EP0745719A2 - Use of carbohydrate compounds as auxiliary agents in the dyeing or printing of fibrous materials - Google Patents

Abstract

The use of carbohydrate cpds. (I) as ancillaries for dyeing or printing fibrous materials with reactive dyes is claimed. (I) are of the formula Z-G-T-R<1>n; in which Z = the residue of a mono-, di- or oligosaccharide or a sugar alcohol with the free valency on a C atom; G = an -O-, -NR<5>-, -O-CO-, -NR<5>-CO- or -NR<5>-SO2- bridge; R<5> = H or 1-4 C alkyl, opt. mono- to tetra-substd. by OH, SO3H, OSO3H or COOH; T = 4-20 C aliphatic, cycloaliphatic or olefinic hydrocarbyl, 6-10 C aryl or 6-10 C aryl-(1-4 C)-alkylene; R<1> = OH, COOH, CN, 1-4 C alkyl, 1-4 C alkoxy, SO3H, 1-10 C alkylsulphonyl, aminosulphonyl, 1-10 C alkylcarbonylamino, 1-10 C alkoxycarbonyl or aminocarbonyl, in which the alkyl or aryl gps. may have OH, NH2, NO2, CN, OMe, SO3H and/or COOH substit(s).; n = 0-3. Also claimed are pad dyeing baths, printing pastes, ink jet inks and dye formulations contg. (I).

Description

The technique of dyeing and printing with fiber-reactive dyes on fiber materials uses highly concentrated dye solutions and printing pastes. The solubility of the dyes is often problematic, so that auxiliaries must be used to improve the solubility.
Especially in block dyeing processes and in textile printing, large amounts of urea are often used as an auxiliary, which usually gets into the wastewater after application, which is ecologically questionable.
In the block cold dwell process and in single-phase printing, the durability of alkaline block liquors and printing pastes leaves much to be desired with many dyes, which leads, for example, to end processes and thus limits the process reliability and reproducibility of the nuances. Ink-jet inks run the risk of the ink solution drying out.

The present invention was based on the task of replacing urea as an aid in dyeing and printing textiles with an ecologically harmless aid without causing coloristic disadvantages in dyeing.

This object was surprisingly achieved by using the carbohydrate compounds defined below.

Z

für den Rest eines Kohlenhydrats aus der Reihe der Mono-, Di- oder Oligosaccharide oder eines Zuckeralkohols steht, wobei die freie Valenz sich an einem Kohlenstoffatom befindet;

G

für ein Brückenglied aus der Reihe -O-, -NR⁵-, -O-CO-, -NR⁵-CO- und -NR⁵-SO₂- steht, worin R⁵ Wasserstoff oder C₁-C₄-Alkyl ist, das durch 1 bis 4 Reste aus der Reihe Hydroxy, Sulfo, Sulfato, Di(C₁-C₄-alkyl)amino oder Carboxy substituiert sein kann;

T

für einen C₄-C₃₀-aliphatischen, cycloaliphatischen oder olefinischen Kohlenwasserstoffrest, für C₆-C₁₀-Aryl oder für C₆-C₁₀-Aryl-C₁-C₄-alkylen steht;

R¹

für Hydroxy, Carboxy, Cyano, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Sulfo, C₁-C₁₀-Alkylsulfonyl, Aminosulfonyl, C₁-C₁₀-Alkylaminosulfonyl oder C₆-C₁₀-Arylaminosulfonyl, C₁-C₁₀-Alkylcarbonyl, Ureido, C₁-C₁₀-Alkylcarbonylamino, C₁-C₁₀-Alkoxycarbonyl oder Aminocarbonyl steht, wobei die Alkyl- oder Arylreste mit 1 oder mehreren der Reste OH, NH₂, NO₂, CN, OCH₃, Sulfo und COOH substituiert sein können;

n

eine Zahl von 0 bis 3 ist, wobei für den Fall, daß n größer als 1 ist, die Reste R¹ auch voneinander verschiedene Bedeutungen haben können,

als Hilfsmittel zum Färben oder Bedrucken von Fasermaterialien mit faserreaktiven Farbstoffen.The present invention relates to the use of carbohydrate compounds of the formula (1)

ZGTR ¹ _n (1)

wherein

Z.

represents the rest of a carbohydrate from the series of mono-, di- or oligosaccharides or a sugar alcohol, the free valence being on a carbon atom;

G

represents a bridge member from the series -O-, -NR ⁵ -, -O-CO-, -NR ⁵ -CO- and -NR ⁵ -SO ₂ -, wherein R ^{5 is} hydrogen or C ₁ -C ₄ alkyl which can be substituted by 1 to 4 radicals from the series hydroxy, sulfo, sulfato, di (C ₁ -C ₄ alkyl) amino or carboxy;

T

represents a C ₄ -C ₃₀ aliphatic, cycloaliphatic or olefinic hydrocarbon radical, C ₆ -C ₁₀ aryl or C ₆ -C ₁₀ aryl-C ₁ -C ₄ alkylene;

R ¹

for hydroxy, carboxy, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo, C ₁ -C ₁₀ alkylsulfonyl, aminosulfonyl, C ₁ -C ₁₀ alkylaminosulfonyl or C ₆ -C ₁₀ arylaminosulfonyl , C ₁ -C ₁₀ alkylcarbonyl, ureido, C ₁ -C ₁₀ alkylcarbonylamino, C ₁ -C ₁₀ alkoxycarbonyl or aminocarbonyl, the alkyl or aryl radicals having 1 or more of the radicals OH, NH ₂ , NO ₂ , CN, OCH ₃ , sulfo and COOH may be substituted;

n

is a number from 0 to 3, where, if n is greater than 1, the radicals R ^{1 can} also have different meanings,

as an aid for dyeing or printing fiber materials with fiber-reactive dyes.

Z

für den Rest einer Pentose, Hexose, eines Oligosaccharids mit 2 bis 40 Monosaccharideinheiten oder eines Zuckeralkohols steht;

G

für -O-, -NH-, -NCH₃-, -NH-CO-, -NCH₃-CO-, -[N(CH₂CH₂OH)]-CO-, -O-CO-, -NHSO₂- oder -NCH₃-SO₂- steht;

T

für C₄-C₃₀-Alkyl, C₄-C₃₀-Alkenyl, Cyclohexyl, Phenyl, Naphth-1-yl, Naphth-2-yl oder Benzyl steht;

R¹

für Hydroxy, Sulfo, Carboxy, Methyl, Ethyl, Methoxy, Ethoxy, Acetyl, C₁-C₄-Alkylsulfonyl, C₁-C₄-Alkylaminosulfonyl, Phenylaminosulfonyl, Naphthylaminosulfonyl, C₁-C₄-Alkylcarbonyl, C₁-C₄-Alkylcarbonylamino oder C₁-C₄-Alkoxycarbonyl steht; und

n

eine Zahl von 0 bis 1 ist.

For the purposes of the present invention, preference is given to compounds of the formula (1) in which

Z.

represents the rest of a pentose, hexose, an oligosaccharide with 2 to 40 monosaccharide units or a sugar alcohol;

G

for -O-, -NH-, -NCH ₃ -, -NH-CO-, -NCH ₃ -CO-, - [N (CH ₂ CH ₂ OH)] - CO-, -O-CO-, -NHSO ₂ - or -NCH ₃ -SO ₂ -;

T

represents C ₄ -C ₃₀ alkyl, C ₄ -C ₃₀ alkenyl, cyclohexyl, phenyl, naphth-1-yl, naphth-2-yl or benzyl;

R ¹

for hydroxy, sulfo, carboxy, methyl, ethyl, methoxy, ethoxy, acetyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ -Alkylcarbonylamino or C ₁ -C ₄ -alkoxycarbonyl; and

n

is a number from 0 to 1.

Z

für einen Rest der Formeln (2a), (2b), (2c), (2d), (2e), (2f) oder (2g) steht

ist, worin

x

eine Zahl von 1 bis 20 ist;

y

eine Zahl von 1 bis 6, bevorzugt 1 oder 2 ist;

R²

Hydroxymethyl, Carboxy, Acetyl oder C₁-C₄-Alkoxymethyl, insbesondere Methoxymethyl, ist, wobei der Rest Alkoxy durch 1 bis 4 Substituenten aus der Reihe Hydroxy, C₁-C₄-Alkoxy, wie Methoxy, Acetyl oder Carboxy substituiert sein kann;

R³

Wasserstoff, Sulfo, Acetyl, C₁-C₄-Alkylsulfonyl, wie Methylsulfonyl, C₆-C₁₀-Arylsulfonyl, wie Phenylsulfonyl, C₁-C₄-Alkyl, das durch einen Substituenten aus der Reihe Hydroxy oder Carboxy substituiert sein kann, wie beispielsweise Methyl, β-Hydroxyethyl oder Carboxymethyl, oder der Rest eines Glucosids ist, wobei die Reste R³ jeweils gleich sind oder voneinander verschiedene Bedeutungen haben;

und

R⁴

für Wasserstoff, Acetyl, Benzoyl oder den Rest eines Peptids oder einer Aminosäure steht.

For the purposes of the present invention, particular preference is given to compounds of the formula (1) in which

Z.

represents a radical of the formulas (2a), (2b), (2c), (2d), (2e), (2f) or (2g)

is what

x

is a number from 1 to 20;

y

is a number from 1 to 6, preferably 1 or 2;

R ²

Is hydroxymethyl, carboxy, acetyl or C ₁ -C ₄ alkoxymethyl, in particular methoxymethyl, where the remainder alkoxy can be substituted by 1 to 4 substituents from the series hydroxy, C ₁ -C ₄ alkoxy such as methoxy, acetyl or carboxy ;

R ³

Hydrogen, sulfo, acetyl, C ₁ -C ₄ alkylsulfonyl, such as methylsulfonyl, C ₆ -C ₁₀ arylsulfonyl, such as phenylsulfonyl, C ₁ -C ₄ alkyl, which can be substituted by a substituent from the series hydroxyl or carboxy, such as, for example, methyl, β-hydroxyethyl or carboxymethyl, or the remainder of a glucoside, where the R ³ radicals are each the same or have different meanings;

and

R ⁴

represents hydrogen, acetyl, benzoyl or the rest of a peptide or an amino acid.

Preferred for R ² is hydroxymethyl, carboxy, HOOC-CH ₂ -O-CH ₂ - and H ₃ CO-CH ₂ -. Hydroxymethyl is particularly preferred.
R ³ is particularly preferably hydrogen, hydroxyethyl, carboxymethyl, sulfo, in particular hydrogen.
Hydrogen is preferred for R ⁴ .
The linking of the radical Z of the formulas (2a), (2b), (2c), (2d), (2e) and (2g) to the bridge G can be α- or β-glycosidic, or it can be a mixture of both forms available.

