EP0590397B1 - Process for the preparation of dyes following the ink-jet print technique on modified fiber materials with anionic textile dyesstuffs - Google Patents

Abstract

There is described a process for dyeing sheetlike fibre materials, in particular those made of or containing cellulose fibres, with anionic dyes, in particular those having fibre-reactive groups, which comprises applying an alkali-free and preferably low-electrolyte or completely electrolyte-free aqueous solution of the anionic dye by the ink-jet printing spray technique to a fibre material which has been pretreated and modified with a compound that contains one or more primary, secondary or tertiary amino groups or quaternary ammonium groups, which amino/ammonium groups may be part of a heterocycle. There is generally no need for an aftertreatment by washing. The costly treatment of waste waters resulting from excess dyeing liquors is eliminated. If fibre-reactive dyes are used, fixation by means of alkali is not necessary; fixation is generally effected by a short heat treatment.

Description

Textile materials such as woven, knitted, game and nonwovens which contain cellulose fibers can be dyed using anionic dyes by known processes. In recent times, modern spraying techniques have been added to the classic dyeing methods of printing, exhausting and padding processes, which was first used on paper under the name "Ink-Jet Printing", later also on textile materials. All processes have in common that alkali is required for fixing the dye to the fiber, especially when dyeing with reactive dyes. The alkali is added to the dyeing process before, after or during the application of the dye to the fiber material; After fixing, the alkali must be removed together with dye hydrolyzates in complex washing processes. In particular, the dye hydrolyzates produced in conventional processes cause heavy bleeding or at least a blurring of sharp contours if they cannot be washed out sufficiently.

The ink-jet or ink-jet printing process is the only way of producing color images quickly, quietly and in high resolution. This process typically uses aqueous inks that are sprayed directly onto the substrate in small droplets. A distinction is made between a continuous process in which the ink is pressed evenly through a nozzle and directed onto the paper or into an ink catcher by an electric field, depending on the pattern to be printed, and an interrupted ink jet or "drop-on-demand""-Procedure, in which the ink is ejected only where a colored dot is to be set, in the latter method exerting pressure on the ink system via a piezoelectric crystal or a heated cannula (bubble or thermo-jet method) and so on an ink drop is thrown out. Such Procedures are in text. Chem. Color. 19 (8), 23-29, and 21 (6), 27-32.

It is also known that by adding alkali-releasing agents, such as halogen acetates, and then steaming, reactive dyes can also be used to dye using the ink-jet method (cf., for example, Japanese patent application publications Sho-63-068680 and Hei- 3-205179). Furthermore, it is known from Japanese Patent Application Publication Sho-63-085188 to coat a textile material with a cationic polymer and then to dye it with anionic dyes using the ink-jet printing process. In this process no covalent bond is achieved as with the use of reactive dyes, but the substrate characteristics are significantly changed by the polymer coating.

in welchen bedeuten:

M

ist ein Wasserstoffatom oder ein Alkalimetall, wie Natrium, Kalium oder Lithium;

k

ist die Zahl 1 oder 2, bevorzugt 2;

R^A

ist Wasserstoff oder Alkyl von 1 bis 3 C-Atomen, das durch Hydroxy oder eine Gruppe der Formel (5a) oder (5b)

substituiert sein kann, in welchen
R¹  Wasserstoff, Methyl oder Ethyl ist,
R²  Wasserstoff, Methyl oder Ethyl ist und
R³  Wasserstoff, Methyl oder Ethyl ist oder
R¹ und R²  zusammen mit dem N-Atom einen aus einem Alkylenrest von 5 bis 8 C-Atomen oder zwei Alkylenresten von 1 bis 4 C-Atomen und einem Sauerstoffatom oder einer Aminogruppe der Formel -NH-gebildeten gesättigten heterocyclischen Rest darstellen, wie beispielsweise den N-Piperazino-, N-Piperidino- oder N-Morpholino-Rest, und
Z^(-)  ein einwertiges Anion bedeutet, wie beispielsweise das Chlorid- oder Hydrogensulfat-Anion, oder ein einem einwertigen Anion äquivalenter Teil eines mehrwertigen Anions ist, wie beispielsweise des Sulfatanions;

R^B

hat eine der für R^A angegebenen Bedeutungen;

X

ist eine Gruppe -O- oder -NH- ;

ER

ist eine Estergruppe;

A und N

bilden zusammen mit 1 oder 2 Alkylengruppen von 1 bis 4 C-Atomen den bivalenten Rest eines heterocyclischen Ringes, bevorzugt eines 5- oder 6-gliedrigen heterocyclischen Ringes, wie beispielsweise des Piperazin-, Piperidin- oder Morpholinringes, worin

A

ein Sauerstoffatom oder eine Gruppe der allgemeinen Formel (a), (b) oder (c)

ist, in welchen
R  ein Wasserstoffatom oder eine Aminogruppe ist oder eine Alkylgruppe von 1 bis 6 C-Atomen, bevorzugt von 1 bis 4 C-Atomen, bedeutet, die durch 1 oder 2 Substituenten aus der Gruppe Amino, Sulfo, Hydroxy, Sulfato, Phosphato und Carboxy substituiert sein kann, oder eine Alkylgruppe von 3 bis 8 C-Atomen, bevorzugt von 3 bis 5 C-Atomen, ist, die durch 1 oder 2 Heterogruppen, die aus den Gruppen -O- und -NH- ausgewählt sind, unterbrochen ist und durch eine Amino-, Sulfo-. Hydroxy-, Sulfato- oder Carboxygruppe substituiert sein kann,
R³  Wasserstoff, Methyl oder Ethyl ist
R⁴  Wasserstoff, Methyl oder Ethyl ist und
Z^(-)  die obengenannte Bedeutung hat;

B

ist die Aminogruppe der Formel H₂N- oder eine Amino- bzw. Ammoniumgruppe der allgemeinen Formel (d) oder (e)

in welchen
R³, R⁴ und Z^(-)  eine der obengenannten Bedeutungen besitzt und
R⁵  Methyl oder Ethyl ist und
R⁶  Wasserstoff, Methyl oder Ethyl bedeutet;

p

ist die Zahl 1 oder 2, bevorzugt 1;

• alkylen ist ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, bevorzugt von 2 bis 4 C-Atomen, der durch 1 oder 2 Hydroxygruppen substituiert sein kann, oder ist ein geradkettiger oder verzweigter, bevorzugt geradkettiger, Alkylenrest von 3 bis 8 C-Atomen, bevorzugt von 3 bis 5 C-Atomen, der durch 1 oder 2 Heterogruppen, die aus den Gruppen -O-und -NH- ausgewählt sind, unterbrochen ist;
• alk ist ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, bevorzugt von 2 bis 4 C-Atomen, oder ist ein geradkettiger oder verzweigter, bevorzugt geradkettiger, Alkylenrest von 3 bis 8 C-Atomen, bevorzugt von 3 bis 5 C-Atomen, der durch 1 oder 2 Heterogruppen, die aus den Gruppen -O- und -NH- ausgewählt sind, unterbrochen ist, und ist bevorzugt ein geradkettiger oder verzweigter Alkylenrest von 2 bis 6 C-Atomen, bevorzugt von 2 bis 4 C-Atomen;

m

ist die Zahl 1 oder 2, bevorzugt 1;

n

ist eine Zahl von 1 bis 4, bevorzugt 1 oder 2;
die Amino-, Hydroxy- und Estergruppen in den Verbindungen (3a) und (3b) können sowohl an einem primären, sekundären oder tertiären C-Atom des Alkylenrestes gebunden sein;

R^C

ist Wasserstoff, Alkoxy von 1 bis 8 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, wie Methoxy, Ethoxy und Propoxy, Halogen, wie Chlor und Brom, Hydroxy, Alkoxy von 2 bis 4 C-Atomen, vorzugsweise Ethoxy, das durch Alkoxy von 1 bis 4 C-Atomen, vorzugsweise Methoxy und Ethoxy, substituiert ist, N-Morpholino, N-Imidazolino oder eine Gruppe der Formel (6)

vorzugsweise Alkoxy von 1 bis 4 C-Atomen und durch Alkoxy von 1 bis 4 C-Atomen substituiertes Alkoxy von 2 bis 4 C-Atomen;

R^D

ist eine Gruppe der allgemeinen Formel (7a) oder (7b)

worin bedeuten:
a  ist die Zahl Null oder 1;
b  ist eine ganze Zahl von Null bis 10, vorzugsweise Null oder 1 bis 5 und insbesondere Null oder 1 bis 3;
c  ist die Zahl 1;
die Summe von (a + b) ist bevorzugt gleich 1 oder größer als 1, insbesondere bevorzugt 1, 2, 3 oder 4;
R⁷  hat eine der Bedeutungen von R^C;
R⁸  ist Alkoxy von 1 bis 8 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, wie Ethoxy und Methoxy, das durch Alkoxy von 1 bis 4 C-Atomen substituiert sein kann, Alkyl von 1 bis 8 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, wie Ethyl und Methyl, Alkenyl von 2 bis 8 C-Atomen, vorzugsweise von 2 bis 4 C-Atomen, oder Phenylen-alkyl mit einem Alkylrest von 1 bis 4 C-Atomen, wobei der Phenylenrest durch Substituenten aus der Gruppe Methyl, Ethyl, Methoxy, Ethoxy, Sulfo und Carboxy substituiert sein kann, und wobei diese Reste R⁸ noch durch eine Gruppe T substituiert sein können;
R⁹  hat eine der Bedeutungen von R^C oder R^E;
D  ist Alkylen von 1 bis 6 C-Atomen, vorzugsweise von 2 bis 4 C-Atomen, das durch Hydroxy, Methoxy, Ethoxy, Sulfo, Sulfato oder Carboxy substituiert sein kann, oder ist Phenylen, das durch Methoxy, Ethoxy, Methyl, Ethyl, Sulfo und/oder Carboxy substituiert sein kann, oder ist Phenylen-alkylen, Alkylen-phenylen, Alkylen-phenylen-alkylen oder Phenylen-alkylen-phenylen, wobei die Alkylengruppen dieser Reste solche von 1 bis 6 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, sind und durch Hydroxy, Methoxy, Ethoxy, Sulfo, Sulfato oder Carboxy substituiert sein können und die Phenylenreste durch Methoxy, Ethoxy, Methyl, Ethyl, Sulfo und/oder Carboxy substituiert sein können;
X¹  ist eine Gruppe der Formel -S- oder -O-, und ist vorzugsweise eine Gruppe der Formel -O- ;
E  ist Cycloalkylen von 5 bis 8 C-Atomen, wie Cyclohexylen und Cyclopentylen, oder Alkylen von 1 bis 6 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, insbesondere von 2 oder 3 C-Atomen, das durch Hydroxy, Methoxy, Ethoxy, Sulfato, Sulfo oder Carboxy substituiert sein kann, oder ist Phenylen, das durch Methoxy, Ethoxy, Methyl, Ethyl, Sulfo und/oder Carboxy substituiert sein kann, vorzugsweise Alkylen von 2 bis 4 C-Atomen;
X²  ist eine Gruppe der Formel -S- , -O-, -NH- oder -N(R)- in welcher R Alkyl von 1 bis 4 C-Atomen, wie Methyl oder Ethyl, ist, und vorzugsweise -O- oder -NH- ;
G  ist Alkylen von 1 bis 6 C-Atomen, vorzugsweise von 2 bis 4 C-Atomen, das durch Hydroxy, Methoxy, Ethoxy, Sulfo, Sulfato oder Carboxy substituiert sein kann, oder ist Phenylen, das durch Methoxy, Ethoxy, Methyl, Ethyl, Sulfo und/oder Carboxy substituiert sein kann, oder ist Phenylen-alkylen, Alkylen-phenylen, Alkylen-phenylen-alkylen oder Phenylen-alkylen-phenylen, wobei die Alkylengruppen dieser Reste solche von 1 bis 6 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, sind und durch Hydroxy, Methoxy, Ethoxy, Sulfo, Sulfato oder Carboxy substituiert sein können und die Phenylenreste durch Methoxy, Ethoxy, Methyl, Ethyl, Sulfo und/oder Carboxy substituiert sein können, oder G kann eine direkte Bindung sein, und ist vorzugsweise Alkylen von 2 bis 4 C-Atomen oder eine direkte Bindung;
T  ist Hydroxy, Thiol oder vorzugsweise eine Gruppe der allgemeinen Formel (8a) oder (8b), insbesondere der Formel (8a)

in welchen
R¹⁰  Wasserstoff oder Alkyl von 1 bis 4 C-Atomen ist, das durch Phenyl, Sulfophenyl, Amino, Thio oder Hydroxy substituiert sein kann,
R¹¹  Wasserstoff, Phenyl, Sulfophenyl oder Alkyl von 1 bis 4 C-Atomen ist, das durch Phenyl, Sulfophenyl, Methoxy, Ethoxy, Amino, Thio oder Hydroxy substituiert sein kann,
R¹²  Wasserstoff oder Alkyl von 1 bis 4 C-Atomen ist, das substituiert sein kann, wie beispielsweise durch Hydroxy, Amino, Thio, Carboxy oder Sulfo, oder Alkenyl von 2 bis 6 C-Atomen, vorzugsweise von 2 bis 4 C-Atomen, ist, und
Z^(-)  die obengenannte Bedeutung hat;
K  ist ein Rest der allgemeinen Formel (9)

in welcher G, X², E, X¹, D, a und b eine der obengenannten, insbesondere bevorzugten, Bedeutungen haben;

