KR100622456B1 - Azo dyes, their preparation and their use - Google Patents

Abstract

The present invention relates to azo dyes comprising at least one structural unit of formula (1).

Formula 1

The azo dyes according to the invention provide dyeings which are particularly suitable for dyeing cotton and wool and having good overall properties.

Azo dyes, reactive dyes, cotton and mock dyeing, light fastness, wet fastness.

Description

Azo dyes, their preparation and their use {Azo dyes, their preparation and their use}             

The present invention relates to novel azo dyes, their preparation and their use.

In recent years, dyeing techniques have intensified requirements regarding the quality of dyes and the suitability of dyeing processes. There is a continuing need for new dyes that have good properties, in particular good properties in application and that can be easily dyed.

In the case of fiber reactive dyes, for example, dyes are currently required which not only have sufficient directivity but also are easy to remove from non-fixed parts. In addition, they should be excellent in coloration rate and high in reactivity, and in particular should provide dyeings with high adhesion. Known dyes cannot meet all of these requirements.

It is therefore an object of the present invention to provide novel azo dyes, in particular azo dyes which are very good in these properties, which are suitable for dyeing and printing textile materials. They provide dyeings with good overall properties, for example light and wet fastnesses.

Accordingly, the present invention relates to azo dyes containing at least one structural unit of formula (1).

The azo dyes according to the invention can belong to various classes of dyes, depending on their coloring application. This classification of dyes is described, for example, in the Venkataraman "the Chemistry of Synthetic dyes" Volume 1, pages 268-303, Academic Press, New York, London 1952 and Volume 6, pages 1- 4, Academic Press, New York, London 1972. The azo dyes according to the invention are preferably acidic direct or reactive dyes for dyeing cotton, wool, leather, paper and wood, especially reactive dyes for dyeing cotton and wool, ie at least one fibrous reactive group. It is a dye which has two or more and can react with hydroxyl groups of cellulose or with reactive centers of natural and synthetic polyamides to form covalent bonds.

The azo dyes according to the invention preferably have the formula (2), (3) or (4).

In the above formula 2 to 4,

A is oxygen, sulfur or radical -NR'- where R 'is hydrogen or C ₁ -C ₁₂ alkyl which may be substituted or unsubstituted and in which oxygen may be involved in the chain,

B is an aliphatic or aromatic crosslinker,

D ₁ , D ₂ and D ₃ are each independently a radical of a benzene-based or naphthalene-based diazo component,

D ₄ is a radical of an aromatic tetraazo component,

R is hydrogen or an aliphatic or aromatic radical, or the radicals R and R 'together with the nitrogen atom form a heterocyclic radical.

C ₁ -C ₁₂ alkyl, preferably C ₁ -C ₆ alkyl, in particular C ₁ -C ₄ alkyl, as R ′, which may be substituted or unsubstituted, may involve oxygen in the chain, for example straight or branched chain, for example , Methyl, ethyl, n- or iso-propyl, n-, iso-, secondary- or tert-butyl, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl , n-decyl, n-undecyl or n-dodecyl. Alkyl radicals as described above may involve one to three oxygen atoms in the chain and may be unsubstituted or substituted with C ₂ -C ₄ alkanoylamino (eg acetylamino or propionylamino), C ₁ -C ₄ alkoxy (eg Methoxy or ethoxy), hydroxyl, sulfo, sulfato, carboxyl, cyano, carbamoyl, sulfamoyl, β-sulfatoethylsulfonyl or β-chloroethylsulfonyl. Preferred substituents of alkyl radicals R 'are hydroxyl, sulfo, carboxyl or sulfato, in particular hydroxyl or sulfato, in particular hydroxyl. Examples of substituted alkyl radicals and alkyl radicals in which oxygen is involved in the chain include β-hydroxyethyl, 2- (β-hydroxyethoxy) ethyl, 2- [2- (β-hydroxyethoxy) ethoxy] Ethyl, 2- (β-chloroethylsulfonyl) ethyl, 2- (β-sulfatoethylsulfonyl) ethyl, β-sulfatoethyl, β-sulfoethyl, carboxymethyl or β-carboxyethyl.

R 'is preferably hydrogen.

Aliphatic crosslinker B is, for example, one to three chain members selected from the group consisting of —NH—, —N (CH ₃ ) — and, in particular, —O— may be involved in the chain and are unsubstituted or hydroxyl C ₂ -C ₁₂ alkylene radicals, in particular C ₂ -C ₆ alkylene radicals, which may be substituted by sulfo, sulfato, cyano or carboxyl. Preferred substituents of the alkylene radicals B are hydroxyl, sulfo or sulfato, in particular hydroxyl.

Aliphatic crosslinkers B are also, for example, C ₅ -C ₉ cycloalkylene radicals, in particular cyclohexylene radicals. The cycloalkylene radicals mentioned may be unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxyl, especially C ₁ -C ₄ alkyl. Can be. In addition, aliphatic crosslinkers B are methylene-cyclohexylene, ethylene-cyclohexylene or methylene-cyclohexylene-methylene radicals in which unsubstituted or cyclohexylene rings are substituted by C ₁ -C ₄ alkyl, in particular methyl.

Aromatic crosslinking members B include, for example, C ₁ -C ₆ alkylenephenylene (eg methylenephenylene); C ₁ -C ₄ alkylenephenylene-C ₁ -C ₄ alkylene (eg methylenephenylenemethylene); Phenylene unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxyl; Or a radical of formula (5).

In Formula 5 above,

Benzene rings I and II are unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxyl,

L is a direct bond, a C ₂ -C ₁₀ alkylene radical which may have one to three oxygen atoms in the chain, or the formula -CH = CH-, -N = N-, -NH-, -CO-, -NH -CO-, -NH-SO _2- , -NH-CO-NH-, -O-, -S- or -SO _2- .

The aromatic crosslinkers B mentioned above are preferably unsubstituted or substituted by sulfo.

When A is oxygen in the dye of the formula (3), the aromatic crosslinker B is preferably substituted with the benzene rings I and II or substituted as defined above and with L as defined above and preferably as defined above. Is a radical. Preferably benzene rings I and II are unsubstituted and L is isopropylene.

B is preferably a C ₂ -C ₁₂ alkylene radical, in particular a C ₂ -C ₆ alkylene radical, in which 1 to 3 —O— are interrupted in the chain and unsubstituted or substituted by hydroxyl or sulfato.

Substituents of the radicals D ₁ , D ₂ and D ₃ are the substituents customary for azo dyes. Examples thereof include: C ₁ -C ₄ alkyl, ie methyl, ethyl, n- or iso-propyl, n-, iso-, secondary- or tert-butyl; C ₁ -C ₄ alkoxy, ie methoxy, ethoxy, n- or iso-propoxy or n-, iso-, secondary- or tert-butoxy; Hydroxy-C ₁ -C ₄ alkoxy; Phenoxy; C ₂ -C ₆ -alkanoylamino, which is unsubstituted or substituted by hydroxyl or C ₁ -C ₄ alkoxy, for example acetylamino, hydroxyacetylamino, methoxyacetylamino or propionylamino; Benzoylamino unsubstituted or substituted by phenyl moiety by hydroxyl, sulfo, halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₁ -C ₆ alkoxycarbonylamino unsubstituted or substituted by hydroxyl, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; Phenoxycarbonylamino unsubstituted or substituted by phenyl moiety by hydroxyl, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; Amino; NC ₁ -C ₄ alkyl- or N, N-di, which is unsubstituted or substituted by hydroxyl, C ₁ -C ₄ alkoxy, carboxyl, cyano, halogen, sulfo, sulfato, phenyl or sulfophenyl -C ₁ -C ₄ alkylamino, for example methylamino, ethylamino, N, N-dimethylamino, N, N-diethylamino, β-cyanoethylamino, β-hydroxyethylamino, N, N-di-β-hydroxyethylamino, β-sulfoethylamino, γ-sulfo-n-propylamino, β-sulfatoethylamino, N-ethyl-N- (3-sulfobenzyl) amino or N- (β-sulfoethyl) -N-benzylamino; Cyclohexylamino; N-phenylamino or NC ₁ -C ₄ alkyl-N-phenylamino unsubstituted or substituted by phenyl moiety by nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, carboxyl, halogen or sulfo; C ₁ -C ₄ alkoxycarbonyl, for example methoxycarbonyl or ethoxycarbonyl; Trifluoromethyl; Nitro; Cyano; Halogen such as fluorine, chlorine, in particular chlorine; Ureido; Hydroxyl; Carboxyl; Sulfo; Sulfomethyl; Carbamoyl; Cabamido; Sulfamoyl; N-phenylsulfamoyl or NC ₁ -C ₄ alkyl-N-phenylsulfamoyl, unsubstituted or substituted by sulfo or carboxyl; And methylsulfonyl or ethylsulfonyl.

