PH26570A - Pad thermofix process for dyeing and printing with reactive dyes and water soluble sulfur dyes in the absence of alkali or reducing agents - Google Patents

Description

! 4 Description : Pad-thermofix process for dyeing and printing : : with reactive dyes and water-soluble sulfur dyes in the absence of alkali or reducing agents

UB-A-4,806,126 discloses that cellulose fibers can be dyed and printed with reactive dyes and even with water-soluble sulfur dyes without alkali or reducing agents if the textile material is pretreated with a wetting agent and . 1 a quaternized reaction product of ; polyethyleneimine with a bifunctional . : ! alkylating agent and then dyed with reactive : } dyes or water-soluble sulfur dyes in a conventional manner, but without alkali or

Ag se reducing agent, and the dyeings are finished by ‘ rinsing, soaping and drying. The conventional ‘ manner covers the cold pad-batch process and j the exhaust dyeing process. i

It has now been found that the dyes mentioned . A

Co ’ i

- - - ‘ i can be fixed on the fiber in this process not only by the cold pad-batch method or by the exhaust method but also by a thermofix method.

The present invention thus provides a process for dyeing and printing with reactive dyes or water-soluble sulfur dyes in the absence of alkali or reducing agents, wherein the textile material to be dyed is pretreated with a wetting agent and an optionally gquaternized reaction product of pelyethyleneimine with a bifunctional alkylating agent, then dyed with 3 oo the dyes mentioned, dried, thermofixed and conventionally finished.

The process according to the invention has the advantage that the long batching times of the cold pad batch process (for example & to 12 hours) are avoided.

An assistant preterred for the pretreatment is known from US 1,588,410. Thére the assistant

— — l,l ' : is exclusively utilized for the aftertreatment af dyeings with reactive dyes. A pretreatment with 'iila assistant and a subsequent dyeing without alkall are not described therein. A process exclusively for aftertreating reactive dyes with compounds orf a aidilar structure is also described in GE raven 2,006.00 00. - Lo The polyethyleneimine required for preparing the preferred pretreating agent conforms to the 1¢ formula 1

HH CH, CH. NH be oH CHe,-- CH, -N 1,1 : J

X whee x ig a radical of the formula - (Cs, CH, -NHD -1, 16 a and b are independently of each other numbers

Tram © to

Ul, the sum a + b being a number from 50 to OY, and

C iz a number from © to 50. -d

_— - ! !

Consequently, the polyethyleneimine used is a molecule containing ~-NH, >NH and -N«< building blocks which are linked with one another by ethylene Lroups. In total the poivethyleneimine contains about bo to Goo ethyleneimineg units. In conventional commeraial products, primarvy, secondary and tertiary nitrogen functions are present in a numzrical ratio of about 1:2:1. le For the reaction with ethyleneimine of the : formula I it is basically possible to use any « ’ known bifunctional alkylating agent. Enown bifunctional alkylating agents conform to the tormala Ii

A ZL = A where A is the radical of an alkylating species and ¥ ia eitner a direct bond or ‘a divalent bridge member.

It is particulary advantazeous to use tor the reaction with the polyvethyleneimines to give

. ’ i the assistants to be used according to the invention those pifunctional alkylating agents of the formula 11 where A is a group of the formula ~OH--Y, where Y is a subsatitutent which is detachable as an anion, in particular chlorine. bromine, iodine or ~-QH, or a group which is detachable as an anion, in particular a sulfato group or a sulfonyloxy group, in particular phenylsulfonyloxy ar p- 1a tolylsulfonyloxy, or an epoxy group # 0 oo 2 and 7, it it is not a direct bond, is a divalent straight-chain or branched radical of the formuata [11

A RA

‘non where nis a number from 1 to 4, & divalent radical of the formula IV “a. (* [.- —- he .- —_ ¢ milo l ‘mm ty

- .-s- -

Co ! where m i= 1 or 2% and I is ~o-. —-3-, -NH-. -CO- , oii or i -, or phenylene.