R^E

ist Wasserstoff, Halogen, wie Chlor und Brom, Hydroxy, Alkyl von 1 bis 8 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, wie Ethyl und Methyl, Alkenyl von 2 bis 8 C-Atomen, vorzugsweise von 2 bis 4 C-Atomen, Alkinyl von 3 bis 8 C-Atomen, vorzugsweise von 3 bis 5 C-Atomen, oder Phenyl oder eine Gruppe der allgemeinen Formel (7a) oder (7b), vorzugsweise Alkyl von 1 bis 4 C-Atomen, oder eine Gruppe der allgemeinen Formel (7a) oder (7b);

R^G

hat eine der für R^C oder R^E genannten Bedeutungen;
mindestens einer der an das Siliciumatom gebundenen Substituenten ist ein hydrolysierfähiger Substituent aus der Gruppe Wasserstoff, Halogen, Alkoxy, Phenoxy, Amino und Amido, wie beispielsweise solche, die anfangs für den Formelrest R^C genannt sind, wobei hiervon Alkoxyreste bevorzugt sind, und daß man die Applikation der Farbstofflösung unter Auwendung der Ink-Jet-Printing-Sprühtechnik (worunter alle Minimalauftrags-Sprühtechniken verstanden werden) durchführt.

With the present invention, a method for dyeing flat fiber materials, in particular those of or with cellulose fibers, with anionic dyes, in particular those with fiber-reactive groups, has now been found, with which brilliant dyeings in light and deep shades with good color strength and excellent contour sharpness are obtained , which is characterized in that an aqueous dye solution which is free of alkali and preferably low in electrolytes or completely free of electrolytes is applied to a fiber material which has been pretreated and modified by a compound which has a compound corresponding to the general formulas (1), (2 ), (3a), (3b) and (4)

in which mean:

M

is a hydrogen atom or an alkali metal such as sodium, potassium or lithium;

k

is the number 1 or 2, preferably 2;

R ^A

is hydrogen or alkyl of 1 to 3 carbon atoms, which is substituted by hydroxy or a group of the formula (5a) or (5b)

can be substituted in which
R ^{1 is} hydrogen, methyl or ethyl,
R ^{2 is} hydrogen, methyl or ethyl and
R ^{3 is} hydrogen, methyl or ethyl or
R ¹ and R ² together with the N atom represent a saturated heterocyclic radical formed from an alkylene radical of 5 to 8 C atoms or two alkylene radicals of 1 to 4 C atoms and an oxygen atom or an amino group of the formula -NH, such as for example the N-piperazino, N-piperidino or N-morpholino radical, and
Z ^{(-) represents} a monovalent anion, such as the chloride or hydrogen sulfate anion, or a part of a polyvalent anion equivalent to a monovalent anion, such as the sulfate anion;

R ^B

has one of the meanings given for R ^A ;

X

is a group -O- or -NH-;

HE

is an ester group;

A and N

together with 1 or 2 alkylene groups of 1 to 4 carbon atoms form the divalent radical of a heterocyclic ring, preferably a 5- or 6-membered heterocyclic ring, such as the piperazine, piperidine or morpholine ring, in which

A

an oxygen atom or a group of the general formula (a), (b) or (c)

is in which
R is a hydrogen atom or an amino group or an alkyl group of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, which can be substituted by 1 or 2 substituents from the group amino, sulfo, hydroxy, sulfato, phosphato and carboxy, or an alkyl group of 3 to 8 carbon atoms, preferably 3 to 5 carbon atoms, which is substituted by 1 or 2 Hetero groups which are selected from the groups -O- and -NH- are interrupted and by an amino, sulfo. Hydroxy, sulfato or carboxy group can be substituted,
R ^{3 is} hydrogen, methyl or ethyl
R ^{4 is} hydrogen, methyl or ethyl and
Z ^{(-) has} the meaning given above;

B

is the amino group of the formula H ₂ N or an amino or ammonium group of the general formula (d) or (e)

in which
R ³ , R ⁴ and Z ^{(-) has} one of the meanings given above and
R ^{5 is} methyl or ethyl and
R ^{6 represents} hydrogen, methyl or ethyl;

p

is the number 1 or 2, preferably 1;

• alkylene is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched, preferably straight-chain, alkylene radical of 3 to 8 carbon atoms -Atoms, preferably from 3 to 5 carbon atoms, which is interrupted by 1 or 2 hetero groups selected from the groups -O-and -NH-;
• alk is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, or is a straight-chain or branched, preferably straight-chain, alkylene radical of 3 to 8 carbon atoms, preferably of 3 to 5 carbon atoms, which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH-, and is preferably a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, preferably of 2 up to 4 carbon atoms;

m

is the number 1 or 2, preferably 1;

n

is a number from 1 to 4, preferably 1 or 2;
the amino, hydroxyl and ester groups in the compounds (3a) and (3b) can be bound either to a primary, secondary or tertiary carbon atom of the alkylene radical;

R ^C

is hydrogen, alkoxy of 1 to 8 carbon atoms, preferably of 1 to 4 carbon atoms, such as methoxy, ethoxy and propoxy, halogen, such as chlorine and bromine, hydroxy, alkoxy of 2 to 4 carbon atoms, preferably ethoxy, that is substituted by alkoxy of 1 to 4 carbon atoms, preferably methoxy and ethoxy, N-morpholino, N-imidazolino or a group of the formula (6)

preferably alkoxy of 1 to 4 carbon atoms and alkoxy of 2 to 4 carbon atoms substituted by alkoxy of 1 to 4 carbon atoms;

R ^D

is a group of the general formula (7a) or (7b)

in which mean:
a is the number zero or 1;
b is an integer from zero to 10, preferably zero or 1 to 5 and in particular zero or 1 to 3;
c is the number 1;
the sum of (a + b) is preferably 1 or greater than 1, particularly preferably 1, 2, 3 or 4;
R ⁷ has one of the meanings of R ^C ;
R ⁸ is alkoxy of 1 to 8 carbon atoms, preferably of 1 to 4 carbon atoms, such as ethoxy and methoxy, which can be substituted by alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms, such as ethyl and methyl, alkenyl from 2 to 8 carbon atoms, preferably from 2 to 4 carbon atoms, or phenylene-alkyl with an alkyl radical of 1 to 4 carbon atoms, the phenylene radical being Substituents from the group methyl, ethyl, methoxy, ethoxy, sulfo and carboxy can be substituted, and these radicals R ^{8 can} also be substituted by a group T;
R ⁹ has one of the meanings of R ^C or R ^E ;
D is alkylene of 1 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, which can be substituted by hydroxy, methoxy, ethoxy, sulfo, sulfato or carboxy, or is phenylene, which is substituted by methoxy, ethoxy, methyl, ethyl , Sulfo and / or carboxy may be substituted, or is phenylene-alkylene, alkylene-phenylene, alkylene-phenylene-alkylene or phenylene-alkylene-phenylene, the alkylene groups of these radicals having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, and can be substituted by hydroxy, methoxy, ethoxy, sulfo, sulfato or carboxy and the phenylene radicals can be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and / or carboxy;
X ¹ is a group of the formula -S- or -O-, and is preferably a group of the formula -O-;
E is cycloalkylene of 5 to 8 carbon atoms, such as cyclohexylene and cyclopentylene, or alkylene of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, in particular of 2 or 3 carbon atoms, which can be replaced by hydroxyl, methoxy, Ethoxy, sulfato, sulfo or carboxy can be substituted, or is phenylene, which can be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and / or carboxy, preferably alkylene of 2 to 4 carbon atoms;
X ² is a group of the formula -S-, -O-, -NH- or -N (R) - in which R is alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, and preferably -O- or -NH-;
G is alkylene of 1 to 6 carbon atoms, preferably of 2 to 4 carbon atoms, which can be substituted by hydroxy, methoxy, ethoxy, sulfo, sulfato or carboxy, or is phenylene, which is substituted by methoxy, ethoxy, methyl, ethyl , Sulfo and / or carboxy may be substituted, or is phenylene-alkylene, alkylene-phenylene, alkylene-phenylene-alkylene or phenylene-alkylene-phenylene, the alkylene groups of these radicals having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, and can be substituted by hydroxy, methoxy, ethoxy, sulfo, sulfato or carboxy and the phenylene radicals can be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and / or carboxy, or G can be a direct bond , and is preferably alkylene of 2 to 4 carbon atoms or a direct bond;
T is hydroxy, thiol or preferably a group of the general formula (8a) or (8b), in particular of the formula (8a)

in which
R ^{10 is} hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfophenyl, amino, thio or hydroxy,
R ^{11 is} hydrogen, phenyl, sulfophenyl or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfophenyl, methoxy, ethoxy, amino, thio or hydroxy,
R ^{12 is} hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted, for example by hydroxy, amino, thio, carboxy or sulfo, or alkenyl of 2 to 6 carbon atoms, preferably of 2 to 4 carbon atoms , is and
Z ^{(-) has} the meaning given above;
K is a radical of the general formula (9)

in which G, X ² , E, X ¹ , D, a and b have one of the above-mentioned, particularly preferred meanings;

R ^E

is hydrogen, halogen, such as chlorine and bromine, hydroxy, alkyl of 1 to 8 carbon atoms, preferably of 1 to 4 carbon atoms, such as ethyl and methyl, alkenyl of 2 to 8 carbon atoms, preferably of 2 to 4 carbon atoms Atoms, alkynyl of 3 to 8 carbon atoms, preferably of 3 to 5 carbon atoms, or phenyl or a group of the general formula (7a) or (7b), preferably alkyl of 1 to 4 carbon atoms, or a group of the general formula (7a) or (7b);

R ^G

has one of the meanings given for R ^C or R ^E ;
at least one of the substituents bonded to the silicon atom is a hydrolyzable substituent from the group consisting of hydrogen, halogen, alkoxy, phenoxy, amino and amido, such as, for example, those which are initially mentioned for the formula radical R ^C , of which alkoxy radicals are preferred, and that carries out the application of the dye solution using the ink-jet printing spray technique (which includes all minimum-order spray techniques).

        -(CH₂)_r-O-(CH₂)_s-     (10c)



        -(CH₂)_r-O-(CH₂)_s-CH(OH)-CH₂-     (10 d)

        -(CH₂)_r-NH-(CH₂)_s-     (10f)



        -(CH₂)_r-S-(CH₂)_s-     (10g)

in welchen

r

eine ganze Zahl von 1 bis 6, vorzugsweise von 2 bis 4, ist,

s

eine ganze Zahl von Null bis 6, vorzugsweise von 1 bis 4, bedeutet,

t

eine ganze Zahl von Null bis 4, vorzugsweise 1 oder 2, ist,

v

eine ganze Zahl von 1 bis 4, vorzugsweise 2 oder 3, ist,

z

eine ganze Zahl von 1 bis 10, vorzugsweise 1 bis 5 und insbesondere 1, ist, und

ALK

einen geradkettigen oder verzweigten Alkylenrest von 1 bis 8 C-Atomen bedeutet, wobei der verzweigte Alkylenrest vorzugsweise ein solcher der Formel

ist, in welcher w eine ganze Zahl von 1 bis 4 ist und R* für Alkyl von 1 bis 3 C-Atomen steht.