The stereochemistry of the sugar residue of the formulas (2a), (2b), (2c), (2d), (2e) and (2g) can be D, L or DL, but preferably D.
In the event that Z is (2c) or (2e), the linkage of the one saccharide monomer unit to the second saccharide unit can be α- or β-glycosidic, or a mixture of both forms may be present, the β-glycosidic being preferred Shortcut. The linking of the repeating disaccharide units can also be of the α- or β-glycosidic type, or a mixture of both forms may be present, the β-glycosidic linkage also being preferred here.

In the event that G is -O- or -NR ⁵ -, the radical Z is preferably a radical of the formulas (2a), (2b), (2c) (2d), (2e) and (2g), in particular (2a).
In the event that G represents -NR ⁵ -CO-, -NR ⁵ -SO ₂ - or -O-CO-, the radical Z is preferably a radical of the formula (2f).

In the event that Z is (2e), the radical T is preferably a C ₁₂ -C ₂₀ alkyl radical which may contain 1 to 10 olefinic double bonds, and R ¹ is preferably hydroxy or carboxy.

The carbohydrate residue of the formula (2a) is preferably the residue of a D-glucopyranoside, D-mannopyranoside or D-galactopyranoside, in particular the residue of a D-glucopyranoside.
The carbohydrate residue of the formula (2b) is preferably the residue of a D-ribofuranoside, D-fructofuranoside or D-glucofuranoside.
The carbohydrate residue of the formula (2c) is preferably a cellobiose, maltose, lactose, a poly or oligo-β-1,4-D-glucose or -α-1,4-D-glucose residue.
The monomer member of the carbohydrate residue of the formula (2d) is preferably an α-1,6-D-glucose or a β-1,6-D-glucose residue.
The carbohydrate residue of the formula (2e) is preferably the residue of a sophorosis.
The carbohydrate residue of the formula (2f) is preferably sorbitol or mannitol.
The carbohydrate residue of the formula (2g) is preferably a D-glucosamine and, together with G, particularly preferably forms the residue of a glucamide if G is -NR ⁵ -CO-.

Furthermore, Z can be the residue of a trisaccharide of the raffinose type.

Examples of preferred structural elements T- [R ¹ ] _n are 3-hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxyphenyl, 2-carboxyphenyl, naphth-2-yl, 6-carboxy-naphth-2-yl, 3-carboxy- naphth-2-yl, 4-carboxyphenyl, 1-carboxy-naphth-2-yl, 5-hydroxy-naphth-2-yl, 8-hydroxy-naphth-2-yl, 3-hydroxy-naphth-2-yl, 6-hydroxy-naphth-2-yl, 7-hydroxy-naphth-2-yl, 6-sulfo-naphth-2-yl, 8-sulfo-naphth-2-yl, 3-hydroxy-6-sulfo-naphth- 2-yl, 8-hydroxy-6-sulfonaphth-2-yl, 6-aminosulfonylnaphth-2-yl, 7- (2'-hydroxyphenyl) aminosulfonylnaphth-2-yl, naphth-1-yl , Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, nC ₁₂ to C ₁₆ alkyl and nC ₁₂ to C ₁₆ alkenyl.

Examples of sugar residues Z are ribose, arabinose, xylose, glucose, mannose, galactose, fructose, glucuronic acid or mannuronic acid.

worin

R^1'

Wasserstoff, Hydroxy, Carboxy, COOCH₃ oder COOC₂H₅ ist;

R^2'

Wasserstoff, Acetyl oder Carboxymethyl ist;

R^1''

Wasserstoff, Hydroxy, Sulfo oder Carboxy, wobei R^1'' und der Pyranosylrest bevorzugt in 2,3- oder 2,6-Position zueinander stehen;

R^5'

Wasserstoff oder Methyl ist;

R⁷

Hydroxy oder Wasserstoff ist;

R^7'

Hydroxy, Methyl oder Wasserstoff ist und bevorzugt in ortho- oder para-Position zu der Sulfonylgruppe steht;

R⁸

Hydroxy oder Wasserstoff, wobei R⁸ und der Saccharylaminocarbonyl-Rest bevorzugt in 2,3- oder 2,6-Position zueinander stehen;

R^9'

für C₇-C₂₀-Alkyl, bevorzugt C₁₁-C₁₇-Alkyl, steht, das 1 bis 3 olefinische Doppelbindungen enthalten kann;

W

für C₁₃-C₁₉-Alkylen, bevorzugt C₁₇-Alkylen, steht, das 1 bis 8 olefinische Doppelbindungen enthalten und/oder verzweigt sein kann;

R¹⁰

für Wasserstoff oder Methyl steht;

R¹¹

für Wasserstoff oder Acetyl steht; und

Q

Wasserstoff, Cyano oder Carboxy ist.

Examples of particularly preferred carbohydrate compounds of the formula (1) are the compounds of the formulas (1a) to (1k)

wherein

R ^{1 '}

Is hydrogen, hydroxy, carboxy, COOCH ₃ or COOC ₂ H ₅ ;

R ^{2 '}

Is hydrogen, acetyl or carboxymethyl;

R ^{1 ''}

Hydrogen, hydroxy, sulfo or carboxy, where R ^{1 ″} and the pyranosyl radical are preferably in the 2,3- or 2,6-position to one another;

R ^{5 '}

Is hydrogen or methyl;

R ⁷

Is hydroxy or hydrogen;

R ^{7 '}

Is hydroxyl, methyl or hydrogen and is preferably in the ortho or para position to the sulfonyl group;

R ⁸

Hydroxy or hydrogen, where R ⁸ and the saccharylaminocarbonyl radical are preferably in the 2,3- or 2,6-position to one another;

R ^{9 '}

represents C ₇ -C ₂₀ alkyl, preferably C ₁₁ -C ₁₇ alkyl, which may contain 1 to 3 olefinic double bonds;

W

represents C ₁₃ -C ₁₉ alkylene, preferably C ₁₇ alkylene, which contains 1 to 8 olefinic double bonds and / or can be branched;

R ¹⁰

represents hydrogen or methyl;

R ¹¹

represents hydrogen or acetyl; and

Q

Is hydrogen, cyano or carboxy.

wobei W¹ ein Rest der Formeln -(CH₂)₁₃-, -(CH₂)₁₅-, -(CH₂)₆-CH=CH-(CH₂)₇- oder -(CH₂)₃-CH=CH-CH₂-CH=CH-(CH₂)₇- oder eine Kombination davon ist.Examples of particularly suitable carbohydrate compounds of the formula (1) are
2-hydroxyphenyl-α-D-galactopyranoside, 2-hydroxyphenyl-α-D-glucopyranoside,
2-hydroxyphenyl-β-D-glucopyranoside, 2-hydroxyphenyl-β-D-galactopyranoside,
2-carboxyphenyl-α-D-galactopyranoside, 2-carboxyphenyl-α-D-glucopyranoside,
2-carboxyphenyl-β-D-glucopyranoside, 2-carboxyphenyl-β-D-galactopyranoside,
4-hydroxyphenyl-α-D-galactopyranoside, 4-hydroxyphenyl-α-D-glucopyranoside,
4-hydroxyphenyl-β-D-glucopyranoside, 4-hydroxyphenyl-β-D-galactopyranoside,
3-hydroxyphenyl-α-D-galactopyranoside, 3-hydroxyphenyl-α-D-glucopyranoside,
3-hydroxyphenyl-β-D-glucopyranoside, 3-hydroxyphenyl-β-D-galactopyranoside,
3,5-dihydroxyphenyl-α-D-galactopyranoside,
3,5-dihydroxyphenyl-α-D-glucopyranoside,
3,5-dihydroxyphenyl-β-D-glucopyranoside,
3,5-dihydroxyphenyl-β-D-galactopyranoside, naphth-2-yl-α-D-galactopyranoside,
Naphth-2-yl-α-D-glucopyranoside, naphth-2-yl-β-D-glucopyranoside,
Naphth-2-yl-β-D-galactopyranoside,
6'-carboxymethyl-naphth-2-yl-α-D-galactopyranoside,
6'-carboxymethyl-naphth-2-yl-α-D-glucopyranoside,
6'-carboxymethyl-naphth-2-yl-β-D-glucopyranoside,
6'-carboxymethyl-naphth-2-yl-β-D-galactopyranoside,
Naphth-1-yl-α-D-galactopyranoside, naphth-1-yl-α-D-glucopyranoside,
Naphth-1-yl-β-D-glucopyranoside, naphth-1-yl-β-D-galactopyranoside,
3-carboxy-naphth-2-yl-α-D-galactopyranoside,
3-carboxy-naphth-2-yl-α-D-glucopyranoside,
3-carboxy-naphth-2-yl-β-D-glucopyranoside,
3-carboxy-naphth-2-yl-β-D-galactopyranoside,
6-carboxy-naphth-2-yl-α-D-galactopyranoside,
6-carboxy-naphth-2-yl-α-D-glucopyranoside,
6-carboxy-naphth-2-yl-β-D-glucopyranoside,
6-carboxy-naphth-2-yl-β-D-galactopyranoside,
1-carboxy-naphth-2-yl-β-D-glucopyranoside,
1-hydroxy-naphth-2-yl-β-D-glucopyranoside,
3-hydroxy-naphth-2-yl-β-D-glucopyranoside,
6-hydroxy-naphth-2-yl-β-D-glucopyranoside,
7-hydroxy-naphth-2-yl-β-D-glucopyranoside,
6-aminosulfonyl-naphth-2-yl-β-D-glucopyranoside,
7- (2'-carboxyphenyl) aminosulfonyl-naphth-2-yl-β-D-glucopyranoside,
8-sulfonaphth-2-yl-β-D-glucopyranoside, 6-sulfonaphth-2-yl-β-D-glucopyranoside,
8-hydroxy-6-sulfonaphth-2-yl-β-D-glucopyranoside,
N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) salicylamide,
N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) salicylamide,
3- {N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl)} - aminocarbonyl-2-naphthol,
3- {N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl)} - aminocarbonyl-2-naphthol,
6- {N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl)} - aminocarbonyl-2-naphthol,
6- {N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl)} - aminocarbonyl-2-naphthol,
N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) stearic acid amide,
N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) stearic acid amide,
N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) oleic acid amide,
N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) oleic acid amide,
N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) palmitic acid amide,
N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) palmitic acid amide,
N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) benzamide,
N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) benzamide,
2'-methoxy-N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) benzamide,
2'-methoxy-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) benzamide,
4'-hydroxy-N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) benzamide,
4'-hydroxy-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) benzamide,
Phenylsulfonyl-N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) amide,
Phenylsulfonyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) amide,
3- {N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl)} - aminosulfonyl-2-naphthol,
3- {N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl)} - aminosulfonyl-2-naphthol,
6-N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl)} - aminosulfonyl-2-naphthol,
6- {N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl)} - aminosulfonyl-2-naphthol,
{4'-methylphenyl} sulfonyl-N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) amide,
{4'-methylphenyl} sulfonyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) amide,
{2'-methylphenyl} sulfonyl-N-methyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) amide,
{2'-methylphenyl} sulfonyl-N- (D-gluco-2,3,4,5,6-pentahydroxyhexyl) amide, and Sophorose lipids and sophorose lipid mixtures, such as

where W ^{1 is} a radical of the formulas - (CH ₂ ) ₁₃ -, - (CH ₂ ) ₁₅ -, - (CH ₂ ) ₆ -CH = CH- (CH ₂ ) ₇ - or - (CH ₂ ) ₃ -CH = CH-CH ₂ -CH = CH- (CH ₂ ) ₇ - or a combination thereof.

