CA2152976A1

CA2152976A1 - Production of aminated regenerated cellulose fibers

Info

Publication number: CA2152976A1
Application number: CA002152976A
Authority: CA
Inventors: Andreas Schrell; Werner Hubert Russ; Bernd Huber
Original assignee: Individual
Current assignee: Hoechst AG
Priority date: 1994-06-30
Filing date: 1995-06-29
Publication date: 1995-12-31
Also published as: DE4422865A1; JPH08113821A; BR9503023A; FI953197A; FI953197A0; KR960001221A; EP0692558A1; CN1120080A

Abstract

Production of aminated regenerated cellulose fibers Modified regenerated cellulose fiber are produced by adding a modifier to a cellulose solution and spinning fibers from the solution or by adding a modifier to a viscose solution and spinning fibers therefrom by the viscose spinning process, the modifier being a polyethyl-eneimine or a reaction product of polyethyleneimine with a bifunctional alkylating agent.

Description

21 ~;29 76 DESCRIPTION

Productlon of amlnated regenerated cellulose flbers The present lnvention relates to the fleld of the textlle dyelng of vlscose flbers.
Vlscose flbers, also known as regenerated cellulose flbers, have essentlally the same dyelng characterlstlcs as cotton flbers. At present, the dyelng of natural or regener-ated celluloslc flbers regulres alkall-donatlng agents and also electrolytes ln order that satlsfactory flxatlon results may be obtalned wlth reactlve dyes. It ls preclsely these needed addltlons, however, whlch are ecologlcally unaccept-able. The future wlll therefore lncreaslngly belong to regen-erated cellulose flbers whlch are dyeable wlthout salt and alkall. One posslbllity ls to modlfy vlscose flbers ln such a way that they resemble anlmal flbers, such as wool or sllk, ln thelr chemlcal behavlor and can be dyed under neutral condl-tlons wlth anlonic dyes wlthout further salt or alkall addl-tlons.
Modlflcatlons of vlscose have already been descrlbed in the llterature. US-A-3 793 419 for lnstance, descrlbes a process for producing vlscose flbers havlng modlfled dyelng characterlstlcs. However, the process ls extremely compll-cated and uneconomlcal. In addition, long-chain polyamlneamldes are used, whlch severely alter the natlve character of the flber because of thelr predomlnantly - 21 ~29 7~

- la -lipophlllc structure. Thls ls evldent for example from the use of dlsperse dyes ln the later dyelng.
Also known ls the addltlon of amlne compounds for lmprovlng the physlcal propertles of vlscose flbers. As well as a multlpllclty of mono- or ollgomerlc amlnes, the lltera-ture also describes polymerlc compounds such as polyethoxy-lated amlnes or polyalkylenepolyamlnes. A revlew of 21 ~29 7~

components and their effects can be found in Gotze, Chemiefasern nach dem Viskoseverfahren, Springer Verlag 1967, p. 635 ff.

Similarly, US-A-3 305 377 describes aminalized fibers.
The additions are aminoethyl- and diethylaminoethyl-celluloses in high concentration, and the dyeing is done exclusively with acid dyes.

us-A-4 806 126, us-A-4 988 365 and CA-A-2 084 585 de-scribe various amino-containing compounds for use as agents for pretreating the surface of cellulose fiber textiles before dyeing. The di~advantage of such proces-ses is an additional process step and yellowing of the fabric.

It is an object of the present invention to provide modified viscose fibers in order that textiles composed of such fibers may be dyed with reactive dyes without salt and alkali and the aforementioned disadvantages of the prior art may be avoided.

It has been found that this object is surprisingly achieved by admixture of below-defined modifiers to a viscose sp;nn;ng solution or a cellulose solution.

The fibers of the present invention can be dyed with reactive dyes without additions of alkali and salts.
Similarly, dyeing with acid dyes is easily possible.

In addition, these fibers, spun by the viscose process, have higher bre~k; ng strengths and bre~k; ng extension compared with conventional viscose fibers not only in the dry but also in the wet state.

