DE4417211A1 - Modified cellulose@ synthetic fibres with affinity for reactive dyes - Google Patents

Abstract

Modified cellulosic synthetic fibres (I) are obtd. by: (a) treating a cellulose soln. with a modifier, and then (b) spinning fibres from the soln.; or by: (a) treating an alkali cellulose soln. with a modifier, then (b) xanthogenic treating and spinning fibres by the viscose process. The modifier is an amine of formula (1a), (1b), (1c), (1d) or (1e), or 2-oxo-1,3-oxazolidine, 4- or 5-aminomethyl-2-oxo-1,3-oxazolidine, 4- or 5-(trimethylammonium-methyl)-2-oxo-1,3-oxazolidine chloride, or 1-(trimethylammonium-methyl)-ethylene-carbonate chloride. (B)p-alk(OH)n(ER) (1b) H2N-alkylene-(ER)m (1c) ClCH2-CH(OH)-CH2-N<+>R<1>2R<2>Z<-> (1e) Z = H, 1-4C alkyl (opt. substd. with 1 or 2 OH gps.), or alkyl-(ER)m-; ER = ester gp.; A + N + 1 or 2 1-4C alkylene gps. = an heterocyclic ring; A = O, R-N<, R-CH< or R<1>R<2>N<+>< Z<->; B = -NH2, -NR<1>R<3> or -N<+>R<1>R<2>R<4> Z<->; R = H, amino, 1-6C alkyl (opt. substd. with 1 or 2 amino, sulpho, OH, sulphato, phosphato or COOH gps.), or 3-8C alkyl with 1 or 2 in-chain O or NH gps. (opt. substd. as before); R<1>, R<2>, R<4> = H, Me or Et; R<3> = Me or Et; Z<-> = anion; alkylene = 2-6C opt. branched alkylene (opt. substd. with 1 or 2 OH), or 3-8C alkylene with 1 or 2 in-chain O or NH gps.; Alk = 2-6C opt. branched alkylene, or 3-8C alkylene with 1 or 2 in-chain O or NH; m = 1 or 2; n = 1-4; p = 1 or 2; in these cpds., the amino, OH and ester gps. may be on prim., sec. or tert. C atoms of the alkylene gps. Also claimed is a process for the prodn. of dyed or printed textile materials from cellulosic fibres modified as above, by: (a) weaving or knitting the modified fibre, and then (b) dyeing or printing the fabric obtd. with anionic textile dye(s) in the absence of additional electrolyte salts or alkali.

Description

The present invention is in the field of textile dyeing Viscose fibers.

Viscose fibers have the same dyeing properties, including regenerated cellulose fibers called, essentially that of cotton fibers. At the current status of Technology is for dyeing cellulosic natural or regenerated fibers Alkaline agents as well as electrolytes are necessary in order to be satisfactory To achieve fixing results with reactive dyes. Just these necessary However, additives represent unacceptable environmental pollution. For the Regenerate fibers are therefore becoming increasingly important in the future on cellulose, which can be dyed without salt or alkali. There is a possibility in modifying the viscose fibers so that their chemical Behavior similar to animal fibers, such as wool or silk, and among neutral ones Conditions with anionic dyes without additional salt or alkali can be colored.

Modifications of viscose have already been described in the literature. The DE-A-19 48 487, for example, describes a process for the production of Viscose fibers with changed dyeing properties. The production turns out but extremely complex and uneconomical. Beyond that Long chain polyaminamides are used, which preserve the native character of the fiber due to the predominantly lipophilic structure of the additives used significantly disturb. This occurs, for example, when using dyes expressed, which in itself is not suitable for dyeing cellulose material are.  

DE-A-14 69 062 also describes aminalized fibers. With the additives are aminoethyl and diethylaminoethyl celluloses in high Concentration, the coloring is done exclusively with acid dyes. Accordingly, the fastness to washing does not meet today's requirements fair.