The compounds of formula (1) and their preparation are known, for example from Pol. J. Chem. (1993), 67 (7), 1251; Liebigs Ann. Chemie (1992), 5,485; Tetrahedron Letters (1979), 52, 5051; Carbohydr. Res. (1977), 53, C11; Acta Chem Scand., Ser. B. (1978), B 32, 72; J. Carbohydr. Chem. (1992), 11 (6), 761; DE-A-4329093; Stanek, Cerny: "The Monosaccharides", Academic Press, Prague 1963.

Suitable dyes for the purposes of the present invention are fiber-reactive dyes from the series of monoazo, bisazo, polyazo, metal complex azo, anthraquinone, metal complex formazan dyes, such as Cu formazans, metal complex phthalocyanine dyes, such as Cu or Ni-phthalocyanine dyes, or triphendioxazine dyes, as are known, for example, from numerous patents, books or publications (for example Venkataraman, K .: The Chemistry of Synthetic Dyes, Vol. VI.).

Of the monoazo dyes, the structural elements listed below are particularly suitable for the application technology described:

Of the bisazo dyes, the compounds listed below are particularly suitable for the application technology described:

Of the anthraquinone dyes, the compounds listed below are particularly suitable for the application technique described:

Of the Cu formazan dyes, the compounds listed below are particularly suitable for the application technology described:

wobei

L₁

C₁-C₆-Alkylen-NH-Z, C₁-C₆-Alkylen-SO₂Y, C₁-C₆-Alkylen-NH-C₁-C₆-alkylen-SO₂Y oder C₁-C₆-Alkylen-O-C₁-C₆-alkylen-SO₂Y und

L₂

C₁-C₆-Alkylen-OSO₃H, C₁-C₆-Alkyen-COOH oder C₁-C₆-Alkylen-SO₃H bedeuten.

Of the triphendioxazine dyes, the compounds listed below are particularly suitable for the application technology described:

in which

L ₁

C ₁ -C ₆ alkylene-NH-Z, C ₁ -C ₆ alkylene-SO ₂ Y, C ₁ -C ₆ alkylene-NH-C ₁ -C ₆ alkylene-SO ₂ Y or C ₁ -C _6- alkylene-OC ₁ -C ₆ -alkylene-SO ₂ Y and

L ₂

C ₁ -C ₆ -alkylene-OSO ₃ H, C ₁ -C ₆ -alkylene-COOH or C ₁ -C ₆ -alkylene-SO ₃ H mean.

Particularly preferred alkylene radicals are ethylene and propylene.

Of the phthalocyanine dyes, the compounds listed below are particularly suitable for the application technology described:

Y

ist Vinyl oder bedeutet ein Ethyl, das in β-Position durch einen unter alkalischen Bedingungen eliminierbaren Substituenten substituiert ist;

R⁶

ist Wasserstoff oder Methyl, bevorzugt Wasserstoff;

Q¹

ist Methoxy, Methyl oder Wasserstoff, bevorzugt Wasserstoff;

Q²

ist Wasserstoff, Hydroxy, Methoxy, Carboxy, Sulfo oder Halogen, bevorzugt Wasserstoff, oder O-Cu, wobei in diesem Fall die Azobrücke und die Hydroxygruppe der Kupplungskomponente ebenfalls mit Cu komplexieren;

Q^1'

hat eine der Bedeutungen von Q¹;

Q^2'

hat eine der Bedeutungen von Q²;

Q³

ist Wasserstoff oder Sulfo;

Q⁴

ist Wasserstoff, Hydroxy, Methoxy, Methyl, Carboxy oder Sulfo, bevorzugt Wasserstoff;

Q⁵

ist Methyl, Methoxy, Amino, Ureido, Acetylamino;

Q⁶

ist Wasserstoff, Sulfo, Methyl oder Methoxy;

Q⁷

ist Wasserstoff, Methyl oder Methoxy;

Q⁸

ist Methyl oder Carboxy;

Q⁹

ist Wasserstoff, Cyano, Aminocarbonyl oder Sulfomethyl;

Q¹⁰

ist Wasserstoff, Methyl, Methoxy, Hydroxy oder O-Cu, wobei in diesem Fall die Azobrücke und die Hydroxygruppe der Kupplungskomponente ebenfalls mit Cu komplexieren;

Q¹¹

ist Methyl, Ethyl oder β-Sulfoethyl;

T²

ist Phenylen oder Naphthylen, bevorzugt 1,4-Phenylen, das durch 1 bis 3 gleiche oder verschiedene Substituenten aus der Reihe Chlor, Methyl, Sulfo oder Carboxy substituiert sein kann;

Z¹

ist Methyl, Ethyl oder Phenyl;

Z²

ist Hydroxy oder hat dieselbe Bedeutung wie Y;

n

ist 0 oder 1;

m

ist 0 oder 1, bevorzugt 0;

r

ist 0 oder 1, bevorzugt 1;

s

ist 0 oder 1, bevorzugt 1;

p

ist 1 bis 3;

q

ist 1 bis 2;

T

ist Phenylen, das durch 1 bis 3 Methylgruppen sowie 1 bis 2 Sulfogruppen substituiert sein kann, wobei insgesamt 3 Substituenten möglich sind;

B

ist ein Brückenglied -S-, -O- oder -NH-;

B²

ist eine direkte Bindung oder ein Brückenglied aus der Reihe -(CH₂)₂-NH-, -(CH₂)₃-NH-, -(CH₂)₂-O-, -(CH₂)₃-O- oder Aminophenylen, wobei der Phenylrest bevorzugt mit einer Sulfogruppe substituiert ist;

R¹²

ist Sulfo oder der Rest einer gegebenenfalls substituierten C₁-C₄-Alkylcarbonylverbindung, bevorzugt β-Carboxyethyl-carbonyl;

Met

ist ein Metallatom, bevorzugt Cu oder Ni;

Pc

ist der Rest eines Phthalocyanins;

A

ist Amino oder

worin Z³ OH oder NH₂ ist;

a

ist eine ganze oder gebrochene Zahl von 0,5 bis 2,5, bevorzugt 1,0 bis 1,9;

b

ist eine ganze oder gebrochene Zahl von 0 bis 4, bevorzugt 1,5 bis 2,5;

c

ist eine ganze oder gebrochene Zahl von 0 bis 2, bevorzugt 0 bis 1,

wobei die Summe $\text{a+b+c}$

eine Zahl zwischen 3 und 4,5, bevorzugt 3,1 und 3,7, ist;

X

ist ein heterocyclischer faserreaktiver Rest, bevorzugt aus der Reihe der Chinoxaline, Triazine und Pyrimidine,
vorzugsweise ein Pyrimidin der Formel

worin B¹ die Bedeutung -SO₂CH₃, Cl oder F; B² die Bedeutung CH₃, Cl oder F haben und mindestens einer der Reste B¹ und B² F oder Cl bedeuten; und Q¹² für Wasserstoff, Chlor, Fluor oder Cyano steht;
oder vorzugsweise ein Triazin der Formeln

worin

Y

eine der obengenannten Bedeutungen hat und

Hal

Chlor oder Fluor ist;

A¹

Amino oder Chlor ist;

alk

für 1,2-Ethylen, 1,3-Propylen oder für -(CH₂)₂-O-(CH₂)₂- steht;

Ar

für 1,3- oder 1,4-Phenylen steht, das durch Methoxy substituiert sein kann;

R'

für Wasserstoff, Methyl, Ethyl oder Phenyl steht;

R''

für Wasserstoff, Methyl oder Ethyl, bevorzugt Wasserstoff, steht;

R'''

für Wasserstoff, Methyl oder Ethyl, bevorzugt Wasserstoff, steht; und

R''''

für Wasserstoff, Chlor oder Methyl, bevorzugt Wasserstoff, steht;

oder X steht für einen Rest der Formel

worin Hal, Q¹², B¹ und B² wie vorstehend definiert sind und

U

C₁-C₆-Alkylen; C₆-Arylen, das durch 1 oder 2 der Reste Sulfo, Carboxy, Methyl und/oder Methoxy substituiert sein kann,

bedeutet.The variables in the formulas given above mean:

Y

is vinyl or is an ethyl which is substituted in the β-position by a substituent which can be eliminated under alkaline conditions;

R ⁶

is hydrogen or methyl, preferably hydrogen;

Q ¹

is methoxy, methyl or hydrogen, preferably hydrogen;

Q ²

is hydrogen, hydroxy, methoxy, carboxy, sulfo or halogen, preferably hydrogen, or O-Cu, in which case the azo bridge and the hydroxy group of the coupling component also complex with Cu;

Q ^{1 '}

has one of the meanings of Q ¹ ;

Q ^{2 '}

has one of the meanings of Q ² ;

Q ³

is hydrogen or sulfo;

Q ⁴

is hydrogen, hydroxy, methoxy, methyl, carboxy or sulfo, preferably hydrogen;

Q ⁵

is methyl, methoxy, amino, ureido, acetylamino;

Q ⁶

is hydrogen, sulfo, methyl or methoxy;

Q ⁷

is hydrogen, methyl or methoxy;

Q ⁸

is methyl or carboxy;

Q ⁹

is hydrogen, cyano, aminocarbonyl or sulfomethyl;

Q ¹⁰

is hydrogen, methyl, methoxy, hydroxy or O-Cu, in which case the azo bridge and the hydroxyl group of the coupling component also complex with Cu;

Q ¹¹

is methyl, ethyl or β-sulfoethyl;

T ²

is phenylene or naphthylene, preferably 1,4-phenylene, which can be substituted by 1 to 3 identical or different substituents from the series chlorine, methyl, sulfo or carboxy;

Z ¹

is methyl, ethyl or phenyl;

Z ²

is hydroxy or has the same meaning as Y;

n

is 0 or 1;

m

is 0 or 1, preferably 0;

r

is 0 or 1, preferably 1;

s

is 0 or 1, preferably 1;

p

is 1 to 3;

q

is 1 to 2;

T

is phenylene, which can be substituted by 1 to 3 methyl groups and 1 to 2 sulfo groups, a total of 3 substituents being possible;

B

is a bridge member -S-, -O- or -NH-;