The radical of the formula (9) and the radical of the general formula - [DX ¹ ] _a - [EX ² ] _b -G- corresponding to this in formula (7a) is preferably a radical of the general formula (10a), (10b), (10c), (10d), (10e), (10f), (10g), (10h), (10i) or (10j), preferably a radical of the general formula (10c), (10d), (10e) , (10f), (10h), (10i) or (10j):

- (CH ₂ ) _r -O- (CH ₂ ) _s - (10c)



- (CH ₂ ) _r -O- (CH ₂ ) _s -CH (OH) -CH ₂ - (10 d)

- (CH ₂ ) _r -NH- (CH ₂ ) _s - (10f)



- (CH ₂ ) _r -S- (CH ₂ ) _s - (10g)

in which

r

is an integer from 1 to 6, preferably from 2 to 4,

s

is an integer from zero to 6, preferably from 1 to 4,

t

is an integer from zero to 4, preferably 1 or 2,

v

is an integer from 1 to 4, preferably 2 or 3,

e.g.

is an integer from 1 to 10, preferably 1 to 5 and in particular 1, and

ALK

is a straight-chain or branched alkylene radical of 1 to 8 carbon atoms, the branched alkylene radical preferably being one of the formula

is in which w is an integer from 1 to 4 and R * is alkyl of 1 to 3 carbon atoms.

R ¹⁰ is preferably hydrogen or alkyl of 1 to 3 carbon atoms, such as methyl and ethyl, and particularly preferably hydrogen, methyl or ethyl, especially hydrogen. R ¹¹ is preferably hydrogen, alkyl of 1 to 4 carbon atoms, in particular methyl and ethyl, phenyl or alkyl of 2 to 4 carbon atoms, which is substituted by methoxy or ethoxy, of which less preferably hydrogen. The group of the formula (8a) preferably represents a secondary amino group, such as in particular the methylamino or ethylamino group.

Preferably only one of the radicals R ^A and R ^{B represents} an alkyl group with a group of the formula (5a) or (5b).

The alkyl, alkenyl and alkylene radicals mentioned for the above formula radicals can be straight-chain or branched. Within the scope of their given meaning, the individual formula residues can have meanings which are the same or different from one another.

Compounds (1), (2), (3a) and (3b) which can be used according to the invention are, for example, β-sulfato-ethylamine, 2-oxo-1,3-oxazolidine, 4-aminomethyl-2-oxo-1,3-oxazolidine, 5-aminomethyl-2-oxo-1,3-oxazolidine, 4- (trimethylammonium-methyl) -2-oxo-1,3-oxazolidine chloride, 5- (trimethylammonium-methyl) -2-oxo-1,3- oxazolidine chloride, 1- (trimethylammonium methyl) ethylene carbonate chloride, N- (β-sulfatoethyl) piperazine, N- [β- (β'-sulfatoethoxy) ethyl] piperazine, N- (γ-sulfato-β- hydroxypropyl) piperidine, N- (γ-sulfato-β-hydroxypropyl) pyrrolidine, N- (β-sulfatoethyl) piperidine, the salts of 3-sulfato-2-hydroxy-1- (trimethylammonium) propane such as 3-sulfato-2-hydroxy-1- (trimethylammonium) propane sulfate, 2-sulfato-3-hydroxy-1-aminopropane, 3-sulfato-2-hydroxy-1-aminopropane, 1- Sulfato-3-hydroxy-2-amino-propane, 3-hydroxy-1-sulfato-2-amino-propane, 2,3-disulfato-1-amino-propane and 1,3-disulfato-2-amino-propane as well Derivatives of these compounds with a different ester group instead of the sulfato group, as with de r phosphato group, an alkanoyloxy group of 2 to 5 carbon atoms, such as the acetyloxy group, the p-tosyloxy and 3,4,5-trimethyl-phenylsulfonyloxy group.

entsprechen, in welcher

R^C

eine der obengenannten Bedeutungen besitzt,

R^H

eine Gruppe der allgemeinen Formel (12a) oder (12b)

ist, in welchen
r  eine ganze Zahl von 1 bis 6, vorzugsweise von 2 bis 4, ist,
t  eine ganze Zahl von Null bis 4, vorzugsweise 1 oder 2, ist,
v  eine ganze Zahl von 1 bis 4, vorzugsweise 2 oder 3, ist,
z  eine ganze Zahl von 1 bis 10, vorzugsweise 1 bis 5 und insbesondere 1, ist, und
ALK  einen geradkettigen oder verzweigten Alkylenrest von 1 bis 8 C-Atomen bedeutet, wobei der verzweigte Alkylenrest vorzugsweise ein solcher der Formel

ist, in welcher w eine ganze Zahl von 1 bis 4 ist und R* für Alkyl von 1 bis 3 C-Atomen steht, und
T¹  eine Aminogruppe der allgemeinen Formel (8c)

ist, in welcher
R¹³  Wasserstoff oder Alkyl von 1 bis 4 C-Atomen ist, das durch Phenyl, Sulfophenyl, Amino, Thio oder Hydroxy substituiert sein kann, oder Carbamoyl ist, das mono- oder disubstituiert sein kann, wie beispielsweise durch Substituenten aus der Gruppe Alkyl von 1 bis 4 C-Atomen, Phenyl, Sulfophenyl, Cycloalkyl von 5 bis 8 C-Atomen und Alkyl von 2 bis 4 C-Atomen, das durch Amino, Thio oder Hydroxy substituiert ist, und bevorzugt Alkyl von 1 bis 4 C-Atomen, wie Methyl und Ethyl, ist;

R^K

Wasserstoff, Alkoxy von 1 bis 8 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, wie Propoxy, Ethoxy und Methoxy, das durch Alkoxy von 1 bis 4 C-Atomen substituiert sein kann, Halogen, wie Chlor und Brom, Hydroxy, Alkyl von 1 bis 8 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, wie Ethyl und Methyl, Alkenyl von 2 bis 8 C-Atomen, vorzugsweise von 2 bis 4 C-Atomen, Alkinyl von 3 bis 8 C-Atomen, vorzugsweise von 3 bis 5 C-Atomen, oder Phenyl oder eine Gruppe der allgemeinen Formel (12a) oder (12b) ist und vorzugsweise Alkyl von 1 bis 4 C-Atomen, Alkoxy von 1 bis 4 C-Atomen, durch Alkoxy von 1 bis 4 C-Atomen substituiertes Alkoxy von 2 bis 4 C-Atomen oder eine Gruppe der allgemeinen Formel (12a) oder (12b) bedeutet, und

R^M

eine der für R^C und R^K genannten Bedeutungen hat.

Of the silane compounds of the general formula (4) which can be used according to the invention, those which contain a secondary amino group and which of the general formula (11)

correspond in which

R ^C

has one of the meanings mentioned above,

R ^H

a group of the general formula (12a) or (12b)

is in which
r is an integer from 1 to 6, preferably from 2 to 4,
t is an integer from zero to 4, preferably 1 or 2,
v is an integer from 1 to 4, preferably 2 or 3,
z is an integer from 1 to 10, preferably 1 to 5 and in particular 1, and
ALK means a straight-chain or branched alkylene radical of 1 to 8 carbon atoms, the branched alkylene radical preferably being one of the formula

is in which w is an integer from 1 to 4 and R * is alkyl of 1 to 3 carbon atoms, and
T ^{1 is} an amino group of the general formula (8c)

is in which
R ^{13 is} hydrogen or alkyl of 1 to 4 carbon atoms, which may be substituted by phenyl, sulfophenyl, amino, thio or hydroxy, or carbamoyl, which may be mono- or disubstituted, such as by substituents from the group of alkyl of 1 to 4 carbon atoms, phenyl, sulfophenyl, cycloalkyl of 5 to 8 carbon atoms and alkyl of 2 to 4 carbon atoms, which is substituted by amino, thio or hydroxy, and preferably alkyl of 1 to 4 carbon atoms, such as methyl and ethyl;

R ^K

Hydrogen, alkoxy of 1 to 8 carbon atoms, preferably of 1 to 4 carbon atoms, such as propoxy, ethoxy and methoxy, which can be substituted by alkoxy of 1 to 4 carbon atoms, halogen, such as chlorine and bromine, hydroxy, Alkyl of 1 to 8 carbon atoms, preferably of 1 to 4 carbon atoms, such as ethyl and methyl, alkenyl of 2 to 8 carbon atoms, preferably of 2 to 4 carbon atoms, alkynyl of 3 to 8 carbon atoms, is preferably from 3 to 5 carbon atoms, or phenyl or a group of the general formula (12a) or (12b) and is preferably alkyl from 1 to 4 carbon atoms, alkoxy from 1 to 4 carbon atoms, by alkoxy from 1 to 4 carbon atoms substituted alkoxy of 2 to 4 carbon atoms or a group of the general formula (12a) or (12b), and

R ^M

has one of the meanings given for R ^C and R ^K.

Silane compounds of the general formula (4) which can be used according to the invention are, for example:
[γ- (β'-aminoethoxy) propyl] trimethoxy silane, [γ- (β'-aminoethylamino) propyl] trimethoxy silane, [γ- (β'-aminoethoxy) propyl] methyl diethoxy silane, [γ- (β'-aminoethyl amino) propyl] methyl dimethoxy silane, 3- or 4-aminophenyltrimethoxy silane , [γ- (4-aminophenoxy) propyl] trimethoxysilane, N- [γ- (trimethoxysilyl) propyl] -N, N-di- (β'-aminoethyl) amine, (γ-aminopropyl ) -trimethoxy-silane, (γ-aminopropyl) -ethoxy-dimethyl-silane, (γ-aminopropyl) -methyl-diethoxy-silane, N, N-bis- [γ- (triethoxysilyl) propyl] amine, [γ- (N, N-dimethylamino) propyl] trimethoxy silane, [γ- (N-methylamino) propyl] trimethoxy silane, (δ-aminobutyl) trimethoxy silane, {4- [N- (β-aminoethyl) amino] methyl} phenethyl trimethoxy silane, [(N-cyclohexyl amino) methyl] methyl diethoxy silane, [γ- (NN diethyl amino) propyl] - trimethoxysilane, [y- (β'-N -methylaminoethoxy) propyl] methyldiethoxysilane, [γ- (β'-N -methylaminoethoxy) propyl] triethoxysilane, [γ - (β'-N-Methylamino-ethoxy) -propyl] -dimethyl-ethoxysilane, 1- {3 '- [β- (N-Methylamino) -ethoxy-methyl] -phenyl} -eth-1-yl- (diethoxy) - (methyl) -silane, 2- {4 '- [β- (N-methy lamino) -ethoxy-methyl] -phenyl} -eth-2-yl- (diethoxy) - (methyl) -silane, 1- {4 '- [β- (N-methylamino) -ethoxy-methyl] -phenyl} - eth-1-yl- (diethoxy) - (methyl) -silane, 2- {3 '- [β- (N-methylamino) -ethoxy-methyl] -phenyl} -eth-2-yl- (diethoxy) - ( methyl) silane, {γ- [β '- (β "aminoethyl) aminoethyl] propyl} trimethoxysilane and 1,3-di (y-aminopropyl) -1,1,3,3-tetramethyl disiloxane.

The compounds (1) and (2) which can be used according to the invention can be prepared in accordance with known procedures, as described in large numbers in the literature (see Houben-Weyl, Methods of Organic Chemistry, 4th edition, volume E4, pages 82-88 and 192 ff.), for example by reacting an alkanediol which has a latent nitrogen-containing functional group in the side chain with phosgene in aqueous solution at a pH between 7 and 9 to prepare the heterocycloaliphatic carbonates or, for example, by reacting Aminoalkanols with phosgene in aqueous solution to the heterocycloaliphatic carbamic acid compounds (2-oxo-1,3-oxazolidines).

The compounds (3a) and (3b) which can be used according to the invention can be prepared in such a way that their corresponding hydroxyl-containing compounds are esterified in a conventional manner by reaction with the acids or the corresponding acylating agents, where, if one of compounds containing amino groups with more than one hydroxyl group, preferably only one of these hydroxyl groups esterified. Such procedures are known in the literature; the compounds which can be used according to the invention can be prepared analogously to such known procedures. For example, the esterification of amino alcohols to their sulfuric acid esters is described in Houben-Weyl, Methods of Organic Chemistry, Volume VI / 2, pages 452-457, and Volume E11, pages 997 ff. Other common modifications of such procedures are based on, for example, stirring the amino alcohol into a large excess of fuming sulfuric acid (see Chem. Ber. 51 , 1160) or on the use of indifferent solvents which serve as the reaction medium in the esterification, the use of which equimolar amounts of concentrated sulfuric acid is possible (see DE-C-825 841). Esterification and acylating agents which can serve as starting compounds for the preparation of the compounds containing ester and amino groups which can be used according to the invention are, for example, sulfuric acid, phosphoric acid, polyphosphoric acid, lower alkane carboxylic acids and their chlorides or anhydrides, such as, for example, acetic acid (glacial acetic acid) and acetic anhydride, benzenesulfonic acid and the on the benzene nucleus by substituents from the group sulfo, carboxy, lower alkyl, lower alkoxy and nitro substituted benzenesulfonic acids or their sulfochlorides. For example, the sulfato compounds can be prepared from the corresponding hydroxy compounds by adding the hydroxy compounds in the required amount, ie preferably an equimolar amount, of concentrated sulfuric acid and stirring them at a temperature between 5 and 30 ° C. for some time until the solution is complete. They are isolated from the sulfuric acid solution by pouring the solution onto ice and neutralization, by precipitating the sulfate ions using calcium carbonate as calcium sulfate and then filtering and evaporating the aqueous solution. The example of the sulfato compounds gives crystalline or semi-crystalline substances which can be used directly in the process of modifying the fiber material.

