DE2747358A1 - METHOD OF AFTER-TREATMENT OF REACTIVE COLORS - Google Patents

Description

Bayer Aktiengesellschaft ι ί <♦ / 3 ο

Central Patents Department. Trademarks and licenses

5090 Leverkusen, Bayerwerk Mi-kl

1 Oct. 0 WT?

Process for the aftertreatment of reactive dyeings

The invention relates to a process for the aftertreatment of reactive dyeings on cellulose fiber materials, which is characterized in that one uses reactive dyes dyed textile material after removal of the loosely adhering dye hydrolyzate with an aqueous solution of polyamines, polyamides, polyurethanes and / or polyureas containing secondary and / or tertiary amino groups treated.

According to the invention to use water-soluble secondary and / or tertiary amino groups containing polyamines, polyamides, polyurethanes and / or polyureas are characterized in that they have a molecular weight of more than 1000, preferably greater than 2500th

Secondary and tertiary polyamines with a molecular weight of at least 1000 which are suitable for the process are, for example:

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A) Polymerization products of ethyleneimine and reaction products of low molecular weight polyvalent amines with compounds which are polyfunctional towards amino groups. Examples of polyvalent amines are:
Cycloaliphatic and araliphatic polyamines such as 1,4-diamino-cyclohexane, 1-aminomethyl-5-amino-1,3,3-trimethyl-cyclohexane, 1,3-bis-aminomethylbenzene and benzylbis- (3-aminopropyl) amine;
but in particular:

1) Amines of the formula

HN ^ _n H _2n * Nh ^ H (D,

in the

R ₁ and R_ independently of one another are hydrogen or

a is optionally substituted by hydroxy, cyano or carbonamido C -.- C ₄ alkyl radical,

m is a number of at least 1, preferably

1 to 4, and

η is a number of at least 2, preferably

2 to 4 mean.

Representatives of these amines are, for example, ethylene diamine, propylene diamine, tetramethylene diamine, hexa-

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methylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine, Ν, Ν-bis - (^ - aminopropyl) -methyleneamine, N ₁ N ¹ -dimethyl-ethylenediamine, N-ß-hydroxyethyl-ethylenediamine, N-.β-ethylenediamine, N- -ß-Carbamidoethyl-ethylenediamine.

2) amines of the formula

Y ^ (CH ₀ -CH-CH ₀ -NH) -ttj _r

in the

Y for oxygen, sulfur or the remainder of an at least divalent aliphatic, cycloaliphatic, araliphatic or aromatic hydroxyl and / or sulfhydryl groups,

R _{3 is} hydrogen or the methyl group,

χ an integer of at least 1, preferably 1-3, is and

ζ stands for an integer of at least 2, preferably 2-4.

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Representatives of these amines are, for example, bis (3-aminopropyl) ethers, Bis (3-aminopropyl) sulfide, ethylene glycol bis (3-aminopropyl ether), Dithioethylene glycol bis (3-aminopropyl ether), neopentylene glycol bis (3-aminopropyl ether), Hexahydro-p-xylylene-glycol-bis- (3-aminopropyl ether) and hydroquinone bis (3-aminopropyl ether).

3) amines of the formula

(CH ₂ -CH-CH ₂ -NH) -H

R ₄ - N ^ (III),

^ (CH ₀ -CH-CH ₀ -NH) -H

^R 6
in the

_{R. for a C 1} -C ₁₈ -alkyl radical optionally substituted by an amino or hydroxyl group and

R _c and R ^. independently represent hydrogen or a methyl group and

ρ and q are a number from 1 to 20, preferably 2 to 5, is.

Representatives of these amines are, for example, ethyl bis (3-aminopropyl) amine, 2-hydroxyethyl bis (3-aminopropyl) amine, n-butyl bis (3-aminopropyl) amine, tris (3-

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aminopropyl) amine and especially methyl bis (3-aminopropyl) amine.