B ²

is a direct bond or a bridge member from the series - (CH ₂ ) ₂ -NH-, - (CH ₂ ) ₃ -NH-, - (CH ₂ ) ₂ -O-, - (CH ₂ ) ₃ -O- or Aminophenylene, the phenyl radical preferably being substituted by a sulfo group;

R ¹²

is sulfo or the residue of an optionally substituted C ₁ -C ₄ alkylcarbonyl compound, preferably β-carboxyethylcarbonyl;

Mead

is a metal atom, preferably Cu or Ni;

Pc

is the rest of a phthalocyanine;

A

is amino or

wherein Z ^{3 is} OH or NH ₂ ;

a

is an integer or fraction from 0.5 to 2.5, preferably 1.0 to 1.9;

b

is an integer or fraction from 0 to 4, preferably 1.5 to 2.5;

c

is an integer or fractional number from 0 to 2, preferably 0 to 1,

being the sum $\text{a + b + c}$

is a number between 3 and 4.5, preferably 3.1 and 3.7;

X

is a heterocyclic fiber-reactive radical, preferably from the series of quinoxalines, triazines and pyrimidines,
preferably a pyrimidine of the formula

wherein B ^{1 is} -SO ₂ CH ₃ , Cl or F; B ² are CH ₃ , Cl or F and at least one of the radicals B ¹ and B ^{2 is} F or Cl; and Q ^{12 represents} hydrogen, chlorine, fluorine or cyano;
or preferably a triazine of the formulas

wherein

Y

has one of the meanings mentioned above and

Hal

Is chlorine or fluorine;

A ¹

Is amino or chlorine;

alk

represents 1,2-ethylene, 1,3-propylene or - (CH ₂ ) ₂ -O- (CH ₂ ) ₂ -;

Ar

represents 1,3- or 1,4-phenylene, which may be substituted by methoxy;

R '

represents hydrogen, methyl, ethyl or phenyl;

R ''

represents hydrogen, methyl or ethyl, preferably hydrogen;

R '''

represents hydrogen, methyl or ethyl, preferably hydrogen; and

R ''''

represents hydrogen, chlorine or methyl, preferably hydrogen;

or X represents a radical of the formula

wherein Hal, Q ¹² , B ¹ and B ^{2 are} as defined above and

U

C ₁ -C ₆ alkylene; C ₆ arylene, which can be substituted by 1 or 2 of the radicals sulfo, carboxy, methyl and / or methoxy,

means.

worin Q^12' Wasserstoff oder Chlor ist.

X¹

hat eine der Bedeutungen von X und ist bevorzugt ein Triazinrest oder ein Rest der Formel

Of the pyrimidine compounds, the following are particularly preferred:

wherein Q ^{12 'is} hydrogen or chlorine.

X ¹

has one of the meanings of X and is preferably a triazine radical or a radical of the formula

Examples of particularly suitable fiber-reactive dyes are
7- (4'-β-sulfatoethylsulfonyl) phenylazo-8-hydroxy-2-acetylamino-6-sulfonaphthalene,
7- (4'-β-sulfatoethylsulfonyl) phenylazo-8-hydroxy-3-acetylamino-6-sulfonaphthalene,
7- (4'-β-sulfatoethylsulfonyl) phenylazo-8-hydroxy-1-acetylamino-3,6-disulfonaphthalene,
7- (4'-β-sulfatoethylsulfonyl) phenylazo-8-hydroxy-1-acetylamino-4,6-disulfonaphthalene,
7- (4'-β-sulfatoethylsulfonyl) phenylazo-8-hydroxy-2-benzoylamino-6-sulfonaphthalene,
7- (4'-β-sulfatoethylsulfonyl) phenylazo-8-hydroxy-3-benzoylamino-6-sulfonaphthalene,
7- (4'-β-sulfatoethylsulfonyl) phenylazo-8-hydroxy-1-benzoylamino-3,6-disulfonaphthalene,
7- (4'-β-sulfatoethylsulfonyl) phenylazo-8-hydroxy-1-benzoylamino-4,6-disulfonaphthalene,
7- [6'-β-sulfatoethylsulfonyl-1-sulfonaphth-2'-yl] azo-8-hydroxy-1-acetylamino-3,6-disulfonaphthalene,
7- [6'-β-sulfatoethylsulfonyl-naphth-2'-yl] azo-8-hydroxy-3-acetylamino-6-sulfo-naphthalene,
7- [8'-β-sulfatoethylsulfonyl-6'-sulfonaphth-2'-yl] azo-8-hydroxy-3-acetylamino-6-sulfonaphthalene,
7- [8'-β-sulfatoethylsulfonyl-naphth-2'-yl] azo-8-hydroxy-3-acetylamino-6-sulfo-naphthalene;
2,7-bis - [(4'-β-sulfatoethylsulfonyl) phenylazo] -8-hydroxy-1-amino-3,6-disulfonaphthalene,
2,7-bis - [(4'-β-sulfatoethylsulfonyl) phenylazo] -8-hydroxy-1-amino-4,6-disulfonaphthalene,
2- (4'-β-sulfatoethylsulfonyl) phenylazo-7- (4 '' sulfophenylazo) -8-hydroxy-1-amino-3,6-disulfonaphthalene,
2- (4'-β-sulfatoethylsulfonyl) phenylazo-7- (2 ", 5" disulfophenylazo) -8-hydroxy-1-amino-3,6-disulfonaphthalene,
2- (4'-β-Sulfatoethylsulfonyl) phenylazo-7- (4 '' - β-sulfatoethylsulfonyl-2 ", 5" - dimethoxy-phenyl-azo) -8-hydroxy-1-amino-3,6 disulfonaphthalene,
2- (4'-β-Sulfatoethylsulfonyl) phenylazo-7- (4 '' - β-Sulfatoethylsulfonyl-2 '' - methoxy-5 '' - methylphenyl-azo) -8-hydroxy-1-amino-3 , 6-disulfonaphthalene,
2- (4'-β-Sulfatoethylsulfonyl) phenylazo-7- {5 '' - (5 '''-chloro-2''', 4 '''-difluoropyrimidin-6''' - yl) - amino-2 '' - sulfo-phenyl-azo} -8-hydroxy-1-amino-3,6-disulfonaphthalene,
2- (4'-β-Sulfatoethylsulfonyl) -phenylazo-7- {5 '' - (2 '''-chloro-4''' - amino-triazin-6 '''- yl) -amino-2'' -sulfo-phenyl-azo} -8-hydroxy-1-amino-3,6-disulfonaphthalene;
7- [1 ', 5''-disulfonaphth-2'-yl] azo-8-hydroxy-3- {5''-chloro-2'',4''-difluoropyrimidin-6''- yl} -amino-6-sulfo-naphthalene,
7- [4 ', 8''-disulfonaphth-2'-yl] azo-8-hydroxy-3- {5''-chloro-2'',4''-difluoropyrimidin-6''- yl} -amino-6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methoxyphenyl] azo-8-hydroxy-3- {5 "chloro-2", 4 "difluoropyrimidin-6" yl} amino -6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methylphenyl] azo-8-hydroxy-3- {5 "chloro-2", 4 "difluoropyrimidin-6" yl} amino -6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methoxyphenyl] azo-8-hydroxy-3- {2 ", 4", 5 "- trichloropyrimidin-6" - yl} amino-6 -sulfonaphthalene,
7- [1'-Sulfo-4'-methoxy-phenyl] azo-8-hydroxy-3- {2 ", 4" - difluoro-pyrimidin-6 "-yl} amino-6-sulfo-naphthalene ,
7- [1 ', 5 "-disulfonaphth-2'-yl] azo-8-hydroxy-3- {2" chloro-4 "amino-triazine-6" yl} amino -6-sulfo-naphthalene,
7- [4 ', 8 "- disulfonaphth-2'-yl] azo-8-hydroxy-3- {2" chloro-4 "amino-triazine-6" yl} amino -6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methoxyphenyl] azo-8-hydroxy-3- {2 "chloro-4" amino-triazine-6 "yl} amino-6-sulfo -naphthalene,
7- [1'-Sulfo-4'-methylphenyl] azo-8-hydroxy-3- {2 "chloro-4" amino-triazine-6 "yl} amino-6-sulfo -naphthalene;
7- [1'-Sulfo-4'-methoxyphenyl] azo-8-hydroxy-3- {2 '' fluoro-4 '' morpholino-triazin-6 '' - yl} amino-6-sulfo -naphthalene,
7- [1'-Sulfo-4'-methoxy-phenyl] azo-8-hydroxy-3- {2 "-fluoro-4" -phenylamino-triazine-6 '' - yl} amino-6-sulfo-naphthalene ,
7- [1'-Sulfo-4'-methoxy-phenyl] azo-8-hydroxy-3- {2 '' - fluoro-4 '' - (2 '''- methylphenyl) amino-triazine-6'' -yl} -amino-6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methoxy-phenyl] azo-8-hydroxy-3- {2 '' - fluoro-4 '' - (N-ethyl-phenyl) -amino-triazine-6 '' - yl} -amino-6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methoxy-phenyl] azo-8-hydroxy-3- {2 '' - fluoro-4 '' - (N-methyl-phenyl) -amino-triazine-6 '' - yl} -amino-6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methoxy-phenyl] azo-8-hydroxy-3- {2 '' fluoro-4 '' - (3 '''- β-sulfatoethylsulfonyl-propyl) amino-triazine -6 '' - yl} -amino-6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methoxy-phenyl] azo-8-hydroxy-3- {2 '' - fluoro-4 '' - (N-phenyl-3 '''- β-sulfatoethyl-sulfonyl- propyl) -amino-triazine-6 '' - yl} -amino-6-sulfo-naphthalene,
7- [1'-Sulfo-4'-methoxy-phenyl] azo-8-hydroxy-3- {2 '' - fluoro-4 '' - (N-phenyl-2 '''- β-sulfatoethyl-sulfonyl- ethyl) amino-triazine-6 '' - yl} -amino-6-sulfo-naphthalene;
1-amino-2-sulfo-4- (3'-β-sulfatoethylsulfonyl) phenylamino anthraquinone,
1-amino-2-sulfo-4- (3'-vinylsulfonyl) phenylamino anthraquinone,
1-amino-2-sulfo-4- (4'-β-sulfatoethylsulfonyl) phenylamino anthraquinone,
1-amino-2-sulfo-4- (4'-vinylsulfonyl) phenylamino anthraquinone;
3,10-bis- {2 '- [(β-carboxyethyl) carbonylamino] ethylamino} -9,13-dichloro-4,11-bis (β-sulfato-ethylsulfonyl) -tripendioxazine,
3,10-bis- [β-sulfatoethyl-amino} -9,13-dichloro-4,11-bis (β-sulfato-ethylsulfonyl) -tripendioxazine,
3,10-bis- {3 '- [2''-fluoro-4''-(2''', 5 '''- disulfophenyl) aminotriazin-6''- yl] amino propyl amino } -9,13-dichloro-4,11-disulfo-triphendioxazin,
3,10-bis- {2 '- [2''-chloro-4''-(2''', 5 '''- disulfophenyl) amino-triazin-6''- yl] amino-ethyl-amino } -9,13-dichloro-4,11-disulfo-triphendioxazin,
3-amino-10 - {[2'-chloro-4 '- (2'',5''- disulfophenyl) aminotriazin-6''- yl]} - amino-9,13-dichloro-4,11 -disulfo-triphendioxazin,
3-amino-10 - {[2'-chloro-4 '- (N-phenyl-3''- β-sulfatoethyl-sulfonyl-propyl) -amino-triazin-6'-yl]} - a mino-9, 13-dichloro-4,11-disulfo-triphendioxazin,
3-Amino-10 - {[2'-chloro-4 '- (2'',5''- disulfophenyl) amino-triazin-6'-yl]} - amino-9,13-dichloro-4,11 -disulfo-triphendioxazin, and
3-Amino-10 - {[2'-chloro-4 '- (3''- sulfophenyl) amino-triazin-6'-yl]} - amino-9,13-dichloro-4,11-disulfo-triphendioxazin .