Freference for ithe reaction with polyethyleneimine to give assistants to be used according to the invention is given to those bifunctional alkylating agents where each A is a group of the formula - CH ~Y which are linked ] with one another by a bridge member of the formula IV, or to those where one otf the 19 radicals A is a group of the formula i : CH -Y which is bonded directly to an epoxy

Eroup.

Examples of such bifunctional alkylating agents are erichlorohydrin, glycide, 1,3

L5 dichioropropan- 2-ol, fp -aichlorodiethyl =ther,

B . Br-dichlorodiethy lamine B B = dichiorodiethyl sulfide, B. pp -dichleorodiethyl sulfoxide, B. Bp -dichiorodiechy!l aulfene, Bs fii-sulratoethyl ether, B. be * . ie diphenylouifonyloxyechyl etner. meta- or paradiepoxyethy lbanzenc, metas or para-— diepoxypropylbeazane, diepoxvibutane, diepoxy-2-

T i , ‘ . § . ; ‘ : ! » methylbutane and diepoxXypropylamine.

To prepare the pretreating agents to he used according to the invention, the polyethyleneimine and the bifunctional alkylating agent are rescted with one another in a weight ratio of from 1W9:@.01 to 1wv:Z.0, preferably 1Wa:@.1 to 10: 1.8.

It must be assumed that in the course of this ; reaction crosslinking bridge members are { oo i hoo 10 incorporated between the rolyethylensimine . chains. An outward sign of this is that the viscosity of the aguesous solutions increases markedly as unorosslinked polysthyleneimine is converted into a product which is crosslinked hy the bifunctional alkylating agent. The: reaction of the polyethyleneimine with the bifunctional alkylating agents can in principle be carried out without solvent. However, for better control over the reaction and better heat dissipation, it is advantageous to carry out the reaction in the presence of an inert — a —-

- —_—————

EE solvent. . Suitable for this purpose are not only organic solvents in which the reactants are soluble, for example lower alcohols, but also in particular water. The reaction can be carried out in the temperature range between -10 and about 160°C. ft is parvicularly advantageous to carry out the reaction at arcund normal room temperature, i.e. within the range between 15 and 48%, The result is a readily controllable reaction which has minimal : energy requirements but leads to very good product quality. The reaction in this form is . : Ln oe . essentially complete in about 1 to Z hours.

To obtain usable assistants which meet particularly tight specifications; that is, To make the process of preparation particularly highly reproducible, it is advantageous after the main reaction has ended to siir the reaction mixture at a defined pi between 9 and “0 19 and at clevated temperature, advantageously between 69 and L0aYC, for several hours, in general © oto 6 hours.

—_— -_ ’ 4 :

The used reaction products of roiyvethvliensimine : with a bifunctional alkylating agent may also be quarernized with Cp-ty-alkyl, preferably Ci~

Cogralkyl, groups. The quaternization can be effected with alkyl halides, preferably alkyl chloriaes, or dialkyl sulirates in a conventional manner.

This above described assistant is applied from an aqueous liquor to the textile material to be dyed or printed together with a wetting and padding assistant customary in the textile

LN ie . . industry. Suitable wetting or padding assistants otf this type are alkanesul fonates, dialkyl sulfosuceinates, dialkyl phosphates or propylene oxide/ethylene oxide block polymers containing from 48 to Bd x by we ight of ethylene cxide., tut in particular nonionic

Compounds. for example ethoxylated nonylphenol.

The textile material can be gray-atate ar

ZQ Freiresated cotton or else cotton-containing © blend fabrics. The process of the invention is rarticularly interesting rar the rretreatment

A — -—

SE or cotton wary yarns with the above-described assistant In the size. Weaving with untreated welt varns and subsequent alkali - or reductant - tree cross-dyeing with reactive dyes or water- 5H soluble sulfur dyes then gives, after the tabric has been washed, a denim effect.

