AU620908B2 - 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

Association.

D. B. Mischlewski THE COMMISSIONER OF PATENTS.

j Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIF 6 to)

(ORIGINAL)

Class I t. Class Application Number: Lodged: Complete Specification Lodged: ;riority: 9 fated Art: Published: TNawriie of Applicant: *Airess of Applicant: Actual Inventor: Address for Service HOECHST AKT'IENGESELLSCHAFT 50 Bruningstrasse, D-6230 Frankfurt/Main Germf any 80, Federal Republic of THOMAS MARTINI, KURT DICKMANNS, KARL-HEINZ KEIL, WERNER MAISCH MDMDWXFEXQCSWa termark Patent Trademark Attorneys 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

Complete Specification for the invention entitled: PAD-THEPMOFIX PROCESS FOR DYEING AND PRINTING WITH REACTIVE DYES AND WATER-SOLUBLE SULFUR DYES IN THE ABSENCE OF ALKALI OR REDUCING

AGENTS

The following statement is a full description of this invention, including the best method of performing it known to US 1.

1 HOECHST AKTIENGESELLSCHAFT HOE 88/F 250 Dr. OT/sch Description Pad-thermofix process for dyeing and printing with reactive dyes and water-soluble sulfur dyes in the absence of alkali or reducing agents US-A-4,806,126 discloses that cellulose fibers can be dyed and printed with reactive dyes and even with watersoluble sulfur dyes without alkali or reducing agents if the textile material is pretreated with a wetting agent and 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 reducing agent, and the dyeings are finished by rinsing, soaping and drying.

The conventional manner covers the cold pad-batch process S* and the exhaust dyeing process.

It has now been found that the dyes mentioned 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 ,.20 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 quaternized reaction product of polyethyleneimine with a bifunctional alkylating agent, then dyed with 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 8 to 12 hours) are avoided.

An assistant preferred for the pretreatment is known from US 4,588,413. There the assistant is exclusively utilized 2 for the aftertreatment of dyeings with reactive dyes. A pretreatment with this assistant and a subsequent dyeing without alkali are not described therein. A process exclusively for aftertreating reactive dyes with compounds of a similar structure is also described in GB Patent 2,006,279.

The polyethyleneimine required for preparing the preferred pretreating agent conforms to the formula I

H-(CH

2

-CH

2 -NH)a -(CH2-CH2-N)b-

I

X

where X is a radical of the formula -(CH 2

-CH

2 .a and b are independently of each other numbers from 0 to 600, the sum a b being a number from 50 to 600, and c is a number from 0 to Consequently, the polyethyleneimine used is a molecule o containing -NH 2 >NH and building blocks which are °linked with one another by ethylene groups. In total the polyethyleneimine contains about 50 to 600 ethyleneimine units. In conventional commercial products, primary, secondary and tertiary nitrogen functions are present in a numerical ratio of about 1:2:1.

f For the reaction with the ethyleneimine of the formula I it is basically possible to use any known bifunctional alkylating agent. Known bifunctional alkylating agents conform to the formula II A Z A where A is the radical of an alkylating species and Z is either a direct bond or a divalent briCge member.

It is particularly advantageous to use for the reaction 3 -3with the polyethyleneimines to give the assistants to be used according to the invention those bifunctional alkylating agents of the formula II where A is a group of the formula -CH 2 where Y is a substituent which is detachable as an anion, in particular chlorine, bromine, iodine or -OH, or a group which is detachable as an anion, in particular a sulfato group or a sulfonyloxy group, in particular phenylsulfonyloxy or p-tolylsulfonyloxy, or an epoxy group /.0 10 0 -CH- CH 2 and Z, if it is not a direct bond, is a divalent straight-chain or branched radical of the formula III -CH2n n 2nwhere n is a number from 1 to 4, a divalent radical of the formula IV -CmH 2 m-D-CmH2m where m is 1 or 2 and D is -SO- or -S02-, or phenylene.

Preference for the 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 2 -Y which are linked with one another by a bridge member of the formula IV, or to those where one of the radicals A is a group of the formula

-CH

2 -Y which is bonded directly to an epoxy group.

Examples of such bifunctional alkylating agents are epichlorohydrin, glycide, 1,3-dichloropropan-2-ol, p,p'dichlorodiethyl ether, ,fi,'-dichlorodiethylamine, 6,p'dichlorodiethyl sulfide, f,p'-dichlorodiethyl sulfoxide, 4 B,f '-dichlorodiethyl sulfone, ,pi'-sulfatoethyl ether, f ,f'-diphenylsulfonyloxyethyl ether, meta- or paradiepoxyethylbenzene, meta- or para-diepoxypropylbenzene, diepoxybutane, diepoxy-2-methylbutane and diepoxypropylamine.