Suitable fiber materials for the purposes of the present invention are those which contain hydroxyl, amino, carbonamide and / or mercapto groups, such as cellulose fibers from the range of native cellulose, such as cotton of various origins, jute, ramie, regenerated fibers such as viscose or chemically modified cellulose, such as cellulose modified by amino groups or cationic groups, or polyamide fibers, such as synthetic polyamides from the series polyamide-6, polyamide-6,6, or protein fibers such as wool or silk, mixtures of the types of fibers mentioned, and also mixtures of cellulose Polyesters such as polyethylene terephthalate / cotton blends, the application of the auxiliaries mentioned on cellulose-containing fiber materials being particularly preferred.

The carbohydrate compounds mentioned are particularly suitable for use in pad dyeing processes such as the pad cold-dwell process or continuous dyeing process and textile printing processes such as single-phase printing or etching printing or the ink-jet process.
Processes which are characterized in that an alkaline pad liquor containing dye and alkali are applied simultaneously are particularly preferred. Furthermore, such processes are particularly preferred in which very high dye concentrations, for example 2 to 10% by weight of dye, based on the dye liquor, or dyes with limited solubility (less than 100 g / l) are applied without auxiliary agents under the conditions of use.
In special cases, the carbohydrate compounds mentioned are also suitable as auxiliaries for dyeings, in the event that the dyes used have poor solubilities under the conditions of use of an alkaline salt liquor, for example only 0.3 to 1% by weight of dye, based on the dye liquor.

The present invention also relates to a dye preparation comprising one or more fiber-reactive dyes and one or more carbohydrate compounds of the general formula (1).

A preferred embodiment of the dye preparations according to the invention is a padding liquor consisting essentially of 0.5 to 10% by weight of a fiber-reactive dye, 0.2 to 2% by weight, preferably 0.4 to 1.6% by weight, one of the carbohydrate compounds defined above, alkali, such as sodium hydroxide solution, sodium carbonate or water glass and optionally further usual auxiliaries and additives, so that the total is 100% by weight.

For example, a padding liquor consists of 5 to 100 parts / l reactive dye, 5 to 40 cm ³ / l sodium hydroxide 32.5% (38 ° Be) or 5 to 20 parts / l sodium carbonate and 2 to 20 parts / l, preferably 4 to 16 parts / l, a carbohydrate compound of the type mentioned and optionally further auxiliaries, 0 to 130 parts / l, preferably 0 to 50 parts / l, water glass (37 to 60 ° Be), and hydrotropic auxiliaries such as 0 to 50 g / l, preferably 0 g / l, urea and / or dispersants such as, for example, condensation products of naphthalenesulfonic acids with formaldehyde.
The padding liquor is padded onto the fabric in the usual way, the liquor being applied by means of a padding chassis over a horizontally arranged pair of rollers and the squeezing rate being adjusted so that a liquor absorption of 40 to 120%, preferably 50 to 90% for cotton or 80 to 100% for viscose, is reached, and then fixed. The fixation can be achieved by keeping the airtightly docked tissue cold within 2 to 48 hours, preferably 3 to 26 hours, at 20 to 35 ° C or by steaming the intermediate dried tissue within 1 to 10 minutes at 90 to 150 ° C or by steaming the wet, padded fabric within 30 seconds to 3 minutes at 90 to 120 ° C in a steamer customary for the application methods described and then aftertreated in the usual manner, such as rinsed and optionally washed in the presence of surfactants.

In the block short dwell process, the pad liquor durability is often improved by the application of water glass, but this technique has certain disadvantages, such as, for example, deposition and incrustation of silica on paddle rollers or machine parts (Textilpraxis Int. 39 (1984), 63; ibid. 153, 262, 269). With the application according to the invention of the carbohydrate compounds mentioned, dyeing can be carried out with a reduced amount or without water glass, which improves the pad liquor durability without the disadvantages mentioned.

The problem of pad dyeing reactive dyes is, among other things, the durability of the alkaline padding liquors, which is noticeable by precipitation in the pad or by reduced color strength. The effect of the reduced color strength is due to hydrolysis of the reactive dye, which is known to any person skilled in the art.
Surprisingly, however, it has now been found that the loss of color strength is reduced when the auxiliaries mentioned are used, which has a considerable advantage in terms of process reliability and economy. This effect is particularly pronounced with dyes from the series of phthalocyanine reactive dyes, such as, in particular, Cu and Ni phthalocyanines. In individual cases, for example when using auxiliaries of the formula (1f), an increase in the coloristic color strength is surprisingly observed after a pad liquor dwell time or standing time in the range from 5 to 20 min.

Another preferred embodiment of the dye preparation according to the invention is a printing paste consisting essentially of 0.5 to 10% by weight of a fiber-reactive dye,
0.2 to 2% by weight, preferably 0.4 to 1.6% by weight, of one of the carbohydrate compounds defined above and further conventional auxiliaries such as, in particular, thickeners and additives, such as sodium nitrobenzenesulfonate and / or softening agents, so that the sum 100 wt .-% results.

For example, for a printing process of cellulose fabric, a printing paste is used which contains 5 to 100 parts of reactive dye, 200 to 300 parts of water, 400 to 500 parts of a sodium alginate thickener, 4 to 30 parts of alkali as sodium carbonate or sodium bicarbonate and 2 to 20 parts of a carbohydrate compound mentioned type and optionally other auxiliaries, such as 10 parts of nitrobenzenesulfonate sodium. This printing paste is printed onto the fabric in the usual way, then fixed in a damper at 90 to 155 ° C. within 3 to 15 minutes, the damper being for example a hanging loop damper, a continuous damper or a star damper, and then aftertreated in the usual way , eg rinsed and optionally washed in the presence of surfactants.

Another preferred embodiment of the dye preparation according to the invention is an improved ink jet ink, consisting essentially of 4 to 10% by weight of a fiber-reactive dye, 1 to 10% by weight, preferably 2 to 7% by weight, one of the The carbohydrate compounds defined above and other conventional auxiliaries and additives, so that the total is 100% by weight.

For ink jet printing, the applied ink contains, for example, 4 to 10% by weight of reactive dye, 1 to 10% by weight of a carbohydrate compound of the formula (1), 5 to 10% by weight of a substance which prevents drying out , such as a polyglycol ether, and optionally a fungicidal agent and 70 to 90% by weight of water. The storage stability of the ink jet inks can advantageously be improved by the application of the carbohydrate compounds mentioned.

The invention furthermore relates to dye preparations which contain the carbohydrate compounds mentioned and which are characterized in that the preparation consists essentially of 20 to 70% by weight of dye, 0.2 to 10% by weight, preferably 2 to 8% by weight. -%, the carbohydrate compound, 10 to 60 wt .-% salt and conventional adjuvants and optionally other auxiliaries, such as dedusting agents, condensation products of naphthalenesulfonic acid with formaldehyde and / or condensed phosphates. The dye preparations can be prepared in a conventional mixer and / or comminution device such as a mill or by spray drying the aqueous solutions containing the substances.

• a) das Hilfsmittel in heißem Wasser vorlegt und den Farbstoff einstreut oder als hochkonzentrierte Lösung zudosiert und nach dem Abkühlen Alkali hinzugibt;
• b) heißes Wasser vorlegt, den Farbstoff einstreut oder als hochkonzentrierte Lösung zudosiert und nach dem Abkühlen oder während des Abkühlens das Hilfsmittel und Alkali hinzugibt;
• c) das Hilfsmittel und den Farbstoff in Wasser bei Temperaturen von 15 bis 40°C einige Zeit unter Rühren löst und eine übliche Menge Alkali hinzugibt.

It is also noteworthy that when certain carbohydrate compounds are used as auxiliaries in the padding liquor, the dye can be dissolved cold, which has advantages over the conventional hot-dissolving process of the prior art due to reduced energy costs. It is furthermore particularly surprising that higher color strengths are obtained than according to the customary methods of the prior art, which is another advantage in terms of application technology brings itself.
The padding liquor can generally be prepared in such a way that

• a) the auxiliary agent is placed in hot water and the dye is sprinkled in or metered in as a highly concentrated solution and alkali is added after cooling;
• b) providing hot water, sprinkling in the dye or metering in as a highly concentrated solution and adding the auxiliary and alkali after cooling or while cooling;
• c) the auxiliary and the dye in water at temperatures of 15 to 40 ° C for some time with stirring and add a usual amount of alkali.

In the case of the alkyl glucosides and aryl glucosides of the formulas (1a) and (1b), the preferred procedure is variant c).

The dye preparations have advantages over the non-formulated dyes in their solubility and the levelness of the dyeings and prints. They differ in the use of a mixture in powder or granule form instead of a separate addition of the auxiliaries to the dye bath.

in Gegenwart von Anthrachinon-2-sulfonsäure-Na-Salz als Farbstoff-Formulierung zubereitet werden kann, was Vorteile für die Löslichkeit und Egalität der Färbungen in tiefen Nuancen bedingt. Anstelle von Anthrachinon-2-sulfonsäure-Na-Salz oder dessen Kombination mit Anthrachinon-2-sulfonsäure können auch die erfindungsgemäßen Kohlenhydrat-Verbindungen, gegebenenfalls in Kombination mit weiteren Hilfsmitteln, wie z.B. Naphthalinsulfonsäure-Formaldehyd-Kondensate, für eine C.I. Reactive Blue 19 Farbstoff-Formulierung verwendet werden. Geeignet sind hierbei Farbstoffzubereitungen, die 1 bis 6 Gew.-%, insbesondere 1,5 bis 4 Gew.-%, der Kohlenhydratverbindungen der Formel (1), insbesondere (1h) und (1f), sowie 0 bis 10 Gew.-% Anthrachinon-2-sulfonsäure und/oder dessen Na-Salz enthalten. Mit den so zubereiteten Farbstoffzubereitungen sind insbesondere im Ausziehfärbeverhalten überraschenderweise höhere Farbstärken erzielbar.DE-A-2 412 964 describes that the dye of the formula (CI Reactive Blue 19)

can be prepared in the presence of anthraquinone-2-sulfonic acid Na salt as a dye formulation, which has advantages for the solubility and levelness of the dyeings in deep shades. Instead of anthraquinone-2-sulfonic acid Na salt or its combination with anthraquinone-2-sulfonic acid, the Carbohydrate compounds according to the invention, optionally in combination with other auxiliaries, such as naphthalenesulfonic acid-formaldehyde condensates, can be used for a CI Reactive Blue 19 dye formulation. Dye preparations containing 1 to 6% by weight, in particular 1.5 to 4% by weight, of the carbohydrate compounds of the formula (1), in particular (1h) and (1f), and 0 to 10% by weight are suitable. Contain anthraquinone-2-sulfonic acid and / or its Na salt. With the dye preparations prepared in this way, surprisingly higher color strengths can be achieved, in particular in the pull-out dyeing behavior.

