EP0690166A2 - Process for dyeing aminated polyester/cotton mix fabric, with disperse reactive dyestuff - Google Patents

Abstract

A process for dyeing cellulose or cellulose/polyester fibre materials (I) comprises modifying the material with amino gp.-contg. cpds. (II) and then dyeing with a fibre-reactive dispersion dye in supercritical CO2. Most pref. (I) are, e.g. 2-oxo-1,3-oxazolidine and corresp. derivs. thereof substd. with 4- or 5-aminomethyl or with 4- or 5-(trimethylammonium-methyl) gps. (chloride salt in the latter type) (5 cpds. listed), or 1-(trimethylammonium-methyl)- ethylene carbonate chloride. PREFERRED PROCESS - Dyeing is carried out at 70-200 (pref. 100-150) degrees C for cellulose fibre and 130-210 (pref. 130-150) degrees C for cellulose/polyester, with a CO2 pressure of 30-400 (pref. 140-250) bar.

Description

In the current state of the art, alkali donors for fixation and electrolytes for better absorption are necessary for dyeing cotton with reactive dyes in order to achieve satisfactory dyeing results. Polyester, on the other hand, is dyed at high temperatures with disperse dyes, which are, however, chemically unstable under alkaline conditions.

DE-A-39 06 724 describes a process for dyeing textile substrates, in which a supercritical fluid containing a dye flows or flows through the substrates. Depending on the type of fluid and the substrate, both disperse and anionic dyes can be used. The dyeing of cotton, also with reactive dyes, is in principle possible according to this, but alkaline auxiliaries are still required in order to covalently bind the reactive dye to the substrate and thus to meet today's requirements for the fastness level.

DE-A-42 30 325, on the other hand, teaches that textile materials made from cellulose with disperse dyes can only be colored unsatisfactorily, in many cases only as soiled fabric, by the process cited above. This problem is solved by pretreating the textile beforehand with a dye-promoting agent. Nothing is said about the fastness properties of a textile dyed in this way, but the fastness to washing and rubbing is below the level required for reactive dyes.

There is therefore a need for a method, textile fibers, preferably those which contain the base body of the α, β-glucose and the polyester at the same time, to be dyed in one bath and using only one class of dye without colored wastewater.

It has now been found with the present invention that, in a surprising manner, with fiber-reactive disperse dyes, without the use of alkaline agents, level and strong dyeings with very good fastness properties, especially fastness to washing and rubbing, are obtained when using a cellulosic fiber or mixed fiber material , which was previously modified by compounds containing amino groups and if one carries out the dyeing process in supercritical CO₂.

The present invention relates to a process for dyeing fiber materials consisting of cellulose fibers or a mixture of cellulose and polyester fibers, characterized in that the fiber material is first modified with one or more compounds containing amino groups and then the modified fiber material with a fiber-reactive disperse dye in supercritical CO₂ colors.

Because of their chemical structure, fiber-reactive disperse dyes are capable of reacting with both cotton and polyester materials at the appropriate temperatures. Fiber-reactive disperse dyes are dyes which, apart from the fiber-reactive group, contain no water-solubilizing group, the fiber-reactive group itself not being a water-solubilizing group.

The dyes which are used according to the invention are described, for example, in US Pat. No. 3,974,160, CH-A-564 515 and Japanese Patent Application Laid-Open JP-3-247,665; JP 92/059347, JP 91 / 035,341, JP 91 / 032,585 and JP 91 / 032,587. The water-insoluble disperse dyes mentioned in these documents contain so-called fiber-reactive residues. Fiber-reactive is generally understood to mean those parts of the molecule which contain hydroxyl groups, for example of cellulose, or Amino and thiol groups, for example wool and silk, synthetic polymers, such as polyamides, or also aminated celluloses, can react and are able to form a covalent chemical bond.