Fiber reactive radicals may also be substituents of the radicals D ₁ , D ₂ and D ₃ .

A fiber reactive radical means a radical capable of reacting with hydroxyl groups of cellulose, amino, carboxyl, hydroxyl and thiol groups of wool and silk, or amino and possibly carboxyl groups of synthetic polyamides to form covalent chemical bonds. do. The fiber reactive radicals in principle bind either directly or via a crosslinking agent to the dye radicals. Suitable fiber reactive radicals are, for example, radicals containing one or more substituents capable of separating aliphatic, aromatic or heterocyclic radicals, or radicals such that these radicals can react with the fiber material, for example vinyl radicals. It contains.

The fiber reactive radicals contained in D ₁ , D ₂ and D ₃ are preferably radicals of the formulas 6a, 6b, 6c, 6d, 6e, 6f or 6g.

-SO ₂ -Y

-NH-CO- (CH ₂ ) _l -SO ₂ -Y

-CONR _2- (CH ₂ ) _m -SO ₂ -Y

-NH-CO-CH (Hal) -CH ₂ -Hal

-NH-CO-C (Hal) = CH ₂

In the above formula 6a to 6g,

Hal is chlorine or bromine,

X ₁ is halogen, 3-carboxypyridin-1-yl or 3-carbamoylpyridin-1-yl,

(7a),

(7b),

(7c),

(7d),

(7e) 또는

(7f)의 섬유 비반응성 또는 섬유 반응성 라디칼인 치환체이고,T ₁ is independently as defined for X ₁ or

(7a),

(7b),

(7c),

(7d),

(7e) or

(7f) is a substituent which is a fiber non-reactive or fiber reactive radical,

R ₁ , R _1a and R _1b are each independently hydrogen or C ₁ -C ₄ alkyl,

의 라디칼이고,R ₂ is hydrogen, unsubstituted or substituted with C ₁ -C ₄ alkyl substituted by hydroxyl, sulfo, sulfato, carboxyl or cyano, or

Is a radical of

R ₃ is hydrogen, hydroxyl, sulfo, sulfato, carboxyl, cyano, halogen, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkanoyloxy, carbamoyl or group-SO ₂ -Y,

alk and alk ₁ are independently of each other straight or branched C ₁ -C ₆ alkylene,

Arylene is a phenylene or naphthylene radical which is unsubstituted or substituted by sulfo, carboxyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen,

Q is a radical —O— or —NR ₁ —, where R ₁ is as defined above,

W is a group -SO ₂ -NR _2- , -CONR ₂ -or -NR ₂ CO-, wherein R ₂ is as defined above,

Y is vinyl or radical -CH ₂ -CH ₂ -U, where U is a group that can be separated under alkylic conditions,

Y ₁ is a group -CH (Hal) -CH ₂ -Hal or -C (Hal) = CH ₂ , where Hal is chlorine or bromine,

l and m are each independently an integer from 1 to 6,

n is the number 0 or 1,

X ₂ is halogen or C ₁ -C ₄ alkylsulfonyl,

X ₃ is halogen or C ₁ -C ₄ alkyl,

T ₂ is hydrogen, cyano or halogen.

Group U which can be separated under alkaline conditions is, for example, -Cl, -Br, -F, -OSO 3 H, -SSO 3 H, -OCO-CH 3, -OPO 3 H 2, -OCO-C ₆ H ₅ , -OSO ₂ -C ₁ -C ₄ alkyl or -OSO ₂ -N (C ₁ -C ₄ alkyl) ₂ . U is preferably the formula _{-Cl, -OSO 3 H, -SSO 3} H, -OCO-CH 3, -OCO-C 6 H 5 or -OPO ₃ H _2, especially -Cl or -OSO ₃ H, especially preferably Preferably -OSO ₃ H.

Thus, examples of suitable radicals Y are vinyl, β-bromo- or β-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl, β-sulfatoethyl and β-thio Sulfatoethyl. Y is preferably vinyl, β-chloroethyl or β-sulfatoethyl, in particular vinyl or β-sulfatoethyl.

R ₁ , R _1a and R _1b are each independently of one another preferably hydrogen, methyl or ethyl, particularly preferably hydrogen.

R ₂ is preferably hydrogen or C ₁ -C ₄ alkyl (eg methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl or tert-butyl), particularly preferably hydrogen, methyl Or ethyl. R ₂ is particularly preferably hydrogen.

R ₃ is preferably hydrogen.

l and m are independently of each other preferably the numbers 2, 3 or 4, particularly preferably the numbers 2 or 3.

Especially preferably, l is the number 3 and m is the number 2.

Substituents T _{1 which} are not fibrous reactive are, for example, the following radicals: hydroxyl; C ₁ -C ₄ alkoxy, for example methoxy, ethoxy, n- or iso-propoxy or n-, secondary-, iso- or tert-butoxy, in particular methoxy or ethoxy (these radicals are Unsubstituted or alkyl residues are substituted, for example, by C ₁ -C ₄ alkoxy, hydroxyl, sulfo or carboxyl); C ₁ -C ₄ alkylthio, for example methylthio, ethylthio, n- or iso-propylthio or n-butylthio (these radicals are unsubstituted or alkyl residues are for example C ₁ -C ₄ alkoxy, Substituted by hydroxyl, sulfo or carboxyl); Amino; N-mono- or N, N-di-C ₁ -C ₆ alkylamino, preferably N-mono- or N, N-di-C ₁ -C ₄ alkylamino (these radicals are unsubstituted or alkyl residues For example, substituted by C ₂ -C ₄ alkanoylamino, C ₁ -C ₄ alkoxy, hydroxyl, sulfo, sulfato, carboxyl, cyano, carbamoyl or sulfamoyl, with oxygen intervening in the alkyl moiety Or not), for example N-methylamino, N-ethylamino, N-propylamino, N, N-di-methylamino or N, N-di-ethylamino, N-β-hydroxyethyl Amino, N, N-di-β-hydroxyethylamino, N-2- (β-hydroxyethoxy) ethylamino, N-2- [2- (β-hydroxyethoxy) ethoxy] ethylamino , N-β-sulfatoethylamino, N-β-sulfoethylamino, N-carboxymethylamino, N-β-carboxyethylamino, N-α, β-dicarboxyethylamino, N-α, γ- Dicarboxypropylamino, N-ethyl-N-β-hydroxyethylami Furnace or N-methyl-N-β-hydroxyethylamino; C ₅ -C ₇ cycloalkylamino, for example cyclohexylamino, wherein the unsubstituted or cycloalkyl ring is substituted, for example, by C ₁ -C ₄ alkyl (particularly methyl) or carboxyl; Phenylamino or NC _1, unsubstituted or substituted by, for example, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, carboxyl, carbamoyl, sulfo or halogen -C ₄ alkyl-N-phenylamino, for example 2-, 3- or 4-chlorophenylamino, 2-, 3- or 4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or 4-sulfophenylamino, disulfophenylamino or 2-, 3- or 4-carboxyphenylamino; Naphthylamino, for example 1- or 2-naphthylamino, 1-sulfo-2, wherein the unsubstituted or naphthyl ring is substituted, for example, by sulfo, preferably by 1 to 3 sulfo groups Naphthylamino, 1,5-disulfo-2-naphthylamino or 4,8-disulfo-2-naphthylamino; Or benzylamino unsubstituted or substituted by a phenyl moiety, for example by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, carboxyl, sulfo or halogen.

Radicals T _{1 which} are not fibrous reactive preferably are C ₁ -C ₄ alkoxy; C ₁ -C ₄ alkylthio; Hydroxyl; Amino; N-mono- or N, N-di-C ₁ -C ₄ alkylamino unsubstituted or substituted by hydroxyl, sulfato or sulfo alkyl residues; Morpholino; Phenylamino; NC ₁ -C ₄ alkyl-N-phenylamino unsubstituted or substituted by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and unsubstituted or substituted by hydroxyl, sulfo or sulfato ; Or naphthylamino unsubstituted or substituted by one to three sulfo groups.

Particularly preferred radicals T _{1 which} are not fibrous reactive are amino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N- β-hydroxyethylamino, N, N-di-β-hydroxyethylamino, morpholino, 2-, 3- or 4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino or NC ₁ -C ₄ -alkyl-N-phenylamino.

X ₁ is preferably halogen, for example fluorine, chlorine or bromine, particularly preferably chlorine or fluorine.

Halogens as T ₂ , X ₂ and X ₃ are, for example, fluorine, chlorine or bromine, in particular chlorine or fluorine.