Various are disclosed in EP-A-0 284 010, EP-A-0 359 188 and EP-A-0 546 476 compounds containing amino groups as agents for pretreating the surface of textiles containing cellulose fibers described before the dyeing process. The disadvantage of such processes is an additional process step and yellowing of the viscose fiber in the course of the modification.

The present invention was based on the object of a method for Modification of viscose fibers to provide textiles to dye such fibers salt and alkali free with reactive dyes and the to avoid mentioned disadvantages of the prior art.

It has been found that this object is surprisingly achieved by admixing below-mentioned amino compounds to alkaline digested Cellulose and subsequent xanthation is dissolved.

The present invention relates to a method for the production modified regenerated cellulose fibers, characterized in that Cellulose first breaks down alkaline (alkali cellulose), then an amine Formulas (1a), (1b), (1c) or (1d)

or an oxazolidinone, in which mean:
Z is hydrogen, C₁-C₄-alkyl, which can be substituted by 1 to 2 OH groups, or alkylene- (ER) - _m
ER is an ester group or a ClCH₂ group;
A and N together with 1 or 2 alkylene groups of 1 to 4 carbon atoms form the remainder of a 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 C atoms, which can be substituted by 1 or 2 substituents from the group amino, sulfo, hydroxy, sulfato, phosphato and carboxy, or an alkyl group of 3 to 8 Carbon atoms which are interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH- and which may 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 ^{(-) have} one of the meanings given above,
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 carbon atoms,
which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH-;
alk is a straight-chain or branched alkylene radical of 2 to 6 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 and is preferably a straight-chain or branched alkylene radical of 2 to 6 carbon atoms,
m is the number 1 or 2;
n is a number from 1 to 4; and in what
the amino, hydroxyl and ester groups can be bound to a primary, secondary or tertiary carbon atom of the alkylene radical, are added and the mixture is allowed to linger for 15 min to 6 hours, preferably 1 to 3 hours, then with carbon disulfide to the xanthate converts and spins into fibers.

Compounds containing amino groups in which the Ester group is a sulfato or phosphato group or a lower one  Alkanoyl group, phenylsulfonyloxy or one on the benzene nucleus Substituents from the group carboxy, lower alkyl, lower alkoxy and Is nitro substituted phenylsulfonyloxy group.

The compounds in particular have been found to be the amino component N- (β-sulfatoethyl) piperazine, N- [β- (β'-sulfatoethoxy) ethyl] piperazine, N- (γ-sulfato-β-hydroxypropyl) piperidine, N- (γ-sulfato-β-hydroxypropyl) - pyrrolidine, N-β-sulfatoethyl-piperidine, 2-sulfato-3-hydroxy-1-aminopropane, 3- Sulfato-2-hydroxy-1-aminopropane, 1-sulfato-3-hydroxy-2-aminopropane, 3-hydroxy-1-sulfato-2-aminopropane, 2,3-disulfato-1-aminopropane or 1,3- Disulfato-2-aminopropane, a derivative of these compounds with another Ester group instead of the sulfato group or N- (2-sulfatoethyl) piperazine sulfate, proven. In addition, there are glycidyltrimethylammonium chloride, aziridine, N-hydroxyethyl aziridine and oxazolidinone are also considered.

In addition, there are also those for the modification of the alkali celluloses Compounds suitable as a reactive residue on the amine component α-chloro-β-hydroxy substitution, preferably the 3-chloro-2-hydroxypropyl Rest. Furthermore, such molecular parts are generally reactive understand that can react with the hydroxyl groups of cellulose and are able to form a covalent chemical bond.

The alkaline digestion of the cellulose is carried out using customary methods, for example with 20 wt .-% sodium hydroxide solution at 20 to 40 ° C, wherein Alkali cellulose is obtained. Then the excess alkali, for example the sodium hydroxide solution removed, for example by pressing or centrifuging.

The amino compounds used for the process according to the invention are either directly in the alkaline medium or in substance Alkali cellulose mass incorporated and show good tolerance. Of the It is added in an amount of 1 to 20% by weight, preferably 1 to 8  % By weight, based on the cellulose content of the alkali cellulose mass.

