1,1'-dihydroxy-2,2'-azonaphthalene-3,4 ', 6,8'-tetrasulfonic acid in 150 parts of water is dissolved in an ice-cold suspension run in from 4 parts of cyanuric chloride, which has been prepared by pouring a solution in 20 parts of acetone onto 50 parts of ice. During and after the addition, the pH is kept at approximately 6.5 by adding a total of 20 parts of a sodium hydroxide solution in portions, the temperature being kept below 10 ^° C. If the pH remains constant, 2.35 parts of benzylamine are added and the mixture is stirred for 3 hours at 4-5 ° C, while 20 parts of an η sodium hydroxide solution are added as needed to maintain the pH at about 7. The solution

- 22 -

709807/118 3

is then poured into 800 parts of acetone, whereupon the precipitated dye is filtered off. The thus obtained Dye is dissolved in 250 parts of water, followed by a solution of 3 »73 parts of nicotinic acid in 20 parts of water, the has been neutralized with η sodium hydroxide solution, added will. The solution is heated to reflux for 10 hours, then cooled and poured into 800 parts of acetone. The unusual one blue dye is filtered off and dried.

In the following table are further examples of the invention Indicated dyes which can be obtained by the "method described in Example 1", however the 16.5 parts of the tetrasodium salt of the copper complex of 8-amino-1,1'-dihydroxy-2,2'-azonaphthalene, V, 6,8'-tetrasulfonic acid replaced by equivalent amounts of the dyes listed in column II and the 2.35 parts of benzylamine be replaced by equivalent amounts of the amines listed in column III. An equivalent amount of pyridinearboxylic acid, which is listed in column IV, replaces the nicotinic acid used in Example 1. Column V gives the colors obtained by a printing process using the obtained dyes.

- 23 709807/1183

TABLE I.

CD CO 00 CD

I.
at
game II III
■ J IV Y 2 Tetrasodium salt of copper com
plexes of 8 ~ amino-1,1'-dihydroxy
2,2'-azonaphthalenes ^ ', 6,8 · -
tetrasulfonic acid Horpholin Nicotinic acid blue 5 If Il Picolinic acid Il 4th Il It Isonicotin
acid Il 5 Il It Colinolic acid Il 6th If Il Lutidic acid Il 7th Il Il Ginchomerone
acid ti 8th It Il Dinicotinic acid Il 9 ti Il Isocinchomerone
acid 10 dd Ethanolainin Nicotinic acid ti 11 ti Sodium salt
of taurine Il It 12th Il Sodium salt
of N-methyl-
taurine It Il 13th Il DiethanoJ.amin It ti 14th ti Sodium ti Iz
from 4'-BuIfO-
benzylamine Il Il

CO 4> CO O

I.
at II It It III IV V game It 15th Pentasodium salt of the mixture of Il Ethanolamine Nicotinic acid black 1: 2 clirome and cobalt complexes Il of 2- (3'-nitro-6'-hydroxyphenyl- azo) -8-amino-1-naphthol-3 »6-di- It sulfonic acid (I. Disodium salt of 6-amino ~ 1- 16 Il hydroxy-2- (2'-sulfophenylazo) - Sodium salt Il It naphthalene-3-sulfonic acid of taurine 17th Disodium salt of 1-amino-4- Sodium salt It Il (2 ·, 4 ', 6'-trimethyl-3'-amino-5 · - of H-methyl- sulfoanilino) anthraquinone-2- taurine 18th sulfonic acid Morpholine Il Il 19th Diethanolamine It ti 20th Il Isonicotin Il acid 21 Ethanolamine ti blue 22nd Il Nicotinic acid Il 23 Sodium salt It It of taurine 24 Sodium salt Il Il of N-methyl- taurine 25th Il Il orange

CO O OD

I.
at
game II III IV V 26th Trisodium salt of 8-amino-1-
hydroxy-2- (2'-sulfophenylazo) -
naphthalene-3 »6-disulphonic acid Sodium salt '
of N-methyl-
taurine Nicotinic acid Red 27 Tetrasodium salt of 8-amino
1-hydroxy-2,2'-azonaphthalene
1 ', 3 * 5', 6-tetrasulfonic acid Benzylamine It It 28 Trisodium salt of 6-methyl-
amino-1-hydroxy-2,2'-azonaph-
thalin-1 ', 3 »5'-trisulfonic acid Sodium salt
of N-methyl-
taui «in Il orange 29 Il Ethanolamine It Il 30th Disodium salt of 8-amino-1-
hydroxy-2-phenylazonaphthalene
3,6-disulfonic acid Sodium salt
of N-methyl-
taurine dd Red 31 Disodium salt of 6-methyl-
amino-1-hydroxy-2- (4'-methoxy-
2'-sulfophenylazo) naphthalene
3-sulfonic acid ti H Scarlet fever 32 Trisodium salt of copper com
plexes of 8-amino-1-hydroxy-2-
(2'-hydroxy-3'-chloro-5'-sulfo-
phenylazo) naphthalene-3 »6-
disulfonic acid Il ti purple 33 Trisodium salt of copper com
plexes of 6-amino-1-hydroxy-
2- (2'-hydroxy-5'-sulfophenyl
azo) naphthalene-315- <iisulfonic acid e Il ti Ruby red 34 Trisodium salt of 2- (4 -'- amino-
2'-ureidophenylazo) naphthalene
3 * 6,8-trisulfonic acid Ethanolamine M. yellow