C ₁ -C ₄ alkylsulfonyl as X ₂ is, for example, ethylsulfonyl or methylsulfonyl, in particular methylsulfonyl.

C ₁ -C ₄ alkyl as X ₃ is, for example, methyl, ethyl, n- or iso-propyl or n-, iso or tert-butyl, in particular methyl.

X ₂ and X ₃ are independently of each other preferably chlorine or fluorine.

T ₂ is preferably cyano or chlorine.

Hal is preferably bromine.

alk and alk ₁ are independently of _one another, for example methylene, ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene or 1,6-hexylene radicals or their side chain isomers .

alk and alk ₁ are each independently of _one another preferably each a C ₁ -C ₄ alkylene radical, particularly preferably an ethylene radical or a propylene radical.

Arylene is preferably unsubstituted, for example, 1,3- or 1,4-phenylene radicals substituted by sulfo, methyl, methoxy or carboxyl, particularly preferably unsubstituted 1,3- Or 1,4-phenylene radical.

Q is preferably -NH- or -O-, particularly preferably -O-.

W is preferably a group of the formula -CONH- or -NHCO-, in particular a group of the formula -CONH-.

n is preferably the number zero.

The reactive radicals of formulas 7a to 7f are preferably

W is a group of the formula -CONH-,

R ₁ , R ₂ and R ₃ are each hydrogen,

Q is a radical -O- or -NH-,

alk and alk ₁ are each independently ethylene or propylene,

Arylene is unsubstituted or substituted phenylene by methyl, methoxy, carboxyl or sulfo,

Y is vinyl or β-sulfatoethyl,

Y ₁ is -CHBr-CH ₂ Br or -CBr = CH ₂ ,

n is a radical of the number zero.

The fiber reactive radicals contained in D ₁ , D ₂ and D ₃ are particularly preferably

Y is vinyl, β-chloroethyl or β-sulfatoethyl,

Hal is bromine,

R ₂ and R _1a are hydrogen,

m is the number 2 or 3,

X ₁ is halogen,

T ₁ is C ₁ -C ₄ alkoxy; C ₁ -C ₄ alkylthio; Hydroxyl; Amino; N-mono- or N, N-di-C ₁ -C ₄ alkylamino unsubstituted or substituted by hydroxyl, sulfato or sulfo alkyl residues; Morpholino; Phenylamino; NC ₁ -C ₄ alkyl-N-phenylamino unsubstituted or substituted by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and unsubstituted or substituted by hydroxyl, sulfo or sulfato ; Or naphthylamino unsubstituted or substituted by 1 to 3 sulfo groups

-NH- (CH ₂ ) _2-3 -SO ₂ Y (7a '),

-NH- (CH ₂ ) _2-3 -O- (CH ₂ ) _2-3 -SO ₂ Y (7b '),

(7c'),

(7c '),

(7d') 또는

(7d ') or

(7f')의 섬유 반응성 라디칼{여기서, Y는 위에서 정의한 바와 같고, Y₁은 그룹 -CH(Br)-CH₂-Br 또는 -C(Br)=CH₂이다}인 화학식 6a, 화학식 6c, 화학식 6d, 화학식 6e 또는 화학식 6f의 라디칼이다.

A fiber reactive radical of (7f ') wherein Y is as defined above and Y ₁ is a group -CH (Br) -CH ₂ -Br or -C (Br) = CH ₂ } A radical of formula 6d, 6e or 6f.

In the case of radicals of formulas 7a 'and 7b', Y is preferably β-chloroethyl. In the case of radicals of formulas 7c 'and 7d', Y is preferably vinyl or β-sulfatoethyl.

Certain embodiments of the invention relate to dyes in which the radicals contained in D ₁ , D ₂ and D ₃ have the formula 6h.

In Formula 6h above,

R _1a and X ₁ are as defined above and preferably as defined above,

T ₃ is a monoazo- or disazo of formula DN = N- (MN = N) _u- K-NR _1- (8) or -NR ₁ -DN = N- (MN = N) _u -K (9) Amino radicals, where D is a radical of the diazo component of the benzene or naphthalene system, M is a radical of the intermediate component of the benzene or naphthalene system, and K is benzene, naphthalene, pyrazolone, 6-hydroxypyrid- Is a radical of a coupling component of a 2-one or acetoacetic acid arylamide system, R ₁ is as defined above and preferably as defined above, u is the number 0 or 1, where D, M and K are azo dyes May have a common substituent).

The term "substituents customary for azo dyes" refers to both fibre-reactive substituents and non-fiber-reactive substituents, for example substituents defined for D ₁ , D ₂ and D ₃ .

Substituents for D, M and K in T _{3 which} are not fibrous reactive preferably are C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, which are unsubstituted or substituted by hydroxyl, sulfo or sulfato, Halogen, carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxyl, sulfomethyl, C ₂ -C ₄ alkanoylamino, unsubstituted or phenyl ring C _1- C ₄ alkyl, C ₁ -C ₄ alkoxy, benzoylamino substituted by halogen or sulfo, or phenyl unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxyl or sulfo .

Monoazo of the formula DN = N- (MN = N) _u- K-NR _1- (8) or -NR ₁ -DN = N- (MN = N) _u -K (9) as defined in T _3- Or the disazoamino radical preferably contains one or more sulfo groups.

Preferred monoazo- or disazoamino radicals T ₃ are represented by formulas 10a, 10b, 10c, 10d, 10e, 10f, 10g, 10h, 10i, 10j, 10k, 10l, 10m. , A radical of the formula 10n, 10o or 10p.

In the above formula 10a to 10p,

(R ₄ ) _0-3 is the same or different 0 to 3 substituents selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxyl and sulfo,

(R ₅ ) _0-3 is halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl; C ₁ -C ₄ alkoxy unsubstituted or substituted by hydroxyl, sulfato or C ₁ -C ₄ alkoxy; The same or different 0 to 3 substituents selected from the group consisting of amino, C ₂ -C ₄ alkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, C ₁ -C ₄ alkylsulfonylamino and sulfo,

Z ₁ is a radical of formula 6a, 6c, 6d, 6e, 6f or 6g, preferably of formula 6a, 6c, 6d or 6e, in particular of formula 6a wherein the radicals mentioned are as defined and preferably defined ),

R ₆ is C ₂ -C ₄ alkanoyl or benzoyl,

(R ₇ ) _0-3 is 0 to 3 identical or different substituents selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxyl and sulfo,

R ₈ and R ₁₀ are independently of each other hydrogen, C ₁ -C ₄ alkyl or phenyl,

R ₉ is hydrogen, cyano, carbamoyl or sulfomethyl,

(R ₁₁ ) _0-3 and (R ₁₂ ) _0-3 are each independently 0 to 3 identical or different groups selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxyl and sulfo It is a substituent.

The number of radicals of the formulas 10a, 10b, 10c, 10d, 10e, 10g and 10h on the naphthyl ring indicates possible bonding positions.

(R ₄ ) _0-3 in the _disazoamino radicals of the formulas 10n and 10p are preferably 0 to 3 sulfo groups.

Particularly preferred monoazo- or disazoamino radicals T ₃ are radicals of the formula 10a, 10b, 10d, 10e, 10f, 10k or 10m, in particular radicals of the formula 10b, 10k or 10m.

Preferably, the radical of formula 6h, wherein R _1a , X ₁ and T ₃ are as defined above and preferably as defined above, is contained in only one of the radicals D ₁ , D ₂ and D ₃ , in particular in D ₁ .

The radicals D ₁ , D ₂ and D ₃ of the benzene- or naphthalene-based substituted or unsubstituted diazo component are independently of one another, for example, unsubstituted, for example C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, sulfo, nitro, carboxyl, or fiber reactive radicals of formulas 6a, 6b, 6c, 6d, 6e, 6f or 6g, in particular formulas 6a, 6c, 6d, 6e or 6f (these fiber reactive radicals are Phenyl or naphthyl as defined above and preferably as defined above).

The radicals D ₁ , D ₂ and D ₃ of the substituted or unsubstituted diazo component of the benzene or naphthalene system are also independently of each other monoazo radicals, for example mono of formula 11 or formula 12, preferably of formula 12 Azo radicals.

-D * -N = N-K *

D * -N = N-K **-

In Formula 11 and Formula 12 above,

D * is a radical of the diazo component of the benzene or naphthalene system,

K * is a radical of the coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide system,

K ** is a radical of the coupling component of a benzene or naphthalene system, where D *, K * and K ** may contain substituents customary for azo dyes.