After the addition of the amino compounds, the reaction mixture for one the above period "ripen", preferably at temperatures of 40 to 80 ° C. The reaction mixture is then added in the usual manner Carbon disulfide reacted to form the cellulose xanthate, expediently at temperatures of 5 to 25 ° C for 0.5 to 2 hours. If necessary, the excess carbon disulfide is removed preferably distilled off and regenerated. The modified in this way Viscose is expediently pressed into an acidic precipitation bath and into fibers spun.

The filterability of the viscose shows no deterioration in comparison with additive free samples, so that no clogging of the in the course of the spinning process Spinneret can be observed. The deformation of the viscose is done according to usual and known methods, such as. B. with spinnerets, one subsequent precipitating bath and, if appropriate, further post-treatment baths.

The modified regenerated cellulose fibers produced according to the invention can after processing to woven and knitted fabrics using various Processes such as pull-out, block and modern printing processes belong to this also ink-jet processes, without the addition of electrolyte salt or alkali Reactive dyes are dyed.

The fibers mentioned are important with regard to dyeing with reactive dyes more affine than conventional viscose fibers, but differ in the other ones desired properties, such as gloss and grip, hardly compared to the conventional viscose fibers.

The textile modified fiber material used for the subsequent dyeing process can be used in all processing states, such as yarn, flake, Comb and piece goods (fabric) are available.  

The modified textile fiber materials are dyed according to the invention analogous to known dyeing methods and printing processes for dyeing or printing of fiber materials with water-soluble textile dyes and under Application of the temperature ranges known for this and usual amounts of dye, but with the exception that for the dye baths, Block liquors, printing pastes and ink jet formulations have an alkaline effect Compounds as they are usually used to fix fiber-reactive Dyes are used, do not have to be added and further it is possible to dispense with the usual additions of electrolyte salts.

For example, the different extraction processes are used as dyeing processes, like dyeing on the jigger and on the reel runner or dyeing out long or short liquor, dyeing in jet dyeing machines, dyeing after Block cold dwell process or after a block hot steam fixing process in Consideration. Conventional printing techniques come as printing processes including ink jet printing and transfer printing.

The dyes that are used to dye the modified cellulose are generally anionic in nature. The fiber-reactive ones are particularly suitable Textile dyes containing hydroxyl groups, for example cellulose, or Amino and thiol groups, for example wool and silk, from synthetic polymers, such as polyamides, or those according to the invention aminated celluloses, can react and form a covalent bond capital. As a fiber-reactive component on the textile dyes especially the sulfatoethylsulfonyl, vinylsulfonyl, chlorotriazinyl and Fluorotriazinyl residue and combinations of these reactive groups called.

As reactive dyes for dyeing or printing according to the invention modified viscose fibers are all water-soluble, preferably anionic Dyes, preferably one or more sulfo and / or carboxy groups own and contain the fiber-reactive groups. You can save the class of fiber-reactive dyes of the class of azo  Developing dyes, direct dyes, vat dyes and Belong to acid dyes, for example azo dyes, copper complex, Cobalt complex and chromium complex azo dyes, copper and Nickel phthalocyanine dyes, anthraquinone, copper formazane, azomethine, Nitroaryl, dioxazin, triphendioxazin, phenazin and stilbene dyes can. Such dyes have been extensively described in the literature, for example in EP-A-0 513 656, and familiar to the person skilled in the art.