B) Polyamides containing secondary and tertiary amino groups and having a molecular weight which are suitable according to the process of at least 1000 are, for example, the known amide group-containing polyamines, in particular the reaction products from:

1) eyeloaliphatic, araliphatic or heterocyclic, preferably aliphatic polyamines, the at least two amino groups capable of amide formation and at least one further primary, secondary or contain tertiary amino group. These polyamines can optionally be mixed with aliphatic, containing eyeloaliphatic, araliphatic or heterocyclic, primary or secondary amino groups Diamines are present, the amount of these diamines is advantageously such that per mole of in the Polyamines in addition to the further containing at least two amino groups capable of amide formation primary, secondary or tertiary amino groups come up to 20 mol% diamines;

2) aliphatic or aromatic dicarboxylic acids, especially saturated ones containing 4 to 10 carbon atoms aliphatic dicarboxylic acids, or their functional derivatives, such as anhydrides, esters, half-esters or amides, or

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3) oC , ß-unsaturated aliphatic monocarboxylic acids or their functional derivatives capable of amide formation, such as anhydrides, esters or amides, and optionally

4) aminocarboxylic acids containing at least 3 carbon atoms or their lactams, in particular £ ~ -caprolactam.

These reaction products are referred to in the literature as "polyamide amines" or "polyamido amines" or "polyamide polyamines", or "polyamino polyamides".

Furthermore, those amine group-containing polyamines, which by reaction with 1,2-alkylenimines 1,2-polyalkylenepolyamine side chains were grafted and as described, for example, in German Offenlegungsschrift 1 802 435 are.

C) Polyurethanes having secondary and tertiary amino groups which are suitable according to the process are, for example called:

The polyamines containing urethane groups made from bis- or higher-functionality Chloroformic acid esters and aliphatic diprimary amines and at least one other secondary or preferably tertiary amino group.

D) Examples of suitable secondary and / or tertiary amino group-containing polyureas are called:

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Polyamines containing urea groups, especially those Reaction products of diisocyanates and aliphatic diprimary amines with one or more secondary amines and / or tertiary nitrogen atoms in the chain and the reaction products of urea and polyvalent ones Amines which enabled at least two to form urea Contain amino groups and at least one secondary or, preferably, tertiary amino group.

These contain amide groups, urethane groups or urea groups Polyamines can also be increased in molecular weight with compounds which are polyfunctional with respect to amino groups.

Examples of compounds that are polyfunctional with respect to amino groups are:

Bifunctional compounds, such as 06 , oJ-alkyl dihalides, for example 1,2-dichloroethane, 1,2-dibromoethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,6-dichlorohexane; CJ, lj'-dihalo ethers, for example 2,2'-dichloro diethyl ether, bis (ß-chloro-isopropyl) ether, bis (4-chloro-butyl ether); Halohydrins or epihalohydrins, for example epichlorohydrin, 1,3-dichloropropanol (2), bis (3-chloro-2-hydroxypropyl) ether, 1-4-dichloro-2,3-epoxy-butane; Bis-epoxy compounds, for example 1,2,3,4-diepoxybutane, diglycidyl ether, A "than-1,2-bis-glycidyl ether, butane-1-4-bisglycidyl ether;

Cj -halocarboxylic acid halides , for example chloroacetyl chloride, 2-chloropropionyl chloride, 3-chloropropionyl chloride, 3-bromopropionyl bromide;

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Vinyl compounds, e.g., divinyl ether, divinyl sulfone, methylenebisacrylamide;

furthermore 4-chloromethyl-1,3-dioxolanone- (2) and 2-chloroethyl chloroformic acid ester, also chloroformic acid ester, 3-chloro-2-hydroxypropyl ether and glycidyl ether of polyalkylene oxides, u.B. Polyethylene oxides, as well as reaction products of 1 to 50 moles of alkylene oxides, such as ethylene oxide and / or propylene oxide with 1 mole of di- or polyhydric polyols or other at least two active hydrogen atoms containing compounds;

trifunctional compounds such as N, N ¹ , N "-triacryloylhexahydro-s-triazine.

Particularly suitable for this process are the polyamines, some of or some of their amino groups consist mostly of tertiary amino groups. Such amines can be derived from the above polyamines A) to D), which contain only or mostly secondary amino groups, easily with the usual alkylating agents produce.

These secondary and / or to be used according to the invention Polyamines, polyamides, polyurethanes and / or polyureas containing tertiary amino groups are for example in German patents 665 791, 730 365, 872 269, 851 550, 1 006 155, 1 034 857, 1 211 922, 1 264 943, 1 301 118, 1,771,814, in British Patents 610,311, 610,443, 775,721, 1,035,296, 1,373,319, U.S. Patents 2,926,154, 2,969,302, 3,311,594 and in French Patents 884,560 and 2,010,727.