O ro co I. oo> O OO <*>

example

35
36
37

38
39
40

41

42

II

Disodium salt of 2- (4-amino-2-acetylaminophenylazo) naphthalene5 »7-disulfonic acid

Disodium salt of 4-nitro-4 '- (4'-methylaminophenylazo) stilben-2 _t 2'-disulfonic acid

Trisodium salt of 4- [4 '- (2 " _ί 5 ¹¹ -disulfophenylazo) -2', 5'-dimethylpnenylazo] -i-naphthylamine-8-sulfonic acid

Pentasodium salt of 4- [4 '- (3 ", 6", 8 "-trisulfonaphth-2" -ylazo) -6'-sulfonaphth .-' 1 '-ylazo] -1-naphthylamine-8-sulfonic acid

Disodium salt of 1- (2 ', 5'-dich.loro-4' -sulfophenyl) -3-methyl-4- (3 "-amino-4" -sulfop] ienylazo; ~ 5-pyrazolone

Trisodium salt of 1- (4'-SuIfO-phenyl) -4- (5 "-amino-4" -sulfoph.enylazo) -5-pyrazolone-3-carbon ~ acid

Trisodium salt of 1 ^ (3'-amino

phenyl) -3-methyl-4- (2 ⁿ , 5 ^ll -disul-

fophenylazo) -5-pyrazolone

Tetrasodium salt of 3- (3'-amino-4'-sulfophenyl) sulfamoyl-copper phthalocyanine-tri-3-sulfonic acid

III

Sodium salt of taurine

Sodium salt of N-methyltaurine

Ethanolamine

Sodium saltζ of N-methyl 1-taurine

Ethanolamine

IV

Isonicotinic acid

Nicotinic acid

Isonicotinic acid

yellow

yellow-brown

red-brown

yellow

turquoise

I.
Bex-
game II III IY V 43 Disodium salt of 4-amino-2'-
nitrodiphenylamine-3,4'-disulfone
acid Ethanolamine ' Isonicotinic acid yellow 44 Disodium salt of 2,9-di- (2'-
aminoethyl amino) -6,13-dich.loro-
triphen- dloxazin-1 _t 8-disulfone-
acid Sodium salt ζ
of! taurine Nicotinic acid blue 45 It Sodium salt
of N-methyl-
taurine ti Il 46 It It Isonicotinic acid ti 47 The trisodium salt of copper
complex of N- (2-hydroxy-5-
sulf o ~ 3- "arainophenyl) -N ^l - (2 '-
carboxy-4'-sulfophenyl) -ms-
phenylformazan ti Nicotinic acid dd 48 Il Ethanolamine ti Il 49 'üäs Dinatrium Salt Iron Anliydro-
3- (4'-amino-3'-sulfoanilino) -7 ~
N-ethyl-N- (3 "- sulf ob enzyl) amino« "
5- (4 "-sulfophenyl) phenazinium-
hydroxide dd dd ti 50 Sodium Sal25 of ^ - (J'-AminO ^ ¹ -
sulfophenylazo) -4-methyl ^M 5 " ^t
cyano-e-hydroxy-N-atiiylpyiidon Sodium salt
VÖin N * Methyl «·
• feäUriii il yellow 51 Disodium salt of * 1 «ΑΜίηο * 4 *"
(2 ', 4', 6 '-trimethyl-3' -äiüiiiiö-
5 '~ sulfoanilino) anthraquinone
2-sulfonic acid affiin Ii blue

I.
at
game II III IV V 52 Disodium salt of 1-amino-4—
(2 ', 4 ·', 6'-trimethyl-5'-amino-5'-
sulfoanilino) anthraquinone-2-
sulfonic acid ß-cyanoethyl ~ '
amine Nicotinic acid blue 53 H Isopropanolamine It Il 54 Il Diisopropanol
amine Il It 55 ·· Sodium salt of
ß-alanine π dd 56 It Sodium salt of
3-sulfobenzyl
amine Il Il 57 Il Di (ß-cyano ätlayl) -
amine Il It 58 Il N-methylbenzyl-
amine dd It 59 Il N-ethylbenzyl-
amine Il Il 60 Il N-methyl
ethanolamine Il It 61 It Sodium salt of
N- (2-hydroxy-
ethyl) -ß-alanine Il ti 62 It Pyrrolidine dd It

I.
at
game II III IV V 65 Disodium salt of i-amino-4—
(2 ', 4', 6'-trimethyl-5 ^L amino-
5'-sulfoanilino) anthraquinone
2-sulfonic acid Piperidine Nicotinic acid "blue 64 Il ß- (4 ~ sulfophenyl) -
ethylamine Il Il 65 Il ff-methy; L-ß- (4-
sulfophenyl) ethyl
amine Il Il

CJ) CO

CO O OO

Example 66

A mercerized cotton fabric is printed with a printing paste of the following composition:

4.5 parts of the dye of Example 18, 10.0 parts urea
30.3 parts of water

50.0 parts low viscosity sodium alginate thickener (10% solution)

1.2 parts of sodium hexametaphosphate, 1.0 part of sodium m-nitrobenzenesulfonate

2.0 parts sulfonated sperm oil / sulfonated pine oil

1.0 part sodium bicarbonate

100.0 parts'.