Unless otherwise stated, these are in the examples below parts listed parts by weight.

example 1

60 parts of a commercial pulp are mixed with 1000 parts of one 18% sodium hydroxide solution added and mixed for 45 minutes. After that time will the excess lye is sucked off through a glass frit. The remaining one moist, strongly alkaline alkaline cellulose cake is then mixed with a solution that 30 parts of N- (2-sulfatoethyl) piperazine sulfate and 300 parts of 18% sodium hydroxide solution contains, slurried and vacuumed again. The alkali cellulose so produced leave to ripen for 60 minutes at 80 ° C, cool to 15 ° C and set 20 Add carbon disulphide so that the temperature does not exceed 30 ° C. After a reaction time of 45 minutes, the yellowish mass is carried into 450 parts of a 4% sodium hydroxide solution and mixes the xanthate to a homogeneous, viscous mass. After degassing, the spinning mass is made using the usual viscose spinning process into a bath containing sulfuric acid, sodium and zinc sulfate spun, stretched in acidic baths, cut, washed, prepared and dried. 10 parts of these dry viscose fibers are then in a dyeing machine mixed with 100 parts of water. The mixture is heated to 60 ° C. and metered overall 0.1 parts of a 50% electrolyte-containing (predominantly sodium-containing) Dye powder of the formula known from DE-A-19 43 904

over a period of 30 min. After a follow-up time of 5 min drained colorless remaining liquor and the material by usual methods washed out and dried. A deep red color is obtained with a strong color very good fastness properties.

Example 2

10 parts of the viscose fibers modified according to Example 1 are in transferred to a dyeing machine and in a liquor ratio of 1:10 with a treated aqueous liquor, which - based on the weight of the dry Ware - 0.1 parts of a reactive dye of the formula known from the DE-A-24 12 964

contains dissolved. The fiber mixture is dyed at 60 ° C. for 30 minutes. The The dyeing thus produced is further treated by rinsing and soaping in the usual way. A deep blue color with very good results is obtained Fastness to use.  

Example 3

100 parts of a moist, strongly alkaline as described in Example 1 Alkalicellulose cake with 3 parts of an aqueous solution, the 50 parts 3-chloro-2-hydroxypropyltrimethylammonium chloride and 50 parts water contains, offset by spraying. Then proceed accordingly Example 1 further. After degassing, the spinning mass is after usual viscose spinning in a sulfuric acid, sodium and zinc sulfate containing bath spun into fibers, stretched in acid baths, cut, washed, prepared and dried.

After weaving you get a textile viscose fabric that is directly in one Dyeing process can be processed by the block method. For this purpose, an aqueous dye solution containing 20 parts of the in 1000 parts by volume Dye of the formula

known from EP-A-0 158 233, Example 1, and 3 parts of a commercially available contains non-ionic wetting agents dissolved, by means of a foulard with a Fleet absorption of 80%, based on the weight of the fabric, at 25 ° C applied to the fabric. The fabric padded with the dye solution is wrapped on a dock, wrapped in plastic wrap and during 4 Let sit at 40 to 50 ° C for hours and then with cold and hot Water, which may contain a commercial surfactant, and optionally then rinsed again with cold water and dried.

A strong, uniformly colored yellow color is obtained, the good one General fastness properties, especially good rub and light fastness properties.  

Example 4

The procedure is as described in Example 1 and sprayed Alkali cellulose obtained with 4 parts of an alkaline solution of 50 parts Glycidyltrimethylammonium chloride in 50 parts of an 18% sodium hydroxide solution. With the cellulose obtained is carried out as described in Example 1. After degassing, spinning, stretching, cutting, washing and drying a fiber is obtained which is dyed by a customary drawing process can be. For this, 20 parts of the pretreated viscose fiber are combined in one Dyeing machine treated with 200 parts of an aqueous liquor, which - based on the weight of the dry goods - 1.5% of the reactive dye of the formula

known from EP-A-0 061 151, example 4, in commercial form and Contains texture. The fiber is dyed with this liquor at 60 ° C. for 30 minutes. The dyeing thus produced is further treated by rinsing and soapy in the usual way. The result is a lively orange color with the for Reactive dyes usually have good fastness properties.