The silane compounds used in accordance with the invention are described in large numbers in the literature and some are commercially available. Not known as species Silane compounds can be synthesized analogously to the procedures for the preparation of the known silane compounds, such as, for example, analogously to the information in German Patent DE-C-1 186 061.

in welcher

R^C

eine der obengenannten Bedeutungen besitzt,

R^P

ein Rest der allgemeinen Formel (14a) oder (14b)

        -(CH₂)_r-Hal     (14b)

ist, in welchen
ALK, t und r  eine der obengenannten Bedeutungen besitzen und
Hal  für ein Halogenatom, vorzugsweise Chloratom, steht,

R^R

Wasserstoff, Alkoxy von 1 bis 8 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, Atomen, wie Propoxy, Ethoxy und Methoxy, das durch Alkoxy von 1 bis 4 substituiert sein kann, Halogen, wie Chlor und Brom, Hydroxy, Alkyl von 1 bis 8 C-Atomen, vorzugsweise von 1 bis 4 C-Atomen, wie Ethyl und Methyl, Alkenyl von 2 bis 8 C-Atomen, vorzugsweise von 2 bis 4 C-Atomen, Alkinyl von 3 bis 8 C-Atomen, vorzugsweise von 3 bis 5 C-Atomen, oder Phenyl oder eine Gruppe der allgemeinen Formel (14a) oder (14b) ist und vorzugsweise Alkyl von 1 bis 4 C-Atomen, Alkoxy von 1 bis 4 C-Atomen, durch Alkoxy von 1 bis 4 C-Atomen substituiertes Alkoxy von 2 bis 4 C-Atomen oder eine Gruppe der allgemeinen Formel (14a) oder (14b) bedeutet, und

R^T

eine der für R^C oder R^R genannten Bedeutungen besitzt,

mit einer Verbindung der allgemeinen Formel (15a) oder (15b)

        MeO - (CH₂)_r - T¹     (15a)



        MeO - (CH₂)_v - T¹     (15b)

in welchen r, v und T¹ eine der obengenannten Bedeutungen besitzen und Me für eine Alkalimetall, wie Natrium und insbesondere Kalium, steht, in einem polaren, organischen, gegebenenfalls mit Wasser mischbaren Lösemittel, das gegenüber den Reaktanten, wie insbesondere Alkoholaten, inert ist, bei einer Temperatur zwischen 0 und 50°C, vorzugsweise zwischen 10 und 40°C, umsetzt.In particular, for example, the silane compounds of the general formula (11) can be prepared by using a compound of the general formula (13)

in which

R ^C

has one of the meanings mentioned above,

R ^P

a radical of the general formula (14a) or (14b)

- (CH ₂ ) _r -Hal (14b)

is in which
ALK, t and r have one of the meanings mentioned above and
Hal represents a halogen atom, preferably chlorine atom,

R ^R

Hydrogen, alkoxy of 1 to 8 carbon atoms, preferably of 1 to 4 carbon atoms, atoms such as propoxy, ethoxy and methoxy, which can be substituted by alkoxy of 1 to 4, halogen, such as chlorine and bromine, hydroxy, alkyl from 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms, such as ethyl and methyl, alkenyl from 2 to 8 carbon atoms, preferably from 2 to 4 carbon atoms, alkynyl from 3 to 8 carbon atoms, preferably from 3 to 5 carbon atoms, or phenyl or a group of the general formula (14a) or (14b) and preferably alkyl from 1 to 4 carbon atoms, alkoxy from 1 to 4 carbon atoms, by alkoxy from 1 to 4 C atoms substituted alkoxy of 2 to 4 carbon atoms or a group of the general formula (14a) or (14b), and

R ^T

has one of the meanings mentioned for R ^C or R ^R ,

with a compound of the general formula (15a) or (15b)

MeO - (CH ₂ ) _r - T ¹ (15a)



MeO - (CH ₂ ) _v - T ¹ (15b)

in which r, v and T ^{1 have} one of the meanings mentioned above and Me stands for an alkali metal, such as sodium and in particular potassium, in a polar, organic, optionally water-miscible solvent which is inert to the reactants, such as, in particular, alcoholates , at a temperature between 0 and 50 ° C, preferably between 10 and 40 ° C.

The starting compounds of the general formulas (15a) and (15b) are prepared in a conventional manner by starting from the corresponding hydroxy compound (amino alcohol) and using the metallic alkali metal, such as sodium and especially potassium, in a manner known per se in the implements solvents mentioned above. As a rule, the reaction takes place at a temperature between 50 and 150 ° C., preferably between 80 and 110 ° C. It is advantageous to choose a solvent with a boiling point which is sufficiently high that the alkali metal can be heated above its melting point in order to simplify and accelerate the reaction.

Solvents suitable for this are, in particular, aliphatic hydrocarbons with a boiling range from 70 to 150 ° C., such as heptane and dodecane, and mixtures thereof, furthermore aromatic hydrocarbons, such as, for example, alkyl-substituted benzenes and naphthalenes, such as in particular toluene and xylene, and furthermore aliphatic, in particular cycloaliphatic Ether compounds such as tetrahydrofuran.

When the compounds of the general formula (13) are reacted with a compound of the general formula (15a) or (15b), the corresponding alkali metal halide is released and precipitates out as a crystalline salt. It is separated off after the reaction, for example by filtration, and the solvent is removed from the batch freed from this by means of fractional distillation and the synthesized silane compound is obtained.

Fiber materials are understood to mean natural and synthetic fiber materials which contain hydroxyl and / or carbonamide groups, such as silk, wool and other animal hair, and also synthetic polyamide fiber materials and polyurethane fiber materials, for example polyamide-4, polyamide-6 and polyamide-11, and in particular fiber materials which Base bodies of α, β-glucose contain, such as cellulose fiber materials, for example cotton, hemp, jute and linen, and their regenerated derivatives, such as viscose silk and cellulose, or mixtures of such fiber materials, the fiber material in the present ink-jet dyeing process as a flat structure (Piece goods), such as woven or knitted fabrics, must be present.

By "anionic dyes" are meant those which are anionic, i.e. contain acidic groups, such as sulfo and carboxy groups, or their salts, such as alkali metal salts, and are accordingly water-soluble. In particular, these are understood to mean those anionic dyes which have a fiber-reactive group, i.e. a group that is usually able to react with the carbonamide or hydroxy groups of the fiber material and to be able to form a connection with them.

The modification of the fiber material with the amino group-containing compounds, such as those of the formulas (1), (2), (3a), (3b) and / or (4), can be carried out, for example, in such a way that the fiber material with one of these compounds which can be used according to the invention or a mixture of such compounds in alkaline aqueous solution and the compound containing amino groups at a temperature between 60 and 230 ° C., preferably between 90 and 190 ° C, can act on the fiber material. The concentration of this compound in the alkaline aqueous solution is generally between 1 and 20% by weight, preferably between 5 and 10% by weight. The alkaline agent, such as sodium hydroxide, sodium carbonate and potassium carbonate, is dissolved in a concentration between 0.1 and 20% by weight, preferably between 5 and 10% by weight. As a rule, this alkaline aqueous solution has a pH between 10 and 14.

The fiber material can be present both in the modification and in the modified form when used in the dyeing process according to the invention in a mixture with other fiber materials, for example in the form of cotton / polyester fiber materials and in the form of blended fabrics with other fiber materials.

The amino group-containing compounds which can be used to modify the fiber material can be brought into contact with the fiber material in an alkaline aqueous solution in a variety of ways, for example by treating the fiber material in an alkaline, aqueous solution of the amino group-containing compound (analogously to a dye-drawing process) at a temperature between 15 and 100 ° C, the modification of the fiber material already taking place, in particular at the higher temperatures. Other possibilities are to pad the fiber material with the aqueous, alkaline solution, to splash or to spray the solution onto the fiber material. If the impregnation of the fiber material with this alkaline, aqueous solution occurs by introducing the fiber material into this solution or by padding (padding), the impregnated material is then squeezed out by excess liquor so that the absorption of this aqueous, alkaline solution between 50 and 120% by weight, preferably between 70 and 100% by weight, based on the fiber material. As a rule, the impregnation (by padding, splashing or treatment in the solution itself) takes place at a temperature between 10 and 60 ° C., preferably at a temperature between 15 and 30 ° C. When the solution is sprayed onto the fiber material, which usually takes place at a temperature between 10 and 40 ° C, a liquid absorption of preferably between 10 and 50% by weight.

If the fiber material is a mercerized cellulose fiber material, the amino group-containing compound that can be used according to the invention can also advantageously be applied to the cellulose fiber material to be modified directly after the mercerization process, in which the mercerized material still contains the alkali, for example by using the aqueous solution to obtain the one obtained after the mercerization process Alkali-impregnated material, if necessary, squeezed to a required liquid content and the alkaline-impregnated material impregnated with the aqueous solution of the compound containing amino groups that can be used according to the invention, the impregnation being carried out by padding, spraying and similar process steps which are customary and known in the art.

After impregnation of the fiber material in one of the various ways specified above, except for the pretreatment according to a pull-out procedure, the impregnated material is dried; as a rule, the drying of the compound modifying the fiber is carried out simultaneously with the drying, a temperature between 100 and 230 ° C., in particular between 120 and 190 ° C., preferably being chosen for the drying and fixing. As a rule, drying and simultaneous fixing take place by treatment with hot air for 1 to 5 minutes. The fiber-modifying compound can be fixed on the fiber material by simple drying at higher temperatures; it can be hung up in drying cabinets to dry and fix the modifying compound on the fiber material and exposed to the required higher temperatures, such as 80 to 105 ° C.

The modified fiber material is aftertreated by rinsing with cold and hot water and optionally by treatment in an aqueous bath containing a small amount of an acid, such as acetic acid, to remove the alkali from the fiber material and then drying. In the dyeing process should use a neutral reacting fiber material if possible.

The dye solutions are applied to the modified fiber material (woven, knitted or non-woven) with the help of commercially available inkjet printers, which are converted if necessary for large-scale purposes. Neutral, preferably aqueous, solutions of the anionic dyes are used, the anionic dyes preferably containing a fiber-reactive group. The dye solutions can contain auxiliaries such as are usually present in the inks for inkjet printers, such as anti-aggregation agents such as N-methyl-pyrrolidone, dimethylformamide and dimethylacetamide, and wetting agents such as ionic or non-ionic surfactants. Other auxiliaries that are usually required for dyeing with anionic, in particular fiber-reactive, dyes can be dispensed with. Their use is even inappropriate and disadvantageous. The anionic dyes are expediently used in the form free from electrolyte salts, such as sodium chloride and sodium sulfate. However, commercially available dye preparations with up to 50% by weight of electrolyte salt can generally also be applied without problems in the process according to the invention using the inkjet printing technique. In multi-color printing, several ink cartridges can be connected in series, which can be controlled with the means common today to generate the print on the moving material web. Modern multi-chamber inkjet cartridges can also be used, with which several colors can be applied in one pass.

The dye solution (ink) is applied to the modified material to be colored in accordance with the inkjet printing process, specifically in tiny drops of ink. The material dyed in this way is then subjected to a treatment with superheated steam, hot air or by means of another energy, such as by means of radiation with electromagnetic waves in the microwave or radio frequency range, the dyes being fixed on the modified fiber material. Especially because of the small amount of dye solution that is on the Subsequent laundry treatment of the colored material is generally not required by means of the ink jet printing process. It is achieved in this way that the dyeing process can be carried out without exposure to any waste water which, for example, contains dye, alkali and electrolyte salts which have not been fixed according to the dyeing processes hitherto customary, or without exposure to other waste products. In accordance with the method according to the invention, strongly colored print samples with the usual good fastness properties are obtained.