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The amount of the substances according to the method used depends on the hydrolyzate content of the fiber to be washed out and is to be determined by preliminary test.

In general, application amounts between 0.5 4%, based on the dry weight of the dyed textile material, proven beneficial.

The pH of the aqueous treatment liquor should be between 3.5 and 11, preferably between 4.5 and 7, are.

Before the aftertreatment according to the invention, the dye hydrolyzate loosely adhering to the fiber is removed by rinsing with water at or near the boiling temperature. The aftertreatment can be carried out on all conventional dyeing and washing machines, such as package winder, packing machine, reel skid, jigger, wide washing machine and jet dyeing machine and depends on the type of previous dyeing process or the presentation of the textile dyed goods in the form of packages, fabrics, round loom goods , Fried animal products, etc. The preferred treatment temperature is 65 - 100 ° C,
2-10 minutes.

at 65-100 ° C, and the preferred treatment time is

Come for the aftertreatment method according to the invention all metal-free water-soluble fiber-active dyes from the azo and anthraquinone series, as well as copper and Ni complexes from the azo and phthalocyanine series with at least 1 sulfo group into consideration, which during the dyeing process Form at least one homopolar dye / fiber bond.

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Such fiber-reactive dyes with groups capable of reacting with cotton and regenerated cellulose are known in large numbers. The following groups, for example, come into consideration as fiber-reactive groups:

Halotriazine, halopyrimidines, haloquinoxaline carbonyl, Halogenphthalazincarbonyl-, Vinylsulfon-, ß-Oxyäthylsulfonester-, Methylsulfonyltriazine, methylsulfonylpyrimidine, Methylsulfonyl benzothiazole, fluorobenzothiazole, ß-Oxyäthylsulfonamidester-, ß-Oxyäthylsulfonalkylaminoester-, ^ XVßromacryloyl, ß-chloropropionyl, ß-chloroacetyl, ß-phenylsulfonylpropionyl, Halopyridazonalkyl-, 2-chlorobenzothiazolesulfonyl-, Alkylsulfonylpyrimidine groups.

These dyes are for example by E. Siegel in "Chimia" (Supplementum 1968) pages 100-114 and K.Venkataraman in "The Chemistry of Synthetic Dyes (1972) Vol. VI.

Cellulose fiber materials are preferably those made from natural cellulose, such as cotton, linen and hemp and made of regenerated cellulose, such as rayon or rayon.

From the different ones due to their affinity for cellulose fibers Reactive dye types are preferably those which have a high substantivity and therefore preferred in the exhaust process or in the cold dwell process can be used. These dyes have the

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known disadvantage that the complete cleaning of the Tex tilmaterials after dyeing causes considerable difficulties. Although the reaction of the reactive dyes with the cellulose fiber takes place under the optimal dyeing conditions in each case in such a way that as high a proportion of the reactive dye used as possible enters into a real homeopolar bond with the fiber, in addition to the reaction between the reactive dye and the fiber, there is also a reaction with the dye solvent and Distributing agent used and acting as a fiber swelling agent water. The Farbstoffhydrolysat formed thereby must after completion of the dyeing process are washed, in order to obtain the optimum fastness properties of the reactive dyeing (GE Kricersky, sowj Total fiber Forsch Textiltechnik 10 (1973) 4, 200 -... 203). Since the dye hydrolyzate is a readily soluble dye in water , the general removal of the dye hydrolyzate from the dye hydrolyzate does not pose a particular problem and can be achieved by repeated rinsing and extraction with boiling water. The complete removal of the trapped inside the fiber Hydrolysatanteils other hand, has remained one has not been satisfactorily solved for practical problem.

The complete removal of the dye hydrolyzate retained by the fiber is all the more time-consuming, the deeper the dyeing , and therefore requires additional water and energy-consuming aftertreatment processes in the case of deep dyeings. In the following patent specifications, processes have been described according to which the dye hydrolyzate is not completely removed from the fiber, but is precipitated on the fiber by means of an aftertreatment with polyguanidines or polyquaternary compounds:

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DT-OS 2 112 878, DT-AS 1 143 784, JA-PS 51 112 987.