The pretreatment with the assistant tosether with a nonionic wetting agent takes place from an aqueous liquor in a conventional manner by lo padding or by the exhaust mathod at : temperatures of about 20 to 7e°(, rreferably 49 fr. to 66°C,or in the size at from &uC to the : ; boil. The liguor is adjusted to a weakly acid rH, preferably pH 6. The amount of assistant is abour J to 19%, preferably 3 to B80 %. on vejght, of fiber. The amount of wetting agent is preferably 2 oto od pel. The: pretreating

Liquor is subsequently saueezned off, and the

Fabir bo do der led. oe The fabric thus pretreated is tnen overpadded with a padding liquor which contains dyes of the types mentioned. The fahric is then dried. ~ 1b a ha ————— —— { . ‘ ’ thermofixed at 120 to Seu for ©.5 to 1d minute and washed cold and hot.

Suitable reactive dyes for this process ave all known types of reactive dyes which contain groups reaclive towards the hydroxyl groups of the cellulose and which rosct under the dyeing conditions described according Lo the invention, preferably by reaction with the above-described polymers fixed on the cellulose material. The reactive groups are for exanple : groups having readily detachable substitutents

A . . which leave behind an electrophilic residue, ’ such as reactive groups of the vinyl sulfone : tyre, halogen substituted groups of the ring systems quinousline, phthalazine. triazine, pyrimidine or pyridazone, or alkylsulfonyl- substituted reactive E— in the case of sulTonylpveimidine 01 sulfonylibenzothiazole dyes. Specific instances are dyes containing ’ 20 Lhe reactive groups rend ratoethyl sulfone, PB chioroethivi sulfone, B-thicsulfatoethyl sul fone, B-rhosphatouthyl sulfone, chiorotriasiayiaminog, dichliorotriazinylaming,

—¥¥¥S§SS—————— OS chlorotriazinyl diamine, : trichloropyrimidylamino, dichloropyrimidylamino, dichloropyridazinylamnino, : trichloropyridazinylamino, dichloropyridazinyl- carbonylaming, so.chlorobenzothiazel-6-vlamino, 2 methylsul fony lbensethiazol-6-ylamino, 2,0 dichlorogquinoxylin H-ylcarbonylamino or q- chloro -B-methyl -2 -methylsulfonylpyrimid-d- yliamino. ' { . . . , lo Suitable nasic structures ror the reactive dyes

SE } Co are .for example water-soluble ‘azo, disazo, formazan anthragquinone, dioxazine or phthalocyanine dyes. Freference 13 given to the use of water-soluble azo and disazo reactive dyes which may also be metal complex reactive dyes. After dyeing, the fabric 1s finished by vinsing, possibly soaping and drying.

The process acaording to the invention can be “i carried out not only with reactive dyes and walter soluble sulfur dves but also with sulfur val dyes.

- - _ oo : . 3 When dyeing with water-soluble sulfur dyes and sulfur vat dyes, the reducing agents normally uaed for these dyes, for example sodium : hydrogen sulfide, sodium dithionite or sodium sulfide, are dispensed with, which reduces the level of pollutants in the waste water.

The process according to the invention ia suitable not oniy for dyeing textile material, but also for printing. In printing, the textile material is printed with a print paste i : which contains a sighting dye and the cationic

Ke, Lo ) assistant to be used. After drying and fixing, ; the textile material is then croass-dyed with reactive dyes or water-soluble dyes, preferably 156 bry the thermofixz method. Alternatively, the cotton fabric pretreated with the assistant described ig printed with a print paste which contalng thao ive but no alkali. The dye is subsequently fixed by heat treatment at from “a Lis to soate, fhe artertretment ia carried out i . in the same way as in dyeing.