Substituents that are not fibrous reactive D *, K * and K ** are preferably C ₁ -C ₄ alkyl or C ₁ unsubstituted or substituted by hydroxyl, C ₁ -C ₄ alkoxy, sulfo or sulfato -C ₄ alkoxy, halogen, carboxyl, sulfo, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxyl, sulfomethyl, C ₂ -C ₄ alkanoylamino, C _1- C ₄ alkylsulfonylamino, benzoylamino unsubstituted or phenyl ring substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen or sulfo, or unsubstituted C ₁ -C ₄ alkyl, C _1- C ₄ alkoxy, halogen, carboxyl or phenyl substituted by sulfo.

Fiber reactive substituents for D *, K * and K ** are preferably radicals of formula 6a, 6c, 6d, 6e or 6f, in particular of formula 6a, wherein these radicals are as defined above and preferably Is the same).

The monoazo radical of formula 11 or formula 12 preferably contains at least one sulfo group.

Preferred monoazo radicals D ₁ , D ₂ and D ₃ of formula 12 are radicals of formula 12a, 12b, 12c, 12d, 12e, 12f, 12g, 12h, 12i or 12j.

In the above formula 12a to 12j,

(R ₄ ) _0-3 is 0 to 3 identical or different substituents selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxyl and sulfo,

Z ₁ is a fiber reactive radical of formula 6a, 6c, 6d, 6e, 6f or 6g, preferably of formula 6a, 6c, 6d or 6e, in particular of formula 6a (these fiber reactive radicals are as defined above and are also preferably defined Is the same as

(R ′ ₅ ) _0-3 is halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl, unsubstituted or hydroxyl, sulfato or C ₁ -C ₄ alkoxy Substituted by C ₁ -C ₄ alkoxy, amino, C ₂ -C ₄ alkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, C ₁ -C ₄ alkylsulfonylamino, sulfo and the fiber reactivity of formula 6f 0 to 3 identical or different substituents selected from the group consisting of radicals wherein R _1a , T ₁ and X ₁ are as defined above and preferably as defined above.

The radicals of formulas 12a, 12b, 12e and 12f on the naphthyl ring represent possible bonding positions.

The radicals D ₁ , D ₂ and D ₃ in the dyes of formula 2 or 3 according to the invention and the radicals D ₁ and D ₂ in the dyes of formula 4 according to the invention are the same or not identical.

Aromatic tetraazo component D ₄ is, for example, phenylene which is unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxyl or Naphthylene or a radical of formula 5 as defined above.

Aromatic tetraazo component D ₄ is also a radical of formula 5a.

Preferably, D ₄ is substituted by a sulfo group, a radical of formula 5a or by one to three, preferably two, radicals of formula 5 and the benzene rings I and II are unsubstituted or by one or two sulfo groups Substituted naphthalene, L is a direct bond, a C ₂ -C ₄ alkylene radical, or a formula -CH = CH-, -NH-, -CO-, -NH-CO-, -NH-SO _2- , -NH -CO-NH-, -O-, -S- or -SO _2- .

Aliphatic radicals R, for example, are radicals defined for C ₁ -C ₁₂ alkyl which are either unsubstituted or substituted as R 'and are interrupted by oxygen. Additionally, examples of R include 2,5-di- (β-chloroethylsulfonyl) pentyl, 2- [2- (β-chloroethylsulfonyl) ethoxy] ethyl or 2- [2- (β-sulfur Radicals such as peytoethylsulfonyl) ethoxy] ethyl.

Aliphatic radicals R are also, for example, C ₅ -C ₇ cycloalkyl radicals, in particular cyclohexyl radicals. The cycloalkyl radicals mentioned are unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, sulfo, halogen or carboxyl, in particular by C ₁ -C ₄ alkyl Can be. Aliphatic radicals R are also methylene-cyclohexyl or ethylene-cyclohexyl radicals which are unsubstituted or in which the cyclohexyl ring is substituted by C ₁ -C ₄ alkyl, in particular methyl.

Aromatic radicals R can be, for example, phenyl or naphthyl unsubstituted or substituted by C ₁ -C ₄ alkyl such as methyl or ethyl; C ₁ -C ₄ alkoxy, for example methoxy or ethoxy; C ₂ -C ₄ alkanoylamino; Carboxyl; Carbamoyl; Sulfo or halogen such as chlorine or bromine; Or fiber reactive radicals of formula 6a, 6b, 6c, 6d, 6e, 6f or 6g, these fiber reactive radicals are as defined above and preferably as defined above. Examples of these are o-, m- or p-chlorophenyl, o-, m- or p-methylphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-sulfophenyl, disulfo Phenyl, o-, m- or p-carboxyphenyl, 1- or 2-naphthyl, 1-sulfo-2-naphthyl, 1,5-disulfo-2-naphthyl, 4,8-disulfo-2 Radicals such as -naphthyl or 4- (β-sulfatoethylsulfonyl) phenyl.

Substituted or unsubstituted phenyl or naphthyl as R is also, for example, a monoazo or disazo radical of the formula (13) or (14).

DN = N- (MN = N) _u -K-

-DN = N- (MN = N) _u -K

In the above formulas (13) and (14),

D is a radical of a diazo component of a benzene or naphthalene system,

M is a radical of an intermediate component of benzene or naphthalene type,

K is a radical of the coupling component of the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one or acetoacetic acid arylamide system,

u is the number 0 or 1.

The monoazo radical as R is a compound of formula 10a, 10b, 10c, 10d, 10e, 10f, 10g, 10h, 10i, 10j when, in certain formulas, the group -NH- is replaced by a direct bond. , 10k, 10l, 10m, 10n, 10o or 10p.

Heterocyclic radicals formed by radicals R and R 'together with a nitrogen atom are, for example, morpholine.

In a preferred embodiment of the azo dye of formula (2), (3) or (4) according to the invention, A is oxygen or radical -NR'-.

When A is a radical -NR'- in the dye of formula 2 or 4 according to the invention, R 'is preferably hydrogen and R is preferably hydrogen, unsubstituted or hydroxyl, sulfo, carboxyl or sulfato C ₁ -C ₄ alkyl, or 2- (β-sulfatoethylsulfonyl) ethyl, which is substituted by, in particular by hydroxyl or sulfato, in particular by hydroxyl.

When A is oxygen in the dye of formula 2 or 4 according to the invention, R is preferably hydrogen or C ₁ -C ₄ alkyl, in particular hydrogen, unsubstituted or substituted by hydroxyl.

In the dyes of formula 3 according to the invention, A is preferably a radical -NR'-, wherein R 'is hydrogen, methyl or ethyl, in particular hydrogen.

In a particularly preferred embodiment of the azo dye of formula 2 or 4 according to the invention, A is oxygen and R is hydrogen.

Preferred are azo dyes of the formula (2) or (4), in particular azo dyes of the formula (2) according to the invention.

The radicals D ₁ , D ₂ and D ₃ are independently of one another preferably each radical of the formula (15) or (16).

In Formulas 15 and 16 above,

(17a) 또는

(17b)의 커플링 성분의 라디칼이고, K is a chemical formula

(17a) or

Radical of the coupling component of (17b),

(7c') 또는

(7d')의 섬유 반응성 라디칼이고, Y는 위에서 정의한 바와 같고, X₁은 염소 또는 불소이고, m은 숫자 2 또는 3이다}이고,Z and Z ₁ independently of _one another are radicals of formula 6a, 6c, 6d, 6e or 6f wherein R _1a and R ₂ are hydrogen, Hal is bromine and Y is vinyl, β-chloroethyl or β-sulfate Toethyl and T ₁ is C ₁ -C ₄ alkoxy; C ₁ -C ₄ alkylthio; Hydroxyl; Amino; N-mono- or N, N-di-C ₁ -C ₄ alkylamino unsubstituted or substituted by hydroxyl, sulfato or sulfo alkyl residues; Morpholino; Phenylamino; NC ₁ -C ₄ alkyl-N-phenylamino unsubstituted or substituted by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and unsubstituted or substituted by hydroxyl, sulfo or sulfato ; Naphthylamino unsubstituted or substituted by one to three sulfo groups; Or chemical formula

(7c ') or

Is a fiber reactive radical of (7d '), Y is as defined above, X ₁ is chlorine or fluorine, m is number 2 or 3},

(R ₄ ) _0-3 and (R ₁₃ ) _0-3 are each independently 0 to 3 identical or different selected from the group consisting of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, carboxyl and sulfo Substituents,

R ' ₅ is hydrogen; Sulfo; Or C ₁ -C ₄ alkoxy which is unsubstituted or substituted by hydroxyl or sulfato by alkyl moiety,

R ′ _5a is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, ureido or a radical of formula 6f wherein the radicals R _1a , T ₁ and X ₁ are defined above As in the same way.

