EP0513656A1 - Process for dyeing of silanes modified with fibermaterials, the modification of fibermaterials with silanes - Google Patents

Abstract

A process for dyeing textile fibre materials with water-soluble dyes, in particular anionic dyes, and of these in particular those having a fibre-reactive group, in which the dyeing is carried out using low-electrolyte or completely electrolyte-free and/or low-alkali or completely alkali-free dyeing liquors or printing pastes and, as the textile material, a fibre material is used which has been modified with a silane compound containing amino groups. The modification of the fibre material is effected by applying the silane compound containing amino groups to the material in aqueous solution and subjecting the impregnated material to heat treatment. In addition, novel silane compounds are described which contain a secondary amino group and can likewise be employed for the purpose mentioned.

Description

The large amounts of salt and / or alkali required for dyeing textiles to increase the substantivity of water-soluble textile dyes and released after the dyeing, with the associated environmental pollution, prompted the search for a new process which made it possible to increase the amounts required To reduce additives drastically or to do without them altogether. Alkali can be neutralized in the dyeing waste water, but this leads to additional salts getting into the waste water, from which they can no longer be removed. It was therefore an object of the present invention to provide a process for dyeing all types of textile fiber materials, such as natural and synthetic fiber materials, for example polyacrylonitrile and polyester fiber materials, and fiber materials of natural and synthetic origin containing hydroxyl and / or carbonamide groups, such as fiber materials made of polyamide-4, polyamide -6 and polyamide-11, silk, wool and other animal hair, and in particular fiber materials which contain the basic body of α- and / or β-glucose, such as cellulose fiber materials, for example cotton, hemp, jute and linen, or their synthetic and regenerated derivatives , such as cellulose acetate, viscose silk and rayon, to be found with only the smallest possible amounts of electrolyte salts, such as sodium chloride and sodium sulfate, or entirely without electrolyte salts and at the same time with only small amounts of an alkaline agent, such as sodium carbonate, sodium hydroxide or water glass, or r can be carried out entirely without such an alkaline agent. The use of alkaline agents is particularly necessary to fix the technically important reactive dyes on the fiber. A dyeing process that is low in salt or completely without salt and at the same time only under The use of small amounts of an alkaline agent or can be carried out entirely without such an alkaline auxiliary is therefore particularly advantageous in the dyeing process using fiber-reactive dyes. Because in addition to the fixing process of the fiber-reactive dye in the aqueous, often strongly alkaline dye liquor, hydrolysis reactions of the fiber-reactive dye can also take place, which is why the fixing on the fiber material is not complete. For this reason, extensive and time-consuming washing and rinsing processes must be carried out after the dyeing process, such as multiple rinsing with cold and hot water and an intermediate neutralization treatment to remove excess alkali on the dyed material and, for example, a boil wash with a nonionic Detergent to ensure the good fastness of the dye.

It has now been found that, surprisingly, dyeings of water-soluble textile dyes, in particular fiber-reactive dyes, with a uniform shade and high color strength and with good fastness to manufacture and use are obtained when using a fiber material which has been modified with a silane compound, with the proviso that at least one of the substituents bonded to the silicon atom, such as, for example, alkyl, alkoxy and phenyl radicals, has a primary, secondary or tertiary amino group, a primary, secondary, tertiary or quaternary ammonium group or a hydroxyl or thiol group, these substituents still can be substituted by further nonionic and / or anionic substituents, and with the proviso that at least one of the substituents bonded to the silicon atom is a substituent which is hydrolyzed by water to the hydroxyl group.
The alkyl and alkoxy substituents are preferably those of 1 to 8 carbon atoms. The use of this fiber material modified with such a silane compound makes it possible to carry out the dyeing process (which also includes printing processes) using low-electrolyte and low-alkali or even electrolyte-free and alkali-free dyeing liquors, which means that the time-consuming post-treatment of the dyeings by rinsing and boiling processes can also be omitted.

The present invention therefore relates to a process for dyeing (including printing) textile fiber materials with water-soluble dyes, in particular anionic dyes, which is characterized in that the dyeing is carried out using low-electrolyte or completely electrolyte-free and / or low-alkali or completely alkali-free dye liquors (including printing pastes ) is carried out and a fiber material modified with an abovementioned silane compound is used as the textile material.

Fiber materials which are modified according to the invention and can be used according to the invention in dyeing processes are all the synthetic and natural fiber materials mentioned above and modified with such silanes. The present invention therefore also relates to textile fiber materials modified with such silanes.

entsprechen, in welcher bedeuten:

R¹

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 (2)

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;

R²

ist eine Gruppe der allgemeinen Formel (3a) oder (3b)

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 oder 2 und ist zwingend 1, falls a gleich Null ist;

die Summe von (a + b) ist bevorzugt gleich 1 oder größer als 1,
   insbesondere bevorzugt 1, 2, 3 oder 4;

A

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 im Falle Von c gleich 1 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 ist vorzugsweise eine Gruppe der Formel -O- oder -NH-, oder ist im Falle von c gleich 2 ein Stickstoffatom;

B

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)- mit R der obengenannten Bedeutung und vorzugsweise -O- oder -NH-;

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, oder D kann eine direkte Bindung sein, falls (a + b) nicht Null ist, und ist vorzugsweise Alkylen von 2 bis 4 C-Atomen oder eine direkte Bindung im Falle von (a + b) gleich 1 oder größer als 1;

T

ist Hydroxy, Thiol oder vorzugsweise eine Gruppe der allgemeinen Formel (4a) oder (4b), insbesondere der Formel (4a)

in welchen

R⁵

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,

R⁶

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,

R⁷

Wasserstoff, 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

X^(-)

ein einwertiges Anion oder ein einem einwertigen Anion äquivalenter Teil eines mehrwertigen Anions ist;

G

ist ein Rest der allgemeinen Formel (5)

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

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 der obigen Bedeutung substituiert sein können;

R⁹

hat eine der Bedeutungen von R¹ oder R³;

R³

ist 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 (3a) oder (3b), 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 (3a) oder (3b);

R⁴

hat eine der für R¹ oder R³ genannten Bedeutungen.