The gossential advantage of the process

-_— eee -_— according te the invewntion is that, as a consequence of the pretreatment with the assistant decribed, the subsequent dyeing can be carvied cut without reducing ageut, without alkali and without fixing agent. As &

CO conseguencea, in the subsequent wash of the tabric after dyeing, no alkali passes into the waste water, so that the salt content of the ’ waste water from the dyehouse is significantly reduced. In addition, t.he pretretmant } described also brings about in some instances a i

SERRE distinct deepening in the shade of the dyeing compared with a dyeing with the =zame amount of reactive dye by a conventional dyeing method. 16 An alkali which is widely used amongst others for fixing reactive dyes 1s sodium zilicate. 1f this sodium silicate is not carefully washed : aft after fixing, troublesome Si @ depoaits can remain on the fabric and hence impair the

Frasncd Tes This io another disadvantage which doappears in rhe process according to the

INVENT on. This novel process, by dispensing ! with the use of alkali, also facilitates che ' washing off of unfixed dye portions, since, in the = ih

! } 4 ; presence of alkalis the cotton fiber swells and ! the unfixed ave 1s absorbed to a greater ! extent. This phenomenon is successfully anticipated by the process according to the invention through the elimination of alkali.

The solubility of reactive dyes, which 1s much restricted by the alkali in conventional processes, ia significantly improved in the i Process acaording to the invention and : 10 increases the stability of the neutral dyeing : Li iguors. i ‘ The Jdyeings prepared by the above-described process acoerding to the invention have good wet fastness properties. 1H Surprisingly, it has also been found that a & wash with perborate containing detergents immediately following soaplng significantly increases the rll liance of the dyeings. if in a denim material the warp yarn has been

Zz pretreated in the manner according to the } invention, the wert yarn, which is undyved or, - lt

- 0. eer

L v { ¢ » : i depending an the: shade of the dye, zlishtly : stained, is made white apain by the rerbhorate- containing detersent, giving a dyeing of high brilliance and a white wett yarn. Tne use of } 5 Fluorescent whitening agents in the washing liquor further increases the brilliance of the dyeings and of the welt yarns.

Thee estffaclts are obtained in particular when the wash is carvied cut between 2a and 509, 19 preferably hetweon 40 and 5090. Orr washing 4 with perborate containing detergents at higher & i temperatures, for example aC to Lea, £} Se preferably A570 to LWOPC, the dyeing can be : whitened in stagas, virtually until the fabric has lost all Jts color. in this way 1it is possible to obtain, in a wanner which 1g very * gentile on the ribers, nonuniform dyeings or fashionable color changes (Stone wash effect).

This effoct io otherwise cnly obrtainabte with

LE sikaline hypochiorite solution and possibly by washing in the presence 01 grunice shones.

The amount 01 alkaliperborate in detergents is between apout 4 end D5 3% by weight. Those

SLT

—_—— —_— —_—— { perborate containing detergents which are suitable here arc described in detail in a "Tenside” 16, page 2400 (1081). In what fol Lowa. two rTormulatlions ave described in more datail as examples: . {. fAnicnicsnonionic surfactants Twa-0hi ‘ Soaps (alkail metal salts of fatty aida) V- 10%

Polyphosphaves 29 huk : 19 Sodium or potassium perborate Li Gh . o Ci. Sodium pilicate G10%

Carboxymethyleel lulose 1 2%

Heutral salts and 5 -20% standardizing agente 16 Fiuncrescent whitening agents P= uo. a ah Ea -

Tet apropy l snebenzenesui bona te

Karty alcohol suitate

CoPat ty acid cthanolamide 6 Sodium carizonate T4-1as” socdium sl ioate Go 10%

Peo i , : , , } by 4 {

T

:

L)

Godium diphosphate 5 ba :

Sodiuin triphosphate sodium peritorate 4 OE : Magnesiun silicate i Th 5 Fiuncrescent whitening agents (LE

Cartonvmethvicel lal oae

Fortunes tii : : fooaamp ia

Cotton warp yarns ars treated as tollows on a ¥ i Lo sizing machine in the size bon . . a0 pl cf polyvinyl aleohol (PVA) ‘