Such strongly basic polyguanidines or polyquaternary compounds are also already used to improve the authenticity substantive dyes have been used (DT-AS 1 111 144, DT-AS 1 131 694, BE-PS 625 711, DDR-PS 67 092 and U.S. Patent 3,334,138). However, their application to cotton and rayon has the disadvantage that the salt-like bond of the dye hydrolyzate to the polyguanidine or to the polyquaternary precipitant is only stable up to a washing temperature of 60 ° C and under the conditions the hot wash required for reactive dyeing, soiling of accompanying fabrics, in particular polyamide accompanying fabrics, not prevented.

Another serious disadvantage of such agents is that they are one of the actual boiling Rewashing of the dye requires independent, time-consuming post-treatment at low temperature during the the precipitant noun draws up. Because when used in the post-wash process, if necessary, in the In the boiling wash liquor, the remaining dye content precipitated due to the polyquaternary compound in the wash bath, which results in colored smearing of the goods.

Other methods of binding the reactive dye hydrolyzate to the fiber consist of a combination of Post-treatment and anti-crease finishing, especially for woven fabrics, with nitrogen-containing condensation products,

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e.g. urea-formaldehyde condensates, causing them to peel off the unfixed dye content is prevented (GB-PS 890 518, FR-PS 846 505, BE-PS 595 382, Be-PS 604 457, BE-PS 617 446, DT-OS 2 601 748).

Such processes always require a thermal aftertreatment at 130-160 ° C. Amer. Dyest. Rep. 49 (1960) 7, 244. However, they are only suitable for those reactive dyes that have reactive groups with more have as an exchangeable halogen atom, for example, dyes with the dichlorotriazine reactive group. The combination of dyeing and anti-crease treatment, however, has the serious disadvantage that the improvement in fastness is tied to a finishing process which is possibly undesirable in terms of the quality of the goods, such as, for example, lower moisture absorption and harder Handle. The problem of washability occurs especially with terry towels, round chair goods and yarn dyes, in which there is a change in the typical fiber properties due to crosslinking and polymer formation in the fiber is undesirable.

It has now surprisingly been found that the use of the compounds to be used according to the invention in one of several customary aqueous aftertreatment baths the customary aftertreatment process after Dyeing deep reactive dyeings to achieve the optimal wet fastness properties is considerably shortened and supported. The dyeings obtained are not only distinguished by an improvement over the previous procedure Wet ironing and boiling water fastness

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jach through the greater clarity of the nuance. this applies especially for the deep red, scarlet and orange tones that are known to be critical in terms of staining and color.

As a particular advantage of the aftertreatment according to the invention both against those washed with water only, not aftertreated, and against those with water as usual washed and then improved in terms of authenticity with polyquaternary compounds or polyguanidines Reactive dyeing is the soft, pleasant, wash-resistant one Highlight the handle of the textile material. That according to the invention The process is therefore particularly suitable for the aftertreatment of deep reactive dyeings that are difficult to wash out on hosiery and terry fabrics as well as cross; pul-dye dyeings with high requirements for wet fastness.

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example 1

100 parts of cotton terry goods are placed on a reel runner at 40 ° with a liquor consisting of:

6 parts of the dye

SO ₃ Na

OH N =

NaO ₃ S

100 parts of anhydrous sodium sulfate

20 parts of soda in 1874 parts of water dyed for 3 1/2 hours by the customary dyeing process and then, after draining off the residual liquor, aftertreated in the following manner with alternating baths of 20OO parts of water each time.

1st bath 10 minutes

2nd bath 10 minutes

3rd bath 10 minutes

4th bath 10 minutes

5th bath 10 minutes

at 25 "at at

at cooking temperature

at boiling temperature with the addition of 2 parts of a 25% strength aqueous solution of the condensation product 1 mole of bis (3-aminopropyl) methyl

amine and 0.87 moles of epichlorohydrin

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according to DT-PS 1 211 922, example 1 6th bath 5 minutes at boiling temperature

The result is a deep red coloration which has been perfectly freed from the hydrolyzate and which was found in the wet ironing test and in the laundry 95 shows no soiling of accompanying fabric.