Different deeply colored shades of the same color tone can be achieved very easily by using the inkjet process, for example by controlling the application quantity of the dye solution, for example by overprinting the same line several times, or by rasterizing and printing a fine dot pattern, which is the case with today's inkjet -Printers, depending on the process, can even be over 400 dpi. A large number of color intensities (color saturations) can be obtained without having to recreate the dyeing liquor.

All water-soluble, preferably anionic dyes, which preferably have one or more sulfo and / or carboxy groups and which can optionally contain fiber-reactive groups, are suitable for the dyeing methods according to the invention. In addition to the class of fiber-reactive dyes, they can belong to the class of azo development dyes, direct dyes, vat dyes and acid dyes, which include, for example, azo dyes, copper complex, cobalt complex and chromium complex azo dyes, copper and nickel phthalocyanine dyes, anthraquinone and copper formazan - And triphendioxazine dyes. Such dyes have been described in numerous literature and are well known to those skilled in the art.

Of the above-mentioned dyes which can be used for the dyeing process according to the invention, the fiber-reactive dyes are preferably used. Fiber-reactive dyes are those organic dyes that contain 1, 2, 3 or 4 fiber-reactive residues of the aliphatic, aromatic or heterocyclic series contain. Such dyes have been extensively described in the literature. The dyes can belong to a wide variety of dye classes, for example the class of monoazo, disazo, polyazo and metal complex azo dyes, such as 1: 1 copper, 1: 2 chromium and 1: 2 cobalt complex monoazo and -Disazo dyes, further the series of anthraquinone dyes, copper and cobalt phthalocyanine dyes, copper formazan dyes, azomethine, nitroaryl, dioxazine, triphendioxazine, phenazine and stilbene dyes. Fiber-reactive dyes are understood to mean those which have a “fiber-reactive” group, ie a group which contains the hydroxyl groups of cellulose, the amino, carboxy, hydroxyl and thiol groups of wool and silk or the amino and possibly carboxy groups of synthetic polyamides can react to form a covalent chemical bond. The fiber-reactive residue can be bound to the dye residue directly or via a bridge member; it is preferably directly or via an optionally monoalkylated amino group, such as, for example, a group of the formula -NH-, -N (CH ₃ ) -, -N (C ₂ H ₅ ) - or -N (C ₃ H ₇ ) -, or via an aliphatic radical, such as a methylene, ethylene or propylene radical or an alkylene radical of 2 to 8 carbon atoms, which is interrupted by one or two oxi and / or amino groups, or via a bridge member containing an amino group, such as for example a phenylamino group attached to the dye residue.

Fiber-reactive radicals are, for example: vinylsulfonyl, β-chloroethylsulfonyl, β-sulfatoethylsulfonyl, β-acetoxy-ethylsulfonyl, β-phosphatoethylsulfonyl, β-thiosulfatoethylsulfonyl, N-methyl-N- (β-sulfatoethyl-sulfonyl) -amino, acryloyl, -CO- CCl = CH ₂ , -CO-CH = CH-Cl, -CO-CCl = CHCl, -CO-CCl = CH-CH ₃ , -CO-CBr = CH ₂ , -CO-CH = CH-Br, -CO -CBr = CH-CH ₃ , -CO-CCl = CH-COOH, -CO-CH = CCl-COOH, -CO-CBr = CH-COOH, -CO-CH = CBr-COOH, -CO-CCI = CCI -COOH, -CO-CBr = CBr-COOH, β-chloro- or β-bromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 3-chloro-3-phenylsulfonylpropionyl, 2,3-dichloropropionyl, 2,3-dibromopropionyl, 2 -Fluoro-2-chloro-3,3-difluorocyclobutane-2-carbonyl, 2,2,3,3-tetrafluorocyclobutane-1-carbonyl or -1-sulfonyl, β- (2,2,3,3-tetrafluorocyclobutyl-1 ) -acryloyl, α- or β-methylsulfonylacryloyl, Propiolyl, chloroacetyl, bromoacetyl, 4- (β-chloroethylsuffonyl) butyryl, 4-vinylsulfonylbutyryl, 5- (β-chloroethylsulfonyl) valeryl, 5-vinylsulfonylvaleryl, 6- (β-chloroethylsulfonyl) caproyl, 6- Vinylsulfonyl-caproyl, 4-fluoro-3-nitro-benzoyl, 4-fluoro-3-nitro-phenylsulfonyl, 4-fluoro-3-methylsulfonyl-benzoyl, 4-fluoro-3-cyano-benzoyl, 2-fluoro-5- methylsulfonyl-benzoyl, 2,4-dichlorotriazinyl-6, 2,4-dichloropyrimidinyl-6, 2,4,5-trichloropyrimidinyl-6, 2,4-dichloro-5-nitro- or -5-methyl- or -5- carboxymethyl- or -5-carboxy- or -5-cyano- or -5-vinyl- or -5-sulfo- or -5-mono-, di- or -trichloromethyl- or -5-methylsulfonylpyrimidinyl-6, 2.5 -Dichlor-4-methylsulfonyl-pyrimidinyl-6, 2-fluoro-4-pyrimidinyl, 2,6-difluoro-4-pyrimidinyl, 2,6-difluoro-5-chloro-4-pyrimidinyl, 2-fluoro-5.6 -dichloro-4-pyrimidinyl, 2,6-difluoro-5-methyl-4-pyrimidinyl, 2,5-difluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-methyl-6-chloro-4-pyrimidinyl , 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5-bromo-2-fluoro-4-pyrimidinyl, 2-fluoro-5- cyan-4-pyrimidinyl, 2-fluoro-5-methyl-4-pyrimidinyl, 2,5,6-trifluoro-4-pyrimidinyl, 5-chloro-6-chloromethyl-2-fluoro-4-pyrimidinyl, 2,6- Difluoro-5-bromo-4-pyrimidinyl, 2-fluoro-5-bromo-6-chloro-methyl-4-pyrimidinyl, 2,6-difluoro-5-chloromethyl-4-pyrimidinyl, 2,6-difluoro-5- nitro-4-pyrimidinyl, 2-fluoro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-6-methyl-4-pyrimidinyl, 2-fluoro-5-chloro-4-pyrimidinyl, 2-fluoro 6-chloro-4-pyrimidinyl, 6-trifluoromethyl-5-chloro-2-fluoro-4-pyrimidinyl, 6-trifluoromethyl-2-fluoro-4-pyrimidinyl, 2-fluoro-5-nitro-4-pyrimidinyl, 2- Fluoro-5-trifluoromethyl-4-pyrimidinyl, 2-fluoro-5-phenyl- or -5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-carbonamido-4-pyrimidinyl, 2-fluoro-5-carbomethoxy-4- pyrimidinyl, 2-fluoro-5-bromo-6-trifluoromethyl-4-pyrimidinyl, 2-fluoro-6-carbonamido-4-pyrimidinyl, 2-fluoro-6-carbomethoxy-4-pyrimidinyl, 2-fluoro-6-phenyl- 4-pyrimidinyl, 2-fluoro-6-cyan-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2-fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro-5-chloro 6-carbomethox y-4-pyrimidinyl, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl, 2,4-bis (methylsulfonyl) pyrimidinyl-4, 2,5-bis (methylsulfonyl) -5-chloropyrimidinyl -4, 2-methylsulfonylpyrimidinyl-4, 2-phenylsulfonyl-pyrimidinyl-4, 2-methylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-5-bromo-6-methylpyrimidinyl-4, 2-methylsulfonyl -5-chloro-6-ethyl-pyrimidinyl-4, 2-methylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, 2-methylsulfonyl-5-nitro-6-methyl-pyrimidinyl-4, 2,5,6 -Tris-methylsulfonyl-pyrimidinyl-4, 2-methylsulfonyl-5,6-dimethyl-pyrimidinyl-4, 2-ethylsulfonyl-5-chloro-6-methylpyrimidinyl-4, 2-methylsulfonyl-6-chloropyrimidinyl-4, 2,6-bis (methylsulfonyl) -5-chloropyrimidinyl-4, 2-methylsulfonyl-6-carboxypyrimidinyl-4, 2-methylsulfonyl-5-sulfopyrimidinyl-4, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl- 4,2-methylsulfonyl-5-carboxypyrimidinyl-4,2-methylsulfonyl-5-cyano-6-methoxypyrimidinyl-4,2,2-methylsulfonyl-5-chloropyrimidinyl-4,2,2-sulfoethylsulfonyl-6-methylpyrimidinyl- 4, 2-methylsulfonyl-5-bromo-pyrimidinyl-4, 2-phenylsulfonyl-5-chloro-pyrimidinyl-4, 2-carboxymethylsulfonyl-5-chloro-6-methyl-pyrimidinyl-4, 2,4-dichloropyrimidine-6- carbonyl or -6-sulfonyl, 2,4-dichloropyrimidine-5-carbonyl or -5-sulfonyl, 2-chloro-4-methylpyrimidine-5-carbonyl, 2-methyl-4-chloropyrimidine-5-carbonyl, 2-methylthio- 4-fluoropyrimidine-5-carbonyl, 6-methyl-2,4-dichloropyrimidine-5-carbonyl, 2,4,6-trichloropyrimidine-5-carbonyl, 2,4-dichloropyrimidine-5-sulfonyl, 2,4-dichloro- 6-methyl-pyrimidine-5-carbonyl or -5-sulfonyl, 2-methylsulfonyl-6-chloropyrimidine-4 and -5-carbonyl, 2,6-bis (methylsulfonyl) pyrimidine-4 or -5-carbonyl, 2- Ethylsulfonyl-6- chloropyrimidine-5-carbonyl, 2,4-bis (methylsulfonyl) pyrimidine-5-sulfonyl, 2-methylsulfonyl-4-chloro-6-methylpyrimidine-5-sulfonyl or -5-carbonyl, 2-chloroquinoxaline-3-carbonyl , 2- or 3-monochloroquinoxaline-6-carbonyl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloroquinoxaline-5- or -6-sulfonyl , 1,4-dichlorophthalazin-6-sulfonyl or -6-carbonyl, 2,4-dichloroquinazoline-7- or -6-sulfonyl or -carbonyl, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl, 2 - or 3- or 4- (4 ', 5'-dichloropyridazon-6'-yl-1') phenylsulfonyl or carbonyl, β- (4 ', 5'-dichloropyridazinon-6'-yl-1' ) -propionyl, 3,6-dichloropyridazin-4-carbonyl or -4-sulfonyl, 2-chlorobenzthiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonyl- or 2-alkylsulfonylbenzothiazole-5 - or -6-carbonyl or -5- or -6-sulfonyl, such as 2-methylsulfonyl- or 2-ethylsulfonylbenzthiazole-5- or -6-sulfonyl or -carbonyl, 2-phenylsulfonyl-benzothiazole-5- or -6-sulfonyl or carbonyl and the corresponding 2-sulfonylbenzothiazole-5 or -6-carbonyl or -sulfonyl derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chlorobenzimidazole-5- or-6, containing sulfo groups in the fused benzene ring -carbonyl or -sulfonyl, 2-chloro-1-methylbenzimidazole-5- or -6-carbonyl or -sulfonyl, 2-chloro-4-methylthiazole- (1,3) -5-carbonyl or -4- or -5- sulfonyl; triazine rings containing ammonium groups, such as 2-trimethylammonium-4-phenylamino- and -4- (o, m- or p-sulfophenyl) -amino-triazinyl-6, 2- (1,1-dimethylhydrazinium) -4-and -4- (o-, m- or p-sulfophenyl) aminotriazinyl-6, 2- (2-isopropylidene-1,1-dimethyl) hydrazinium-4-phenylamino- and -4- (o-, m- or p-sulfophenyl) aminotriazinyl-6, 2-N-aminopyrrolidinium-, 2-N-aminopiperidinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -aminotriazinyl-6, 4-phenylamino- or 4- (sulfophenylamino) triazinyl-6, which, in the 2-position, the 1,4-bis-aza-bicyclo [2,2,2] octane or the 1,2-bis-aza-bicyclo- [ Contain 0.3,3] octane bound in a quaternary manner, 2-pyridinium-4-phenylamino- or -4- (o-, m- or p-sulfophenyl) -amino-triazinyl-6 and corresponding 2-oniumtriazinyl-6 radicals which are substituted in the 4-position by alkylamino, such as methylamino, ethylamino or β-hydroxyethylamino, or alkoxy, such as methoxy or ethoxy, or aryloxy, such as phenoxy or sulfophenoxy.