Compounds containing amino groups which are suitable for modifying the fiber material are described in EP-A-0 546 476, EP-A-0 580 091, EP-A-0 286 597, EP-A-0 151 370 and in Japanese Publication Hei-5-5279 and form part of the disclosure of the present invention. In addition, those compounds are also suitable for the pretreatment which are described, for example, in DE-A-29 30 738 as aftertreatment agents.

in welcher bedeuten:

R^A

ist Wasserstoff oder Alkyl von 1 bis 3 C-Atomen, das durch Hydroxy oder eine Gruppe der Formel (2) oder (3)

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-Piperazin-, N-Piperidin- oder N-Morpholin-Rest, und

Z^(-)

ein Anion bedeutet, wie beispielsweise das Chlorid-, Hydrogensulfat- oder Sulfatanion;

R^B

hat eine der für R^A angegebenen Bedeutungen;

W

ist eine direkte Bindung oder eine Gruppe der Formel -CHR^C-, in welcher R^C eine der für R^A angegebene Bedeutungen besitzt;

X

ist eine Gruppe -O- oder -NH-.

Compounds which can preferably be used for modifying fiber materials are, for example, the compounds corresponding to the general formula (1) described in EP-A-0 580 091

in which mean:

R ^A

is hydrogen or alkyl of 1 to 3 carbon atoms, which is substituted by hydroxyl or a group of the formula (2) or (3)

can be substituted in which

R¹

Is hydrogen, methyl or ethyl,

R²

Is hydrogen, methyl or ethyl and

R³

Is hydrogen, methyl or ethyl or

R¹

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 -Piperazine, N-piperidine or N-morpholine residue, and

Z ^(-)

represents an anion, such as the chloride, hydrogen sulfate or sulfate anion;

R ^B

has one of the meanings given for R ^A ;

W

is a direct bond or a group of the formula -CHR ^C -, in which R ^{C has} one of the meanings given for R ^A ;

X

is a group -O- or -NH-.

Preferably only one of the radicals R ^A , R ^B and R ^{C represents} an alkyl group with a group of the formula (2) or (3).

Such hetero-cycloaliphatic compounds which can be used according to the invention are, for example, 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 and 1- (trimethylammonium methyl) ethylene carbonate chloride.

The compounds which can be used according to the invention can be prepared according to known procedures, as are described in numerous publications (see Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume E4, pages 82-88 and 192ff.), 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 for the preparation of the heterocycloaliphatic carbonates or, for example, by reacting aminoalkanols with phosgene in aqueous solution to give the heterocycloaliphatic carbamic acid compounds (2-oxo-1,3-oxazolidines).

entsprechen, in welchen bedeuten:

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,

R¹

Wasserstoff, Methyl oder Ethyl ist,

R²

Wasserstoff, Methyl oder Ethyl ist und

Z^(-)

ein Anion bedeutet, wie beispielsweise das Chlorid-, Hydrogensulfat- oder Sulfatanion;

B

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

in welchen

R¹, R² und Z^(-)

eine der obengenannten Bedeutungen besitzt und

R³

Methyl oder Ethyl ist und

R⁴

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 können sowohl an einem primären, sekundären oder tertiären C-Atom des Alkylenrestes gebunden sein.Aliphatic compounds containing amino and ester groups that can be used according to the invention are, for example, the compounds described in EP-A-0 546 476, which have the general formulas (1a) and (1b)

correspond in which mean:

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 1 to 4 carbon atoms, which are substituted by 1 or 2 substituents from the group amino, sulfo, hydroxy, sulfato, phosphato and carboxy may, or is an alkyl group 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 by one Amino, sulfo, hydroxyl, sulfato or carboxy group can be substituted,

R¹

Is hydrogen, methyl or ethyl,

R²

Is hydrogen, methyl or ethyl and

Z ^(-)

represents an anion, such as the chloride, hydrogen sulfate or sulfate anion;

B

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

in which

R¹, R² and Z ^(-)

has one of the meanings mentioned above and

R³

Is methyl or ethyl and

R⁴

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 are formed by 1 or 2 hetero groups, which from the Groups -O- and -NH- are selected, is interrupted;
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 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 2 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 can be bound to a primary, secondary or tertiary carbon atom of the alkylene radical.

Compounds containing ester and amino groups which can be used according to the invention are, for example, N- (β-sulfatoethyl) piperazine, N- (β-sulfatoethyl) piperazine sulfate, 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-amino propane, 3-sulfato-2-hydroxy-1-amino propane, 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 and derivatives of these compounds with a different ester group instead of the sulfato group, such as with the phosphato, acetyloxy, p-tosyloxy and 3,4,5-trimethyl-phenylsulfonyloxy group.