Hos af polyethviene glycol . 4 8/1 of the potassium salt of di

Ueaethyihenyl phiosphate 1 fs 20d Sf the polvethyiocneimine condeneoat bon Prevrcdiie LiiA deme ribed In aamgde Toor

Testo ber FL Past drier, ot Uatent

App bicarion blr 0 Tou 500 2) Poisgiine package TR re bn xk thish perrormance i

Ole eee Plast)

Io

- -_ — ; . , if ; The varn hac a speed of Gi msmin. ana the

A i _ ] es a nO § tigquor temperature 1s HO boo wa al, \ i After leaving the size bor, the ootbom Warps

A . . a . - yr ! are dried hy contact heat at ahout 1300. i 5 Instead of PVA it is also possible to use 3 : uninodi fied or medified starch or mixtures of i unmodified or modified starch sod PVA. The uze i oT carborymetbyvicellulose or carboxymethyl pe br starch as sizing agent la aot possiibe since, pi 10 if they are used together witli the cationic by ks atkylethylone imine condensate, precipitations

H Carr oooul. Thereatler the cotiorn warps are ’ 4 . . - Co . : woven witlo, Lhe cotton wert, and the Tabric ! Obtained do overpuadded on a range Comprising a bE 15 dyeing padder and a dover with a olution whieh - containg for example i 1 gd of Oli. Reactive Blue 10 (e001. Nao. Glooe) arid A on 1 of wetting agent tethoexviated . LH ney Tohienol 1

Arcer drying. tha tabric ia thermorixed at ! DEO for 1 minute. A customary artertreatment for reactive dyes of rinsing. svaplng ory at

MY

; : the boil and further rinsing then gives even without the quantity of alkali normally : necessary for fixing the reactive dyes a dyeing i on the warps of good all-round fastness : 5 properties. The pretreatment of these cotton : warps with the polyethyleneimine condensation ' 4 © product furthermore brings about a significantly deeper shade than is obtained by : standard alkali fixation. The weft, on being aftertreated by rinsing and soaping, becomes virtually white again. The result is thus a k fabric with a denim effect. 1 | Example 2

Co oA Sn denim fabbic” sized and dyed under Example 1

E . 15 is treated after the final rinsing and scaping ' .

Eo " process with b g/1 of a customary perborate- § containing detergent (Na perborate content 20% i : by weight) at 50 - 60°C for 10 to 20 minutes. .

Es : v

The result obtained is a significantly more

Yi 3 20 briiliant shade of this denim fabric with 4 preservation of full strength and intensity of i the dyeing. What is more, the white of the :

I" ; 21 - 4 : rT } :

3 o

BE weft yarn is still further improved iby a : significant amount compared with a denim fabric i 4 dyed in the same way but not washed with a g perborate-containing detergent. i

B 5 Example 3

Instead of the Reactive Blue 19 recipe

RB mentioned in Example 1, the fabric is § oo impregnated with

BE 05 g/1 of Solubilised Sulphur Red 11. . ; 10 After-treatment and finishing as under 1. A / deep red dyeing is obtained. ] fot * Example 4

ERE a] ig iy... A, Bleached cotton fabric is overpadded cold on

Eo a 2- or 3-roll padder with a solution containing . : bo 15 60 5/1 of the polyethyleneimine- . 5 vi ‘ : - condensation product of

E Example 1 . and 2 8/1 of the potassium salt di-2- un ethylhexyl phosphate and, after drying, is ’ . 20 padded with a liquor containing i 10 g/1 of Reactive Red 1 (C.I. No. 18158)

EB - 99 iy fh 1

B n i ' and a gl of a wetting agent i : 84 © (ethoxylated nonylphencl).