The present invention accordingly provides modified regenerated cellulose fibers produced by adding a modi-fier to a cellulose solution and sp;nn;ng fibers from the solution, or by ~; ng a modifier to a viscose solution and sp;nn;ng fibers by the viscose sp;nn;ng process, which comprises using as the modifier a polyethyleneimine of the formula (I) H-(CH2-CH2-N-)a-CH2-cH2-l-H (I)~
X X

where X is hydrogen or a radical of the formula - (CH2-CH2-NH) c-H' a is from 50 to 600, and c is from 0 to 50, or a reaction product of a polyethyleneimine of the formula (I) with a bifunctional alkylating agent of the formula (II) A-Z-A (II) where A is a group of the formula -CH2-Y, wherein Y is a substituent that is detachable as an anion, in particular chlorine, bromine, iodine or -OH, or a group that is detachable as an anion, in particular the sulfato group or a sulfonyloxy group, in parti-cular phenylsulfonyloxy or p-tolylsulfonyloxy, or the epoxy group /o\

and Z is a direct bond or a bivalent straight-chain or branched radical of the formula (III) -CnH2n- (III) where n is from 1 to 4, a bivalent radical of the formula (IV) ~CmH2m~D~CmH2m~ (IV) 2l~2976 where m i8 1 or 2 and D is -O-, -S-, -NH-, -CO-, -SO-, -SO2- or phenylene;

or a polymeric reaction product of an epihalohydrin with ammonia or with an amine of the formula (V) R N\ ( V ) where A is hydrogen, alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms, R i~ alkyl having 1 to 5 carbon atoms, hydroxy-alkyl having 1 to 5 carbon atoms, a group of the formula -- a I ky I en-N~--a I ky I en-N-A
A n H

a group of the formula -- a I ky I en-X-a I ky I eln-N -- a I ky I en-X-o I ky I en-N-A
A, n H

where n is from O to 5, and X i8 oxygen or ~ulfur;

or R and A are together -a I ky I en \
NH
-a I ky I en /

or an aliphatic heterocycle with or without a further hetero atom from the group 0, S and N, and alkylen i~ in each case C1-C6-alkylene, preferably C2-C3-alkylene;

2l~297~
_ -- 5 or a water-soluble organic polyba~e preparable by reaction of a mixture con~i6ting of 1 part by weight of one or more compounds of the formula VI
R20Co_R10_CooH (VI) and of 0.5 to 1.5 partR by weight of one or more polyalkyleneimines of the formula VII
H2N (CH2), --tN-(CH2)~--N--(CH2), ~ NH2 (Vll) with 0.01 to 5% by weight, ba~ed on the mixture of the compounds of the formulae VI and VII, of one or more bifunctional alkylating agentR, in which case R10 is a direct bond, an alkylene radical having 1 to 10 carbon atoms, an alkenylene radical having 2 to 10 carbon atoms or a phenylene radical, R20 i8 a radical of the formula VIII

H2N-(cH2)u-NH~(cH2)u-NH ) w (Vl I I ) or a radical of the formula IX

2N (CH2)v~l~(CH2)V-- I-- (CH2)V tNH- (IX) T1 and T2 are each hydrogen or the radical ((CH2)~-NH)y~H~
T3 and T4 are each hydrogen or the radical ((CH2)v-NH)z-H, 8, U and v are each 2, 3, 4 or 5, w is 0, 1, 2 or 3, t, x, y and z are each a number ~ufficiently large that the compound of the formula VII or the radical of the formula IX have an average molecular weight of 2000 to 30000.

21 529 7~

The polyethyleneimine of the formula (I) is a molecule containing -NH2, ~NH and -N~ building blocks joined together by ethylene groups. Altogether, the poly-ethyleneimine contains about 50 to 600 ethyleneimine units. In customary commercial products primary, second-ary and tertiary nitrogen functions are in a numerical ratio of about 1:2:1. The reaction with the polyethylene-imine of the formula (I) can in principle be carried out with any known bifunctional alkylating agent.

Preference for the reaction with polyethyleneimine is given to those bifunctional alkylating agents in which each A is a group of the formula -CH2-Y joined together by a bridge member of the formula (IV) or those in which one A is a group of the formula -CH2-Y attached directly to an epoxy group.

Examples of such bifunctional alkylating agents are epichlorohydrin, glycide, 1,3-dichloropropan-2-ol, dichlorodiethyl ether, ~,~'-dichlorodiethylamine, ~
dichlorodiethyl sulfide, ~,~'-dichlorodiethyl sulfoxide, ~,~'-dichlorodiethyl sulfone, ~,~'-disulfatoethyl ether, ~,~'-diphenylsulfonyloxyethyl ether, meta- or para-diepoxyethylbenzene, meta- or para-diepoxypropylbenzene, diepoxybutane, diepoxy-2-methylbutane and diepoxypropyl-amine.