To prepare the compounds which can be used according to the invention, it is possible to start from the corresponding compounds containing hydroxyl groups and to esterify the hydroxyl groups in a customary manner by reaction with the acids or the corresponding acylating agents, where, if one starts from compounds containing amino groups with more than one hydroxyl group, preferably only one of these hydroxy groups esterified. Such practices are known in the literature; the compounds which can be used according to the invention can be prepared analogously to such known procedures.

The methods for carrying out the modification of the fiber material are described in the published publications.

Fiber materials which are used according to the invention are all the polymers which contain the basic structure of α, β-glucose alone or as a mixture with polyester fibers.

The textile-modified fiber material that is 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).

The dyeing according to the invention from supercritical carbon dioxide is carried out, for example, by adding the modified textile material together with the fiber-reactive disperse dye in solid form to a pressure-resistant dyeing apparatus and heating it to the dyeing temperature under CO₂ pressure, or by heating and the desired CO₂- Pressure. CO₂ is preferably filled in the form of dry ice in the dyeing apparatus or recondensed from connected systems of comparable pressure. The dyeing temperatures used in the process according to the invention for modified cotton fibers are between 70 and 200 ° C., preferably between 100 and 150 ° C., and for cellulose / polyester blended fabrics between 120 and 210 ° C., preferably 120 and 150 ° C.

The pressure to be used in the process according to the invention must be at least so great that the CO₂ is present in a supercritical state. This pressure usually varies between 30 bar and 400 bar, preferably between 140 bar and 250 bar. At the preferred dyeing temperature for cellulose materials of approximately 130 ° C., the pressure is approximately 200 bar.

The liquor ratio during dyeing varies between a value of 1: 2 to 1: 100. After reaching the dyeing temperature, the desired pressure is set, if this has not already been reached due to the temperature increase. The temperature and pressure are then kept for some time, e.g. Kept constant for 0.5 to 60 minutes, taking suitable measures, e.g. Circulation of the dyeing liquors ensures intensive mixing of the textile material and dyeing liquor. After the dyeing process, the pressure is reduced, either quickly by opening the valve and releasing the pressure or in several stages.

In the examples below, "parts" are parts by weight.

example 1

und 330 g festem CO₂ zusammengebracht. Nach dem Verschließen des Autoklaven wird der Inhalt auf 130°C erhitzt, wobei sich ein Druck von ca. 225 bar einstellt. Man hält die Temperatur über 30 min konstant, kühlt langsam ab und entspannt den Autoklaven stufenweise. Man erhält eine farbstarke gelbe Färbung mit sehr guten Gebrauchsechtheiten.5 parts of a polyester / cotton blend pretreated in accordance with Example 19a of EP-A1-0 546 476 are dried and in a 0.5 liter autoclave with 0.1 part of the yellow dye of the formula

and 330 g of solid CO₂ brought together. After closing the autoclave, the contents are heated to 130 ° C, which results in a pressure of approx. 225 bar. The temperature is kept constant for 30 minutes, slowly cooled and the autoclave is gradually released. A strong yellow color with very good fastness properties is obtained.

Example 2

5 parts of a cotton fabric pretreated in accordance with Example 12a of EP-A1-0 546 476 are dried and in a 0.5 liter autoclave with 0.1 part of the dye from DE-A-20 08 811, Example 102 and 330 g of solid CO₂. The procedure followed is as described in Example 1 of this application, and a strong, level, level yellow dyeing is obtained, the fastness of which is equivalent to that of the dyeing obtained in accordance with the prior art in all respects.

Further examples

The dyeing of pretreated cotton or cotton blended fabrics is carried out according to the instructions in Examples 1 and 2 and dyeing is carried out using the fiber-reactive disperse dyes listed below by the process described above and similarly good results are obtained:

Claims (9)