Example 5

From an alkali cellulose prepared according to the information in Example 4 after the usual process steps for spin viscose a fiber material modified viscose manufactured without salt and alkali additives in one Exhaust process is colored reactive. For this you wrap 30 parts Viscose fiber on a bobbin and treats the yarn in one Yarn dyeing machine, the 450 parts (based on the weight of the goods) one Fleet, the 0.6 parts, based on the initial weight of the goods, one electrolyte-containing dye (predominantly containing sodium chloride) of the general  formula

known from DE-A-28 40 380, Example 1, contains and heats to 60 ° C, the fleet alternating from the inside out and the outside in is pumped. After 60 minutes at this temperature, the liquor is drained off and rinsed and washes the color obtained after the usual conditions. Man receives a yellow colored fiber with the general good fastness properties for Reactive dyes.

Further examples

The procedure for modifying the viscose is as described in the example 4 and dyes using the reactive dyes listed below by conventional methods, but without alkali or salt additives and receives similar good results, as in the previous examples.

Claims (7)

1. A process for the production of modified regenerated cellulose fibers, characterized in that cellulose is first broken down under alkaline conditions (alkali cellulose), then an amine of the formulas (1a), (1b), (1c) or (1d) or an oxazolidinone, in which mean:
Z is hydrogen, C₁-C₄-alkyl, which can be substituted by 1 to 2 OH groups, or alkylene- (ER) - _m ,
ER is an ester group or a ClCH₂ group;
A and N together with 1 or 2 alkylene groups of 1 to 4 carbon atoms form the remainder of a 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 C atoms, which can be substituted by 1 or 2 substituents from the group amino, sulfo, hydroxy, sulfato, phosphato and carboxy, or an alkyl group of 3 to 8 Carbon atoms which are interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH- and which may 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 ^{(-) have} one of the meanings given above,
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 carbon atoms,
which can be substituted by 1 or 2 hydroxyl groups, or is a straight-chain or branched alkylene radical of 3 to 8 carbon atoms which is interrupted by 1 or 2 hetero groups selected from the groups -O- and -NH-;
alk is a straight-chain or branched alkylene radical of 2 to 6 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; and in what
the amino, hydroxyl and ester groups can both be bound to a primary, secondary or tertiary carbon atom of the alkylene radical, add and allow the mixture to linger for 15 minutes to 6 hours, then reacted with carbon disulfide to form the xanthate and spun into fibers. 2. The method according to claim 1, characterized in that the amine N- (β-sulfatoethyl) piperazine, N- [β- (β'-sulfatoethoxy) ethyl] piperazine, N- (γ-sulfato-β-hydroxypropyl) piperidine, N- (γ-sulfato-β-hydroxypropyl) - pyrrolidine, N-β-sulfatoethyl-piperidine, 2-sulfato-3-hydroxy-1-aminopropane, 3- Sulfato-2-hydroxy-1-aminopropane, 1-sulfato-3-hydroxy-2-aminopropane, 3-hydroxy-1-sulfato-2-aminopropane, 2,3-disulfato-1-aminopropane or 1,3- Disulfato-2-aminopropane, N-2 (sulfatoethyl) piperazine sulfate, Glycidyltrimethylammonium chloride, aziridine, N-hydroxyethyl aziridine or Is oxazolidinone. 3. The method according to claim 1, characterized in that the amine has a 3-chloro-2-hydroxypropyl residue. 4. The method according to at least one of claims 1 to 3, characterized characterized in that the amine in an amount of 1 to 20, preferably 1 to 8, percent by weight, based on the cellulose content of the alkali cellulose mass, is added. 5. The method according to at least one of claims 1 to 4, characterized characterized in that the amine / alkali cellulose mixture for a period of 1 up to 3 hours and at a temperature of 40 to 80 ° C.   6. Process for producing a dyed or printed textile material from regenerated cellulose fibers, characterized in that one after one or more of claims 1 to 5 Cellulose regenerated fiber material processed into a woven or knitted fabric and this with one or more reactive dyes in the absence of additional electrolyte salt or alkali colors or prints. 7. The method according to claim 6, characterized in that the modified cellulose regenerated fiber material printed by the ink-jet method becomes.