The polyethyleneimine and the bifunctional alkylating agent are reacted with each other in a weight ratio of 100:0.01 to 100:2, preferably 100:0.1 to 100:1.

The reaction products of an epihalohydrin with NH3 or an amine of the formula (V) to be used according to the present invention are prepared by reacting an epihalo-hydrin, preferably epichlorohydrin, with ammonia or an amine of the formula (V) at temperatures of about 60 to 70C in water or a lower alcohol as solvent. These amines may optionally also be quaternized with Cl-C4-alkyl groups, preferably Cl-C3-alkyl groups. The quaternization 21 ~29 76 -can be carried out wlth alkyl halldes, preferably alkyl chlor-ldes, or dlalkylsulfonates by known methods.
Examples of sultable amlnes conformlng to the above-lndlcated formula (V) are monomethylamlne, monoethylamlne, monopropylamlne, monolsopropylamlne, monobutylamlne, mono-lsobutylamlne, monooxyethylamlne, monooxypropylamlne, ethylenedlamlne, dlamlnopropanes, dlamlnobutanes, dlamlno-hexanes, 3,3'-dlaminodipropyl ether, piperazine, monooxyethyl-ethylenedlamlne, dloxyethylethylenedlamlne, diethylenetrl-amine, dlpropylenetrlamlne and trlethylenetetramine. Thepreparatlon of these compounds ls descrlbed ln detall ln US-A-3 544 363.
Water-soluble, organlc polybases are descrlbed ln US-A 4 977 239. Preference ls glven to a mlxture obtalned by reactlng polyethylenelmlne wlth the condensatlon product of diethylenetriamine and adipic acid (1:1) and also ethanolic epichlorohydrin, as described in Example I of US-A-4 977 239.
In order that the modifiers remain occluded in the fibers and are not washed out in the course of the subsequent coagulation, stretching and washlng processes, relatlvely hlgh molecular welghts and hence relatlvely long molecular chalns are regulred. To obtaln an lmprovement ln the physlcal fiber propertles lt is not necessary for the modlfiers to remaln ln the flbers, but an lmprovement ln the dyelng propertles can only be achleved lf the modiflers remaln ln the flbers.
The mlnlmum molecular weight for the modifiers of the present inventlon to become occluded ln the flbers to a suffl-21529 7~

- 7a -clent degree ls 400; excellent results are obtalned wlth molecular welghts above 1000.
The amount of modlflers occluded ln the vlscose flbers of the present lnventlon ls advantageously 0.1 to 20%
by welght, preferably 1 to 10% by welght, based on the total 21 S2~ 7~

weight of the viscose fibers modified according to the present invention. The decisive factor for the amount of modifier to be used is the level of amino groups.

If the fibers of the present invention are produced by the viscose sp;nn;ng process, first the cellulose is subjected to an alkaline digestion (alkalicellulose), then reacted with carbon disulfide, and dissolved in water or dilute alkali metal hydroxide solution, and then this viscose solution has the modifier added to it. In an alternative embodiment, the modifier is added directly to the alkalizing alkali metal hydroxide solution and the modified alkalicellulose is then reacted with carbon disulfide to form the xanthate. The addition of the modifier during the alkalizing enh~nces the reactivity of the cellulose for the xanthation. This permits the production of a spinning solution of better filterability and a reduction in the CS2 or alkali metal hydroxide solution requirements. The reaction with carbon disulfide is advantageously carried out at temperatures of 15 to 30C. After the dissolving, the modified cellulose fibers of the present invention are obtained by subsequent 8p; nn; ng into an acid spin bath.

If the fibers of the present invention are produced by other customary processes for producing cellulosic fibers from solution familiar to the person skilled in the art, for example the cupro process, the Lyocell process and the process via low-substituted cellulose ethers, then the cellulose is dissolved in a ~uitable organic solvent, admixed with the modifier and spun into fibers directly from the solution. The most favorable option is addition immediately prior to the sp;nn;ng, in which case the mixing and homogeneous distribution can be effected by means of known mixing systems with the aid of static or dynamic mixing systems. However, the addition can also take place in any desired preliminary stage of sp;nn;ng dope production.

21S297~

The advantage of the modifier of the present invention i8 the simple technical use, since it can be incorporated directly or as an aqueous preparation having a strength of more than 50%. This makes it possible, on the one hand, to achieve high levels of occlusion and, on the other, to avoid negative consequences for physical fiber properties due to dilution effects.