in welcher Hal Chlor oder Fluor ist und Q eine Amino-, Alkylamino-, N,N-Dialkylamino-, Cycloalkylamino-, N,N-Dicycloalkylamino-, Aralkylamino-, Arylamino-, N-Alkyl-N-cyclohexylamino-, N-Alkyl-N-arylaminogruppe oder eine Aminogruppe bedeutet, die einen heterocyclischen Rest enthält, welcher einen weiteren ankondensierten carbocyclischen Ring aufweisen kann, oder Aminogruppen, worin das Aminostickstoffatom Glied eines N-heterocyclischen Ringes ist, der gegebenenfalls weitere Heteroatome enthält, sowie Hydrazino- und Semicarbazidogruppen, wobei die genannten Alkylreste geradkettig oder verzweigt und niedrigmolekular und höhermolekular sein können, bevorzugt solche mit 1 bis 6 Kohlenstoffatomen sind. Als Cycloalkyl-, Aralkyl- und Arylreste kommen insbesondere Cyclohexyl-, Benzyl-, Phenethyl-, Phenyl- und Naphthylreste in Frage; heterocyclische Reste sind vor allem Furan-, Thiophen-, Pyrazol-, Pyridin-, Pyrimidin-, Chinolin-, Benzimidazol-, Benzthiazol- und Benzoxazolreste. Als Aminogruppen, worin das Aminostickstoffatom Glied eines N-heterocyclischen Ringes ist, kommen vorzugsweise Reste von sechsgliedrigen N-heterocyclischen Verbindungen in Betracht, die als weitere Heteroatome Stickstoff, Sauerstoff oder Schwefel enthalten können. Die oben genannten Alkyl-, Cycloalkyl-, Aralkyl- und Arylreste, die heterocyclischen Reste sowie die N-heterocyclischen Ringe können zusätzlich substituiert sein, z.B. durch Halogen, wie Fluor, Chlor und Brom, Nitro, Cyan, Trifluormethyl, Sulfamoyl, Carbamoyl, C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Acylaminogruppen, wie Acetylamino oder Benzoylamino, Ureido, Hydroxy, Carboxy, Sulfomethyl oder Sulfo. Als Beispiele für derartige Aminogruppen seien genannt: -NH₂, Methylamino, Ethylamino, Propylamino, Isopropylamino, Butylamino, Hexylamino, β-Methoxyethylamino, γ-Methoxypropylamino, β-Ethoxyethylamino, N,N-Dimethylamino, N,N-Diethylamino, β-Chlorethylamino, β-Cyanethylamino, γ-Cyanpropylamino, β-Carboxyethylamino, Sulfomethylamino, β-Sulfoethylamino, β-Hydroxyethylamino, N,N-Di-β-hydroxyethylamino, γ-Hydroxypropylamino, Benzylamino, Phenethylamino, Cyclohexylamino, Phenylamino, Toluidino, Xylidino, Chloranilino, Anisidino, Phenetidino, N-Methyl-N-phenylamino, N-Ethyl-N-phenylamino, N-β-Hydroxyethyl-N-phenylamino, 2-, 3- oder 4-Sulfoanilino, 2,5-Disulfoanilino, 4-Sulfomethylanilino, N-Sulfomethylanilino, 2-, 3- oder 4-Carboxyphenylamino, 2-Carboxy-5-sulfophenylamino, 2-Carboxy-4-sulfophenylamino, 4-Sulfonaphthyl-(1)-amino, 3,6-Disulfonaphthyl-(1)-amino, 3,6,8-Trisulfonaphthyl-(1)-amino, 4,6,8-Trisulfonaphthyl-(1)-amino, 1-Sulfonaphthyl-(2)-amino, 1,5-Disulfonaphthyl-(2)-amino, 6-Sulfonaphthyl-(2)-amino, Morpholino, Piperidino, Piperazino, Hydrazino und Semicarbazido.Particularly interesting fiber-reactive radicals are fluorine and chloro-1,3,5-triazine radicals of the formula (16)

in which Hal is chlorine or fluorine and Q is an amino, alkylamino, N, N-dialkylamino, cycloalkylamino, N, N-dicycloalkylamino, aralkylamino, arylamino, N-alkyl-N-cyclohexylamino, N- Alkyl-N-arylamino group or an amino group which contains a heterocyclic radical which may have a further fused-on carbocyclic ring, or amino groups in which the amino nitrogen atom is a member of an N-heterocyclic ring which optionally contains further heteroatoms, and hydrazino and semicarbazido groups , where the alkyl radicals mentioned can be straight-chain or branched and low molecular weight and higher molecular weight, preferably those having 1 to 6 carbon atoms. Suitable cycloalkyl, aralkyl and aryl radicals are, in particular, cyclohexyl, benzyl, phenethyl, phenyl and naphthyl radicals; Heterocyclic residues are especially furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzothiazole and benzoxazole residues. As Amino groups, in which the amino nitrogen atom is a member of an N-heterocyclic ring, are preferably residues of six-membered N-heterocyclic compounds which may contain nitrogen, oxygen or sulfur as further heteroatoms. The alkyl, cycloalkyl, aralkyl and aryl radicals mentioned above, the heterocyclic radicals and the N-heterocyclic rings can additionally be substituted, for example by halogen, such as fluorine, chlorine and bromine, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, C. ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo. Examples of such amino groups are: -NH ₂ , methylamino, ethylamino, propylamino, isopropylamino, butylamino, hexylamino, β-methoxyethylamino, γ-methoxypropylamino, β-ethoxyethylamino, N, N-dimethylamino, N, N-diethylamino, β- Chloroethylamino, β-cyanoethylamino, γ-cyanopropylamino, β-carboxyethylamino, sulfomethylamino, β-sulfoethylamino, β-hydroxyethylamino, N, N-di-β-hydroxyethylamino, γ-hydroxypropylamino, benzylamino, phenethylamino, cyclohexylamino, phenidino, phenylamino, phenylamino, phenylamino, phenylamino Chloranilino, anisidino, phenetidino, N-methyl-N-phenylamino, N-ethyl-N-phenylamino, N-β-hydroxyethyl-N-phenylamino, 2-, 3- or 4-sulfoanilino, 2,5-disulfoanilino, 4- Sulfomethylanilino, N-sulfomethylanilino, 2-, 3- or 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-4-sulfophenylamino, 4-sulfonaphthyl- (1) -amino, 3,6-disulfonaphthyl- (1st ) -amino, 3,6,8-trisulfonaphthyl- (1) -amino, 4,6,8-trisulfonaphthyl- (1) -amino, 1-sulfonaphthyl- (2) -amino, 1,5-disulfonaphthyl- (2nd ) - amino, 6-sulfonaphthyl- (2) -amino, morpholino, piperidino, piperazino, hydrazino and semicarbazido.

Furthermore, Q can be an amino radical of the general formula -NR ²⁰ R ²¹ , in which R ^{20 is} hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, and R ^{21 is} phenyl, which is directly by a fiber-reactive radical of the vinylsulfone series or is substituted by a methylamino, ethylamino, methylene, ethylene or propylene group and which can also be substituted by 1 or 2 substituents from the group methoxy, ethoxy, methyl, ethyl, chlorine, carboxy and sulfo, or R ²¹ alkyl of 2 to 4 carbon atoms, such as ethyl or n-propyl, which is substituted by a fiber-reactive group of the vinylsulfone series, or alkylenephenyl with an alkylene radical of 1 to 4 carbon atoms, the phenyl of which is substituted by a fiber-reactive radical of the vinylsulfone series, or in which R ²⁰ and R ^{21 are} both alkyl of 2 to 4 carbon atoms, such as ethyl and n-propyl, which are substituted by a fiber-reactive group from the vinylsulfone series, or in which R ²⁰ and R ^{21 are} both alkylene of 3 to 8 carbon atoms, which are interrupted by 1 or 2 oxy and / or amino groups and to which a fiber-reactive group is terminated Vinyl sulfone series is bound.

Fiber-reactive groups of the vinylsulfone series are those of the general formula -SO ₂ -Y, in which Y is vinyl or ethyl which is substituted in the β-position by an alkali-eliminable substituent, such as, for example, chlorine, sulfato, phosphato, thiosulfato, acetyloxy, Sulfobenzoyloxy and dimethylamino.

The dyeings of the modified cellulose fiber materials obtainable in the manner according to the invention, as already mentioned, do not require any further aftertreatment after the dye has been fixed on the substrate, in particular no complicated aftertreatment process including washing. If necessary at all, it is sufficient to rinse the colored substrate once or several times with warm or hot and, if appropriate, cold water, which may optionally contain a nonionic wetting agent or a fiber-reactive aftertreatment agent, such as, for example, condensation products from one mole of cyanuric chloride and two moles of 4- (β -Sulfatoethylsulfonyl) aniline, from equivalent amounts of cyanuric chloride, 4- (β-sulfatoethylsulfoanyl) aniline and 4,8-disulfo-2-amino-naphthalene or from equivalent amounts of cyanuric chloride, 4-sulfo-aniline and 4.8- Disulfo-2-aminonaphthalene. The use of a fiber-reactive aftertreatment agent is advisable if the fiber material modified according to the invention has been dyed only in slight depths of shade or if a dye has been used which does not have satisfactory fiber reactivity. In these cases, there are still sufficient dye-reactive spots on the modified fiber, which, for example, can react with other dyes in rinsing baths contaminated with these dyes. Through this aftertreatment, the still active areas of the invention modified fiber is deactivated, and the originally desired clear color is obtained even in a rinsing water used in a technical process and contaminated with dyes. In addition, a final boiling treatment of the colored substrate with a washing solution to improve the fastness properties is not necessary.

The following examples serve to illustrate the invention. The parts mentioned are parts by weight, the percentages are percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume such as kilograms to liters.

Example A

For the synthesis of an amino group-containing compound which can be used according to the invention and which serves to modify the fiber material, a mixture of 750 parts by volume of a 100% strength sulfuric acid and 75 parts by volume of a 20% sulfuric acid-containing sulfuric acid (20% strength oleum) is added 10 ° C slowly with stirring 500 parts by volume of N- (β-hydroxyethyl) piperidine, the reaction temperature being kept between 20 and 25 ° C with constant cooling. After the reaction has ended, the reaction mixture is stirred into 1000 parts of ice water, the pH is adjusted to 4 with calcium carbonate, the batch is briefly heated to 50 ° C. and the calcium sulfate formed is then filtered off. Calcium ions still present are precipitated from the filtrate with sodium oxalate. After the calcium oxalate has been separated off, the aqueous solution of the N- (β-sulfatoethyl) piperidine is evaporated to dryness under reduced pressure. A yellow, oily product is obtained which crystallizes and melts at 124 ° C. with decomposition.

Example B

To produce a mixture of the compounds 3-sulfato-2-hydroxy-1-aminopropane and 2-sulfato-3-hydroxy-1-aminopropane, 92.9 parts of 2,3-dihydroxy-1-amino are added with stirring -propane in 98 parts of 96% sulfuric acid, the reaction temperature being kept at 20 to 25 ° C. by external cooling. The reaction mixture is worked up and the 3-sulfato-2-hydroxy-1-aminopropane is isolated in the same manner as described in Example A.

Example C

100 parts of 2,3-dihydroxy-1- (trimethylammonium) propane chloride are slowly introduced into 110 parts of 100% strength sulfuric acid at a temperature of 20.degree. C., the mixture is stirred for a few hours and the reaction is ended isolates the ester compound formed in the manner given in Example A. An oily product is obtained as a mixture of 3-sulfato-2-hydroxy-1- (trimethylammonium) propane and 2-sulfato-3-hydroxy-1- (trimethylammonium) propane sulfate.

Example D

To prepare N- (γ-sulfato-β-hydroxypropyl) piperidine, slowly add 100 parts of N- (β, γ-dihydroxypropyl) piperidine to 67 parts of 100% sulfuric acid with stirring at 20 ° C. . The mixture is stirred for a further hour and the piperidine compound according to the invention is isolated in the manner described in Example A. It is initially obtained as an oily product which crystallizes after some time. It melts at 170 to 175 ° C with decomposition.

Example E

To prepare N- (γ-sulfato-β-hydroxy-propyl) pyrrolidine, 50 parts of N- (β, γ-dihydroxy-propyl) pyrrolidine in 98 parts of 100% sulfuric acid are slowly added with stirring at 20 ° C. . The batch is stirred for a further hour and the compound formed is then isolated as an oily product in the manner given in Example A.

