DE2843645A1 - Washing-out of unfixed reactive dyes - using aq. solns. of alkoxylated poly:amine surfactant to improve wash-fastness - Google Patents

Abstract

In the washing-out of unfixed reactive dyes from cellulose fibres or their blends with other fibres, by aq. baths of 15-100 degrees C, an alkoxylated polyamine and with cloud point of a 1% aq. soln. of 18 degrees C min. is used. This is made by reaction of 100 parts amine with at least 2N atoms and at least one alkoxylatable gp. in an N atom, with 50-10000 parts of (a) ethylene oxide, and (b) propylene oxide or butylene oxide, or mixts. of (a) and (b) in molar ratio 0.2-5:1. Washing efficiency is improved over that of known nontoxic surfactants, resulting in better wash-fastness of the dyed prod.

Description

Process for washing out unfixed reactive ink

fabrics of cellulose fibers The invention relates to a method for Washing of unfixed reactive dyes from cellulose fibers afterwards the dyeing of cellulose fibers with reactive dyes or textile materials, which consist of cellulose fibers or contain them in a mixture with other fibers, by the action of aqueous liquors containing an auxiliary at temperatures from 15 to 1000C.

After the dyeing of textiles there is usually a rewash carried out. It is used to add unfixed dye and possibly still to remove any aids present on the goods. When dyeing cellulose fibers a chemical reaction takes place with reactive dyes, which is usually the case does not proceed quantitatively. The non-chemically fixed dye portion must be from washed out of the dyed material so that the dyed goods have optimal wet fastness properties Non-fixed and not washed-out dye components lead to staining and staining of accompanying textiles. It does not fix reactive dye components for removal Aids are already used on cellulose fibers belonging to the class of Assign non-ionic surfactants or anionic synthetic detergents permit.

The non-ionic surfactants used for this purpose are for example Reaction products of a higher fatty alcohol with ethylene oxide or reaction products of 1 mole of isononylphenol with 10 moles of ethylene oxide used. Suitable anionic synthetic detergents for washing out reactive dyes are for example Fatty alcohol sulfates or dodecylbenzenesulfonate.

The aim of this treatment is to remove the non-fixed reactive dye components irreversibly removed from the colored material. The effectiveness of the known Aid for washing out reactive dyes is still in need of improvement.

The object of the invention is to provide an aid for the initially described To show method that has a higher effectiveness than the previous one for this Purpose used.

According to the invention, the object is achieved by using as an aid alkoxylated polyamines are used, which have a cloud point in 1 Aiger aqueous solution of at least 180C and by reacting 100 parts by weight of an amine with at least 2 nitrogen atoms and at least one alkoxylatable group on Nitrogen atom with a) ethylene oxide and b) propylene oxide or butylene oxide or mixtures from a) and b), the molar ratio a: b 0.2: 1 to 5: 1 and the sum of the parts by weight a) + b) is 50 to 10,000.

Achieved when using the auxiliaries to be used according to the invention there is an improvement over the aids previously used for this purpose the wash fastness of the dyed material.

according to the invention, cellulose fibers dyed with reactive dyes are used or textile materials consisting of cellulose fibers or a mixture of them treated with other fibers. Usual fiber blends are for example Cotton and polyester, cotton and polyamide, cotton and polyacrylonitrile. The textile material to be dyed can be in different processing stages, for example, as a flake, card sliver, yarn, woven or knitted fabric.

For dyeing cellulose fibers or containing cellulose fibers reactive dyes are used in textile materials. Under reactive dyes All dyes are to be understood as containing cellulose or wool or synthetic Polyamides form a covalent bond and dye these fibers. There come all reactive dyes are considered. The type of reactive group in the dyes does not play a role in the washing out of the unfixed dye components according to the invention. The following groups deserve special mention as reactive anchors for reactive dyes: Monochlorotriazine, dichlorotriazine, trichloropyrimidine, difluorochloropyrimidine, Dichloroquinoxaline, acrylamide, chlorpropionylamide and vinyl sulfone groups or Groups which form a vinyl sulfone group in an alkaline medium.