The modifiers of the present invention are particularly suitable for use with viscose fibers, since not only the dyeing characteristics but also the physical properties of the fibers are improved.
Following the addition, the sp;nn;ng solutions can be further processed by the known proce~ses of fiber manu-facture. Serious changes to the processes are not neces-sary. In the case of the viscose sp;nn;ng process, theprocess changes known from the use of modifiers, for example an increased stretch ratio, can be used with success.

There is no deterioration in the filterability of the viscose compared with addition-free samples, 80 that no plugging of the spinneret is observed in the course of the spinning process. If the modifier is added during the alkalization, an improvement in the filterability is observed. The forming of the viscose is carried out by customary and known methods, for example by means of spinnerets and a subsequent coagulation bath with or without further aftertreatment baths.

The modified regenerated cellulose fibers produced according to the present invention can after processing into woven and knitted fabrics be dyed with reactive dyes by means of a very wide range of processes, such as exhaust, padding and modern printing processes, including inkjet processes, without the use of additional electro-lyte salt or alkali.

The fibers of the present invention have significantly 21 S29 7~

more affinity for reactive dyes than conventional viscose fibers, but otherwise hardly differ from conventional viscose fibers in the otherwise desired properties, such as hand.

The fibers of the present invention spun by the vi~cose process or from a solution are dyeable with reactive dyes without additional alkali and salt and also with acid dyes. The cellulose fibers of the invention spun by the viscose process, in addition, are notable for improved dry and wet strengths.

The textile modified fiber material which iB used for subsequent dyeing processes can be present in all pro-cessing states, for instance as yarn, staple, slubbing and piece goods (fabrics).

The modified textile fiber materials are dyed according to the present invention analogously to known processes for dyeing or printing fiber materials with water-soluble textile dyes and through the use of the temperature ranges and customary dyestuff quantities known for this purpose, except that the dyebaths, padding liquors, print pastes or inkjet formulations require no addition of alkaline compounds, as customary for fixing fiber-reactive dyes, nor customary additions of electrolyte salts.

Suitable dyeing processes include for example the various exhaust processes, such as dyeing on the jigger or on the reel beck or dyeing from long or short liquor, dyeing in jet dyeing machines, dyeing by short-time pad-batch processes or by a pad-superheated steam fixation proce~s.
Suitable printing processes include conventional printing techni~ues, including inkjet printing and transfer printing.

The dyes which are used for dyeing the modified cellulose are generally anionic in nature. Of particular suit-21 ~29 76 ability are the fiber-reactive textile dyes which are capable of reacting with hydroxyl groups, for example of cellulose, or amino and thiol groups, for example of wool and silk, of synthetic polymers, such as polyamides, or else the celluloses aminated according to the present invention, to form a covalent bond. Suitable fiber-reactive components on the textile dyes include in particular sulfatoethylsulfonyl, vinylsulfonyl, chloro-triazinyl and fluorotriazinyl and also combinations thereof.

Suitable reactive dyes for dyeing or printing cellulose fibers modified according to the present invention include all water-soluble, preferably anionic, dyes which preferably have one or more sulfo and/or carboxyl groups and which contain fiber-reactive groups. They can belong to the class of the azoic dyes, the class of the direct dyes, the class of the vat dyes and the class of the acid dyes, the copper complex, cobalt complex and chromium complex dyes, copper and nickel phthalocyanine dyes, anthraquinone, copper formazan, azomethine, nitroaryl, dioxazine, triphendioxazine, phenazine and stilbene dyes.
These dyes have been numerously described in the litera-ture, for example in -EP-A-0 513 656, and are perfectly familiar to the person skilled in the art.

Unless otherwise stated, parts in the Examples which follow are by weight.

Example 1 2800 parts of a spinning viscose having a cellulose content of 8.9%, an alkali content of 5% and a viscosity of 38 falling-ball seconds over 20 cm at 30C are admixed with 80 parts of a polyethyleneimine having an average molecular weight of 3000 to 5000 and reacted with epichlorohydrin (24% strength). The modified poly-ethyleneimine was prepared as described in Example 1 of US Patent 4,588,413.
After devolatilization the sp;nn;ng dope is spun by ~ ~ - 12 - 21 S29 7 customary viscose sp; nn; ng processes into a bath which contains sulfuric acid, sodium ~ulfate and zinc sulfate to form fibers, which are stretched in acid baths, cut, washed, spinfinished and dried.