Example F

wird in einem Siedebereich zwischen 95 und 120°C bei 5·10^-2 mbar abgetrennt.To prepare a silane compound which can be used according to the invention, 67.9 parts of N-methylaminoethanol are slowly added to 35.2 parts of potassium in 1000 parts by volume of tetrahydrofuran, the exothermic reaction being kept at a temperature between 30 and 40 ° C. by external cooling. The mixture is then heated under reflux until the potassium has reacted completely (about 5 hours). The mixture is then cooled to about 20 ° C. and 190.3 parts of γ-chloropropyl- (methyl) - (diethoxy) -silane are added, the reaction temperature being kept below 40 ° C. by external cooling if necessary. After the reaction has taken place, the precipitated potassium chloride is filtered off and the filtrate is freed from tetrahydrofuran by distillation. The product is then subjected to vacuum distillation. The compound [γ- (β'-N-methylaminoethoxy) propyl] methyl diethoxysilane of the formula

is separated in a boiling range between 95 and 120 ° C at 5 · 10 ^-2 mbar.

Example G

durch fraktionierte Destillation bei einem Siedebereich zwischen 104 und 118°C bei 5 • 10^-2 mbar.To prepare a silane compound which can be used according to the invention, the procedure of Example A is followed, but the equivalent amount of γ-chloropropyl-triethoxysilane is used instead of the γ-chloropropyl-methyl-diethoxy-silane compound. The [γ- (β'-N-methylaminoethoxy) propyl] triethoxysilane of the formula according to the invention is obtained

by fractional distillation at a boiling range between 104 and 118 ° C at 5 • 10 ^-2 mbar.

Example H

durch fraktionierte Destillation bei einem Siedebereich zwischen 90 und 105°C bei 5 • 10^-2 mbar.A silane compound is prepared according to the procedure of Example A, but instead of the γ-chloropropyl-methyl-diethoxy-silane compound, the equivalent amount of (γ-chloropropyl) - (dimethyl) - (ethoxy) -silane is used. The compound according to the invention [γ- (β'-N-methylaminoethoxy) propyl] - (dimethyl) - (ethoxy) silane of the formula is obtained

by fractional distillation at a boiling range between 90 and 105 ° C at 5 • 10 ^-2 mbar.

Example J

entsprechen, werden in einem Siedebereich zwischen 165°C und 200°C/10 mbar abgetrennt, wobei sich für die vier einzelnen Verbindungen folgende Fraktionen ergeben:

• 1-{3'-[β-(N-Methylamino)-ethoxy-methyl]-phenyl}-eth-1-yl-(diethoxy)-(methyl)-silan: Kdp.: 165°C/10 mbar ;
• 1-{4'-[β-(N-Methylamino)-ethoxy-methyl]-phenyl}-eth-1-yl-(diethoxy)-(methyl)-silan: Kdp.: 174°C/10 mbar ;
• 2-{3'-[β-(N-Methylamino)-ethoxy-methyl]-phenyl}-eth-2-yl-(diethoxy)-(methyl)-silan: Kdp.: 185°C/10 mbar ;
• 2-{4'-[β-(N-Methylamino)-ethoxy-methyl]-phenyl]-eth-2-yl-(diethoxy)-(methyl)-silan: Kdp.: 197°C/10 mbar.

36.7 parts of N-methylaminoethanol are slowly added to 20.1 parts of potassium in 700 parts by volume of tetrahydrofuran, the exothermic reaction being kept at a temperature between 30 and 40 ° C. by external cooling. The mixture is then heated under reflux until the potassium has reacted completely (about 5 hours) and then 147.7 parts of a mixture (in a ratio of the meta / para isomers of about 70: at a temperature between 20 and 35 ° C. are added: 30) of [3'- and 4'-chloromethyl-phenyl-1- and -2-ethyl] -methyl-diethoxysilane. After the reaction has taken place, the precipitated potassium chloride is filtered off and the filtrate is freed from tetrahydrofuran by distillation. The product is then subjected to vacuum distillation. The compounds according to the invention obtained as a mixture and having the formulas

are separated in a boiling range between 165 ° C and 200 ° C / 10 mbar, the following fractions resulting for the four individual compounds:

• 1- {3 '- [β- (N-Methylamino) -ethoxy-methyl] -phenyl} -eth-1-yl- (diethoxy) - (methyl) -silane: bp: 165 ° C / 10 mbar;
• 1- {4 '- [β- (N-Methylamino) -ethoxy-methyl] -phenyl} -eth-1-yl- (diethoxy) - (methyl) -silane: bp: 174 ° C / 10 mbar;
• 2- {3 '- [β- (N-Methylamino) -ethoxy-methyl] -phenyl} -eth-2-yl- (diethoxy) - (methyl) -silane: bp: 185 ° C / 10 mbar;
• 2- {4 '- [β- (N-Methylamino) -ethoxy-methyl] -phenyl] -eth-2-yl- (diethoxy) - (methyl) -silane: bp: 197 ° C / 10 mbar.

example 1

• a) A fabric of mercerized and bleached cotton is impregnated with a 20 to 25 ° C aqueous solution of 50 parts of sodium hydroxide and 50 parts of 2-oxo-1,3-oxazolidine in 1000 parts of water with a liquor absorption of 75%. The material is then treated with hot air at 180 ° C. for 45 seconds, with both the drying and the fixing of the oxazolidinone compound taking place on the tissue. The material is then treated in cold and hot water at 60 ° C. and, if appropriate, in an aqueous bath containing acetic acid until residual alkali has been removed from the tissue.
• b) The modified cotton fabric is passed through one or two rollers for guiding and tensioning the fabric under an ink jet printer and using an aqueous 6% dye solution of the dye of the formula known from DE-A-19 43 904
  
  printed with high application of the dye solution. The fabric printed in this way is then steamed at 100 ° C. for 30 seconds, then rinsed with cold and hot water, the hot water being able to contain a commercially available wetting agent, optionally rinsed again with cold water and dried.

With a minimal liquor application and minimal wastewater pollution, a strong, sharp red color print is obtained, which has good general fastness properties, in particular good fastness to washing and light.

Example 2

• a) A mercerized and bleached cotton fabric is impregnated with an aqueous solution of 37.5 parts of sodium hydroxide and 75 parts of 2-oxo-1,3-oxazolidine in 1000 parts of water at a temperature between 25 and 30 ° C with a liquor absorption of 85% and then treated to fix the oxazolidinone compound on the fiber material for about 2.5 minutes with hot air at 150 ° C., the impregnated fabric being dried at the same time. The modified material is then freed from excess alkali by treatment with cold water at 60 ° C.
• b) The modified, dried fabric is printed, for example, in a commercially available office inkjet printer with water-soluble fiber-reactive dyes, the basic colors of the subtractive color mixture (yellow, cyan, magenta and additionally black) being applied in one operation. For the subsequent fixation, use a damper at 105 ° C and then wash it hot.

Example 3

• a) A fabric made of mercerized and bleached cotton is washed with a 25 to 30 ° C aqueous solution of 80 parts of [γ- (β'-amino-ethoxy) propyl] trimethoxy silane in 1000 parts of water with glacial acetic acid a pH of 5.5 is set, impregnated with a liquor absorption of 72%. The material is then dried with hot air at 130 ° C. for 5 minutes and the silane compound is simultaneously fixed on the material.
• b) The modified, dried cotton fabric is attached to a base and printed with aqueous solutions of fiber-reactive dyes in a commercially available office inkjet printer, the basic colors of the subtractive color mixture (yellow, cyan, magenta and additionally black) being applied in four individual courses in succession will. For the subsequent fixation, use a damper at 105 ° C and then wash it hot.
• c) To produce an orange print, one can, for example, use the dye of the formula known from EP-A-0 061 151
  
  (in the form of the alkali metal salt). A sharply contoured pattern is obtained with minimal application of the dye solution and without waste water. After the dye has been fixed in a damper, real orange colorations are obtained.

Example 4

• a) A mercerized and bleached cotton fabric is washed with an aqueous solution of 50 parts of [γ- (β'-aminoethylamino) propyl] trimethoxysilane in 1000 parts of water, which is brought to pH 5.5 with glacial acetic acid is set, padded at a temperature of 25 to 30 ° C with a liquor absorption of 72%. The silane compound is then fixed on the cotton and the padded fabric is simultaneously dried by treatment with hot air at 130 ° C. for about five minutes.
• b) The modified, dried cotton fabric is on a flatbed printer with exclusive movement of the print head in one Operation printed using a fiber-reactive dye, such as a dye described in the preceding or following examples. The printed material is then treated with dry heat to fix the dye and, if necessary, is then washed cold.

Example 5

• a) A mercerized and bleached cotton fabric is washed with an aqueous solution of 50 parts of [γ- (β'-aminoethylamino) propyl] trimethoxysilane in 1000 parts of water, which is brought to pH 5.5 with glacial acetic acid is set, padded at a temperature of 25 to 30 ° C with a liquor absorption of 72%. The silane compound is then fixed on the cotton and the padded fabric is simultaneously dried by treatment with hot air at 130 ° C. for about five minutes.
• b) The cotton fabric modified in this way is drawn in directly with the aid of one or two rubber rollers and printed in one operation with fiber-reactive dyes in the basic colors of the subtractive color mixture using an ink-jet printer. The subsequent fixation can be carried out, for example, by microwave radiation. The dyes are really fixed on the material, so that a post-wash does not usually appear necessary.

Example 6

• a) A fabric made from a commercially available polyacrylic fiber with a liquor absorption of 84%, based on the weight of the fiber material, with an aqueous solution of 50 parts of [β- (γ'-aminopropylamino) ethyl] trimethoxy silane in 1000 Parts of water, which is adjusted to pH 5.5 with glacial acetic acid, are padded. The padded fabric is then exposed to a temperature of 100 ° C. for five minutes, whereby both the fixing of the silane compound on the material and the drying of the material take place.
• b) The fabric modified in this way is printed in a commercially available inkjet printer using an aqueous solution of a black reactive dye and aqueous solutions of fiber-reactive dyes whose basic colors yellow, cyan and magenta correspond to a subtractive color mixture. The dyes are then fixed in a steamer at 130 ° C. After-washing is not necessary.
• c) To produce a brilliant red, sharp-edged print, the procedure described under b) can be carried out, using only the aqueous solution of the dye of the formula known from Example 1 of European Patent EP-B-0 032 187 using a commercially available inkjet printer
  
  printed on the fabric.

A real print with sharp contours is obtained.

Example 7

• a) A fabric made of commercially available pure silk is impregnated with the silane solution given in Example 3 with a liquor absorption of 80% and then dried at 120 ° C. for 3 minutes, the silane compound being fixed on the silk fiber at the same time.
• b) The material modified in this way is attached to a base and printed in a commercial office inkjet printer with aqueous dye solutions, the basic colors of the subtractive color mixture (yellow, cyan, magenta and additionally black) in four individual courses be applied in a row. The dyes are then fixed on the material using a damper at 105 ° C. The material dyed in a sharp-edged print pattern is then washed hot.

Example 8

• a) A fabric of mercerized and bleached cotton is impregnated with a 20 to 25 ° C aqueous solution of 50 parts of sodium hydroxide and 50 parts of 1-N- (β-sulfatoethyl) piperazine in 1000 parts of water with a liquor absorption of 90%. The material is then treated with hot air at 150 ° C. for 2.5 minutes, with both the drying and the fixing of the piperazine compound taking place on the tissue. The material thus obtained is then treated in cold water at 60 ° C. and, if appropriate, in an aqueous bath containing acetic acid until residual alkali has been removed from the tissue.
• b) The modified cotton fabric is in a commercially available inkjet printer with an aqueous solution of the dye of the formula known from EP-A-0 061 151
  
  (in the form of the alkali metal salt) printed. It is then fixed in a damper at 130 ° C. After-washing is not necessary. A sharp orange print with good fastness properties is obtained.

Example 9

• a) A fabric of mercerized and bleached cotton is padded with a 20 to 25 ° C aqueous solution of 50 parts of sodium hydroxide and 50 parts of the monosulfate of 2,3-dihydroxy-1-aminopropane in 1000 parts of water with a liquor absorption of 90% . The impregnated material is then treated with hot air at 150 ° C. for 2.5 minutes to fix the aminopropane compound on the material with simultaneous drying and then washed in cold and 60 ° C. hot water until the excess alkali has been completely removed and then dried.
• b) The fabric so modified is in a commercial office inkjet printer with the aqueous solution of the dye of the formula known from European Patent EP-B-158 233
  
  printed in a desired pattern. The dye is then fixed using dry heat at 120 ° C. A strongly colored, sharply contoured yellow print is obtained (if the dye solution is applied evenly by the inkjet printer, a strongly colored, uniformly colored yellow color) is obtained with the usual good fastness properties.