C ₁ -C ₄ alkyl as R ₄ , R ′ _5a and R ₁₃ independently of one another, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, tert-butyl or Isobutyl, preferably methyl or ethyl, especially methyl.

C ₁ -C ₄ -alkoxy as R ₄ , R ′ ₅ , R ′ _5a and R ₁₃ independently of one another, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or Isobutoxy, preferably methoxy or ethoxy, in particular methoxy. R ' ₅ may be unsubstituted or the alkyl moiety may be substituted by hydroxyl or sulfato.

Halogens as R ₄ and R ₁₃ are, independently of one another, for example fluorine, chlorine or bromine, preferably chlorine or bromine, in particular chlorine.

C ₂ -C _{4 -alkanoylamino} as R ′ _5a is, for example, acetylamino or propionylamino, in particular acetylamino.

The radical R ′ _5a of formula 6f is preferably N-mono- or N, N-di-C wherein R _1a is hydrogen and T ₁ is unsubstituted or the alkyl moiety is substituted by hydroxyl, sulfato or sulfo. ₁ -C ₄ alkylamino; Morpholino; Phenylamino; NC ₁ -C ₄ alkyl-N-phenylamino unsubstituted or substituted by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and unsubstituted or substituted by hydroxyl, sulfo or sulfato ; A naphthylamino unsubstituted or substituted by one to three sulfo groups, and X ₁ is a fluorine or chlorine.

In the radical of the coupling component of formula 17b, the sulfo group in ring ii is preferably bonded at the 3- or 4-position. When ring ii contains a sulfo group, the radical of formula 17b is preferably bonded to ring ii at the 1-, 2- or 3-position. If no sulfo group is present in ring ii, the radical of formula 17b is preferably bonded to ring ii in the 2- or 3-position.

The radicals D ₁ , D ₂ and D ₃ independently of one another are particularly preferably the radicals of the formulas 15a, 15b, 15c, 15d or 16a, respectively.

In Formula 15a to Formula 15d and Formula 16a above,

R ' ₅ is hydrogen; Sulfo; Or ethoxy unsubstituted or the alkyl moiety is substituted by hydroxyl or sulfato,

R ' _5a is hydrogen, methyl, ethyl, methoxy, ethoxy, acetylamino, propionylamino or ureido,

(R ₁₃ ) _0-2 are 0 to 2 identical or different substituents selected from the group consisting of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfo, in particular methyl, methoxy and sulfo,

Y ₁ is a group —CH (Br) —CH ₂ —Br or —C (Br) = CH ₂ ,

Y is vinyl, β-chloroethyl or β-sulfatoethyl, in particular vinyl or β-sulfatoethyl,

m is the number 2 or 3, in particular 2.

The numbers in the radicals of formulas 15a, 15c and 15d represent possible binding positions of the fiber reactive radicals.

D ₁ , D ₂ and D ₃ are independently of each other, in each case, preferably a radical of the formula 15a, 15b or 16a.

In certain embodiments of the invention as defined above wherein the radicals belonging to D ₁ , D ₂ and D ₃ represent formula 6h, D ₁ is preferably a radical of formula 18.

In Formula 18 above,

X ₁ is chlorine or fluorine, in particular chlorine,

T ₃ is a monoazo- or disazoamino radical of the formula 10a, 10b, 10d, 10e, 10f, 10k or 10m {in these formulas 10a to 10m, the radicals (R ₄ ) _0-3 , (R ₅ ) _0-3 , R ₈ , R ₁₀ , R ₉ and (R ₁₁ ) _0-3 are as defined above and Z ₁ is Y is vinyl, β-chloroethyl or β-sulfatoethyl, in particular vinyl or β-sulfato Ethyl-SO ₂ -Y (6a), -CONH- (CH ₂ ) _2-3 -SO ₂ -Y (6c '), -NH-CO-CH (Br) -CH ₂ -Br (6d') or -NH-CO-C (Br) = CH ₂ (6e '), preferably a radical of formula 6a, wherein D ₂ and D ₃ are each independently of the radicals (R ₁₃ ) _0-2 , Y, Y ₁ and m are radicals of formula 15a, 15b, 15c or 15d as defined above.

Preferred dyes are the compounds of formula 2a.

In Formula 2a above,

D ₁ , D ₂ and D ₃ are each independently a radical of the formula 15a, 15b, 15c, 15d or 16a, preferably of formula 15a, 15b or 16a, in each case a radical D ₁ At least one of D ₂ and D ₃ contains a fiber reactive group, or

D ₁ is a radical of formula 18 (wherein X ₁ is chlorine and T ₃ is a radical of formula 10a, 10b, 10d, 10e, 10f, 10k or 10m, preferably formula 10b, 10k or 10m) , D ₂ and D ₃ are independently of each other, in each case a radical of the formula 15a, 15b, 15c or 15d, preferably 15a or 15b, at least one of the radicals D ₂ and D ₃ is a fiber It contains reactive groups.

Preferably, at least two of the radicals D ₁ , D ₂ and D ₃ in the dye of formula 2a contain a fiber reactive group.

The present invention also encompasses coupling one or more diazoated amines together or in a predetermined order to a compound containing one or more structural units of formula 19 to obtain azo dyes containing one or more structural units of formula 1 It relates to a method for producing an azo dye according to the present invention.

One or more diazotized amines means, for example, two or three diazotized amines.

Suitable amines for the preparation of azo dyes according to the invention are, for example, benzene-based or naphthalene-based aromatic amines which can be diazotized and coupled according to methods known per se, for example described in the literature. Which may be mentioned (see Vencataraman "The Chemistry of Synthetic dyes" Volume 1, pages 210-214 and 409-441, Academic Press, New York, London 1952).

The amine is, for example, an alkali metal nitrite such as sodium nitrite at a temperature of, for example, -5 to 40 ° C, preferably -5 to 10 ° C, in an inorganic acid medium (eg hydrochloric acid medium). To diazotize.

Coupling to the coupling component of formula (19) is itself at an acidic or neutral to weakly alkaline pH, for example at pH 1 to 10, for example at a temperature of -5 to 40 ° C, preferably 0 to 30 ° C. It is performed in a known manner.

The coupling reaction is preferably carried out first in a strong acid medium, for example pH 1, and then slowly increasing the pH of the reaction mixture as the reaction increases, for example to pH 5-8.

An azo dye of formula (2) wherein A is oxygen and R is hydrogen and D ₁ = D ₂ ≠ D ₃ or D ₂ = D ₃ ≠ D ₁ , for example, is preferably acidic, with about one molar equivalent of the diazotized amine of formula 20a Reaction in a medium with about 1 molar equivalent of a compound of formula 19a yields a compound of formula 21a and then a compound of formula 21a with about 2 molar equivalents of diazotized amine of formula 20b at increased pH.

D ₁ -NH ₂

D ₂ -NH ₂

In the above formulas 19a, 20a, 20b and 21a,

D ₁ and D ₂ are as defined above and preferably defined as well.

A is oxygen, sulfur or radical -NR'-, wherein R 'is as defined above and preferably as defined above, R is an aliphatic or aromatic radical and D ₁ = D ₂ ≠ D ₃ or D ₂ = The azo dye of Formula 2, wherein D ₃ ≠ D ₁ , for example, reacts about 1 molar equivalent of the compound of Formula 22a with about 1 molar equivalent of the compound of Formula 23 by a method known per se to obtain a compound of Formula 22b Obtained by reducing the compound of 22b to the compound of formula 19c by a method known per se, and then further reacting the compound of formula 19c with the diazotized amine of formula 20a and the diazotized amine of formula 20b in a manner similar to that described above. do.

R-AH

In the above formulas 19c, 22b and 23,

R is as defined above and preferably as defined above.

Azo dyes of Formula 3 wherein D ₁ = D ₂ ≠ D ₃ or D ₂ = D ₃ ≠ D ₁ may, for example, contain about 2 molar equivalents of the compound of Formula 22a by about one mole equivalent of the compound of Formula 24 Reaction with an equivalent yields a compound of formula 22c and a compound of formula 22b is reduced to a compound of formula 19d by a method known per se, and then the compound of formula 19d is prepared in a similar manner as described above Obtained by stepwise further reaction with 20b diazotized amine.

HA-B-AH

In the above formulas 19d, 22c and 24,

A and B are as defined above and preferably defined as well.

The reducing conditions of the compound of formula 22b and the compound of formula 22c are advantageously selected such that any functional group present in R, R 'or B is not reduced. Such selective reduction reactions are known and are widely described in the literature.

The dyes of formulas (2) and (3) according to the invention in which D ₁ ≠ D ₂ ≠ D ₃ can be obtained following the procedure described above, provided that, instead of the diazotized amines D ₂ -NH ₂ , for example, two dia Mixtures of crude amines D ₂ -NH ₂ and D ₃ -NH ₂ , for example 1: 1 mixtures, are used. In principle, these dyes are obtained as a mixture.