Example 2

100 parts of a cotton yarn are in the form of 500 g packages on a yarn dyeing machine at 40 with a liquor consisting of:

6 parts of the dye

50 parts of anhydrous sodium sulfate,

20 parts soda,
924 parts of water

Dyed for 2 hours using the usual method and then after draining off the remaining liquor post-treated in the following way:

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1 . bath 5 Minutes 2. bath 5 Minutes 3. bath 10 Minutes 4th bath 5 Minutes 5. bath 1O Minutes

Rinse in the overflow at 25 Rinse in the overflow at 65 Boil with 2000 parts of water, rinse in overflow when boiling with 20000 parts of a solution consisting of

2 parts of a 30% aqueous solution of one obtained by polymerizing ethyleneimine obtained polyethyleneimine

(Viscosity 125 mPas at 25 °)

in

998 parts of water

6th bathroom

5 minutes rinse in the overflow at 25

The result is a deep blue coloration which has been perfectly freed from the hydrolyzate, which is particularly evident in the wet ironing test and in the laundry at 95 ° shows no soiling of accompanying fabrics. If the same is used instead of the polyethyleneimine Amount of a condensation of 1 mole of triethylenetetramine and 1 mole of 1,2-dichloroethane according to Example 11 of GB-PS 775 721 obtained polyethylene polyamine, one obtains an equally well washed out, deep blue coloration with optimal Authenticity properties.

Example 3

100 parts of a cotton terry product are mixed with 100 parts of a liquor consisting of:

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Share dye

NaO

Parts of sodium bicarbonate,
Share urea and
Parts water impregnated,

Min. Dried at 120 ° and condensed for 5 minutes at 150 °.

Subsequently, the following treatment is carried out on the jigger:

Rinsing with 600 parts of water at 25 °. Rinsing with 600 parts of water at 25 ° Rinse with 600 parts of water at 25 °. Boil with 600 parts of water. Boil with 600 parts of water with the addition of 2 parts

a 20% aqueous solution of 1,2-dichloroethane (0.17 mol per base-val) enlarged basic polyamide from:

1 . bath 10 Minutes 2. bath 10 Minutes 3. bath 10 Minutes 4th bath 10 Minutes 5. bath 10 Minutes

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1.05 moles of diethylenetriamine

1.00 moles of adipic acid

0.50 mol ^ι ζ -caprolactam

0.04 moles of adipic acid hydrazide

Influence product 1 of DT-PS 1 771 814

6. Bath boil for 10 minutes with 600 parts of water

7. Bath rinsing for 10 minutes in the overflow at 25 ° C.

A deep blue dyeing with excellent wet iron fastness properties and wash fastness properties is obtained.

If, instead of the basic polyamide, one according to DT-OS 1 720 905 Example 6 made of urea is used and methyl bis (3-aminopropyl) amine in a molar ratio 1: 1 made basic polyurea, this gives an equally good coloration.

Example 4

Parts of a knitted cotton fabric are placed on a reel runner at 50 with a liquor consisting of:

Share the dye

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^(S0 3 ^{Na )} 2.5

160 parts of anhydrous sodium sulfate,

20 parts of soda
1815 parts of water

Dyed 3 hours according to the usual dyeing process and then, after draining off the remaining liquor, in the following manner with alternating baths of each
20OO parts of water after-treated:

1. bath 10 Minutes 2. bath 10 Minutes 3. bath 10 Minutes 4th bath 10 Minutes 5. bath 10 Minutes

at 25 ^υ

at 25 °

at 25 °

at cooking temperature

at boiling temperature with the addition of 8 parts of the 10% aqueous solution of the after Example 3 of DB-PS 1,264,943 produced basic polyamide polyurea.

6th bathroom

10 mins

Rinse in the overflow at 25 ° C.

A deep turquoise coloration which has been perfectly freed from the hydrolyzate is obtained, which in the case of Naßbü

and shows when washing accompanying fabrics.

no soiling

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If, instead of 8 parts of the 10% strength basic polyamide polyurea solution, 4 parts of the 20% strength solution of polyamine 4, a basic polyamide containing acid groups, prepared according to DT-OS 2,156,215, are obtained, the dyeings are just as good.

A good result is also obtained when using a polyamidepolyamine, which according to specification of the DT-PS 730 365 of methylene-bis- (3-aminopropyl) amine and methyl acrylate in the molar ratio 1: was prepared. 1

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Claims (3)

Claims ο η / η ο C ρ 1. Process for the aftertreatment of reactive dyes dyeings produced on cellulose fiber materials, characterized in that the fiber materials are with the aqueous solution of polyamines, polyamides and polyurethanes containing secondary and / or tertiary amino groups and / or polyureas treated. 2. The method according to 1, characterized in that the polymers have a molecular weight of more than 1000, 3. The method according to claim 1, characterized in that the polymers have a molecular weight of more than 2500. Le A 18 460 - 22 - 909817/0358