10 parts of these dry viscose fibers are then admixed in a dyeing apparatus with 100 parts of water The tempera-ture is raised to 60C and a total of 0.1 part of a 50%
strength electrolyte (pre~nm;n~ntly sodium)-cont~;n;ng dye powder of the formula, known from DE-A-19 43 904 o NaO~S 503No is metered in over a period of 30 minutes. Following a further liquor circulation period of 5 minutes the remaining, almost colorless liquor is dropped and the material is conventionally washed and dried. The result obtained is a strong and deep red dyeing having very good use fastness properties.

Example 2 10 parts of the viscose fiber~ modified as described in Example 1 are transferred into a dyeing apparatus and treated in a liquor ratio of 10:1 with an aqueous liquor which, based on the weight of the dry fibers, contain~ in solution 0.1 part of a reactive dye of the formula, known from DE-A-24 12 964 SO~Na ~ O`'~~~OSO~Na The flber mlxture ls dyed at 60C for 30 mlnutes. The dyeing thus produced 18 further treated by rlnslng and soaplng ln a conventlonal manner. The result obtalned ls a deep blue dyelng havlng very good use fastness propertles.

Example 3 A vlscose splnnlng dope ls prepared as descrlbed ln Example 1 uslng a reactlon product of polyethylenelmlne (mol-ecular mass 3000 to 5000) and eplchlorohydrln.
After devolatlllzatlon the splnnlng solutlon ls spun by cus-tomary vlscose splnnlng processes lnto a bath contalnlngsulfurlc acld, sodlum sulfate and zlnc sulfate to form flbers, whlch are stretched ln acld baths, cut, washed, splnflnlshed and drled.
Weavlng glves a textlle vlscose fabrlc whlch can be further processed dlrectly ln a pad-dyelng process. For thls the fabrlc has applled to lt at 25C an agueous dye solutlon whlch, per 1000 parts by volume, contalns in solutlon 20 parts 21~29 7~

- 13a -of the dye of the formula N~D3S ~ N ~ 002Na Ho>l\N~N\~
30~\ll ~SO3Na o known from EP-A-O 158 233, Example 1, and 3 parts of a commer-clal nonionic wettlng agent, by means of a 215297~
-pad-mangle to a liquor pickup of 80%, based on weight of fiber. The fabric padded with the dye solution is wound onto a batching roller, wrapped in plastic film, left at from 40 to 50C for 4 hours and then rinsed with cold and hot water, which may contain a commercial surfactant, and if necessary subsequently rinsed once more with cold water and dried.

The result obtained is a strong level yellow dyeing which has good all round fastness properties, especially good rub and light fastness properties.

Example 4 A viscose spinning dope is prepared as described in Example 1 using a reaction product of polyethyleneimine (molecular mass 3000 to 5000) and epichlorohydrin.
Devolatilization, spi nn; ng, stretching, cutting, washing and drying gives a fiber which can be dyed by a conven-tional exhaust process. To this end 20 parts of the pretreated viscose fiber are treated in a dyeing appara-tus with 200 parts of an aqueous liquor which, based on weight of fiber, contains 1.5% of the reactive dye of the formula NaO3SO "~~~~S ~ oO~S ~ NHCOCH3 known from EP-A-O 061 151, Example 4, in commercial form and consistency. The fiber is dyed with this liquor at 60C for 30 min. The dyeing thus obtained i8 further treated by rinsing and soaping in a conventional manner.
The result obtained is a vivid orange dyeing having the customary good fastness properties of reactive dyes.

2ls297~

Example 5 A viscose sp;nn;ng dope is prepared as described in Example 1 using a reaction product of polyethyleneimine (molecular mass 3000 to 5000) and epichlorohydrin.
An alkali cellulose produced as described in Example 4 is used to produce, by the process steps customary for spinning viscoses, a modified viscose fiber material which can be reactively dyed in an exhaust process without salt or alkali. To this end, 30 parts of viscose fiber are wound to a package and the yarn is treated in a yarn dyeing apparatus which contains 450 parts (based on weight of fiber) of a liquor which contains 0.6 part, based on weight of fiber, of an electrolyte (pre~s~inAntly sodium chloride)-contA;n;ng dye of formula S 0 3 N a ~ ~

N a 0 3 S --~J

known from DE-A-28 40 380, Example 1, and is heated to 60C, the liquor being pumped alternately in to out and out to in. After 60 min at this temperature the liquor is dropped, and the dyeing obtained is rinsed and washed under the customary conditions. The result obtained is a level yellow fiber having the generally good fastness properties of reactive dyes.