Particularly suitable chromophore of these reactive dyes are those from the series of anthraquinone dyes, the metal-free or metal-containing ones Azo and phthalocyanine dyes, the oxazine and thiazine dyes.

Reactive dyes are described in detail in the Color Index.

In the case of fiber blends, the cellulose fibers are used for dyeing Reactive dyes and, for the other fibers, those which come into consideration in each case Dyes used. J. bas coloring of the cellulosic material or the pure cellulose fibers is carried out on known devices according to known ones Process, e.g. discontinuous after the extraction process in the reel runner, the Nozzle dyeing machine, the circulation apparatus in a long liquor with a liquor ratio from 1:10 to 1: 100 or in a jigger with a liquor ratio of 1: 3 to 1: 5. It is also possible to use the block-and-hold method to dye the material in a semicontinuous manner to carry out and to use continuous dyeing processes, namely single-bath processes, in which the padding liquor already contains all additives, especially the alkalis for contains the fixation of the reactive dyes. This subheading includes, for example, block thermosetting processes, Pad-drying process as well as single-bath pad-steaming process. But you can too Two-bath dye by using the alkalis for the fixation of the reactive dyes applies to the goods in a separate operation. This includes the familiar Two-bath pad steaming process, alkali shock process and Standfast process. at the semi-continuous and continuous mode of operation can be used with and work without intermediate drying.

Especially when dyeing mixtures of polyester / cellulose with reactive and disperse dyes can be dyed continuously using the following methods are: one-bath two-stage process in which the padding liquor contains both the reactive as well as the disperse dye, but does not contain any salt or alkali. Man pads, dries, heat-sets the disperse dye, then pads salt and alkali on, attenuates, the reactive dyes being fixed on the cellulose fibers are, rinses and washes out according to the invention. Another way of doing this is the one-bath one-step procedure tdem the log fleet next to Reactive and disperse dyes already have to fix the reactive dyes necessary alkali and as an additional diffusion medium approx. 50 to 60 g / l urea contains. In this process, the material is padded, dried and thermosolated and then washed out according to the invention.

The cellulose fibers dyed with reactive dyes are according to the invention Washed out with liquors that contain special alkoxylated polyamines as auxiliaries.

The polyamines are made by reacting an amine with at least 2 basic nitrogen atoms and at least one alkoxylatable group on each Nitrogen atom produced by alkoxylation. Here you can first a) ethylene oxide and then b) propylene oxide or butylene oxide to the amines in question attach. The sequence of the alkoxylation steps can also be reversed, i.e. propylene oxide and / or butylene oxide are first added to the amine and left the product obtained then only react with ethylene oxide. However, it is also possible the amines in question with a mixture of a) ethylene oxide and b) propylene oxide and / or butylene oxide to implement. In this case the alkylene oxide units are the derive from the alkylene oxides of groups a) and b), statistically in the alkoxylation product distributed.