Silane compounds which are used according to the invention to modify the fiber materials are, for example, those which have the general formula (1)

correspond in which mean:

R¹

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 (2)

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

R²

is a group of the general formula (3a) or (3b)

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 or 2 and is mandatory 1 if a is zero;

the sum of (a + b) is preferably 1 or greater than 1,
particularly preferably 1, 2, 3 or 4;

A

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 can be substituted by methoxy, ethoxy, methyl, ethyl, Sulfo and / or carboxy can be substituted, or is phenylene-alkylene, alkylene-phenylene, alkylene-phenylene-alkylene or phenylene-alkylene-phenylene, where the alkylene groups of these radicals are those of 1 to 6 carbon atoms, preferably of 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;

X¹

in the case of c is 1 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 is preferably a group of the formula -O- or -NH-, or in the case of c is 2 is a nitrogen atom;

B

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, by hydroxyl, methoxy, ethoxy , Sulfato, sulfo or carboxy, or is phenylene, which can be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and / or carboxy, preferably alkylene of 2 to 4 carbon atoms;

X²

is a group of the formula -S-, -O-, -NH- or -N (R) - with R having the meaning given above and preferably -O- or -NH-;

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 can be 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 Are 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 D can be a direct bond , if (a + b) is not zero, and is preferably alkylene of 2 to 4 carbon atoms or a direct bond in the case of (a + b) equal to 1 or greater than 1;

T

is hydroxyl, thiol or preferably a group of the general formula (4a) or (4b), in particular of the formula (4a)

in which

R⁵

Is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfophenyl, amino, thio or hydroxy, or carbamoyl, which can be mono- or disubstituted, for example by substituents from the group 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,

R⁶

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,

R⁷

Is hydrogen, 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 , and

X ^(-)

is a monovalent anion or a part of a polyvalent anion equivalent to a monovalent anion;

G

is a radical of the general formula (5)

in which D, X², B, X¹, A, a and b have one of the above-mentioned, particularly preferred meanings;

R⁸

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, is 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, or phenylene-alkyl with an alkyl radical of 1 to 4 carbon atoms, the phenylene radical being characterized by substituents the group methyl, ethyl, methoxy, ethoxy, sulfo and carboxy can be substituted, and these radicals R⁸ can also be substituted by a group T of the above meaning;

R⁹

has one of the meanings of R¹ or R³;

R³

is 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 , preferably from 3 to 5 carbon atoms, or phenyl or a group of the general formula (3a) or (3b), preferably alkyl from 1 to 4 carbon atoms, alkoxy from 1 to 4 carbon atoms, by alkoxy from 1 to 4 C-substituted alkoxy of 2 to 4 C atoms or a group of the general formula (3a) or (3b);

R⁴

has one of the meanings given for R¹ or R³.

        -(CH₂)_n - O - (CH₂)_m -   (6c)





        -(CH₂)_n - O - (CH₂)_m - CH(OH) - CH₂ -   (6d)

        - (CH₂)_n - NH - (CH₂)_m -   (6f)





        - (CH₂)_n - S - (CH₂)_m -   (6g)

in welchen

n

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

m

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

k

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

p

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

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

The radical of the formula (5) and the radical of the general formula - [A-X¹] _a - [B-X²] _b -D- corresponding to this in formula (3a) is preferably a radical of the general formula (6a), (6b ), (6c), (6d), (6e), (6f), (6g), (6h), (6i) or (6j), preferably a radical of the general formula (6c), (6d), ( 6e), (6f), (6h), (6i) or (6j):

- (CH₂) _n - O - (CH₂) _m - (6c)





- (CH₂) _n - O - (CH₂) _m - CH (OH) - CH₂ - (6d)

- (CH₂) _n - NH - (CH₂) _m - (6f)





- (CH₂) _n - S - (CH₂) _m - (6g)

in which

n

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

m

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

k

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

p

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

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

R⁵ is preferably hydrogen, alkyl of 1 to 3 carbon atoms, such as methyl and ethyl, or cyclohexyl and particularly preferably hydrogen, methyl or ethyl, especially hydrogen. R⁶ 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 (4a) preferably represents a secondary amino group, such as in particular the methylamino or ethylamino group.

Further silane compounds which can be used according to the invention are, for example, polymeric silane compounds, such as siloxanes and polyethyleneimines, which are substituted by at least one silane radical, such as, for example, polyethyleneimines composed of 2 to 5 ethyleneimine units, of which 1 to 3 amino groups are represented by a radical of the general formula (7)
in which G, R¹, R⁸ and R⁹ one of the above, particularly preferred, Have meanings which are substituted, G being preferably a radical of the general formulas (6a) to (6f), (6i) and (6j). Polymeric siloxanes are those which are derived from disiloxane or from those having 3 to 5 silicon atoms, the silicon atoms being substituted by the radicals R¹, R² and R⁹, the radical R² preferably being bonded to the terminal silicon atoms.

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.

Hydrolysable substituents bonded to the silicon atom are, for example, hydrogen atoms, halogen atoms, alkoxy, phenoxy, amino and amide radicals, such as, for example, those which are initially mentioned for the formula radical R 1. Of these, alkoxy radicals are preferred.

entsprechen, in welcher

R¹

eine der obengenannten Bedeutungen besitzt,

R¹²

eine Gruppe der allgemeinen Formel (9a) oder (9b)

ist, in welchen

n

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

m

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

k

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

p

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 r 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 (4c)

ist, in welcher

R

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;

R¹³

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 (9a) oder (9b) 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 (9a) oder (9b) bedeutet, und

R¹⁴

eine der für R¹ und R¹³ genannten Bedeutungen hat.

The silane compounds used in accordance with the invention are described in large numbers in the literature and some are commercially available. Silane compounds not known as species can be synthesized analogously to the procedures for the preparation of the known silane compounds, such as, for example, analogous to the information in German Patent No. 1 186 061. Of the new silane compounds according to the general formula (1) which can be used according to the invention, those which contain a secondary amino group and those of the general formula (8) should be emphasized in particular

correspond in which

R¹

has one of the meanings mentioned above,

R¹²

a group of the general formula (9a) or (9b)

is in which

n

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

m

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

k

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

p

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 r is an integer from 1 to 4 and R * is alkyl of 1 to 3 carbon atoms, and

T¹

an amino group of the general formula (4c)

is in which

R

Is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfophenyl, amino, thio or hydroxy, or carbamoyl, which can be mono- or disubstituted, for example by substituents from the group 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, is;

R¹³

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, preferably from 3 to 5 carbon atoms, or phenyl or a group of the general formula (9a) or (9b) and 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 (9a) or (9b), and

R¹⁴

has one of the meanings given for R¹ and R¹³.