Process for dyeing fiber materials consisting of cellulose fibers or a mixture of cellulose and polyester fibers, characterized in that the fiber material is first modified with one or more compounds containing amino groups and then the modified fiber material is dyed with a fiber-reactive disperse dye in supercritical CO₂. Process according to Claim 1, characterized in that the compound containing amino groups corresponds to the formula (1)

in which mean: R ^A is hydrogen or alkyl of 1 to 3 carbon atoms, which is substituted by hydroxyl or a group of the formula (2) or (3)

can be substituted in which 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 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-, preferably the N -Piperazine, N-piperidine or N-morpholine residue, and Z ^{(-) represents} an anion, preferably the chloride, hydrogen sulfate or sulfate anion; R ^B has one of the meanings given for R ^A ; W is a direct bond or a group of the formula -CHR ^C -, in which R ^{C has} one of the meanings given for R ^A ; X is a group -O- or -NH-. A method according to claim 2, characterized in that the amino group-containing compound 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 and 1- (trimethylammonium-methyl) -ethylene carbonate- is chloride. Process according to Claim 1, characterized in that the compound containing amino groups corresponds to the formula (1a) or (1b),

in which mean: 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, preferably a 5- or 6-membered heterocyclic ring, in which A is 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, 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 Is a C atom which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH- and can be substituted by an amino, sulfo, hydroxyl, sulfato or carboxy group, R¹ is hydrogen, methyl or ethyl, R² is hydrogen, methyl or ethyl and Z ^{(-) represents} an anion; B is the amino group of the formula H₂N or an amino or ammonium group of the general formula (d) or (e)

in which R¹, R² and Z ^{(-) has} one of the meanings given above and R³ is methyl or ethyl and R⁴ represents hydrogen, methyl or ethyl; p is the number 1 or 2;
alkylene is a straight-chain or branched alkylene radical of 2 to 6 C atoms, which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched alkylene radical of 3 to 8 C atoms, which is formed by 1 or 2 hetero groups, which consist of the Groups -O- and -NH- are selected, is interrupted;
alk is a straight-chain or branched alkylene radical of 2 to 6 C atoms, or is a straight-chain or branched alkylene radical of 3 to 8 C atoms, which is selected by 1 or 2 hetero groups selected from the groups -O-and -NH- , is interrupted; m is the number 1 or 2; n is a number from 1 to 4; the amino, hydroxyl and ester groups can be bound to a primary, secondary or tertiary carbon atom of the alkylene radical. Method according to Claim 4, characterized in that in the compounds of the formulas (1a) and (1b) A and N together form a piperazine, piperidine or morpholine ring, R is a hydrogen atom, an alkyl group with 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 with 3 to 5 carbon atoms which is interrupted by 1 or 2 hetero groups -O- or -NH-; Z ^{(-) is} a chloride, bisulfate or sulfate anion; p is the number 1;
alkylene is a straight-chain or branched alkylene radical of 2 to 4 carbon atoms, which can be substituted by 1 or 2 hydroxyl groups, or a straight-chain alkylene radical of 3 to 5 carbon atoms, which can be substituted by 1 or 2 hetero groups -O- or -NH- is interrupted;
alk is a straight-chain or branched alkylene radical of 2 to 4 carbon atoms, or a straight-chain alkylene radical of 3 to 5 carbon atoms which is interrupted by 1 or 2 hetero groups -O- or -NH-; m the number 1 and n is the number 1 or 2. A method according to claim 4 or 5, characterized in that the amino group-containing compound N- (β-sulfatoethyl) piperazine, N- (β-sulfatoethyl) piperazine sulfate, N- [β- (β'-sulfatoethoxy) ethyl] piperazine , N- (γ-sulfato-β-hydroxypropyl) piperidine, N- (γ-sulfato-β-hydroxypropyl) pyrrolidine, N- (β-sulfatoethyl) piperidine, a salt of 3-sulfato-2- hydroxy-1- (trimethylammonium) propane, 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 and a derivative of these compounds with a phosphato-, acetyloxy -, p-Tosyloxy or 3,4,5-trimethyl-phenylsulfonyloxy ester group. Process according to at least one of Claims 1 to 6, characterized in that, in the case of cellulose fiber materials, the dyeing temperatures are between 70 and 200 ° C, preferably 100 and 150 ° C. Method according to at least one of claims 1 to 6, characterized in that, in the case of cellulose fiber / polyester fiber mixtures, the Dyeing temperatures between 130 and 210 ° C, preferably between 130 and 150 ° C. Method according to at least one of claims 1 to 8, characterized in that the CO₂ pressure is 30 to 400 bar, preferably 140 to 250 bar.