Azo dyes of formula (4), wherein A is oxygen, R is hydrogen, and D ₁ = D ₂ , for example, first about 1 molar equivalent of tetraazodiated diamine of formula 20c is about 2 molar equivalents of compound of formula 19a in hydrochloric acid medium And a compound of formula 21b to obtain a compound of formula 21b, and then the compound of formula 21b at an elevated pH of the diazotized amine of formula D ₁ -NH ₂ , wherein D ₁ is as defined above and preferably as defined above. Obtained by reaction with about 4 molar equivalents.

H ₂ ND ₄ -NH ₂

In Formula 20c and 21b above,

D ₄ is as defined above and is preferably defined as well.

Dyes of formula (4) according to the invention wherein A is oxygen, sulfur or radicals -NR'- and R is an aliphatic or aromatic radical and D ₁ = D ₂ can be obtained following the procedure described above, provided that the compounds of formula 19a Instead, equimolar amounts of the compound of formula 19c are used.

A dye of formula 4 according to the invention wherein D ₁ ≠ D ₂ may be obtained according to the procedure described above, provided that instead of the diazotized amine D ₂ -NH ₂ , for example, two diazotized amines D ₁ -NH Mixtures of ₂ and D ₂ -NH ₂ , for example 1: 1 mixtures, are used. In principle, these dyes are obtained as a mixture.

Compounds of formulas 19a, 20a, 20b, 20c, 22a, 23 and 24 are known or may be obtained by methods known per se.

Useful direct dyes are in accordance with the present invention that must contain at least one of the halogenotriazinyl radicals of formula 6f (wherein X ₁ is chlorine or fluorine and T ₁ is a non-fiber reactive radical) as a fiber reactive radical. can be obtained from a dye, for example, the present invention described above correspond to an amount of a compound of formula T ₁ -H to the content of the Syrian possess halogeno note the dyes according to (wherein, T ₁ is a fiber-reactive in the bar as defined above, It can be obtained by further reacting with). In particular, T ₁ -H is ammonia, unsubstituted or substituted amine as defined above, or morpholine. This reaction can be carried out by a method known per se.

The dyes according to the invention are suitable for dyeing a wide variety of materials, in particular fiber materials containing hydroxyl groups or nitrogen. Examples of such materials are cellulose fiber materials of all types, such as paper, silk, leather, wool, polyamide fibers and polyurethane. Such fibrous materials are, for example, natural cellulose fibers such as cotton, flax and hemp and pulp and regenerated cellulose. The dyes according to the invention are also suitable for dyeing or printing the hydroxyl group containing fibers contained in blends, such as blends of cotton with polyester fibers or polyamide fibers.

The present invention therefore also relates to the use of the compounds of formula 1 for dyeing or printing fiber materials containing hydroxyl groups or nitrogen, in particular fiber materials containing cotton.

The dyes according to the invention can be applied and fixed in various ways, in particular in the form of aqueous dye solutions and printing pastes. They are suitable not only for the adsorption method but also for dyeing by the feather method, which can be used at low temperatures and require only a very short vaporization time in the pad-vapor method. High adhesion, easy removal of washing from non-fixed parts, and very little difference in adsorption and adhesion. That is, the soap loss is very small. The dyes according to the invention are not only particularly suitable for printing on cotton, but also for the printing of nitrogen-containing fibers such as wool, silk or woolen textiles.

Dyes according to the invention, in particular dyeings and printings produced using reactive dyes, have high color strength and fiber-dye binding stability not only in the acidic range but also in the alkaline range, and also have good light and wet fastness properties (e.g. washing Color fastness, water fastness, seawater fastness, cross-dyeing fastness and sweat fastness). A uniform dyed dye is obtained on the fibers and the surface.

The following examples illustrate the invention. Unless indicated otherwise, temperatures are in ° C., parts are by weight, and% data are by weight. The relationship between parts by weight and parts by volume is equal to that between kg and liter.

Example 1 :

의 라디칼이다) 17.3부를 물 215부에 도입하고 혼합물을 균질하게 혼합한다. 4N 아질산나트륨 용액 25부를 0℃에서 생성된 용액에 첨가한 다음, 진한 염산 20부를 0 내지 5℃에서 서서히 적가한다. 혼합물을 이 온도에서 1시간 동안 교반한다.Amines of formula D ₁₀ -NH ₂ , wherein D ₁₀ is

17.3 parts are introduced into 215 parts of water and the mixture is mixed homogeneously. 25 parts of 4N sodium nitrite solution are added to the resulting solution at 0 ° C, and then 20 parts of concentrated hydrochloric acid are slowly added dropwise at 0-5 ° C. The mixture is stirred at this temperature for 1 hour.

Example 2 :

의 라디칼이다) 56.2부를 물 220부에 도입하고 혼합물을 균질하게 혼합한다. 우선, 4N 아질산나트륨 용액 50부와 31% 나프탈렌설폰산 용액 90부를 10℃에서 생성된 현탁액에 첨가한다. 이어서, 혼합물을 15 내지 20℃에서 3시간 동안 교반한다.Amines of formula D ₁₁ -NH ₂ , wherein D ₁₁ is

56.2 parts are introduced into 220 parts of water and the mixture is mixed homogeneously. First, 50 parts of 4N sodium nitrite solution and 90 parts of 31% naphthalenesulfonic acid solution are added to the resulting suspension at 10 ° C. The mixture is then stirred at 15-20 ° C. for 3 hours.

Examples 3 to 33 :

The diazo compounds of the amines listed in Table 1 include the amines of the formula D _xy -NH ₂ listed in Table 1 instead of the amines of the formula D ₁₀ -NH ₂ or D ₁₁ -NH ₂ used in Examples 1 or 2; It may be prepared according to a method similar to that described in Example 1 or 2 except that the molar amount is used.

Example 34 :

의 라디칼이다) 16부를 중성 조건하에 물 160부에 용해시킨다. 여기에 진한 염산 13부에 이어서 4N 아질산나트륨 용액 19.5부를 0℃에서 서서히 첨가한다. 디아민을 반응시켜 상응하는 테트라아조 화합물을 수득할 때, 과량의 아질산 염이 설팜산의 첨가에 의해 파괴된다. Diamine of the formula H ₂ ND ₄₃ -NH ₂ , wherein D ₄₃ is

Is dissolved in 160 parts of water under neutral conditions. To this was added 13 parts of concentrated hydrochloric acid followed by 19.5 parts of 4N sodium nitrite solution slowly at 0 ° C. When the diamine is reacted to give the corresponding tetraazo compound, the excess nitrite salt is destroyed by the addition of sulfamic acid.

Examples 35-37 :

The tetraazo compounds of the diamines listed in Table 2 are described in Example 34 if an equimolar amount of the diamine of the formula H ₂ ND _xy -NH ₂ is used instead of the diamine of the formula H ₂ ND ₄₃ -NH ₂ mentioned in Example 34. It can be prepared in a similar manner to the process.

Example 38 :

a) Primary Coupling Reaction: A solution of 15.2 parts of 3,5-diaminobenzoic acid in 100 parts of 2N hydrochloric acid is added to the acid diazo compound obtained according to Example 1 at 0? 5 占 폚. The pH of the reaction mixture is adjusted to 3.2 for 4 hours using 40% sodium acetate solution. The resulting mixture is then stirred at 6-7 ° C. for a further 30 minutes. The compound of formula 101 is obtained in the form of the free acid.

b) Secondary coupling reaction: The acid diazo compound obtained according to example 2 is added to a suspension of the compound of formula 101 obtained in step a) at 7 ° C. and pH 3.2. The pH of the resulting reaction mixture is adjusted to 3.5 over 45 minutes at 12-15 ° C. with 40% sodium acetate solution and again at 6.3 over 15 hours at 15-19 ° C. with sodium bicarbonate. The resulting mixture is then stirred at about 25 ° C. for an additional 45 minutes. The resulting solution is treated with 450 parts of acetone, the pH is adjusted to 1.5 with concentrated hydrochloric acid, and then 4.6 parts of potassium chloride are added. The dye precipitated by precipitation is filtered off and washed with acetone. 70.1 parts of the compound of formula 102 are obtained in the form of a free acid, which dyes cotton and wool in orange color with excellent overall properties.

Examples 39-108 :

The dye of formula 103 may be prepared from the diazo dyes described in Examples 1-33 in a similar manner to the procedure described in Example 38.

In the above formula 103,

D ¹ _xy and D ² _xy are in each case the radicals listed in Table 3, which radicals are as defined in Examples 1 and 2 and Table 1.