Example 6 A viscose sp;nn;ng dope i~ prepared a~ described in Example 1 using a polybase prepared as described in Example 1 Of US-A-4 977 239 from polyethyleneimine, a diethylenetriamine - adipic acid conden~ation product (1:1) and ethanolic epichlorohydrin.

21S297~

Devolatilization, sp;nn;ng, stretching, cutting, w~sh;ng and drying gives a fiber which can be dyed by a conven-tional exhaust process. To this end 20 parts of the pretreated visco~e fiber are treated in a dyeing appara-tus with 200 parts of an aqueous liquor which, based onweight of fiber, contains 1.5% of the reactive dye of the formula NaO3SO "~~~'5 ~ ~O35 NHCOCH3 known from EP-A-0 061 151, Example 4, in commercial form and consistency. The fiber i8 dyed with this liquor at 60C for 30 min. The dyeing thus obtained is further treated by rinsing and soaping in a conventional manner.
The result obtained is a vivid orange dyeing having the customary good fastness properties of reactive dyes.

Further examples Example 6 is repeated using the reactive dyes listed hereinafter, which are applied by conventional processes but without alkali or salt additions. The results ob-tained are similar.

2ls297~

) OH SO~H

H2H - CO - NH ~ N-N ~ oran~e SO,H ~
8) S03H ~ NH ~ ~ Cl HO~S ~ N-N ~
~ HO~S ~ NH - CO ~ N ~ oran~e SOSH SO~H N Cl 9) 50~H OH
H~C - CO - NN ~ N-N ~ N
HO~S ~ NH ~ \N SO~N scarlet NH

10) SO~H OH

CH~O ~ N-N ~
H0~5 ~ NH - CO ~ ~ ~ Cl scarlet SO~H HO NH - CO ~ N ~ Cl H; S ~ ~ Cl 50~H Cl SO~H HO NH y ~ N
12) ~ H;~S ~ Cl red 21 ~29 7~

13) ~C2 - C0 ~[~ C0 ~35 0~ - Cll ~ - Cl~ 2 - O - 50~1 ~o ~ 50~H red 4) /I SO~H I 2 Cu-c 52 IIH~S02 ~ Ctl2 - CH2 - O - SO~H
_ 2 turquolse CuPc = copper phthalocyanine 1 5) /I SO~Il I 2 N I ~c - _ SO2 - NH~so2 - CH2 - CH2 - O - SO~H

NiPc = nickel phthalocyanine 16) HO NH2 H055 - O - CH2 - CH2 - 02S ~3 HO 5~SO H
I

~S02 ~ CH2 - CH2 - O - SO~H

dark blue /cu \
(17) / ~ \

HO~S -- O - CH2 -- CH2 -- 025~Ho~Z~ H~!~ COOH

SO~H
a"tl " acile 21s2976 H O N H ~ ~ C I
HO~S - O - CH2 - CHS - 502~H;~s~ C I red Examples of dyeing with direct dyes Example 6 is repeated using the below-listed direct dyes in conventional processes, but without salt additions.
The resulting dyeings are deep and have good general fastness properties:
C.I. Direct Blue 108 C.I. No. 51 320;
C.I. Direct Blue 199 of the formula /SO~NH4 C u P c Pc = phthalocyanine (52NH2)3 C.I. Direct Yellow 34 C.I. No. 29 060;
C.I. Direct Red 79 C.I. No. 29 065;
C.I. Direct Violet 9 C.I. No. 27 885;
C.I. Direct Brown 126 C.I. No. 29 085;
C.I. Direct Orange 69 C.I. No. 29 055;
C.I. Acid Blue 113 C.I. No. 26 360;
C.I. Acid Blue 40 C.I. No. 26 125