Accordingly, the present invention also relates to these new silane compounds of the general formula (8), their preparation and, as already stated at the beginning, their use for modifying fiber material.

in welcher

R¹

eine der obengenannten Bedeutungen besitzt,

R^A

ein Rest der allgemeinen Formel (11a) oder (11b)

        ― (CH₂)_n ― Hal   (11b)



ist, in welchen

alk, k und n

eine der obengenannten Bedeutungen besitzen und

Hal

für ein Halogenatom, vorzugsweise Chloratom, steht,

R^B

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 (11a) oder (11b) 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 (11a) oder (11b) bedeutet, und

R^C

eine der für R¹ oder R^B genannten Bedeutungen besitzt,

mit einer Verbindung der allgemeinen Formel (12a) oder (12b)



        MeO - (CH₂)_n - T¹   (12a)





        MeO - (CH₂)_p - T¹   (12b)



in welchen n, p 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.Analogously to the other silane compounds of the general formula (1) which can be used according to the invention, the silane compounds of the general formula (8) can be prepared, for example, according to the invention by using a compound of the general formula (10)

in which

R¹

has one of the meanings mentioned above,

R ^A

a radical of the general formula (11a) or (11b)

- (CH₂) _n - Hal (11b)



is in which

alk, k and n

have one of the meanings mentioned above and

Hal

represents a halogen atom, preferably chlorine atom,

R ^B

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 (11a) or (11b) 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 (11a) or (11b) means, and

R ^C

has one of the meanings given for R 1 or R ^B ,

with a compound of the general formula (12a) or (12b)



MeO - (CH₂) _n - T¹ (12a)





MeO - (CH₂) _p - T¹ (12b)



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

The starting compounds of the general formulas (12a) and (12b) 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 sufficiently high boiling point so that the alkali metal can be heated above its melting point in order to simplify and accelerate the reaction.

Solvents suitable for this purpose are, in particular, aliphatic hydrocarbons with a boiling range from 70 to 150 ° C., such as, for example, 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 compound of the general formula (8) is reacted according to the invention with a compound of the general formula (12a) or (12b), the corresponding alkali metal halide is liberated 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.

Examples of silane compounds which can be used according to the invention are:
[γ- (β'-aminoethoxy) propyl] trimethoxysilane, [γ- (β'-aminoethylamino) propyl] trimethoxysilane, [γ-β'-aminoethoxy) propyl] methyl -diethoxysilane, [γ- (β'-aminoethylamino) propyl] methyldimethoxysilane, 3- or 4-aminophenyltrimethoxysilane, [γ- (4-aminophenoxy) propyl] trimethoxy -silane, N- [γ- (trimethoxysilyl) propyl] -N, N-di- (β'-aminoethyl) amine, (γ-aminopropyl) trimethoxysilane, (γ-aminopropyl) ethoxy- dimethyl silane, (γ-aminopropyl) methyl diethoxy silane, N, N-bis- [γ- (triethoxysilyl) propyl] amine, [γ- (N, N-dimethylamino) propyl] - trimethoxysilane, [γ- (N-methylamino) propyl] trimethoxysilane, (δ-aminobutyl) trimethoxysilane, {4- [N- (β-aminoethyl) amino] methyl] phenethyl- trimethoxysilane, [(N-cyclohexylamino) methyl] methyldiethoxysilane, [γ- (NN-diethylamino) propyl] trimethoxysilane, [γ- (β'-N-methylamino -ethoxy) -propyl] -methyl-diethoxy-silane, [γ- (β'-N-methylamino-ethoxy) -propyl] -triethoxy-silane, [γ- (β'-N-methylamino-ethoxy) -propyl] -dimethyl-ethoxy-silane, 1- {3 '- [β- (N-methylamino) ethoxy-methyl] phenyl} -eth-1-yl- (diethoxy) - (methyl) -silane, 2- {4' - (β- (N-methylamino ) -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, 1,3-di- (γ-aminopropyl) -1,1,3,3-tetramethyl- disiloxane and through
[γ- (Trimethoxysilyl) propyl] and / or [γ- (methyldimethoxysilyl) propyl] groups substituted polyethyleneimine of 3 to 5 ethyleneimine units.

The modification of the textile fiber material takes place according to the invention in such a way that the textile fiber material is preferably mixed with an aqueous solution of the silane compound which contains the silane in a concentration between 0.1 and 20% by weight contains between 5 and 10% by weight. This silane solution can be applied to the textile fiber material by treatment in the aqueous dye liquor itself (analogous to a dye-drawing process) or by padding or spraying. If the fiber material is impregnated with the silane solution by introducing the material into this solution or by padding (padding), the impregnated material is then squeezed off from excess liquor, so that the liquor absorption is between 50 and 120% by weight, preferably between 70 and 100 wt .-%, based on the weight of the fiber material. The impregnation is carried out at a temperature between 10 and 60 ° C, preferably at a temperature between 15 and 30 ° C. If the aqueous silane solution is applied to the fiber material by spraying, the liquid absorption is generally chosen between 10 and 50% by weight.

The fiber material impregnated with the silane solution is then dried, the drying usually being carried out simultaneously with the fixing of the silane compound on the fiber material. Drying and fixing are preferably carried out at elevated temperature, for example at a temperature between 100 and 230 ° C., preferably between 100 and 150 ° C. and in particular between 110 and 135 ° C., this treatment by hot air for 2 to 5 minutes or by saturated steam can be done. The fixation can also be done by simply drying the suspended, impregnated material in drying cabinets. Furthermore, it is possible to carry out the fixing in such a way that the impregnated material is initially packed in a moist state, if appropriate in an airtight manner, at room temperature (15 to 25 ° C.) or slightly elevated temperature (up to 40 ° C.) stored for 24 hours and then carried out the fixation at high temperature as indicated above.

Post-treatment of the textile material modified in this way is generally not necessary.

The textile fiber material that is modified according to the invention as well as in The modified form used in the dyeing process according to the invention can be present in all processing states, such as yarn, flake, sliver and piece goods (fabric), as well as in the form of mixed fiber materials, such as cotton / polyester fiber materials, such as mixed fabrics.