The dry printing is 6 min at a temperature of 175 ° C steamed.

The thickener, printing aid and unfixed dye are removed by subjecting the printing to the following wash treatment:

(a) 3 aain rinsing in cold water,

(b) 10 min boiling in a 2 g / l aqueous solution of an ioni ~ see biodegradable detergent at 100 ⁰ C,

(c) 1 aHn rinse in cold water.

The resulting printing shows a deep blue coloration, the is stable against hand washing and machine washing.

There is no deterioration in the behavior of the above printing paste found when it is stored ^{for 28 days at 20 ° C.}

- 31 709807/1183

Example 67

The procedure is as in Example 62, except for the printing 5 min at 102 ° 0 is steamed. Similar results are obtained.

Example 68

The procedure is as in Example 62 except that 3 parts of the dye from Example 2 are substituted for the 4.5 parts of the dye of Example 18 can be used.

The resulting printing shows a reddish-blue color.

Example 69

The procedure is as in Example 62, except that 2.5 parts of the Example 22 dye can be used in place of the 4.5 parts of Example 18 dye.

The resulting Bedrucianig has a bright blue color.

- 32 709807/1183

Claims (1)

PATENT CLAIMS t have, where D is a chromophoric radical ₉ R is H or C ^ -Alky! ₉ R stands for H, alkyl or substituted alkyl, R stands for substituted alkyl, or R and R together stand for <= · (CHg) ^ =, - (OHo) c- or - stand, ίΓ for one defined above Is anion and η is 1 or 2 ₀ 2. reactive dyes according to claim 1 _5, characterized in that D stands for a chromophoric radical of the copper-containing monoazo or anthraquinone series. 3. reactive dyes according to claim 1 or 2, characterized in that that R stands for H. 4 ·. Reactive dyes according to one of Claims 1 to 3, characterized characterized in that R represents H or methyl. 5. reactive dyes according to any one of claims 1 to 3, da- 1 2 characterized in that R and E are the same. 6. reactive dyes according to any one of claims 1 to 3 »da- Λ 2 characterized in that R stands for -H, -CH _Z odai · R ρ P and R is hydroxypropyl or -CH ₂ CH ₂ Z, where Z is -OH, -CN, -COOH or -SO ^ H. - 33 7 0 9 8 0 7/1183 Reactive dyes according to one of Claims 1 to 3 »characterized in that E stands for -H, -CH, or - and R stands for, _ ν Γ ~ Λ -ν.cn; 2 ρ where ρ is 1 or 2 and q is O or 1. 8. reactive dyes according to any one of claims 1 to 3, da- 1 2 characterized in that the group -UR R for N-Morpho- lino, N- (ß-hydroxyethyl) -ß-carboxyäthylamino, N-pyrrοlidino ^ N-Piperidino stands. 9 · reactive dyes according to one of claims 1 to 3 »da- Ί 2 characterized in that the group -NS R for ß-hydroxy- äthylamino, di (ß-hydroxyethyl) amino, ß-carboxyäthylamino, ß-sulfoäthylamino, F-methyl-ß-sulfoäthylamino, benzylamino, 3- or 4-sulfobenzylamino or N-morpholino. 10 * reactive dyes according to any one of claims 1 to 9, characterized characterized in that η stands for 1 and the carboxy group is on the 3- or 4-slope of the pyridinium ring is located. 11. reactive dyes according to claim 10, characterized in that that the carboxy group is in the 3-position of the pyridinium ring is located. 12. Reactive dyes according to one of claims 1 to 11, characterized in that they are in the form of an alkali metal salt exhibit. 13 · reactive dyes according to claim 12, characterized in that the alkali metal consists of sodium. Process for the preparation of the reactive dyes according to claim 1, characterized in that there is a triazinyl dye the formula: - 34 709807/118 3 263430! D-N- C ^ ^ G-N I 1 -H \ _H 2 .... (2) R N. N K- with a pyridine carboxylic acid of the formula? -f-V ' ^Cc00H) 2 1 2 or a salt thereof, where D, R, R, R and a have the meanings given in claim 1 and X represents a substituent which forms an anion can. 15 · Use of the reactive dyes according to claim 1 in common = sam with an acid-binding agent for dyeing CeIIn = loose textile materials « 16. Use according to claim 15 _S, characterized in that the textile material is a cellulose / polyester mixture o - 35 -709807/118 3