Es

Fo i : , The dyeing is dried and thermorixed at Tal 1, 8 for 1 minute, both steps being carried out as y 5 in Example 1. 3 a rm . p y . . 7 The result is a deep red dyeing having ood i oa all round fastness properties. } i of

Bi Keactive Ked 1 is replaced by

Ll Co Ce . i, iv g,1 of Lolubilised Sulphur Blue 7 bl 19 (2.1. No. H3441), dx b and the Trabrie is dried and thermotfixed at 1 i. “a0 for 1 minute. The result is a deep blue d Aye ing naving Zood all round faatness 3 properties. 14 Prample ©

A bleached PEs Jcotton fabric 1s ove rpadded cold on oa oor gerald padder with a solution or : ow a2] ofr poivethyleneimine condensation product as in BErample 1

Coo

- A - —_— a — ty a

Es bs ol 4 £] b! and 2 a, of the potassium salt i. i die cthylhexyl i k ;

LE phosphate i ¥, ~ . » on x 3 : and, after drying, is padded wath & liquor i ho 5 containing : ji 150 g/l of Se lubilised Sulphur ke Red 11 + ¥ 39 go of a black dye ) Co i comprising :

Bit i. 4 10 Disperse Blue 165 (C. 1. i! if " 11077),

Disperce Orange 29 a! by (CLT. 26077) and i 2. : Disperse hed 184 and

Ea hi 15 “ g/l of ethoxylated

Ha * ; ’

Fy . nonylphenol. ees i ’ i

Fi i N i . . rin Ce = 8 The fabric is then dried at 1207C, thermofixed 3 at one for 1 minute, rinsed, scaped and £

Fite . I : ; rinsed once more. I'he result 1s & black/red

Ey , “i two-color dyeing. - 24

Claims (1)

1. ; CLATHS:

   ; I. A process for dyeing and: Printing with : 3 reactive dyes ar Water sojulije Suitur dyes in the abaence OL alkaij Or reducing agents, wherein the textile material to be dved ig : pretreated with g wetting agent and an Optionally Quarternizaed reaction product of : rolyethyleneimine With “ bifunctional alkylating agent, then dyed with reactive dyes E 10 or water-zoiuble sulfur dyes, dried, : 3 g thernofixed si, a temperature between [ono arc i 200°C top ¥W.5 to 1 minute Arid conventionally Lo tinished. he i oo 2. A process tor dyeing and Erinting with i lo reactive dyes Or water-aojabje sulfur dyes in i i: the abssence of alkali or reducing agents, 4 Co wherein 4 wary varn ig retreated witch a

   Li . i wetting R8ent and a seaction product of v Polyethylencimine with zt Bifunctional 1 MY] Alkyrating agent. tosethop With the size in a Gloing bath, Lhe thus treaced Warp yarn is i woven with an untreated wete Yarn and then dyed ; ] i

   ! . i b with the reacusd dyes, dried, thermolfixed at a t i § temperature between 109% and 290YC for 9.5 to I minute and conventionally finished.

   J. The process as claimed in claim 1, wherein the reaction product iz used in an amount orf 3 to 10% by weisht of fiber.

   L 4. The process as claimed in claim 2 wherein a ; reaction prodact or polyvethyleneimine with J i epichlorohydrin, 1,3 -dichleropropan-2-aol or iv mirouraes thereof is used.

   5. The process az claimed in claim 4, wherein Lo a reaction product of polvethyvlensimine with a : bitunctional alkylating agent in a reactant y Lo Co . a welght ratio or 13:0. 01 to 1ev:2 1s usea. ; f { i = r Co a —- . ‘ 5 . < . .

   6. The proces: as claimed in claim i, wherein i a padding asgicvant is addes vo the dye padding liguor. 1 i

   7. The procers as claimed in oblaim | wherein = dB

   —_— r — i § y 2 the dyeings or prints are subsequently washed fh bi fi with & detergent which contains a perborate with or without a& perborate activator ancl Lo = LY pm mem en by a ~ 3 = -, a rd ttuoresecent whitening agents. ; i ! [ V b I Si : i he be on i) o E igh . Batis. [A ” a Hl Fo B 1 i! . a5 a ] 2 i i bh: 13 in Hi A 3 1 K/ = 2 Fi i i