The dyes dyed cotton and wool with good overall properties in the colors shown in Table 3.

Example 109 :

a) Primary coupling reaction: A solution of 15.2 parts of 3,5-diaminobenzoic acid in 100 parts of 2N hydrochloric acid is added to the acid diazo compound obtained according to Example 34 at 0? 5 占 폚. The pH of the reaction mixture is adjusted to 3.2 for 4 hours using 40% sodium acetate solution. The resulting mixture is then stirred at 6-7 ° C. for a further 30 minutes. The compound of formula 104 is obtained in the form of the free acid.

b) Secondary coupling reaction: The acid diazo compound obtained according to example 2 is added to a suspension of the compound of formula 104 obtained in step a) at 7 ° C. and pH 3.2. The pH of the resulting reaction mixture is adjusted to 3.5 over 45 minutes at 12-15 ° C. with 40% sodium acetate solution and again at 6.3 over 15 hours at 15-19 ° C. with sodium bicarbonate. The resulting mixture is then stirred at about 25 ° C. for an additional 45 minutes. The resulting solution is treated with 450 parts of acetone, the pH is adjusted to 1.5 with concentrated hydrochloric acid, and then 4.6 parts of potassium chloride are added. The dye precipitated by precipitation is filtered off and washed with acetone. 68 parts of the compound of formula 105 are obtained in the form of a free acid, which dyes cotton and wool in a brown-orange color with excellent overall properties.

Examples 110-113 :

Dye of formula 106 may be prepared from the tetraazo compounds shown in Table 2 and the diazo compounds described in Examples 2 and 4 in a similar manner to the procedure described in Example 109.

In Formula 106 above,

D ¹ _xy and D ² _xy are in each case the radicals listed in Table 4, which radicals are as defined in Table 2 and Examples 2 and 4.

The dyes dye cotton and wool well in the color shown in Table 4 with excellent overall properties.

Example 114 :

A solution of 10.1 parts of 3,5-diaminobenzoic acid in 67 parts of 2N hydrochloric acid is added to the acid diazo compound suspension obtained according to Example 2 at 0? 5 占 폚. Adjust the pH of the reaction mixture to 3.2 for 1 hour with 40% sodium acetate solution, again to 5.8 for another 1 hour with sodium bicarbonate, and then 7.8 over 45 minutes with 20% sodium carbonate solution. Adjust to. The resulting solution is adjusted to pH 0.8 with concentrated hydrochloric acid, and then 80 parts of acetone and 112 parts of potassium chloride are added. The dye precipitated by precipitation is filtered off and washed with acetone. 64.6 parts of the compound of formula 107 are obtained in the form of a free acid, so that the cotton and wool are dyed in orange color with excellent overall characteristics.

Examples 115-140 :

Dyes having the formula 108 can be prepared from the diazo compounds described in Examples 3 to 5, 9 to 12, 14, 15, 20 and 23 to 25 in a manner similar to the procedure described in Example 114.

In Formula 108 above,

D _xy is in each case the radicals listed in Table 5 and these radicals are as defined in Table 1.

The dyes dyed cotton and wool with good overall properties with the colors listed in Table 5.

Example 141 :

14.4 parts of 2-sulfo-4- (β-sulfatoethylsulfonyl) aniline and 22.7 parts of 4- (β-sulfatoethylsulfonyl) aniline are introduced into 120 parts of water and the resulting mixture is stirred homogeneously. . First, 30 parts of 4N sodium nitrite solution and subsequently 50 parts of 31% naphthalenesulfonic acid solution are added to the resulting suspension at 10 ° C. The mixture is then stirred at 15-20 ° C. for 3 hours. To this suspension is added a solution of 6.1 parts of 3,5-diaminobenzoic acid in 40 parts of 2N hydrochloric acid at 0-5 占 폚. The pH of the reaction mixture was adjusted to 3.2 for 1 hour at 0-5 ° C. with 40% sodium acetate solution, again to 5.8 for 1 additional hour using sodium bicarbonate, followed by 20% sodium carbonate solution. Adjust to 7.8 over 45 minutes. The resulting solution is evaporated. 66.9 parts of a product comprising a mixture of a compound of formula 109, a compound of formula 110, a compound of formula 111, a compound of formula 112, a compound of formula 113 and a compound of formula 114 are obtained.

In Chemical Formulas 109 to 114 above,

D ₁₁ and D ₁₃ are as defined in Examples 2 and 4.

This dye mixture dyes cotton and wool orange color with good overall properties.

Example 142 :

a) 22.3 parts of 2-aminonaphthalenesulfonic acid are introduced into 215 parts of water, and the mixture is stirred homogeneously. 25 parts of 4N sodium nitrite solution are added to the resulting solution at 0 ° C. and 20 parts of concentrated hydrochloric acid are slowly added at 0-5 ° C. The mixture is stirred at this temperature for 1 hour.

b) 30.3 parts of 2-amino-1,5-naphthalenedisulfonic acid are introduced into 215 parts of water and the mixture is stirred homogeneously. 25 parts of 4N sodium nitrite solution are added to the resulting solution at 0 ° C. and 20 parts of concentrated hydrochloric acid are slowly added at 0-5 ° C. The mixture is stirred at this temperature for 1 hour.

c) 28.1 parts of 4- (β-sulfatoethylsulfonyl) aniline are introduced into 110 parts of water and the mixture is stirred homogeneously. First 25 parts of 4N sodium nitrite solution and subsequently 45 parts of 31% naphthalenesulfonic acid are added to the resulting suspension at 10 ° C. The mixture is then stirred at 15-20 ° C. for 3 hours.

d) Primary coupling reaction: A solution of 15.2 parts of 3,5-diaminobenzoic acid in 100 parts of 2N hydrochloric acid is added to the acid diazo compound suspension obtained in step a) at 0-5 ° C. The pH of the reaction mixture is adjusted to 3.2 for 4 hours using 40% sodium acetate solution. The resulting mixture is then stirred at 6-7 ° C. for a further 30 minutes.

e) Secondary coupling reaction: The acid diazo compound suspension obtained according to step b) is added to the suspension obtained in step d) at 7 ° C. and pH 3.2. The pH of the resulting reaction mixture is adjusted to 4.5 over 45 minutes using 40% sodium acetate solution. The resulting mixture is then stirred for about 30 minutes at about 15 ° C.

f) tertiary coupling reaction: the acid diazo compound suspension obtained according to step c) is added to the suspension obtained according to step e) at 15 ° C. and pH 4.5. The pH of the reaction mixture is adjusted to 6.3 for 1 hour with sodium bicarbonate. The mixture is then stirred at about 25 ° C. for an additional 45 minutes. 450 parts of acetone are added to the resulting solution, then adjusted to pH 1.5 with concentrated hydrochloric acid, and 4.6 parts of potassium chloride are added. The product precipitated by precipitation is filtered off and washed with acetone. 72 parts of a product comprising essentially the compound of Formula 115 in the form of a free acid and which stains cotton and wool in orange color with excellent overall properties are obtained.

Examples 143-192 :

Dye essentially comprising the compound of Formula 116 can be prepared from the diazo compound described in Examples 2, 4 and 29-33 by a similar method as the procedure described in Example 142.

In Formula 116 above,

D ¹ _xy , D ² _xy and D ³ _xy are in each case the radicals listed in Table 6, which radicals are described in Example 2 and Table 1.

The dyes dye cotton and wool with good overall properties in the colors shown in Table 6.

The procedure described in Examples 38 to 108 and 114 to 192 is repeated, but instead of 3,5-diaminobenzoic acid, the compound of formula 117, the compound of formula 118, the compound of formula 119, the compound of formula 120 or Use in equimolar amounts. Additional useful dyes may be prepared that dye cotton and wool well in general.

The procedure described in Examples 109-113 is repeated, using compound of formula 117, compound 118 or compound 119 in equimolar amounts in place of 3,5-diaminobenzoic acid. Again, additional useful dyes can be prepared that dye cotton and wool well in general.

The compound of formula 117, the compound of formula 118, the compound of formula 119, the compound of formula 120 and the compound of formula 121 are known or can be prepared in a similar manner from known compounds.

Staining Instructions I

100 parts of cotton fabric are introduced at 1500 ° C. in a salt bath comprising 45 g / l sodium chloride at 60 ° C. and 2 parts of the reactive dye obtained according to Example 38. After 45 minutes at 60 ° C., 20 g / l calcined sodium carbonate is added. Staining is continued for an additional 45 minutes at this temperature. The dyed product is then washed, soaped with a nonionic detergent for 15 minutes at the boiling point, washed again and then dried.

As an alternative to the given instructions, it may be dyed at 80 ° C instead of 60 ° C.