To prepare the pretreating agents to be used according to the invention, the polyethyleneimine and the bifunctional alkylating agent are reacted with one another in a weight ratio of from 100:0.01 to 100:2.0, preferably 100:0.1 to 10 100:1.0.

It must be assumed that in the course of this reaction crosslinking bridge members are incorporated between the polyethyleneimine chains. An outward sign of this is that the viscosity of the aqueous solutions increases markedly 15 as uncrosslinked polyethyleneimine is converted into a product which is crosslinked by 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 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 100°C. It is particularly advantageous to carry out the reaction at around normal room temperature, i.e. within the range between 15 and 45 0

C.

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 essentially complete in about 1 to 2 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 stir the reaction 5 mixture at a defined pH between 9 and 10 and at elevated temperature, advantageously between 60 and 100 0 C, for several hours, in general 2 to 6 hours.

The used reaction products of polyethyleneimine with a bifunctional alkylating agent may also be quaternized with Ci-C 4 -alkyl, preferably Ci-C 3 -alkyl, groups. The quaternization can be effected with alkyl halides, preferably alkyl chlorides, or dialkyl sulfates in a conventional manner.

S* .*10 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 S in the textile industry. Suitable wetting or padding assistants of this type are alkanesulfonates, dialkyl sulfosuccinates, dialkyl phosphates or propylene oxide/ ethylene oxide block polymers containing from 40 to 80 by weight of ethylene oxide, but in particular nonionic compounds, for example ethoxylated nonylphenol. The 0 textile material can be gray-state or pretreated cotton S* **20 or else cotton-containing blend fabrics. The process of S the invention is particularly interesting for the pre- I treatment of cotton warp yarns with the above-described assistant in the size. Weaving with untreated weft yarns S. and subsequent alkali- or reductant-free cross-dyeing with reactive dyes or water-soluble sulfur dyes then gives, after the fabric has been washed, a denim effect.

I The pretreatment with the assistant together with a j nonionic wetting agent takes place from an aqueous liquor in a conventional manner by padding or by the exhaust method at temperatures of about 20 to 70°C, preferably to 60 0 C, or in the size at from 80 0 C to the boil. The liquor is adjusted to a weakly acid pH, preferably pH 6.

The amount of assistant is about 3 to 10 preferably 3 to 8 on weight of fiber. The amount of wetting agent is preferably 2 to 4 g/l. The pretreating liquor is subsequently squeezed off, and the fabric is dried.

-*7 I S. S

S

S

000

S

6 The fabric thus pretreated is then overpadded with a padding liquor which contains dyes of the types menprefercy tioned. The fabric is then dried, thermofixed 4 at 120 to 200°Cfor 0.5 to 1 minute and washed cold and hot.

Suitable reactive dyes for this process are all known types of reactive dyes which contain groups reactive towards the hydroxyl groups of the cellulose and which react under the dyeing conditions described according to the invention, preferably by reaction with the abovedescribed polymers fixed on the cellulose material. The reactive groups are for example groups having readily detachable substituents which leave behind an electrophilic residue, such as reactive groups of the vinyl *I sulfone type, halogen-substituted groups of the ring 95 systems quinoxaline, phthalazine, triazine, pyrimidine or pyridazone, or alkylsulfonyl-substituted reactive groups in the case of sulfonylpyrimidine or sulfonylbenzothiazole dyes. Specific instances are dyes containing the reactive groups p-sulfatoethyl sulfone, f-chloroethyl 20 sulfone, -thiosulfatoethyl sulfone, p-phosphatoethyl sulfone, chlorotriazinylamino, dichlorotriazinylamino, chlorotriazinyl diamino, trichloropyrimidylamino, dichloropyrimidylamino, dichloropyridazinylamino, trichloropyridazinylamino, dichloropyridazinylcarbonylamino, 2-chlorobenzothiazol-6-ylamino, 2-methylsulfonylbenzothiazol-6-ylamino, 2,3-dichloroquinoxylin-6-ylcarbonylamino or 4-chloro-5-methyl-2-methylsulfonylpyrimid-3-ylamino.

Suitable basic structures for the reactive dyes are for example water-soluble azo, disazo, formazan, anthraquinone, dioxazine or phthalocyanine dyes. Preference is given to the use of water-soluble azo and disazo reactive dyes which may also be metal complex reactive dyes. After dyeing, the fabric is finished by rinsing, possibly soaping and drying.

The process according to the invention can be carried out

S..

S

.5

S

7 not only with reactive dyes and water-soluble sulfur dyes but also with sulfur vat dyes.

When dyeing with water-soluble sulfur dyes and sulfur vat dyes, the reducing agents normally used 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.

S..

5 1 1 15 The process according to the invention is suitable not only for dyeing textile material, but also for printing.