The molar ratios used in the reaction with the amines Alkylene oxides a): b) correspond approximately to the proportions of alkylene oxide units a) and b) in the alkoxylated amine formed. The ratio of alkylene oxides to the Groups a): b) is 0.2: 1 to 5: 1, preferably 0.3: 1 to 3: 1. 100 parts by weight of an amine or an amine mixture of the type specified above are 50 up to 10,000, preferably 200 to 5,000 parts by weight of alkylene oxides (sum of %) + b)) implemented. J Suitable amines are, for example, ethylenediamine, 2-dimethylaminoethylamine, 2-diethylaminoethylamine; 1,2-propylenediamine, 1 3-diaminopropane, 3-methylaminopropylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 3-cyclohexylaminopropylamine; 1,4-diaminobutane, 4-diethylaminobutylamine; l-diethylamino-4-aminopentane; Hexamethylenediamine, 2,5-dimethylhexane-2,5-diamine; 4,9-dioxadodecane-1,12-diamine; 6, 6-dimethyl-4, 8-dioxaundecane-1,1l-diamine; Diethylenetriamine, diethylenetriamino-oleic acid amide; Diethylenetriamino lauric acid amide; Dipropylenetriamine; Bis (3-aminopropyl) methylamine; 1,2-bis (3-aminopropylamino) ethane; Bis (6-aminohexyl) amine; Triethylenetetramine, tripropylenetetramine; Tetraethylene pentamine, Tetrapropylene pentamine, polyamines, e.g., polyethyleneimine; 2-aminomethylcyclopentylamine; 1,1-bis (4-aminophenyl) cyclohexane; 4,4'-diaminodicyclohexyl methane; 3,3'-dimethyl-4,4'-diaminodicyclohexyl methane; 2,2'-bis (4-aminocyclohexyl) propane; 4,4'-diaminodiphenylmethane; N, N'-dimethyl-4,4'-diaminodiphenylmethane; 3,3'-dimethyl-4,4-diaminodiphenylmethane; Tris - (2-aminoethyl) amine, tris (2-aminopropyl) amine; Aminoethylethanolamine; o-phenylenediamine, p-phenylenediamine; 4-lminopyridine; 2-aminopyridine; l-hydroxyethyl-2-dodecyl - imidazoline; l-aminoethyl-2-dodecyl-imidazoline; l-hydroxyethyl-2-heptadecenyl-imidazoline; Piperazine; 1- (2-hydroxyethyl) piperazine; 1- (2-aminoethyl) piperazine; 1,4-bis (3 - aminopropyl) piperazine; 1- (2-aminopropyl) piperridine.

The auxiliaries to be used according to the invention are also included Characterized with the help of their cloud point, which in 1% aqueous solution above a temperature of 180C. The cloud point is in accordance with DIN 53 917, implementation provisions 6.1 (August 1973) determined. The amines in question have an alkoxylatable one Group.

This should include, above all, NH groups, as well as alkylene groups alkoxylation bonded to the nitrogen atom bare groups such as Carboxyl groups, carbonamide groups, SH groups or OH groups are understood. Suitable amines are above all ol, W diamines, such as ethylenediamine and hexamethylenediamine and polyamines such as triethylenetetramine, tetraethylene pentamine and diethylenetriamine as well as polyethyleneimines.

The amines mentioned are preferably initially treated with propylene oxide and / or butylene oxide and then with ethylene oxide to form block copolymers implemented. The resulting compounds can also be characterized in this way be that they have 1 to 30 propylene oxide and / or butylene oxide units per alkoxylatable NH group and contain 1 to 30 ethylene oxide units.

The wax liquors contain the auxiliaries to be used according to the invention in an amount of 0.2 to 10, preferably 0.5 to 5 g / l. The pH of the wash liquor is generally below 7, preferably working in a pH range from 4 to 6.5. The dyed material is washed out by washing it with the cold one Brings wash liquor in contact and the liquor gradually to a temperature up increased close to the boiling point. The treatment is preferably carried out with reactive dyes colored cellulosic material in the temperature range of 15 to 800C. Washout can also be done by putting the colored material in brings in the liquor that has already been heated to a higher temperature, e.g. 60 ° C. In general it is sufficient if you start washing out at room temperature with the liquor the textile material contained therein is heated to 80 ° C. within 30 minutes and the treatment is carried out for 10 minutes at 80.degree. The fleet is then drained, and rinses one or more times with hot or cold water.

The invention is illustrated in more detail by means of the following examples. The parts given in the examples are parts by weight. The cloud point of the alkoxylated amines were determined in accordance with DIN 53,917.

Production of the alkoxylated polyamines will be 1 mole of ethylenediamine presented in an autoclave and at a temperature of 100 to 130 0C with 20 Moles of propylene oxide reacted. The propylene oxide is used in accordance with the consumption introduced into the autoclave. After the reaction has ended, it is also pressed According to consumption, add 5 moles of ethylene oxide to the autoclave. The reaction is running in the presence of a basic catalyst at 100 to 1400C. After a total reaction time of about 17 hours is allowed to cool and a polyalkoxylated amine is obtained in 1% aqueous solution has a cloud point of 580C. The molar ratio from ethylene oxide to propylene oxide is 0.25. The reaction product is as follows referred to as aid A.