The dyeing of textile fiber materials modified in this way takes place analogously to the known dyeing methods and printing processes for dyeing or printing fiber materials with water-soluble textile dyes, such as anionic dyes, in particular fiber-reactive dyes, and using the temperature ranges and customary amounts of dye known for this purpose, but with the amount of dye according to the invention Exception that for the dye baths, padding liquors and printing pastes of the dyeing process according to the invention, an addition of alkaline compounds, such as are usually used for fixing fiber-reactive dyes, such as sodium carbonate, potassium carbonate, sodium hydroxide solution and water glass, can be largely or completely excluded and furthermore the usual addition of electrolyte salts, which in particular should increase the migration of the dye on the fiber, or not only in geri Narrow dimensions, i.e. up to a maximum of 10 g per liter of dye bath or dye liquor is required. The dyeing process according to the invention is accordingly carried out within a pH range between 4 and 8, preferably between 4.5 and 7, and in particular at a pH range between 5 and 6.

Dyeing processes which can be used according to the invention are, for example, the various exhaust processes, such as dyeing on the jigger and on the reel runner or dyeing from a long or short liquor, dyeing in jet dyeing machines, dyeing using the pad-cold-dwell method or after a block hot steam fixing process. With the pull-out process you can work in the usual liquor ratio of 1: 3 to 1:20. The dyeing temperature can be between 30 and 90 ° C, preferably it is at a temperature below 60 ° C; As can be seen from the above-mentioned application of the pad-cold residence method according to the invention, dyeing is also advantageous at room temperature (10 to 30 ° C) possible.

In the dyeing processes according to the invention, the customary auxiliaries, such as surfactants (wetting agents), urea, thiourea, thiodiethylene glycol, thickeners and leveling aids or auxiliaries which improve the solubility of dyes in the concentrated padding liquors, such as, for example, condensation products from formaldehyde and optionally alkyl-substituted naphthalenesulfonic acids, can be used. be used. As a rule, however, they are not required in the process according to the invention or are only required in very small amounts, namely in a maximum of up to 20% of the amount required to be used in the processes of the prior art, in comparison with the prior art is.

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 dyes mentioned above which can be used for the dyeing process according to the invention, the fiber-reactive dyes are preferably used. Fiber-reactive dyes are organic dyes which contain 1, 2, 3 or 4 fiber-reactive radicals from the aliphatic, aromatic or heterocyclic series. Such dyes have been widely described in the literature. The dyes can belong to a wide variety of dye classes, such as the class of monoazo, disazo, polyazo, metal complex azo, such as 1: 1 copper, 1: 2 chromium and 1: 2 cobalt complex monoazo. and disazo dyes, also the range of anthraquinone dyes, copper and nickel phthalocyanine dyes, copper formazan dyes, azomethine, nitroaryl, dioxazine, triphendioxazine, phenazine and stilbene dyes. Fiber-reactive radicals are to be understood here as those which bind to the hydroxyl groups of cellulose, the amino, carboxy, hydroxyl and thiol groups of wool and silk or to the amino and possibly carboxy groups of synthetic polyamides to form a covalent chemical bond able to react. The fiber-reactive residues 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 (CH₃) -, -N (C₂H₅) - or -N (C₃H₇) -, or via an aliphatic radical, such as one Methylene, ethylene or propylene radical or an alkylene radical of 2 to 8 carbon atoms, which can be interrupted by one or two oxy and / or amino groups, or via a bridge member containing an amino group, such as a phenylamino group, to the Dye residue bound.

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.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 = CH₂, -CO-CH = CH-Cl, -CO-CCl = CHCl, -CO-CCl = CH-CH₃, -CO-CBr = CH₂, -CO-CH = CH-Br, -CO-CBr = CH-CH₃, -CO-CCl = CH-COOH, -CO-CH = CCl-COOH, -CO-CBr = CH-COOH, -CO-CH = CBr-COOH, -CO-CCl = CCl-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-chloroethylsulfonyl) butyryl, 4-vinylsulfonylbutyryl, 5- (β-chloroethylsulfonyl) valeryl, 5-vinylsulfonylvaleryl, 6- ( β-chloroethyl-sulfonyl) -caproyl, 6-vinylsulfonyl-caproyl, 4-fluoro-3-nitro-benzoyl, 4-fluoro-3-nitrophenylsulfonyl, 4-fluoro-3-methyl-sulfonylbenzoyl, 4-fluoro-3-cyanbenzoyl, 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-methylsulfonyl-pyrimidinyl-6, 2,5-dichloro-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-chloro-4-pyrimidinyl, 2-fluoro-5-nitro-6-chloro-4-pyrimidinyl, 5 -Brom-2-fluoro-4-pyrimidinyl, 2-fluoro-5-cyan-4-pyrimidinyl, 2-fluoro-5-methyl-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, 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-phenyl-4-pyrimidinyl, 2-fluoro-6-cyano-4-pyrimidinyl, 2,6-difluoro-5-methylsulfonyl-4-pyrimidinyl, 2- Fluoro-5-sulfonamido-4-pyrimidinyl, 2-fluoro-5-chloro-6-carbomethoxy-4-pyrimidinyl, 2,6-difluoro-5-trifluoromethyl-4-pyrimidinyl, 2,4-bis (methylsulfonyl) - pyrimidinyl-4, 2,5-bis (methylsulfonyl) -5-chloro-pyrimidinyl-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-chloromethyl-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-chloro-pyrimidinyl-4, 2 -Methylsulfonyl-6-carboxy-pyrimidinyl-4, 2-methylsulfonyl-5-sulfopyrimidinyl-4, 2-methylsulfonyl-6-carbomethoxy-pyrimidinyl-4, 2-methylsulfonyl-5-carboxy-pyrimidinyl-4, 2-methylsulfonyl-5-cyan-6-methoxypyrimidinyl-4, 2-methylsulfonyl-5-chloropyrimidinyl-4, 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-carbon yl, 2- or 3-monochloroquinoxaline-6-sulfonyl, 2,3-dichloroquinoxaline-5- or -6-carbonyl, 2,3-dichloroquinoxaline-5- or -6-sulfonyl, 1,4-dichlorophthalazine-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- Dichloropyridazine-4-carbonyl or -4-sulfonyl, 2-chlorobenzthiazole-5- or -6-carbonyl or -5- or -6-sulfonyl, 2-arylsulfonyl- or 2-alkylsulfonylbenzthiazole-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 ones condensed on Benzene ring containing sulfo groups 2-sulfonylbenzothiazole-5 or -6-carbonyl or -sulfonyl derivatives, 2-chlorobenzoxazole-5- or -6-carbonyl or -sulfonyl, 2-chlorobenzene zimidazole-5- or -6-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-phenylamino- 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- or 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 via a nitrogen bond the 1,4-bis- contain aza-bicyclo [2,2,2] octane or the 1,2-bis-aza-bicyclo- [0,3,3] octane bound in quaternary form, 2-pyridinium-4-phenylamino- or 4- (o- , m- or p-sulfophenyl) amino-triazinyl-6 and corresponding 2-oniumtriazinyl-6 radicals which are 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, are substituted.
Particularly interesting fiber-reactive radicals are fluorine and chloro-1,3,5-triazine radicals of the formula (13)