Example 10

A mercerized and bleached cotton fabric is impregnated with an aqueous solution of 50 parts of sodium hydroxide and 100 parts of the monosulfate of 2,3-dihydroxy-1-aminopropane in 1000 parts of water at a temperature between 25 and 30 ° C with a liquor absorption of 85% and then to Fixation of the aminopropane compound on the fiber material treated with hot air at 150 ° C. for about 3 minutes, the impregnated fabric drying at the same time. The modified material is then freed from excess alkali by treatment with cold water at 60 ° C.

The thus modified, dried material is passed under a stainless steel sheet with the aid of a rubber roller and printed in one operation with the aqueous solutions of fiber-reactive dyes in the basic colors of the subtractive color mixture by means of an ink jet print head which works according to the "drop on demand" process. The web is then passed through a continuously working microwave dryer for fixation. The dyed material can then be finished by washing; however, a short, hot wash bath and subsequent drying is usually sufficient.

Example 11

• a) A fabric of mercerized and bleached cotton is obtained with a 20 to 25 ° C aqueous solution of 50 parts of sodium hydroxide and 32 parts of 1-N- (β-sulfatoethyl) piperazine in 1000 parts of water with a liquor absorption of 90% on the weight of the fabric, impregnated in a commercially available foulard. The padded fabric is then dried; the piperazine compound is fixed on the tissue by means of heat treatment at 180 ° C. The tissue is then rinsed in cold water at approximately 60 ° C. until residual alkali has been removed from the tissue.
• b) The fabric modified according to a) is stretched on a roller in a commercially available inkjet printer which works according to the "continuous flow principle". While the roller is rotating, a multicolor image is printed out using aqueous solutions of four dyes using the four-color printing technique (the ejection of the dye solutions in the ink-jet printer can be controlled, for example, by a computer program). After printing, the tissue is at 105 ° C for 15 minutes steamed; this is followed by post-treatment in a hot, soap-containing washing bath followed by rinsing with hot and cold water. To prevent contamination of the fund, small amounts of ammonia or diethanolamine can be added to the wash bath. The following can be used, for example, as dyes which can be used in four-color printing: the copper phthalocyanine dye known from Example 2 of DE-A-1 179 317 as the "cyan component"; the yellow dye known from Example 56 of DE-B-2 634 909; the red dye known from Example 3 of EP-A-0 158 233 as "magenta component"; the black dye known from the table in columns 17/18 of DE-B-1 544 538.

The fabric obtained shows a very sharp color print of the chosen pattern; the dye itself has good wash fastness.

Example 12

• a) A viscose fabric is in a commercially available foulard with a 20 to 25 ° C warm aqueous solution of 50 parts of sodium hydroxide and 32 parts of 1-N- (β-sulfatoethyl) piperazine in 1000 parts of water with a liquor absorption of 90%, based on the weight of the fabric, impregnated. The fabric is then dried and subjected to a heat treatment at 180 ° C. for about 45 seconds, the piperazine compound being fixed on the fabric. This is followed by post-treatment in cold and hot water at around 60 ° C until residual alkali has been removed from the tissue.
• b) After drying, the modified cotton fabric obtained under a) is printed in accordance with the information in Example 11b) in the commercially available inkjet printer mentioned there in accordance with four-color printing, the four dye components being the following: The one from Example 2 of DE-A-1 179,317 known copper phthalocyanine dye as "cyan component"; the yellow dye (22) known from US-A-3,926,944; the one from Example 15 the German Auslegeschrift 1 126 647 known red dye as "magenta component" and the black dye known from Color Index CI Reactive Black 5.

The fabric obtained shows a very sharp color print of the chosen pattern; the dye itself has good wash fastness.

Example 13

• a) A cotton twill (quality raw white, raw material, weight 200 g / kg) is washed with an aqueous liquor containing 60 parts of 1-N- (β-sulfatoethyl) piperazine, 100 parts of sodium hydroxide, 5 parts of a commercially available nonionic and detergent and 6 parts of a commercial agent for stabilizing the liquor and for protecting the fibers in 1000 parts of water, impregnated with a liquor absorption of 100%. The impregnated fabric is docked and exposed to a temperature between 95 and 103 ° C for 60 minutes. The fabric is then post-treated in boiling water, to which a commercially available surfactant can be added in order to remove the water-soluble contaminants on the fabric. After further rinsing with warm and cold water and drying, a textile fabric with a degree of desizing of 9 (Tegewa rating) and a suction head of 6.5 cm / 30 min are obtained.
• b) The cotton fabric modified according to a) is clamped in an inkjet printer which works according to the piezo principle. With the help of a computer, a multicolor image is printed out using the solutions of three dyes according to the three-color printing technique, the following being used as dyes:
  The blue dye known from Example 21 of DE-B-2 634 909; the yellow dye (22) known from US-A-3,926,944; the red dye known from Example 1 of EP-A-0 022 575 as the "magenta component". After the printing process, the dyes are fixed on the fabric by steaming for 15 minutes with superheated steam at 105 ° C then washed in a hot, soap-containing washing bath and then rinsed clear with warm and cold water. To prevent soiling of the white fund, small amounts of ammonia or diethanolamine can be added to the wash bath.

Examples 14 to 44

To produce further dyeings according to the procedure according to the invention, it is assumed that a cellulose fiber material modified according to the invention, such as, for example, a cellulose fiber material modified in accordance with the above exemplary embodiments, is printed on using the procedure of an inkjet printer, for example analogously using one of the methods described in the above exemplary embodiments, using aqueous solutions of one or more known dyes specified in the table examples below (the dyes are written in the form of the free acid; however, they are used in the form of their alkali metal salts). Clear, strong-colored print samples are obtained with the color shade given in the respective table example and the fastness properties, in particular good fastness to washing, which are good for the respective dye.

Claims (3)

1. A process for dyeing sheetlike fiber materials, in particular those made of or containing cellulose fibers, with anionic dyes, in particular those having fiber-reactive groups, which comprises applying an alkali-free and preferably low-electrolyte or completely electrolyte-free aqueous solution of the anionic dye by the inkjet printing spray technique to a fiber material which has been pretreated and modified with a compound of the formula (1) or (2)

   

   where

   M   is a hydrogen atom or an alkali metal,

   k   is 1 or 2, preferably 2,

   R^A   is hydrogen or alkyl of 1 to 3 carbon atoms which may be substituted by hydroxyl or a group of the formula (5a) or (5b)

   

   where

   R¹   is hydrogen, methyl or ethyl,

   R²   is hydrogen, methyl or ethyl, and

   R³   is hydrogen, methyl or ethyl, or

   R¹ and R²   together with the nitrogen atom are a saturated heterocyclic radical formed from an alkylene radical of 5 to 8 carbon atoms or two alkylene radicals of 1 to 4 carbon atoms and an oxygen atom or an amino group of the formula -NH-, and

   Z^(-)   is an anion,

   R^B   has one of the meanings specified for R^A, and

   X   is -O- or -NH-;

   or a compound of the formula (3a) or (3b)

   

   

   where

   ER   is an ester group,

   A and N   together with 1 or 2 alkylene groups of 1 to 4 carbon atoms form the bivalent radical of a heterocyclic ring in which

   A   is an oxygen atom or a group of the formula (a), (b) or (c)

   

   where

   R   is a hydrogen atom, an amino group, an alkyl group of 1 to 6 carbon atoms which may be substituted by 1 or 2 substituents selected from the group consisting of amino, sulfo, hydroxyl, sulfato, phosphato and carboxyl, or an alkyl group of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from -O- and -NH- and may be substituted by an amino, sulfo, hydroxyl, sulfato or carboxyl group,

   R³   is hydrogen, methyl or ethyl,

   R⁴   is hydrogen, methyl or ethyl, and

   Z^(-)   is an anion,

   B   is an amino group of the formula H₂N- or an amino or ammonium group of the formula (d) or (e)

   

   in which

   R³, R⁴ and Z^(-)   are each as defined above,

   R⁵   is methyl or ethyl, and

   R⁶   is hydrogen, methyl or ethyl,

   p   is 1 or 2, preferably 1,

   alkylen is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms which may be substituted by 1 or 2 hydroxyl groups, or a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from -O- and -NH-,

   alk is a straight-chain or branched alkylene radical of 2 to 6 carbon atoms or a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from -O- and -NH-,

   m   is 1 or 2,

   n   is from 1 to 4,

   and the amino, hydroxyl and ester groups can be attached to a primary, secondary or tertiary carbon atom of the alkylene radical; or a compound of the formula (4)

   

   where

   R^C   is hydrogen, alkoxy of 1 to 8 carbon atoms, halogen, hydroxyl, alkoxy of 2 to 4 carbon atoms with alkoxy of 1 to 4 carbon atoms as substituent, N-morpholino, N-imidazolino or a group of the formula (6)

   

   R^D   is a group of the formula (7a) or (7b)

   

   

   where

   a   is zero or 1,

   b   is an integer from zero to 10,

   c   is 1, the sum (a + b) is equal to or greater than 1,

   R⁷   has one of the meanings of R^c,

   R⁸   is alkoxy of 1 to 8 carbon atoms with or without alkoxy of 1 to 4 carbon atoms as substituent, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms or phenylenealkyl where the alkyl radical has 1 to 4 carbon atoms and the phenylene radical may be substituted by substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, sulfo and carboxyl, each of which radicals R⁸ may be additionally substituted by a group T,

   R⁹   has one of the meanings of R^C or R^E,

   D   is alkylene of 1 to 6 carbon atoms which may be substituted by hydroxyl, methoxy, ethoxy, sulfo, sulfato or carboxyl, or is phenylene which may be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and/or carboxyl, or is phenylenealkylene, alkylenephenylene, alkylenephenylenealkylene or phenylenealkylenephenylene, in each of which the alkylene group or groups has or have from 1 to 6 carbon atoms and may be substituted by hydroxyl, methoxy, ethoxy, sulfo, sulfato or carboxyl and the phenylene radical or radicals may be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and/or carboxyl,

   X¹   is a group of the formula -S- or -O-, and is preferably a group of the formula -O-

   E   is cycloalkylene of 5 to 8 carbon atoms or alkylene of 1 to 6 carbon atoms which may be substituted by hydroxyl, methoxy, ethoxy, sulfato, sulfo or carboxyl, or is phenylene which may be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and/or carboxyl,

   X²   is a group of the formula -S-, -O-, -NH- or -N(R)- where R is alkyl of 1 to 4 carbon atoms,

   G   is alkylene of 1 to 6 carbon atoms which may be substituted by hydroxyl, methoxy, ethoxy, sulfo, sulfato or carboxyl, or is phenylene which may be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and/or carboxyl, or is phenylenealkylene, alkylenephenylene, alkylenephenylenealkylene or phenylenealkylenephenylene, in each of which the alkylene group or groups has or have from 1 to 6 carbon atoms and may be substituted by hydroxyl, methoxy, ethoxy, sulfo, sulfato or carboxyl and the phenylene radical or radicals may be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and/or carboxyl, or G can be a direct bond,

   T   is hydroxyl, thiol or a group of the formula (8a) or (8b)

   

   

   where

   R¹⁰   is hydrogen or alkyl of 1 to 4 carbon atoms which may be substituted by phenyl, sulfophenyl, amino, thio or hydroxyl,

   R¹¹   is hydrogen, phenyl, sulfophenyl or alkyl of 1 to 4 carbon atoms which may be substituted by phenyl, sulfophenyl, methoxy, ethoxy, amino, thio or hydroxyl,

   R¹²   is hydrogen, alkyl of 1 to 4 carbon atoms which may be substituted, or alkenyl of 2 to 6 carbon atoms, and

   Z^(-)   is an anion,

   K   is a radical of the formula (9)

   

   where G, X², E, X¹, D, a and b are each as defined above,

   R^E   is hydrogen, halogen, hydroxyl, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, alkynyl of 3 to 8 carbon atoms or phenyl or a group of the formula (7a) or (7b),

   R^G   has one of the meanings mentioned for R^C or R^E, and

   at least one of the substituents attached to the silicon atom is a hydrolyzable substituent selected from the group consisting of hydrogen, halogen, alkoxy, phenoxy, amino and amido.
2. The process of claim 1, wherein the dye is a fiber-reactive dye.
3. A sheetlike fiber material dyed as claimed in claim 1.