The effectiveness of the compounds of the formula (1), in which the radical Z is a formula member (2a) or (2f), is particularly surprising because it is known from the literature that certain carbohydrate compounds such as lower alkyl glucosides, e.g. Methyl-D-glucoside, and glucose (Luttringer & Dussy, Melliand Textilber. 62, 1981, 84) or sorbitol (Hildebrand: Venkataram VI. Reactive Dyes, Academic Press, 1972, page 335) prefer to react with fiber-reactive dyes and thus a reduction the color strength would be expected when applying such compounds. Surprisingly, however, it was found that this is not the case for the compounds of the formulas (2a) and (2f) mentioned, and on the contrary, an increase in the color strength is achieved with a suitable dyeing process and correctly selected amounts.

The following examples demonstrate the technical applicability of the procedure according to the invention, which is advantageous over the dyeing method of the prior art in relation to the color strength of the dyeings obtained. The pad liquor durability is particularly advantageously improved, as is demonstrated by the dyeings after various residence times of the liquors before application.

The amounts of the dyes used are calculated as customary formulations, in particular containing adjusting agents in the form of salt, the actual dye content of the dye formulations being given in brackets.

Alkaline boiled and bleached cotton was used as the fiber material in the examples.

Example 1:

(C.I. Reactive Orange 16) wird in 100 Teilen Wasser unter Zusatz von 3 Teilen Natriumsulfat bei 40 bis 50 °C angerührt. Man gibt sodann 0,62 Teile der Aryl-β-D-glucopyranosid-Verbindung der Formel

hinzu und rührt einige Zeit. Anschließend werden nach Abkühlen auf 20-25°C 6 ml einer 6,5 gew.-%igen Natronlauge hinzugesetzt. Die so erhaltene Klotzflotte wird nach bestimmten Standzeiten t₁ oder umgehend (t₁=0) mit einem Foulard auf Baumwollgewebe bei einem Abquetschdruck von 6,1 kg/cm² und einer Laufgeschwindigkeit von 1 m/min, entsprechend einer Flottenaufnahme von ca. 80 %, aufgebracht. Das Gewebe wird kantengerade aufgerollt, unter Feuchtigkeitsausschluß für eine bestimmte Verweilzeit (t₂) gelagert, gewaschen und getrocknet. Man erhält eine farbstarke orange Färbung.
Die nachfolgende Tabelle zeigt die erhaltenen Farbstärken als Farbstärkekenngröße K/S nach der Methode von Melliand Textilber. 1986, 562.2.0 parts (49.7%) of the dye of the formula

(CI Reactive Orange 16) is stirred in 100 parts of water with the addition of 3 parts of sodium sulfate at 40 to 50 ° C. 0.62 part of the aryl-β-D-glucopyranoside compound of the formula is then added

and stir for some time. Then, after cooling to 20-25 ° C., 6 ml of a 6.5% strength by weight sodium hydroxide solution are added. The padding liquor obtained in this way is, after certain standing times, t ₁ or immediately (t ₁ = 0) with a foulard on cotton fabric at a squeezing pressure of 6.1 kg / cm ² and a running speed of 1 m / min, corresponding to a liquor absorption of approx. 80 %, applied. The fabric is rolled up straight, stored with exclusion of moisture for a certain dwell time (t ₂ ), washed and dried. A strong orange coloration is obtained.
The table below shows the color strengths obtained as color strength parameter K / S according to the Melliand Textilber method. 1986, 562.

The color strengths obtained are given as a reference when dyeing according to the urea method of the prior art (Textile Practice Int. 39 (1984), 63; ibid. 153, 262, 269) in order to document the advantageous procedure of the invention. Coloring agent on CI Reactive Orange 16 (49.7%) Amount of 2-hydroxyphenyl-β-D-glucopyranoside used t ₁ K / S dwell time t ₂ 4h / 24h Comparison with 100 g / l urea 4h / 24h 20 g / l 6.2 g / l 0 min 9.96 / 11.16 7.36 / 8.83 dito dito 5 min 7.80 / 9.87 not possible dito dito 15 minutes 6.72 / 8.51 not possible not possible:
no coloring is possible because the padding liquor fails,
or only irregular stains are obtained.

Example 2:

If a padding liquor of 40 g / l and 12.3 g / l of the 2-hydroxyphenyl-β-D-glucopyranoside compound from Example 1 and 8 ml of NaOH (6.5%) are applied analogously to Example 1, then obtained the coloring results shown in the table. Coloring agent on CI Reactive Orange 16 (49.7%) Amount of 2-hydroxyphenyl-β-D-glucopyranoside used t ₁ K / S dwell time t ₂ 4h / 24h Comparison with 100 g / l urea 4h / 24h 40 g / l 12.3 g / l 0 min 12.04 / 15.46 9.44 / 13.30 dito dito 5 min 9.17 / 13.72 not possible

Example 3:

und Farbstoffe in der in folgender Tabelle angegebenen Menge eingesetzt, wobei bei einem Farbstoffeinsatz von 20 g/l mit 6 ml Natronlauge (6,5 %) und bei 40 g/l mit 8 ml Natronlauge (6,5 %) gefärbt wird, so werden ebenfalls farbstarke Färbungen erhalten. Farbstoffeinsatz Einsatzmenge an Glucopyranosid t₁ K/S Verweilzeit t₂ 4h / 24h Vergleich mit 100 g/l Harnstoff 4h / 24h 20 g/l C.I. Reactive Orange 16 (49,7 %ig) 6,7 g/l 2-Carboxyphenyl-β-D-glucopyranosid 0 min 11,49/11,46 7,36/8,83 dito dito 5 min 8,91/11,04 nicht möglich dito dito 15 min 6,06/9,99 nicht möglich 40 g/l C.I. Reactive Orange 16 (49,7 %ig) 13,5 g/l 2-Carboxyphenyl-β-D-glucopyranosid 0 min 12,11/16,56 9,44/13,30 dito dito 5 min 9,80/16,02 nicht möglich Instead of the glucoside compound from Example 1, a β-D-glucopyranoside of the formula

and dyes used in the amount given in the following table, dyeing being carried out with a dye use of 20 g / l with 6 ml of sodium hydroxide solution (6.5%) and at 40 g / l with 8 ml of sodium hydroxide solution (6.5%) strong colorations are also obtained. Dye insert Amount of glucopyranoside used t ₁ K / S dwell time t ₂ 4h / 24h Comparison with 100 g / l urea 4h / 24h 20 g / l CI Reactive Orange 16 (49.7%) 6.7 g / l 2-carboxyphenyl-β-D-glucopyranoside 0 min 11.49 / 11.46 7.36 / 8.83 dito dito 5 min 8.91 / 11.04 not possible dito dito 15 minutes 6.06 / 9.99 not possible 40 g / l CI Reactive Orange 16 (49.7%) 13.5 g / l 2-carboxyphenyl-β-D-glucopyranoside 0 min 12.11 / 16.56 9.44 / 13.30 dito dito 5 min 9.80 / 16.02 not possible

Example 4:

und Farbstoffe in der in folgender Tabelle angegebenen Menge eingesetzt, wobei bei einem Farbstoffeinsatz von 20 g/l mit 6 ml Natronlauge (6,5 %) und bei 40 g/l mit 8 ml Natronlauge (6,5 %) gefärbt wird, so werden ebenfalls farbstarke Färbungen erhalten: Farbstoffeinsatz Einsatzmenge an Glucopyranosid t₁ K/S Verweilzeit t₂ 4h / 24h Vergleich mit 100 g/l Harnstoff 4h / 24h 20 g/l C.I. Reactive Orange 16 (49,7 %ig) 4,2 g/l 0 min 11,97/12,11 7,36/8,83 dito dito 5 min 11,22/11,49 nicht möglich dito dito 15 min 10,36/10,46 nicht möglich dito 8,3 g/l 0 min 10,62/11,91 7,36/8,83 dito dito 5 min 9,87/10,87 nicht möglich dito dito 15 min 9,51/9,85 nicht möglich dito 12,5 g/l 0 min 11,52/11,81 7,36/8,83 dito dito 5 min 10,60/10,87 nicht möglich dito dito 15 min 9,85/10,26 nicht möglich 40 g/l C.I. Reactive Orange 16 (49,7 %ig) 16,7 g/l 0 min 16,32/17,33 9,44/13,30 dito dito 5 min 14,84/16,68 nicht möglich dito dito 15 min 14,40/16,02 nicht möglich Instead of the glucoside compound from Example 1, a carboxymethylated naphthyl glucoside of the formula

and dyes used in the amount given in the following table, dyeing being carried out with a dye use of 20 g / l with 6 ml of sodium hydroxide solution (6.5%) and at 40 g / l with 8 ml of sodium hydroxide solution (6.5%) strong colorations are also obtained: Dye insert Amount of glucopyranoside used t ₁ K / S dwell time t ₂ 4h / 24h Comparison with 100 g / l urea 4h / 24h 20 g / l CI Reactive Orange 16 (49.7%) 4.2 g / l 0 min 11.97 / 12.11 7.36 / 8.83 dito dito 5 min 11.22 / 11.49 not possible dito dito 15 minutes 10.36 / 10.46 not possible dito 8.3 g / l 0 min 10.62 / 11.91 7.36 / 8.83 dito dito 5 min 9.87 / 10.87 not possible dito dito 15 minutes 9.51 / 9.85 not possible dito 12.5 g / l 0 min 11.52 / 11.81 7.36 / 8.83 dito dito 5 min 10.60 / 10.87 not possible dito dito 15 minutes 9.85 / 10.26 not possible 40 g / l CI Reactive Orange 16 (49.7%) 16.7 g / l 0 min 16.32 / 17.33 9.44 / 13.30 dito dito 5 min 14.84 / 16.68 not possible dito dito 15 minutes 14.40 / 16.02 not possible