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, as well as hydrazino and semicarbazido groups , wherein said alkyl radicals can be straight-chain or branched and low molecular weight and higher molecular weight, preferably those with 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 is, preferably residues of six-membered N-heterocyclic compounds into consideration, which may contain nitrogen, oxygen or sulfur as further heteroatoms. The above-mentioned alkyl, cycloalkyl, aralkyl and aryl radicals, 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, C₁ -C₄-alkyl, C₁-C₄-alkoxy, acylamino groups such as acetylamino or benzoylamino, ureido, hydroxy, carboxy, sulfomethyl or sulfo. Examples of such amino groups are: -NH₂, 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, phenylamino, tolinoino, toluid , 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- (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 and semicarbazido.

Furthermore, Q can be an amino radical of the general formula -NR²⁰R²¹, in which R²⁰ is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, and R²¹ is phenyl which is obtained through a fiber-reactive radical of the vinylsulfone series directly or via a methylamino , Ethylamino, methylene, ethylene or propylene group is substituted and which can also be substituted by 1 or 2 substituents from the group methoxy, ethoxy, methyl, ethyl, chlorine, carboxy and sulfo, or R²¹ alkyl of 2 to 4 C- Atoms is such as ethyl or n-propyl which is substituted by a fiber reactive group of the vinyl sulfone series, or alkylene phenyl 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 R²⁰ and R²¹ are both alkyl of 2 to 4 carbon atoms, such as ethyl and n-propyl, by a fiber-reactive group of the vinyl sulfone series are substituted, or in which R²⁰ and R²¹ 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 of the vinylsulfone series is bonded.
Fiber-reactive groups of the vinyl sulfone series are those of the general formula -SO₂-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 do not require any further aftertreatment after removal from the dyebath or after the dye has been fixed on the substrate, in particular no complicated aftertreatment process including washing. As a rule, it is sufficient to rinse the colored substrate once or several times with warm or hot and, if appropriate, cold water, if appropriate using a nonionic wetting agent. A final boiling treatment of the dyed 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

wird in einem Siedebereich zwischen 95 und 120°C bei 5·10⁻² mbar abgetrennt.
¹H-NMR-Analyse:

δ =

0,06 ppm (CH₂),   0,11 ppm (Si-CH₃),   1,25 ppm (2xCH₃),
1,62 ppm (CH₂),   2,43 ppm (N-CH₃),   2,68 ppm (CH₂),
3,39 ppm (CH₂),   3,43 ppm (CH₂),   3,56 ppm (2xCH₂).

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 of the invention [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.
1 H-NMR analysis:

δ =

0.06 ppm (CH₂), 0.11 ppm (Si-CH₃), 1.25 ppm (2xCH₃),
1.62 ppm (CH₂), 2.43 ppm (N-CH₃), 2.68 ppm (CH₂),
3.39 ppm (CH₂), 3.43 ppm (CH₂), 3.56 ppm (2xCH₂).

in welcher s eine Zahl von 1 bis 4 bedeutet, zuzuordnen.In addition to these dominant signals, resonances occur with a practically identical shift, in a total proportion of approximately 20%. From mass spectrometric analysis, these polymeric ethers correspond to a general formula

in which s is a number from 1 to 4.

Example B

durch fraktionierte Destillation bei einem Siedebereich zwischen 104 und 118°C bei 5·10⁻² mbar.To prepare a silane compound according to the invention, the procedure of Example A is followed, but the equivalent amount of γ-chloropropyl-triethoxy-silane 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 C

durch fraktionierte Destillation bei einem Siedebereich zwischen 90 und 105°C bei 5·10⁻² mbar.To prepare a silane compound according to the invention, the procedure of Example A is followed, but instead of the γ-chloropropyl-methyl-diethoxy-silane compound, the equivalent amount of (γ-chloropropyl) - (dimethyl) - (ethoxy) -silane is used a. The compound of 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 D

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, which have 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 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, which 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 cotton fabric modified in this way is dyed analogously to a conventional pull-out dyeing process:
  100 parts of the modified fabric are placed in 2000 parts by volume of an aqueous dye solution, the 2 parts of a 50% electrolyte-containing (predominantly sodium chloride) dye powder of the known dye of the formula
  
  in the form of the alkali metal salt (ie 1 part of this dye and 1 part of the Electrolyte) contains dissolved, the dyebath is heated to 60 ° C within 30 minutes, and the dyeing process is continued at this temperature for 60 minutes. The dyed fabric is then rinsed with cold and hot water, the hot water may contain a commercially available wetting agent, optionally rinsed again with cold water and dried.
  A strong, uniformly colored orange coloration is obtained which has good general fastness properties.

Example 2

• 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 then dyed in accordance with a block-cold-dyeing process. For this purpose, an aqueous dye solution which contains 20 parts of 1000 parts by volume of 20 parts of the dye powder described in Example 1, 100 parts of urea and 3 parts of a commercially available nonionic wetting agent, using a padder with a liquor absorption of 80%, based on the weight of the Fabric, applied to the fabric at 25 ° C. The fabric padded with the dye solution is wound up on a dock, wrapped in a plastic film and left at 20 to 25 ° C for 16 hours and then with cold and hot water, which may or may not contain a commercially available wetting agent, and then again if necessary cold water rinsed and dried.
  A strong, uniformly colored orange coloration is obtained which has good general fastness properties.

Example 3

• a) A fabric made of 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 5 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 dyed according to a conventional padding process, for example analogously to the procedure of Example 2b. For this purpose, an aqueous dye liquor containing 28 parts of 1000 parts by volume of a 50% electrolyte-containing (predominantly sodium chloride) dye powder of the dye of the formula known from Example 1 of European Patent No. 0 032 187
  
  Contains 100 parts of urea and 3 parts of a commercially available nonionic wetting agent dissolved by means of a foulard with a liquor absorption of 80%, based on the weight of the fabric, at 20 ° C. on the fabric. The padded fabric is then wound onto a dock, wrapped in a plastic film and left at 20 ° C for 16 hours and then washed with cold and hot water, which may or may not contain a commercially available nonionic surfactant, and, if appropriate, again with cold water and dried.
  A strong, uniformly colored red dyeing with the usual good fastness properties is obtained.