Aids A to H are characterized in the table, in which is indicated from which amine they were prepared, as well as the order the alkoxylation reactions was what cloud point the adjuvants have, how the molar ratio of ethylene oxide to propylene oxide in the alkoxylated amines is and how many parts by weight of alkylene oxide (= sum of ethylene oxide + propylene oxide) were used per 100 parts by weight of amine. The alkoxylation took place in appropriate Way as described above.

Table 1 Auxiliary Amine Alkoxylation Haze Molar Parts By Weight order point ratio alkylene oxide 1. + 2. nis per 100 Ge (° C) ÄO: PO parts by weight Amine A ethylenediamine PO ÄO 58 0.25 2300 B triethylenetetramine PO ÄO 100 2.0 1500 C tetraethylene pentamine PO ÄO 62 1.0 1620 D tetraethylene pentamine ÄO PO 58.5 1.0 1620 E trisaminopropylamine PO ÄO 43 0.5 850 F 1,6-hexamethylenediamine PO ÄO 35 0.33 1500 G amine mixture of 1 mol each of diethylenetriamine + triethylenetetramine + PO ÄO 42.5 0.47 1830 tetraethylene pentamine H polyethylene imine (degree of polymerisation PO ÄO 46 0.5 3500 Pn # 1000) PO = propylene oxide ÄO = ethylene oxide example 1 100 parts of a cotton fabric are in a reel skid with a liquor ratio of Dyed 1:20 in a dye bath containing 5 g / l soda calc.

70 g / l table salt 2 ml / l sodium hydroxide solution 380bs and 3 parts by weight of the blue reactive dye of the color - index number C.I. 61 211 contains. The fleet temperature is increased from 20 to 800C within 30 minutes and at this temperature Held for 60 minutes.

This is followed by the washout procedure for the unfixed reactive dye carried out in the following way: The dye liquor is completely drained. then is made up with cold water, 2 g / l of the auxiliary A are added and with acetic acid adjusted to a pH of approx. 5. After heating the fleet to approx. 90 ° C or

until boiled and held at this temperature for 10 minutes the fleet is drained. The tissue is first briefly hot to simmering Water and then rinsed once with cold water.

The result is a blue coloration with good wash fastness (according to DIN 54 011, test 4, at 950C), grade 5.

For comparison, a sample of the above is used instead of the aid A. The dyeing described is washed out with a liquor containing 2 g / l of a nonionic Contains auxiliary obtained by reacting 1 mole of isononylphenol and 10 moles of ethylene oxide was produced, the result is a coloration which is obtained under the same test conditions a wash fastness of 3 is assigned.

Example 2 100 parts of a cotton yarn wound on cheeses are in a circulation apparatus (cross-coil dyeing apparatus) at a liquor ratio dyed 1:10 in a dyebath containing 5 g / l soda calc.

80 g / l Glauber's salt 2 ml / l sodium hydroxide solution 38be # and 4 parts by weight of the yellow reactive dye of the color - index number C.I. 13 245 contains. the The liquor temperature is increased to 800C within 30 minutes and at this point Maintained temperature for 75 minutes. The washout process of the reactive dye dyed cotton yarn is carried out in the manner described in Example 1, however, instead of the auxiliary indicated there, 2 g / l of the auxiliary are used E. A yellow dyeing with good wash fastness, rating 5, is obtained.

Example 3 A desized cotton fabric which has been pretreated as usual is on a padder with a liquor pick-up of approx. 80% (based on the weight the dry goods) padded with a liquor at room temperature, which in liters of water contains: 30 g / l of the reactive dye with the color index number C.I. 61 205: 1 30 g / l Glauber's salt calc. and 10 g / l of a polyacrylate as a thickener.

After intermediate drying on a hot flue at 1200C, the fabric becomes continuously developed on a pad steam system, initially on the Foulard with a chemical liquor at room temperature with a liquor pickup is padded by approx. 80%. The aqueous liquor contains 250 g / l Glauber's salt calc. and 40 ml / l sodium hydroxide solution 38 ° Bé.