Staining Instructions II

0.1 part of the dye according to Example 38 is dissolved in 200 parts of water, and 0.5 parts of sodium sulfate, 0.1 part of the leveling aid (the amount based on the condensation product of the higher aliphatic amine and ethylene oxide) and 0.5 part of sodium acetate are added. The pH is then adjusted to 5.5 using acetic acid (80%). The salt bath is heated to 50 ° C. for 10 minutes and 10 parts of wool is added. The salt bath is heated to a temperature of 100 ° C. for about 50 minutes and dyed at this temperature for 60 minutes. The bath is then cooled to 90 ° C. and the dyed product is recovered. The wool is washed with hot and cold water and then spin-dried and dried.

Printing instructions

100 parts of a stop thickener comprising 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodium bicarbonate with 3 parts of the dye obtained according to Example 141 with rapid stirring. Sprinkle on. The cotton fabric thus obtained is printed and then dried, and the resulting printing is steamed with saturated steam at 102 ° C. for 2 minutes. The printed fabric is then washed and soaped at boiling, then washed and dried again.

The novel azo dyes of the present invention not only have sufficient directivity, but also can be easily removed from non-fixed parts, provide a dyeing having excellent color fastness, high wet fastness, excellent coloration rate, high reactivity, and high adsorption rate. It is suitable for dyeing and printing fibrous materials, in particular cotton and wool fibers.

Claims (12)

Azo dyes containing at least one structural unit of formula (1). Formula 1

The azo dye according to claim 1, wherein the azo dye of the formula (2), (3) or (4). Formula 2

Formula 3

Formula 4

In the above formula 2 to 4, A is oxygen, sulfur or radical -NR'- where R 'is hydrogen or C ₁ -C ₁₂ alkyl which may be substituted or unsubstituted and in which oxygen may be involved in the chain, B is an aliphatic or aromatic crosslinker, D ₁ , D ₂ and D ₃ are each independently a radical of a benzene-based or naphthalene-based diazo component, D ₄ is a radical of an aromatic tetraazo component, R is hydrogen or an aliphatic or aromatic radical, or the radicals R and R 'together with the nitrogen atom form a heterocyclic radical. Claim 3 was abandoned when the setup registration fee was paid. The azo dye according to claim 2, wherein A is oxygen or a radical -NR'-. Claim 4 was abandoned when the registration fee was paid. The azo dye according to claim 2 or 3, wherein A is oxygen and R is hydrogen. Claim 5 was abandoned upon payment of a set-up fee. 4. Azo dyes according to claim 2 or 3 according to claim 2. The azo dye according to claim 2 or 3, wherein the radicals D ₁ , D ₂ and D ₃ are each independently a radical of formula 15 or formula 16. Formula 15

Formula 16

In Formulas 15 and 16 above, K is a chemical formula

(17a) or

Radical of the coupling component of (17b), Z and Z ₁ are each independently of the formula -SO ₂ -Y (6a), -CONR _2- (CH ₂ ) _m -SO ₂ -Y (6c), -NH-CO-CH (Hal) -CH ₂ -Hal (6d), -NH-CO-C (Hal) = CH ₂ (6e) or

Radical of (6f), wherein R _1a and R ₂ are hydrogen, Hal is bromine, Y is vinyl, β-chloroethyl or β-sulfatoethyl, and T ₁ is C ₁ -C ₄ alkoxy; C ₁ -C ₄ alkylthio; Hydroxyl; Amino; N-mono- or N, N-di-C ₁ -C ₄ alkylamino unsubstituted or substituted by hydroxyl, sulfato or sulfo alkyl residues; Morpholino; Phenylamino; NC ₁ -C ₄ alkyl-N-phenylamino unsubstituted or substituted by sulfo, carboxyl, acetylamino, chlorine, methyl or methoxy and unsubstituted or substituted by hydroxyl, sulfo or sulfato ; Naphthylamino unsubstituted or substituted by one to three sulfo groups; Or chemical formula

(7c ') or

Is a fiber reactive radical of (7d '), Y is as defined above, X ₁ is chlorine or fluorine, m is number 2 or 3}, (R ₄ ) _0-3 and (R ₁₃ ) _0-3 are each independently 0 to 3 identical or different selected from the group consisting of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, carboxyl and sulfo Substituents, R ' ₅ is hydrogen; Sulfo; Or C ₁ -C ₄ alkoxy which is unsubstituted or substituted by hydroxyl or sulfato by alkyl moiety, R ′ _5a is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkanoylamino, ureido or a radical of formula 6f wherein the radicals R _1a , T ₁ and X ₁ are defined above As in the same way. The azo dye according to claim 6, wherein the radicals D ₁ , D ₂ and D ₃ are each independently of the radicals of formula 15a, 15b, 15c, 15d or 16a. Formula 15a

Formula 15b

Formula 15c

Formula 15d

Formula 16a

In Formula 15a to Formula 15d and Formula 16a above, R ' ₅ is hydrogen; Sulfo; Or ethoxy unsubstituted or substituted by hydroxyl or sulfato alkyl residues, R ' _5a is hydrogen, methyl, ethyl, methoxy, ethoxy, acetylamino, propionylamino or ureido, (R ₁₃ ) _0-2 is 0 to 2 identical or different substituents selected from the group consisting of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfo, Y ₁ is a group —CH (Br) —CH ₂ —Br or —C (Br) = CH ₂ , Y is vinyl, β-chloroethyl or β-sulfatoethyl, m is the number 2 or 3. The azo dye according to claim 2 or 3, wherein D ₁ is a radical of the formula (18). Formula 18

In Formula 18 above, X ₁ is chlorine or fluorine, T ₃ is a chemical formula

10a,

10b),

(10d),

10e,

(10f),

(10k) or

Radicals of (10m) {in these Formulas 10a to 10m, (R ₄ ) _0-3 is 0 to 3 identical selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, carboxyl and sulfo Or a different substituent, and (R ₅ ) _0-3 is halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C ₁ -C ₄ alkyl; C ₁ -C ₄ alkoxy unsubstituted or substituted by hydroxyl, sulfato or C ₁ -C ₄ alkoxy; 0 to 3 identical or different substituents selected from the group consisting of amino, C ₂ -C ₄ alkanoylamino, ureido, hydroxyl, carboxyl, sulfomethyl, C ₁ -C ₄ alkylsulfonylamino and sulfo, R ₈ And R ₁₀ are independently of each other hydrogen, C ₁ -C ₄ alkyl or phenyl, R ₉ is hydrogen, cyano, carbamoyl or sulfomethyl, and (R ₁₁ ) _0-3 are independently of each other C ₁ -C ₄ 0 to 3 identical or different substituents selected from the group consisting of alkyl, C ₁ -C ₄ alkoxy, halogen, carboxyl and sulfo, Z ₁ is —SO ₂ —Y (6a), —CONH— (CH ₂ ) _{2- A} radical of ₃ -SO ₂ -Y (6c '), -NH-CO-CH (Br) -CH ₂ -Br (6d') or -NH-CO-C (Br) = CH ₂ (6e ') , Y is vinyl, β-chloroethyl or β-sulfatoethyl), and D ₂ and D ₃ are each independently of the formula

(15a),

(15b),

(15c) or

A radical of (15d), wherein (R ₁₃ ) _0-2 is 0 to 2 identical or different substituents selected from the group consisting of halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and sulfo, Y ₁ Is a group -CH (Br) -CH ₂ -Br or -C (Br) = CH ₂ , Y is as defined above and m is the number 2 or 3). 8. The azo dye of claim 7, wherein the azo dye of formula 2a. Formula 2a

In Formula 2a above, D ₁ , D ₂ and D ₃ are each independently a radical of the formula 15a, 15b, 15c, 15d or 16a, wherein at least one of the radicals D ₁ , D ₂ and D ₃ is fiber reactive Contains groups, D ₁ is a radical of formula 18 (wherein X ₁ is chlorine, T ₃ is a radical of formula 10a, 10b, 10d, 10e, 10f, 10k or 10m), D ₂ and D ₃ is, in each case, independently of one another, a radical of formula 15a, 15b, 15c or 15d and at least one of the radicals D ₂ and D ₃ contains a fiber reactive group. The method of claim 1, comprising coupling at least one diazotized amine together or in a predetermined order to a compound containing at least one structural unit of formula 19 to obtain an azo dye containing at least one structural unit of formula 1. Method for producing azo dyes according. Formula 19

A method for dyeing or printing textile materials containing hydroxyl groups or nitrogen containing azo dyes according to claim 1 or azo dyes obtained according to the production method of claim 10. Claim 12 was abandoned upon payment of a registration fee. The method of claim 11, wherein the cellulosic fiber material is dyed or printed.