Example 4

• 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 dyed in a customary drawing process. For this purpose, 10 parts of this material are added in 200 parts by volume of an aqueous dye solution, the 0.2 parts of a 50% electrolyte-containing dye powder of the known dye of the formula
  
  contains dissolved. The dyeing takes place at 30 ° C for 30 minutes. The dyed fabric is then rinsed with cold and warm water at 30 to 35 ° C, which may optionally contain a commercially available nonionic surfactant, then washed again with cold water and dried if necessary.
  A strong blue dyeing is obtained which, in terms of fastness properties and its other qualities, is similar to dyeings which are obtained using the customary dyeing methods of the prior art.

Example 5

• a) A fabric made from a commercially available polyester staple fiber is according to the details of Example 1 padded with the aqueous solution of the silane compound there with a liquor absorption of 95%. The material is then dried and the silane compound is fixed on the material for 5 minutes at 130 ° C.
• b) The polyester fabric modified in this way is then dyed in a drawing-out process. For this purpose, it is not necessary, as is customary in the prior art for dyeing polyester fibers, to use high dyeing temperatures, and the dyeing of the modified polyester fabric can be carried out according to the invention using an anionic dye:
  100 parts of the modified polyester fabric are placed in 2000 parts by volume of an aqueous dye solution which contains 2 parts of the dye powder described in Example 4 of the blue anthraquinone dye specified therein dissolved. The dyebath is heated to 60 ° C. for 30 minutes and the dyeing process is continued for 30 minutes at this temperature. The dyeing removed from the dyebath is then rinsed with cold and hot water, which may or may not contain a commercially available nonionic surfactant, if necessary then rinsed again with warm and cold water and dried. A strong, blue, level dyeing with high fastness properties is obtained.

Example 6

• a) A fabric made of mercerized and bleached cotton with a 25 to 30 ° C warm aqueous solution of 80 parts of [γ- (β'-amino-ethoxy) propyl] methyl diethoxy silane in 1000 parts of water with Glacial acetic acid is adjusted to a pH of 5.5, 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 cotton fabric thus modified is dyed in the procedure described in Example 1b) with the azo dye given there. It becomes a strong, uniformly colored orange color obtained, which has good general fastness properties.

Example 7

• a) A fabric made of 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 [γ- (β'-aminoethylamino) propyl] 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 5 minutes, both fixing the silane compound to the material and drying the material.
• b) The fabric modified in this way is dyed in accordance with a conventional padding process, for example in accordance with the information in Example 3b), using the azo dye indicated there. A strong, uniformly colored red dyeing with the usual good fastness properties is obtained.

Example 8

• a) A fabric of mercerized and bleached cotton is washed with a solution of 80 parts of [γ- (β'-N-methylamino-ethoxy) propyl] methyl-diethoxy-silane (Example A) in 1000 parts of water with glacial acetic acid was adjusted to a pH of 5.5, impregnated with a liquor absorption of 70%, based on the weight of the cotton. The tissue impregnated with this solution is then exposed to a hot air stream of 130 ° C. for 5 minutes.
• b) 100 parts of the modified cotton fabric obtained according to section a) are in 2000 parts of an aqueous solution with about 1 part of the known monoazo dye of the formula
  
  given. The dye bath is heated to 60 ° C. in the course of 30 minutes and the dyeing process is continued at this temperature for 60 minutes. The dyed fabric is then removed from the bath and first rinsed with cold, then with warm water at 30 to 35 ° C., which may or may not contain a commercially available nonionic surfactant, and then rinsed again with cold water and dried.
  A strong yellow color is obtained with good fastness properties, high color strength and a uniform appearance; the quality of the dyeing corresponds to the dyeings obtained with this dye according to the dyeing methods of the prior art.

Example 9

• a) A fabric made from a commercially available mercerized cotton fiber is washed with a solution of 80 parts of [γ- (β'-N-methylamino-ethoxy) propyl] triethoxysilane in 1000 parts of water, which is brought to a pH of 5.5 was set, with a fleet absorption of 80%. The impregnated fabric is then exposed to a hot air stream of 130 ° C. for 3 minutes, both the fixing of the silane compound on the fiber material and the drying of the material itself.
• b) the cotton fabric modified according to section a) is padded with a solution of 20 ° C. from 28 parts of the monoazo dye known from Example 1 of European Patent No. 0 032 187 in 1000 parts of water by means of a padder with a liquor absorption of 80%, then rolled up on a dock, wrapped in plastic wrap and left at 25 ° C for four hours. The dyed fabric is then washed with cold and hot water, which may contain a non-ionic surfactant, then rinsed again with cold and hot water and then dried. A strong red color with good fastness properties is obtained; the quality of the dyeing corresponds to the dyeings obtained with this dye in accordance with the customary dyeing methods of the prior art.

Example 10

• a) A fabric made of mercerized and bleached cotton is washed with a solution at 20 to 25 ° C. with a pH of 5.5 of 70 parts of [γ- (β'-N-methylamino-ethoxy) propyl] dimethyl- ethoxy-silane 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, both fixing the silane compound on the fabric and drying it.
• b) 100 parts of the fabric modified according to a) are placed in 2000 parts of an aqueous dye solution of 2 parts of a 50% electrolyte-containing (predominantly sodium chloride-containing) dye powder of the monoazo dye known from Example 1 of European Patent No. 0 032 187. The dye bath is heated to 60 ° C. within 30 minutes and the dyeing process is continued at this temperature for a further 60 minutes. The color obtained is removed and rinsed twice with water, the first rinse water may contain a commercially available surfactant, and then dried. A uniformly deep-red-dyed fabric is obtained with good fastness properties, which correspond to those of dyeing with this dye, which was produced by a customary dyeing process of the prior art for fiber-reactive dyes.