Example 5

(C.I. Reactive Blue 19), enthaltend 5 Gew.-% Anthrachinon-2-sulfonsäure, werden in 100 Teilen Wasser unter Zusatz von 3 Teilen Natriumsulfat bei 40-50°C angerührt. Man gibt sodann 1 Teil der Kohlenhydratverbindung der Formel

die unter dem Namen Arbutin bekannt ist, hinzu und rührt einige Zeit. Anschließend werden nach Abkühlen auf 20-25°C 1,2 ml einer 32 %igen Natronlauge hinzugesetzt. Die so erhaltene Klotzflotte wird nach bestimmten Standzeiten t₁, oder umgehend (t₁ = 0) mit einem Walzenfoulard auf Baumwollgewebe bis zu einer Abquetschrate entsprechend einer Flottenaufnahme von 70 % aufgebracht. Das Gewebe wird kantengerade aufgerollt, unter Feuchtigkeitsausschluß für eine Verweilzeit von 24 h gelagert, mehrfach ausgewaschen und getrocknet. Man erhält farbstarke brillantblaue Färbungen.
Die nachfolgende Tabelle zeigt die erhaltenen Farbstärken als gewichtete Farbstärkekenngröße ΣK/S(λ) nach der Methode von Melliand Textilber. 1986, 562. Als Bezug sind die erhaltenen Farbstärken angegeben, wenn nach den üblichen Klotz-Kurzverweil-Verfahren (z.B. Textilpraxis Int. 39 (1984), 63; ibid. 153, 262, 269), dem Harnstoffverfahren, dem Normalverfahren und dem Wasserglasverfahren gefärbt wird, um die vorteilhatte Verfahrensweise der Erfindung zu dokumentieren. Das Normalverfahren wird in der heutigen Praxis aufgrund schlechter Prozeßsicherheit meist nicht mehr verwendet. Farbstoff Zeit t₂/min Arbutin 10 g/l Harnstoffverfahren Wasserglasverfahren Normalverfahren 40 g/l C.I. Reactive Blue 19 0 79.63 63.47 67.39 64.33 dito 10 75.11 62.64 63.74 58.83 2.0 parts of the dye (37%) of the formula

(CI Reactive Blue 19), containing 5% by weight of anthraquinone-2-sulfonic acid, are stirred in 100 parts of water with the addition of 3 parts of sodium sulfate at 40-50 ° C. 1 part of the carbohydrate compound of the formula is then added

known as the arbutin, and stir for some time. After cooling to 20-25 ° C, 1.2 ml of a 32% sodium hydroxide solution are then added. The padding liquor obtained in this way is, after certain standing times, t ₁ or immediately (t ₁ = 0) with a roll pad on cotton fabric up to one Squeezing rate applied according to a liquor absorption of 70%. The fabric is rolled up in a straight line, stored for a 24-hour period with exclusion of moisture, washed out several times and dried. Strong blue brilliant dyeings are obtained.
The table below shows the color strengths obtained as a weighted color strength parameter ΣK / S (λ) according to the Melliand Textilber method. 1986, 562. The color strengths obtained are given as a reference when using the customary block-short dwell method (eg Textile Practice Int. 39 (1984), 63; ibid. 153, 262, 269), the urea method, the normal method and the water glass method is colored to document the advantageous procedure of the invention. The normal process is mostly no longer used in current practice due to poor process reliability. dye Time t ₂ / min Arbutin 10 g / l Urea process Water glass process Normal procedure 40 g / l CI Reactive Blue 19 0 79.63 63.47 67.39 64.33 dito 10th 75.11 62.64 63.74 58.83

Reference stains:

The urea process padding liquor contains 100 g / l urea instead of the carbohydrate compound. The water glass process padding liquor contains 100 g / l urea and 95 g / l water glass (20 ° Be) instead of the carbohydrate compound;
Normal procedure: without water glass and urea

Unformulated CI Reactive Blue 19 produces spotty stains on the given substrate under the conditions used.

Example 6

If the procedure is as in Example 5 and 1 part of a customary sophorose-lipid mixture is used instead of arbutin as auxiliary, level-brilliant brilliant blue dyeings with the color strengths as indicated in the table are also obtained. dye Time t ₂ / min Disaccharide 10 g / l Urea process Water glass process Normal procedure 40 g / l CI Reactive Blue 19 0 73.71 63.47 67.39 64.33 dito 10th 71.18 62.64 63.74 58.83

Example 7

verwendet, so erhält man farbstarke türkisblaue Färbungen.
Die nachfolgende Tabelle zeigt die erhaltenen Farbstärken als gewichtete Farbstärkekenngröße ΣK/S(λ) nach der Methode von Melliand Textilber. 1986, 562. Als Bezug sind die erhaltenen Farbstärken angegeben, wenn nach den üblichen Klotz-Kurzverweil-Verfahren gefärbt wird (s. Beispiel 5), um die vorteilhafte Verfahrensweise der Erfindung zu dokumentieren. Einsatzmenge Farbstoff (39 %ig) Zeit t₂/min Arbutin 10 g/l Harnstoffverfahren Wasserglasverfahren 40 g/l 0 49.97 34.34 39.92 dito 10 49.96 31.84 38.67 20 g/l 0 28.96 19.23 24.17 dito 10 26.29 20.06 22.93 The procedure is as in Example 5, but instead of CI Reactive Blue 19, the Cu-phthalocyanine dye of the formula

used, you get strong turquoise blue colorations.
The table below shows the color strengths obtained as a weighted color strength parameter ΣK / S (λ) according to the Melliand Textilber method. 1986, 562. The color strengths obtained are given as a reference if dyeing is carried out using the customary block-dwell method (see Example 5) in order to document the advantageous procedure of the invention. Amount of dye used (39%) Time t ₂ / min Arbutin 10 g / l Urea process Water glass process 40 g / l 0 49.97 34.34 39.92 dito 10th 49.96 31.84 38.67 20 g / l 0 28.96 19.23 24.17 dito 10th 26.29 06/20 22.93

Example 8:

If the procedure is as in Example 7, but the carbohydrate compound from Example 6 is used instead of arbutin, level turquoise blue dyeings with the same color strength are also obtained with the color strengths as given in the table: Amount of dye used (39%) Time t ₂ / min Disaccaride from Example 6 10 g / l Urea process Water glass process 40 g / l 0 44.40 34.34 39.92 dito 10th 44.29 31.84 38.67 20 g / l 0 25.63 19.23 24.17 dito 10th 23.59 06/20 22.93

Example 9

werden in 100 Teilen Wasser unter Zusatz von 3 Teilen Natriumsulfat bei 40 bis 50°C angerührt. Man gibt sodann 1 Teil der in der Tabelle gekennzeichneten Kohlenhydrat-Verbindung hinzu, und rührt einige Zeit. Anschließend werden nach Abkühlen auf 25°C 1,2 ml einer 32 %igen Natronlauge hinzugesetzt. Die so erhaltene Klotzflotte wird nach bestimmten Standzeiten t₁ oder umgehend (t₁=0) mit einem Foulard auf Baumwollgewebe bis zu einer Abquetschrate entsprechend einer Flottenaufnahme von 70 % aufgebracht. Das Gewebe wird kantengerade aufgerollt, unter Feuchtigkeitsausschluß für eine Verweilzeit von 24 h gelagert, gewaschen und getrocknet. Man erhält farbstarke brillante rote Färbungen.
Die nachfolgende Tabelle zeigt die erhaltenen Farbstärken als gewichtete Farbstärkekenngröße ΣK/S(λ) (siehe Beispiel 5). Farbstoff einsatz Zeit t₂/min Arbutin 10 g/l Disaccharid aus Bsp. 6 10 g/l Harnstoffverfahren Wasserglasverfahren 20 g/l 0 50.67 53.26 45.92 46.54 dito 10 40.07 40.24 38.50 40.8 4 parts of the dye (43%) of the formula

are stirred in 100 parts of water with the addition of 3 parts of sodium sulfate at 40 to 50 ° C. 1 part of the carbohydrate compound indicated in the table is then added and the mixture is stirred for some time. After cooling to 25 ° C., 1.2 ml of a 32% sodium hydroxide solution are then added. The padding liquor obtained in this way is applied after a certain standing time t ₁ or immediately (t ₁ = 0) with a foulard to cotton fabric up to a squeezing rate corresponding to a liquor absorption of 70%. The fabric is rolled up straight, stored with exclusion of moisture for a residence time of 24 hours, washed and dried. Strong, brilliant red dyeings are obtained.
The table below shows the color strengths obtained as a weighted color strength parameter ΣK / S (λ) (see Example 5). Dye insert Time t ₂ / min Arbutin 10 g / l Disaccharide from Ex. 6 10 g / l Urea process Water glass process 20 g / l 0 50.67 53.26 45.92 46.54 dito 10th 40.07 40.24 38.50 40.8

Example 10

If, analogously to Example 1, a padding liquor containing the dyes mentioned in the following table in the stated amount and carbohydrate compounds of the amounts mentioned in the table as auxiliaries is used without using urea, the dyeing results shown in the table are obtained. As a comparison, dyeings are shown which were carried out without auxiliary agents, but with 100 g / l urea.

Example 11

1 kg of dye powder of the dye shown in the table below is dissolved in 2.5 l of water. X g of the carbohydrate compound given in the table in aqueous solution, in aqueous suspension, dissolved in a solvent or as a liquid is added to this solution. The mixture is stirred for some time at a pH of 5 to 6 and a temperature of 20 to 25 ° C and the product is isolated by evaporation at 60 ° C under reduced pressure.

A dye preparation is obtained which, in the case of dyeings on cellulose fibers, has advantages in the coloristic color strengths, with the dyeing results given in the table. Level, strong, brilliant dyeings with good fastness properties are obtained.