The goods run through a steamer for 60 seconds at 102-105 ° C, then through the water lock of the damper, in which cold water overflows flows (as the first rinsing process) and then to wash out the unfixed reactive dye through the washing machine, which consists of 6 compartments: 1st compartment: cold water in the Overflow 2nd compartment: hot, almost boiling water 3rd compartment: washing bath with 2 g / l Auxiliary B, pH = 5 (acetic acid), 500C 4th compartment: Wash bath with 2 g / l auxiliary B, boiling 5th compartment: hot, almost boiling water 6th compartment: cold water in the overflow.

The result is a blue dyeing with good wash fastness.

For comparison, it is found that when using 2 g / l one Reaction product of 1 mole of isononylphenol + 10 moles of ethylene oxide instead of the auxiliary The result is a dyeing whose washfastness is one grade worse.

'Example 4 100 parts of a polyester wound on the piece of tree / Cotton (67/33) blend fabrics are in a circulation apparatus at a liquor ratio dyed 1:20 in a dyebath containing 0.5 ml / l acetic acid 60% 1 g / l of a condensation product from ß-naphthalenesulfonic acid and formaldehyde 1.5 parts of the disperse dye the C.I. No. 60,756 0.4 parts of the disperse dye having the C.I. No. 26 080 0.2 part of the disperse dye having the C.I. No. 61 115 contains.

The temperature is increased from 50 to 1300C and in about 30 minutes holds at this temperature for 60 minutes.

The cotton content is then dyed using a liquor ratio 1:20 in a fresh bath containing 5 g / l soda calc.

2 ml / l sodium hydroxide solution 380Be 1 g / l polyphosphate 1 g / l sodium m-nitrobenzenesulfonate 30 g / l common salt 3 parts by weight of the reactive dye of the formula by increasing the temperature from 200C to 800C in 30 minutes and then leaving it at this temperature for 60 minutes.

The washing process is then carried out as described in Example 1, where 3 g / l of aid D was used instead of aid A in the washing bath will. A brown dyeing with good wash fastness is obtained.

Example 5 A desized cotton fabric which has been pretreated as usual is on a padder with a liquor pick-up of approx. 80% (based on the weight the dry goods) padded with a liquor at room temperature, which in liters of water 40 g / l of the reactive dye of the color index no.

C.I. 61 200 16 ml / l sodium hydroxide solution 380Be6 contains 30 g / l Glauber's salt.

The goods are wrapped on a dock without intermediate drying and let it rest for 24 hours while rotating. Then the goods are in accordance with the procedure described in example 3 washed out on a washing machine, in order to irreversibly detach the non-fixed components of the reactive dye. Man receives a blue coloration with good wash fastness.

Claims (5)

patent claims 1. Process for washing out unfixed reactive dyes of cellulose fibers following the dyeing of cellulose fibers with reactive dyes or textile materials which consist of cellulose fibers or a mixture of them with other fibers contain, through the action of aqueous liquors, an auxiliary contain, at temperatures from 15 to 1000C, characterized in that as Aids used alkoxylated polyamines, which in 1 pointer aqueous solution Have a cloud point of at least 18 ° C and st eile by converting 100 weight an amine with at least 2 nitrogen atoms and at least one alkoxylatable Group on the nitrogen atom with a) ethylene oxide and b) propylene oxide or butylene oxide or mixtures of a) and b) are obtained, the molar ratio a: b 0.2: 1 to 5: 1 and the sum of the parts by weight a) + b) is 50 to 10,000. 2. The method according to claim 1, characterized in that as an aid alkoxylated diamines can be used. 3. The method according to claim 1, characterized in that as an aid alkoxylated polyalkylenepolyamines can be used. 4. The method according to claim 1, characterized in that as an aid alkoxylated polyethyleneimines are used. 5. The method according to claims 1 to 4, characterized in 'characterized that the auxiliaries are used in an amount of 0.2 to 10 g / l in the liquor.