Example 11

• a) A fabric made of mercerized and bleached cotton is washed with a 25 to 30 ° C warm aqueous solution with a pH of 5.5 from 80 parts of an isomer mixture of compounds of the chemical structure 3'- and 4 '- [β- (N-methylamino) -ethoxy-methyl] -phenethyl- ( diethoxy) - (methyl) -silane (from Example D) padded in 1000 parts of water with a liquor absorption of 75%. The impregnated fabric is then exposed to a hot air stream of 130 ° C. for 3 minutes, during which both the silane compounds are fixed on the fiber and the material is dried.
• b) The cotton fabric modified according to a) is dyed according to the procedure of Example 8b). A strong, uniformly colored yellow color with good fastness properties is obtained; the quality of the dyeing corresponds to the dyeings obtained with this dye in accordance with the usual exhaust dyeing processes for fiber-reactive dyes of the prior art.

Example 12

• a) A fabric of mercerized and bleached cotton with a 25 to 30 ° C aqueous solution of 80 parts of the silane compound of Example A in 1000 parts of water, which is adjusted to a pH of 5.5 with glacial acetic acid, with a Fleet absorption of 72% impregnated. 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 cotton fabric modified in this way is dyed according to a pull-out dyeing proof:
  100 parts of the modified fabric are placed in 2000 parts by volume of an aqueous dye solution, the 2 parts of a 50% electrolyte-containing (predominantly sodium chloride) dye powder of the known dye of the formula
  
  contains dissolved in the form of the alkali metal salt (ie 1 part of this dye and 1 part of the electrolyte), the dyebath is heated to 60 ° C within 30 minutes, and the dyeing process is continued at this temperature for 60 minutes. The dyed fabric is then rinsed with cold and hot water, the hot water may contain a commercially available wetting agent, optionally rinsed again with cold water and dried.
  A strong, uniformly colored orange coloration is obtained which has good general fastness properties.

Claims (20)

Process for dyeing textile fiber materials with water-soluble dyes, preferably anionic dyes, which may contain one or more fiber-reactive groups, using aqueous dye solutions, padding liquors and printing pastes in which the dye is dissolved, characterized in that a textile fiber material is used as the substrate , which has been modified with a silane compound, with the proviso that at least one of the substituents bonded to the silicon atom has a primary, secondary or tertiary amino group, a primary, secondary, tertiary or quaternary ammonium group or a hydroxyl or thiol group, the to the Substituents bonded to the silicon atom can also be substituted by further nonionic and / or anionic substituents, and with the proviso that at least one of the substituents bonded to the silicon atom is a substituent which hydrolyzes to the hydroxyl group by water rt, and that in the absence of an alkaline agent or in the presence of an extremely small amount of an alkaline agent and / or in the absence or in the presence of only small amounts of an electrolyte. Process according to Claim 1, characterized in that the silane compound is a compound of the general formula (1)

in which mean: R¹ is hydrogen, alkoxy of 1 to 8 carbon atoms, halogen, hydroxy, alkoxy of 2 to 4 carbon atoms, which is substituted by alkoxy of 1 to 4 carbon atoms, N-morpholino, N-imidazolino or a group of Formula (2)

R² is a group of the general formula (3a) or (3b)

in which mean: a is the number zero or 1; b is an integer from zero to 10; c is the number 1 or 2 and is mandatory 1 if a is zero; A is alkylene of 1 to 6 carbon atoms, which can be substituted by hydroxy, methoxy, ethoxy, sulfo, sulfato or carboxy, or is phenylene, which can be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and / or carboxy , or is phenylene-alkylene, alkylene-phenylene, alkylene-phenylene-alkylene or phenylene-alkylene-phenylene, the alkylene groups of these radicals being those of 1 to 6 carbon atoms and by hydroxyl, methoxy, ethoxy, sulfo, sulfato or carboxy may be substituted, and the phenylene radicals may be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and / or carboxy; X 1 in the case of c is 1 is a group of the formula -S-, -O-, -NH- or -N (R) -, in which R is alkyl of 1 to 4 carbon atoms, or in the case of c 2 is a nitrogen atom; B is cycloalkylene of 5 to 8 carbon atoms or alkylene of 1 to 6 carbon atoms, which can be substituted by hydroxy, methoxy, ethoxy, sulfato, sulfo or carboxy, or is phenylene, which is substituted by methoxy, ethoxy, methyl, ethyl , Sulfo and / or carboxy may be substituted; X² is a group of the formula -S-, -O-, -NH- or -N (R) - with R having the meaning given above; D is alkylene of 1 to 6 carbon atoms, which can be substituted by hydroxy, methoxy, ethoxy, sulfo, sulfato or carboxy, or is phenylene, which can be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and / or carboxy , or is phenylene-alkylene, alkylene-phenylene, alkylene-phenylene-alkylene or phenylene-alkylene-phenylene, the alkylene groups of these radicals being those of 1 to 6 carbon atoms and by hydroxyl, methoxy, ethoxy, sulfo, sulfato or carboxy may be substituted, and the phenylene radicals may be substituted by methoxy, ethoxy, methyl, ethyl, sulfo and / or carboxy, or D may be a direct bond if (a + b) is not zero; T is hydroxy, thiol or a group of the general formula (4a) or (4b)

in which R⁵ is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfophenyl, amino, thio or hydroxy, or carbamoyl, which can be mono- or disubstituted, R⁶ 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, R⁷ is hydrogen, alkyl of 1 to 4 carbon atoms, which may be substituted, and X ^{(-) is} a monovalent anion or a part of a polyvalent anion equivalent to a monovalent anion; G is a radical of the general formula (5)

in which D, X², B, X¹, A, a and b have one of the meanings mentioned above; R⁸ is alkoxy of 1 to 8 carbon atoms, which can be substituted by alkoxy of 1 to 4 carbon atoms, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms or phenylene-alkyl with an alkyl radical of 1 to 4 carbon atoms, where the phenylene radical can be substituted by substituents from the group consisting of methyl, ethyl, methoxy, ethoxy, sulfo and carboxy, and these radicals R⁸ can also be substituted by a group T of the above meaning; R⁹ has one of the meanings of R¹ or R³; R³ is hydrogen, alkoxy of 1 to 8 carbon atoms, which can be substituted by alkoxy of 1 to 4 carbon atoms, halogen, hydroxy, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, alkynyl from 3 to 8 carbon atoms, phenyl or a group of the general formulas (3a) and (3b); R⁴ has one of the meanings given for R¹ or R³. A method according to claim 1 or 2, characterized in that the substrate is a cellulose fiber material modified with a silane compound of the general formula (1). Process according to at least one of Claims 1 to 3, characterized in that the substrate is colored at a temperature between 10 and 30 ° C. Process according to at least one of Claims 1 to 3, characterized in that the substrate is colored at a temperature between 30 and 60 ° C. Process according to at least one of Claims 1 to 5, characterized in that the silane compound is a compound of the general formula (8)

is in which mean: R¹ is hydrogen, alkoxy of 1 to 8 carbon atoms, halogen, hydroxy, alkoxy of 2 to 4 carbon atoms, which is substituted by alkoxy of 1 to 4 carbon atoms, N-morpholino, N-imidazolino or a group of Formula (2)