The color strength parameter is the K / S color strength, the amount used for dyeing within a series of the same dye being transmission-normalized to the same color strength in the dyeing liquor and thus being directly comparable. table Dyeing results of dye preparations (pull-out dyeings on cotton fabric, liquor ratio 1:10) Dye preparation amount used Use of auxiliaries in g (= x) per kg of dye preparation Coloring conditions g / l Na ₂ SO ₄ , g / l soda / ml / l NaOH 38 ° Be Dyeing temperature ° C Color strength Σ K / S CI Reactive Blue 19 2.93% 40 g / kg GA 12/14 50/5/2 40 114.7 3.21% 80 g / kg GA 12/14 50/5/1 60 88.1 2.81% 20 g / kg GA 12/14 50/5/0 80 78.5 CI Reactive Blue 19 2.81% 20 g / kg GA 16/18 50/5/2 40 105.3 3.21% 40 g / kg GA 16/18 50/5/1 60 102.5 CI Reactive Blue 19 2.94% 40 g / kg sophorose lipid 50/5/2 40 121.9 2.94% 40 g / kg sophorose lipid 50/5/1 60 112.0 2.94% 40 g / kg sophorose lipid 50/5/0 80 86.0 Dyeing results in the pad cold dwelling process, 25 ° C., 24 h dwell time, dyeing process as example 1 without urea Dye preparation amount used Use of auxiliaries in g (= x) per kg of dye preparation Coloring conditions g / l Na ₂ SO ₄ , g / l soda / ml / l NaOH 38 ° Be Dyeing temperature ° C Color strength Σ K / S CI Reactive Blue 19 41.9 g / l 40 g / kg sophorose lipid as in example 1 as in example 1 86.3 42.7 60 g / kg sophorose lipid 85.5 50.7 80 g / kg sophorose lipid 72.6 CI Reactive Blue 19 41.9 g / l 40 g / kg GA 12/14 as in example 1 as in example 1 77.8 39.9 g / l 40 g / kg GA 16/18 81.8 41.9 g / l 60 g / kg GA 16/18 89.9 GA 12/14 = mixture of fatty acid-N-methyl-glucamide in a weight ratio of 3.2: 1 C12: C14
GA 16/18 = mixture of fatty acid-N-methyl-glucamide in a weight ratio of 1.7: 1 C16: C18
Unformulated CI Reactive Blue 19 was used as a comparison, but this resulted in spotty stains which could not be measured by reflectance spectrometry, so that no direct comparison is possible.

Claims (16)

Use of carbohydrate compounds of the formula (1)

ZGTR ¹ _n (1)

wherein Z represents the remainder of a carbohydrate from the series of the mono-, di- or oligosaccharides or a sugar alcohol, the free valence being on a carbon atom; G represents a bridge member from the series -O-, -NR ⁵ -, -O-CO-, -NR ⁵ -CO- and -NR ⁵ -SO ₂ -, wherein R ^{5 is} hydrogen or C ₁ -C ₄ alkyl is which can be substituted by 1 to 4 radicals from the series hydroxyl, sulfo, sulfato, di (C ₁ -C ₄ alkyl) amino or carboxy; T represents a C ₄ -C ₃₀ aliphatic, cycloaliphatic or olefinic hydrocarbon radical, C ₆ -C ₁₀ aryl or C ₆ -C ₁₀ aryl-C ₁ -C ₄ alkylene; R ¹ for hydroxy, carboxy, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, sulfo, C ₁ -C ₁₀ alkylsulfonyl, aminosulfonyl, C ₁ -C ₁₀ alkylaminosulfonyl or C ₆ -C ₁₀ -Arylaminosulfonyl, C ₁ -C ₁₀ -alkylcarbonyl, ureido, C ₁ -C ₁₀ -alkylcarbonylamino, C ₁ -C ₁₀ -alkoxycarbonyl or aminocarbonyl, the alkyl or aryl radicals having 1 or more of the radicals OH, NH ₂ , NO ₂ , CN, OCH ₃ , SO ₃ H and COOH may be substituted; n is a number from 0 to 3, where, if n is greater than 1, the radicals R ^{1 can} also have different meanings, as an aid for dyeing or printing fiber materials with fiber-reactive dyes. Use according to claim 1, characterized in that Z represents the residue of a pentose, hexose, an oligosaccharide with 2 to 40 monosaccharide units or a sugar alcohol; G for -O-, -NH-, -NH-CO-, -NCH ₃ -, -NCH ₃ -CO-, - [N (CH ₂ CH ₂ OH)] - CO-, -NHSO ₂ -, -N -CH ₃ -SO ₂ - or -O-CO-; T is C ₄ -C ₃₀ alkyl, C ₄ -C ₃₀ alkenyl, cyclohexyl, phenyl, naphth-1-yl, naphth-2-yl or benzyl; R ¹ for hydroxy, sulfo, carboxy, methyl, ethyl, methoxy, ethoxy, acetyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, C ₁ -C ₄ alkylcarbonyl, C ₁ - C ₄ alkylcarbonylamino or C ₁ -C ₄ alkoxycarbonyl; and n is a number from 0 to 1. Use according to claim 1 or 2, characterized in that Z represents a radical of the formulas (2a) to (2g)

is what x is a number from 1 to 20; y is a number from 1 to 6, preferably 1 or 2; R ^{2 is} hydroxymethyl, carboxy, acetyl or C ₁ -C ₄ alkoxymethyl, where the remainder alkoxy can be substituted by 1 to 4 substituents from the series hydroxy, C ₁ -C ₄ alkoxy, acetyl or carboxy; R ^{3 is} hydrogen, sulfo, acetyl, C ₁ -C ₄ alkylsulfonyl, C ₆ -C ₁₀ arylsulfonyl, C ₁ -C ₄ alkyl, which may be substituted by a substituent from the series hydroxyl or carboxy, or the rest of one Is glucoside, where the radicals R ^{3 are in} each case identical or have different meanings; and R ^{4 represents} hydrogen, acetyl, benzoyl or the rest of a peptide or an amino acid. Use according to claim 3, characterized in that the carbohydrate residue of the formula (2a) is a D-glucopyranoside residue;
of the formula (2b) a D-ribofuranoside, D-fructofuranoside or D-glucofuranoside residue;
of the formula (2c) a cellobiose, maltose, lactose or oligo-β-1,4-D-glucose or oligo-α-1,4-D-glucose residue;
of the formula (2d) an α-1,6-D-glucose or a β-1,6-D-glucose residue;
of formula (2e) a sophorose residue;
of the formula (2f) a sorbitol or mannitol residue; and
of formula (2g) is a D-glucosamine residue or a D-glucosamide residue;
or the carbohydrate residue represents the rest of a raffinose. Use according to at least one of claims 1 to 4, characterized in that the group -T- [R ¹ ] _{n has} the meaning 3-hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxyphenyl, 2-carboxyphenyl, naphth-2-yl, 6- Carboxy-naphth-2-yl, 3-carboxy-naphth-2-yl, 4-carboxyphenyl, 1-carboxy-naphth-2-yl, 5-hydroxy-naphth-2-yl, 8-hydroxy-naphth-2- yl, 3-hydroxy-naphth-2-yl, 6-hydroxy-naphth-2-yl, 7-hydroxy-naphth-2-yl, 6-sulfo-naphth-2-yl, 8-sulfo-naphth-2- yl, 3-hydroxy-6-sulfonaphth-2-yl, 8-hydroxy-6-sulfonaphth-2-yl, 6-aminosulfonylnaphth-2-yl,
7- (2'-Hydroxyphenyl) aminosulfonyl-naphth-2-yl, naphth-1-yl, butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, nC Has ₁₂ to C ₁₆ alkyl and nC ₁₂ to C ₁₆ alkenyl. Use according to at least one of claims 1 to 5, characterized in that the carbohydrate compound is one or more compounds of the formulas (1a) to (1k)

wherein R ^{1 'is} hydrogen, hydroxy, COOCH ₃ , COOC ₂ H ₅ or carboxy; R ^{2 'is} hydrogen, acetyl or carboxymethyl; R ^{1 ″ is} hydrogen, hydroxyl, sulfo or carboxy, where R ^{1 ″} and the pyranosyl radical are preferably in the 2,3- or 2,6-position to one another; R ^{5 'is} hydrogen or methyl; R ^{7 is} hydroxy or hydrogen; R ^{7 'is} hydroxy, methyl or hydrogen and is preferably in the ortho or para position to the sulfonyl group; R ^{8 is} hydroxy or hydrogen, where R ⁸ and the saccharylaminocarbonyl radical are preferably in the 2,3- or 2,6-position to one another; R ^{9 'represents} C ₇ -C ₂₀ alkyl, which may contain 1 to 3 olefinic double bonds; W represents C ₁₃ -C ₁₉ alkylene, preferably C ₁₇ alkylene, which contains 1 to 8 olefinic double bonds and / or can be branched; R ^{10 represents} hydrogen or methyl; R ^{11 represents} hydrogen or acetyl; and Q is hydrogen, cyano or carboxy. Use according to at least one of claims 1 to 6, characterized in that the fiber-reactive dye is a dye from the series of the monoazo, bisazo, polyazo, metal complex azo, anthraquinone, metal complex formazane, metal complex phthalocyanine or triphendioxazin. Dyes is. Use according to at least one of claims 1 to 7, characterized in that the fiber material is or contains cellulose fibers, regenerated cellulose fibers, cellulose fibers modified by amino groups or cationic groups, polyamide fibers, a mixture of the fibers mentioned or a mixture of cellulose fibers and polyester fibers. Use according to at least one of claims 1 to 8, characterized in that the dyeing is carried out by a block dyeing process and the printing is carried out by a single-phase printing, etching printing or the ink jet process. Dye preparation containing one or more fiber-reactive dyes and one or more carbohydrate compounds of the formula (1) according to one or more of claims 1 to 6. Dye preparation according to claim 10, characterized in that it consists of a padding liquor consisting of
0.5 to 10% by weight of a fiber-reactive dye,
0.2 to 2% by weight, preferably 0.4 to 1.6% by weight, of one of the carbohydrate compounds defined in one or more of claims 1 to 6, water and other customary auxiliaries and additives, so that the total is 100 % By weight is. Dye preparation according to claim 10, characterized in that it is a printing paste consisting of
0.5 to 10% by weight of a fiber-reactive dye,
0.2 to 2% by weight, preferably 0.4 to 1.6% by weight, of one of the carbohydrate compounds defined in one or more of claims 1 to 6 and further conventional auxiliaries and additives, so that the total is 100% by weight. -% is. Dye preparation according to claim 10, characterized in that it consists of an ink jet ink consisting essentially of
4 to 10% by weight of a fiber-reactive dye,
1 to 10% by weight, preferably 2 to 7% by weight, of one of the carbohydrate compounds defined in one or more of claims 1 to 6, water and other customary auxiliaries and additives, so that the total is 100% by weight, is. Dye preparation according to claim 10, consisting of
20 to 70% by weight of a fiber-reactive dye,
0.2 to 10% by weight, preferably 2 to 8% by weight, of one of the carbohydrate compounds defined in one or more of claims 1 to 6;
10 to 60 wt .-% electrolyte salt, water and other conventional auxiliaries and additives, so that the total is 100 wt .-%. Dye preparation according to claim 14, consisting of 20 to 70 wt .-% of the dye of the formula

1 to 6% by weight of one of the carbohydrate compounds defined in one or more of claims 1 to 6,
0 to 10% by weight of anthraquinone-2-sulfonic acid and / or its Na salt, and of water, electrolyte salt and, if appropriate, other conventional auxiliaries and additives, so that the total is 100% by weight. A process for the preparation of a dye preparation according to claim 11, characterized in that the carbohydrate compound, the fiber-reactive dye and optionally other conventional auxiliaries and additives are dissolved in water at a temperature of 15 to 40 ° C and mixed with alkali.