In printing, the textile material is printed with a print paste which contains a sighting dye and the cationic assistant to be used. After drying and fixing, the textile material is then cross-dyed with reactive dyes or water-soluble dyes, preferably by the thermofix method.

Alternatively, the cotton fabric pretreated with the assistant described is printed with a print paste which contains the dye but no alkali. The dye is subsequently fixed by heat treatment at from 130 to 200 0 C. The aftertreatment is carried out in the same way as in dyeing.

*SS*

S

5

S.,

i 0S S S 20 The essential advantage of the process according to the invention is that, as a consequence of the pretreatment with the assistant described, the subsequent dyeing can be carried out without reducing agent, without alkali and without fixing agent. As a consequence, in the subsequent wash of the fabric 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, the pretreatment described also brings about in some instances a distinct deepening in the shade of the dyeing compared with a dyeing with the same amount of reactive dye by a conventional dyeing method. An alkali which is widely used amongst others for fixing reactive dyes is sodium silicate. If this sodium silicate is not carefully washed off after fixing, troublesome SiO 2 deposits can remain on the fabric and hence impair the handle. This is another disadvantage which disappears in 7 -8the process according to the invention. This novel process, by dispensing with the use of alkali, also facilitates the washing off of unfixed dye portions, since, in the presence of alkali, the cotton fiber swells and the unfixed dye is 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 is much restricted by the alkali in conventional processes, is significantly improved in the process according to the invention and Goincreases the stability of the neutral dyeing liquors.

The dyeings prepared by the above-described process according to the invention have good wet fastness "015 properties.

00 Surprisingly, it has also been found that a wash with perborate-containing detergents immediately following S.soaping significantly increases the brilliance of the dyeings. If in a denim material the warp yarn has been pretreated in the manner according to the invention, the S.weft yarn, which is undyed or, depending on the shade of the dye, slightly stained, is made white again by the perborate-containing detergent, giving a dyeing of high brilliance and a white weft yarn. The use of fluorescent whitening agents in the washing liquor further increases the brilliance of the dyeings and of the weft yarns.

These effects are obtained in particular when the wash is carried out between 20 and 50'C, preferably between and 50 0 C. On washing with perborate-containing detergents at higher temperatures, for example 501C to 100 0 C, preferably 85 0 C to 100 0 C, the dyeing can be whitened in stages, virtually until the fabric has lost all its color. In this way it is possible to obtain, in a manner which is very gentle on the fibers, nonuniform dyeings or fashionable color changes (stone wash effect). This effect is I i .L l I 7 9 otherwise only obtainable with alkaline hypochlorite solution and possibly by washing in the presence of pumice stones.

The amount of alkaliperborate in detergents is between about 4 and 25 by weight. Those perborate-coAtaining detergents which are suitable here are described in detail in "Tenside" 18, page 246 (1981). In what follows, two formulations are described in more detail as examples: Se .4

S

5

S

54~ 0*55 5*5S4 1. Anionic/nonionic surfactants Soaps (alkali metal salts of fatty acids) Polyphosphates Sodium or potassium perborate Sodium silicate 15 Carboxymethylcellulose Neutral salts and standardizing agents Fluorescent whitening agents 2. Soap Tetrapropylenebenzenesulfonate 20 Fatty alcohol sulfate Fatty acid ethanolamide Sodium carbonate Sodium silicate Sodium diphosphate Sodium triphosphate Sodium perborate Magnesium silicate Fluorescent whitening agents Carboxymethylcellulose Perfume oil 10 25 0 10 20 50 10 25 3 10 1 2 5 20 1 -2 35 50 14 18 6 10 5 8 4 6 1 3 0.03 5 .5

S.

S

S.

S's..

S

.5

SS

S S

S.

Example 1 Cotton warp yarns are treated as follows on a sizing machine in the size box: g/l of polyvinyl alcohol (PVA) -B 10 g/l of polyethylene glycol 4 g/l of the potassium salt of di- 2-ethylhexyl phosphate 100 g/l of the polyethyleneimine condensation product as described in Example 1 of Table 1, last line, of Patent Application EP 0,133,933 Liquor pickup 100 to 120 (high-performance squeeze rollers) The yarn has a speed of 60 m/min, and the liquor temperature is 80 to After leaving the size box, the cotton warps are dried by contact heat at about 130 0

C.

15 Instead of PVA it is also possible to use unmodified or modified starch or mixtures of unmodified or modified starch and PVA. The use of carboxymethylcellulose or carboxymethyl starch as sizing agent is not possible since, if they are used together with the cationic alkylethyleneimine condensate, precipitations can occur.

Thereafter the cotton warps are woven with the cotton weft, and the fabric obtained is overpadded on a range comprising a dyeing padder and a dryer with a solution which contains for example e*

S

10 g/l of C.I. Reactive Blue 19 No. 61200) and 4 g/l of wetting agent (ethoxylated nonylphenol).