Claims

1) Modified regenerated cellulose fiber produced by adding a modifier to a cellulose solution and spinn-ing fibers from the solution, or by adding a modi-fier to a viscose solution and spinning fibers by the viscose spinning process, which comprises using as the modifier a polyethyleneimine of the formula (I) (I), where X is hydrogen or a radical of the formula - (CH2-CH2-NH) c-H, a is from 50 to 600, and c is from 0 to 50, or a reaction product of a polyethyleneimine of the formula (I) with a bifunctional alkylating agent of the formula (II) A-Z-A (II) where A is a group of the formula -CH2-Y, wherein Y
is a substituent or a group that is detachable as an anion, and Z is a direct bond or a bivalent straight-chain or branched radical of the formula (III) -CnH2n- (III) where n is from 1 to 4, a bivalent radical of the formula (IV) -CmH2m-D-CmH2m- (IV) where m is 1 or 2 and D is -O-, -S-, -NH-, -CO-, -SO-, -SO2- or phenylene;

or a polymeric reaction product of an epihalo-hydrin with ammonia or with an amine of the formula (V) (V) where A is hydrogen, alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms, R is alkyl having 1 to 5 carbon atoms, hydroxyalkyl having 1 to 5 carbon atoms, a group of the formula a group of the formula where n is from 0 to 5, and X is oxygen or sulfur;

or R and A are together or an aliphatic heterocycle with or without a further hetero atom from the group O, S and N, and alkylen is in each case C1-C6-alkylene;
or a water-soluble organic polybase preparable by reaction of a mixture consisting of 1 part by weight of one or more compounds of the formula VI
R20CO-R10-COOH (VI) and of 0.5 to 1.5 parts by weight of one or more polyalkyleneimines of the formula VII
(VII) with 0.01 to 5% by weight, based on the mixture of the compounds of the formulae VI and VII, of one or more bifunctional alkylating agents, in which case R10 is a direct bond, an alkylene radical having 1 to 10 carbon atoms, an alkeny-lene radical having 2 to 10 carbon atoms or a phenylene radical, R20 is a radical of the formula VIII

H2N-(CH2)u-NH ? (CH2)u-NH )-w (V I I I ) or a radical of the formula IX
(IX) T1 and T2 are each hydrogen or the radical ((CH2)s-NH)y-H, T3 and T4 are each hydrogen or the radical ((CH2)v-NH)z-H, s, u and v are each 2, 3, 4 or 5, w is 0, 1, 2 or 3, t, x, y and z are each a number sufficiently large that the compound of the formula VII or the radical of the formula IX have an average molecular weight of 2000 to 30000.

2) The modified regenerated cellulose fiber of claim 1 wherefor Y is chlorine, bromine, iodine, -OH, a sulfato group, a sulfonyloxy group, preferably a phenylsulfonyloxy group or p-tolylsulfonyloxy group, or the epoxy group

3) The modified regenerated cellulose fiber of claim 1 or 2 wherefor a reaction product of a polyethylene-imine of the formula (I) with a bifunctional alkyl-ating agent selected from the group consisting of epichlorohydrin, glycide, 1,3-dichloropropan-2-ol, .beta.,.beta.'-dichlorodiethyl ether, .beta.,.beta.'-dichlorodiethyl-amine, .beta.,.beta.'-dichlorodiethyl sulfide, .beta.,.beta.'-dichloro-diethyl sulfoxide, .beta.,.beta.'-dichlorodiethyl sulfone, .beta.,.beta.'-disulfatoethylether, .beta.,.beta.'-diphenylsulfonyloxy-ethyl ether, meta- or para-diepoxyethylbenzene, meta- or para-diepoxypropylbenzene, diepoxybutane, diepoxy-2-methylbutane and diepoxypropylamine is used.

4) The modified regenerated cellulose fiber of claim 3 wherefor the polyethyleneimine of the formula (I) has been reacted with the bifunctional alkylating agent in a weight ratio of 100:0.01 to 100:2, preferably 100:0.1 to 100:1.

5) The modified regenerated cellulose fiber of at least one of claims 1 to 4 wherefor the modifier has a molecular weight of at least 1000.

6) The modified regenerated cellulose fiber of at least one of claims 1 to 5 wherein the amount of occluded modifier is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the modified cellulose fiber.

7) The modified regenerated cellulose fiber of at least one of claims 1 to 6, spun by a viscose spinning process.

8) The modified regenerated cellulose fiber of at least one of claims 1 to 6, spun by the cupro process or by the Lyocell process.

9) A process for dyeing and printing fiber materials with water-soluble textile dyes, which comprises carrying out the dyeing with a dye solution which is free of additional electrolyte salts and additional alkali and using a cellulose fiber material modified as claimed in at least one of claims 1 to 8.

10) The process of claim 9 wherein the dye contains a fiber-reactive group.

11) The process of claim 9 wherein the dye is a direct dye.