R¹² is a group of the general formula (9a) or (9b)

in which n is an integer from 1 to 6, m is an integer from zero to 6, k is an integer from zero to 4, p is an integer from 1 to 4, z is an integer from 1 to 10, preferably from 1 to 5, alk denotes a straight-chain or branched alkylene radical of 1 to 8 carbon atoms and T¹ is an amino group of the general formula (4c)

is in which R is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfophenyl, amino, thio or hydroxy, or is mono- or disubstituted carbamoyl; R¹³ is hydrogen, alkoxy of 1 to 8 carbon atoms, which can be substituted by alkoxy of 1 to 4 carbon atoms, halogen, hydroxy, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, alkynyl from 3 to 8 carbon atoms, phenyl or a group of the general formulas (9a) and (9b); R¹⁴ has one of the meanings given for R¹ or R¹³. Process according to Claim 6, characterized in that the radical R¹² in the compound (8) is a radical of the general formula (9b). A method according to claim 6 or 7, characterized in that the radical T¹ is the methylamino or ethylamino group. A textile fiber material, preferably cellulose fiber material, which is modified by a silane compound of claim 1. Process for modifying a textile fiber material, characterized in that at least one silane compound according to claim 1 is applied to the textile fiber material and subjected to a heat treatment of 100 to 230 ° C. Process according to Claim 10, characterized in that the silane compound is a compound of the general formula (8)

is in which mean: R¹ is hydrogen, alkoxy of 1 to 8 carbon atoms, halogen, hydroxy, alkoxy of 2 to 4 carbon atoms, which is substituted by alkoxy of 1 to 4 carbon atoms, N-morpholino, N-imidazolino or a group of Formula (2)

R¹² is a group of the general formula (9a) or (9b)

in which n is an integer from 1 to 6, m is an integer from zero to 6, k is an integer from zero to 4, p is an integer from 1 to 4, z is an integer from 1 to 10, preferably from 1 to 5, alk denotes a straight-chain or branched alkylene radical of 1 to 8 carbon atoms and T¹ is an amino group of the general formula (4c)

is in which R is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfophenyl, amino, thio or hydroxy, or is mono- or disubstituted carbamoyl; R¹³ is hydrogen, alkoxy of 1 to 8 carbon atoms, which can be substituted by alkoxy of 1 to 4 carbon atoms, halogen, hydroxy, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, alkynyl from 3 to 8 carbon atoms, phenyl or a group of the general formulas (9a) and (9b); R¹⁴ has one of the meanings given for R¹ or R¹³. Process according to Claim 11, characterized in that the radical R¹² in the compound (8) is a radical of the general formula (9b). A method according to claim 11 or 12, characterized in that the radical T¹ is the methylamino or ethylamino group. Process according to at least one of Claims 10 to 13, characterized in that the heat treatment is carried out at a temperature between 100 and 150 ° C. Silane compound according to the general formula (8)

in which mean: R¹ is hydrogen, alkoxy of 1 to 8 carbon atoms, halogen, hydroxy, alkoxy of 2 to 4 carbon atoms, which is substituted by alkoxy of 1 to 4 carbon atoms, N-morpholino, N-imidazolino or a group of Formula (2)

R¹² is a group of the general formula (9a) or (9b)

in which n is an integer from 1 to 6, m is an integer from zero to 6, k is an integer from zero to 4, p is an integer from 1 to 4, z is an integer from 1 to 10, preferably from 1 to 5, alk denotes a straight-chain or branched alkylene radical of 1 to 8 carbon atoms and T¹ is an amino group of the general formula (4c)

is in which R is hydrogen or alkyl of 1 to 4 carbon atoms, which can be substituted by phenyl, sulfophenyl, amino, thio or hydroxy, or is mono- or disubstituted carbamoyl; R¹³ is hydrogen, alkoxy of 1 to 8 carbon atoms, which can be substituted by alkoxy of 1 to 4 carbon atoms, halogen, hydroxy, alkyl of 1 to 8 carbon atoms, alkenyl of 2 to 8 carbon atoms, alkynyl from 3 to 8 carbon atoms, phenyl or a group of the general formulas (9a) and (9b); R¹⁴ has one of the meanings given for R¹ or R¹³. Compound according to Claim 15, characterized in that R¹ is alkoxy of 1 to 4 C atoms or alkoxy of 2 to 4 C atoms substituted by alkoxy of 1 to 4 C atoms. Compound according to claim 15 or 16, characterized in that R¹³ alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms substituted alkoxy of 2 to 4 carbon atoms or one Group of the general formula (9a) or (9b). Compound according to at least one of Claims 15 to 17, characterized in that R¹⁴ alkyl of 1 to 4 C atoms, alkoxy of 1 to 4 C atoms or alkoxy of 2 to 4 C atoms substituted by alkoxy of 1 to 4 C atoms Atoms. Process for the preparation of a silane compound of the general formula (8) of claim 15, characterized in that a compound of the general formula (10)

in which R¹ has one of the meanings mentioned in claim 15, R ^{A is} a radical of the general formula (11a) or (11b)

- (CH₂) _n - Hal (11b)



is in which alk, k and n have one of the meanings mentioned in claim 15 and Hal represents a halogen atom, R ^{B is} hydrogen, alkoxy of 1 to 8 carbon atoms, which can be substituted by alkoxy of 1 to 4 carbon atoms, halogen, hydroxy, 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 general formula (11a) or (11b) and R ^{C has} one of the meanings given for R 1 or R ^B , with a compound of the general formula (12a) or (12b)



MeO - (CH₂) _n - T¹ (12a)





MeO - (CH₂) _p - T¹ (12b)



in which n, p and T¹ have one of the meanings given in Claim 15 and Me represents an alkali metal, in a polar, organic, optionally water-miscible solvent which is inert to the reactants, at a temperature between 0 and 50 ° C implements. Use of a silane compound of claim 15 for modifying a textile fiber material, preferably cellulose fiber material.