After drying, the fabric is thermofixed at 200 0 C for 1 minute. A customary aftertreatment for reactive dyes of rinsing, soaping off at the boil and further rinsing then gives even without the quantity of alkali normally necessary for fixing the reactive dyes a dyeing on the warps of good all-round fastness properties. The 11 pretreatment of these cotton warps with the polyethyleneimine condensation 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 fabric with a denim effect.

Example 2 The denim fabric sized and dyed under Example 1 is treated after the final rinsing and soaping process with 5 g/l of a customary perborate-containing detergent (Na perborate content 20 by weight) at 50 60 0 C for 10 to minutes.

The result obtained is a significantly more brilliant i shade of this denim fabric with preservation of full S 15 strength and intensity of the dyeing. What is more, the white of the weft yarn is still further improved by a Ssignificant amount compared with a denim fabric dyed in the same way but not washed with a perborate-containing detergent.

Example 3 Instead of the Reactive Blue 19 recipe mentioned in Example 1, the fabric is impregnated with g/l of Solubilised Sulphur Red 11.

After-treatment and finishing as under 1. A deep red dyeing is obtained.

Example 4 A bleached cotton fabric is overpadded cold on a 2- or 3roll padder with a solution containing g/l of the polyethyleneimine condensation product of Example 1 and 2 g/l of the potassium salt di-2-ethylhexyl phosphate and, after drying, is padded with a liquor containing g/l of Reactive Red 1 No. 18158) and 2 g/l of a wetting agent (ethoxylated nonylphenol).

II I _1 I/ r_• S12- The dyeing is dried and thermofixed at 200 0 C for 1 minute, both steps being carried out as in Example 1.

The result is a deep red dyeing having good all-round fastness properties.

Reactive Red 1 is replaced by g/l of Sulubilised Sulphur Blue 7 (C.I.

No. 53441), and the fabric is dried and thermofixed at 200 0 C for 1 minute. The result is a deep blue dyeing having good allround fastness properties.

Example A bleached PES/cotton fabric is overpadded cold on a 2or 3-roll padder with a solution of 60 g/l of polyethyleneimine condensation product as in Example 1 and 2 g/l of the potassium salt di-2-ethylhexyl phosphate and, after drying, is padded with a liquor containing 150 g/l of Solubilised Sulphur Red 11 30 g/l of a black dye comprising Disperse Blue 165 11077), Disperse Orange 29 26077) and Disperse Red 184 and 2 g/l of ethoxylated nonylphenol.

"25 The fabric is then dried at 120°C, thermofixed at 2000C Sfor 1 minute, rinsed, soaped and rinsed once more. The result is a black/red two-color dyeing.

,A

Claims (8)

1. A process for dyeing and printing with reactive dyes or water-soluble sulfur dyes in the absence of alkali or or C0o 27tol 14c1i4q reducing agents, wherein theValter al to.be dyed is pretreated with a wetting agent and an optionally 1uaternized reaction product of polyethyleneimine with a bifunctiona.,. al1ylating agent, then dyed with the dyes 1nA 'q 0(n PZV£ fi ItXor mentio edA ried, thermofixed and conventionally finished.

2. The process as claimed in claim 1, wherein the warp yarn is pretreated with a wetting agent and a reaction product of polyethyleneimine with a bifunctional alkylating agent together with the size in a sizing bath.

3. The process as claimed in claim 1, wherein the reac- tion product is preferably used in an amount of 3 to 10% on weight of fiber.

4. The process as claimed in claims1,whreinwhereac-a 4.The process as claimed in claims 1 to 3, wherein reaction product of polyethyleneimine with epichloro- hydrin, l,3-dichloropropan-2-ol or mixtures thereof is 00 aused.

The process as claimed in claims 1 to 4, wherein a 0, *reaction product of polyethyleneimine with a bifunctional alkylating agent in a reactant weight ratio of 100:0.01 to 100:2 is used.

6. The process as claimed in claim 1, wherein a polymeric padding assistant is added to the dye padding liquor.

7. The process as claimed in claims 1 to 6, wherein the dyeings or prints are subsequently washed with a deter- gent which contains a perborate with or without a per- borate activator and fluorescent whitening agents. Px 4 _d(W I MVS W us 4,58

8. The fixing S. S *5 a *08S 0 a. OSS S S L 14 8. The process as claimed in claim 1, wherein thermo- fixing is carried out at 120 to 200 0 C for 0.5 to 1 minute. DATED this 7th day of September 1989. HOECHST AKTIENGESELLSCHAFT WATERMARK PATENT TRADEMARK ATTORNEYS 50 QUEEN STREET MELBOURNE. VIC. 3000. 0S SB 6O S 0 S Sr S 55 S 5.55 S f. S* 5.55 S S S 5 .5 SOS. 55 55 1* S S d~