DE19703447A1 - Complexing agents for textile dyeing and pre- or post- treatment - Google Patents

Abstract

The use of bis-(dicarboxylic acid) diaminoalkylene derivatives of formula (I) as complex-forming agents in textile dyeing and pre- or post-treatment is claimed. In (I), R<1>, R<2> = H, 1-8C alkyl, 2-8C alkenyl, phenyl, benzyl, or 1-4C hydroxyalkyl or hydroxy-halo-alkyl; M = H, alkali metal, ammonium or substituted ammonium; l, m, n = 0-6; A1 = 2-3C alkylene, optionally substituted on one, two or all C atoms with one or two hydroxy, 1-6C alkyl, 2-6C alkenyl, 3-6C cycloalkyl, or 3-8C cycloalkenyl, aryl, alkylaryl, heteroaryl or alkyl-heteroaryl groups. Also claimed are: (i) a process for the pretreatment, post-treatment or dyeing of textiles or textile precursors in the manufacture or processing of textiles, in which the material is subjected to a treatment bath containing 0.01-20 (preferably 0.1-10, more preferably 0.5-3) g/l (I), and (ii) baths used for this process containing (I) in the above amounts.

Description

The invention relates to the use of bis (dicarboxylic acid) diaminoalkylene derivatives of the formula (I)

in the
R ¹ and R ^{2 are} H, a C ₁ to C ₈ alkyl or a C ₂ -C ₈ alkenyl, phenyl or benzyl, hydroxyalkyl or hydroxyhalogen alkyl having 1 to 4 carbon atoms,
M denotes hydrogen, alkali metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts,
l, m and n each represent numbers from 0 to 6 and
A _{1 is} an alkylene with 2 or 3 carbon atoms, which is unsubstituted or on one, two or all C atoms, once or twice with hydroxy, a C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₈ cycloalkylene nyl, aryl, alkylaryl, hetaryl, alkylhetaryl radical may be substituted.

The invention further relates to a method for pretreatment and aftertreatment or dyeing of textiles or textile precursors in textile production and / or textile processing as well as pre-, post-treatment or dyeing baths for use in the manufacture or processing of Textiles or their preliminary stages.

When pretreating textiles, the textile material should be as large as possible are freed from interfering accompanying substances of the fibers, so that an oxidati ve bleach (e.g. with hydrogen peroxide) and the following dyeing and / or Printing on the textile material is facilitated or only made possible.

Especially in the case of bleaching with hydrogen peroxide, in the case of cellulose-containing textiles often show greater damage to goods. Furthermore because of the growth and production-related, strong impurities of the fibers often only insufficient bleaching effects, measured as white just received.

The pretreatment of cotton-containing textile goods is achieved optimal effects are therefore often carried out in several stages; in the case of the pre knitted fabrics and yarns are treated in two stages (pre extraction or alkaline decoction and bleaching) and in the case of Three-stage fabrics (desizing and alkaline decoction and bleaching). Heavy metals and alkaline earth interfere with bleaching with hydrogen peroxide lien in cotton because of its origin, its growth and / or the harvesting conditions are included to different degrees.  

Of the elements mentioned, heavy metal ions in particular catalyze such as Fe, Cu, Mn or Zn, the radical decomposition of the peroxide (Destabili sation) and often lead to poor bleaching results and too severe damage to the goods. Alkaline earth metals can also be good Prevent bleaching results. In principle there are two options To minimize the disruptive influence of the metal cations, namely the one Use of complexing agents directly in the bleaching liquor or one separate pre-cleaning of the fibers, e.g. B. also in the context of desizing, before the actual bleaching stage.

The above-mentioned metal ions interfere with the dyeing process in that when it affects the uniformity of the color and the color yield gene.

In order to counteract these effects of the metal compounds contained in the cotton or in the water used, ions have hitherto been used in the textile industry as complexing agents for alkaline earth metals and especially heavy metal ions, such as, for. B. Cu ² ⁺, Fe ² ⁺, Mn ² ⁺ ions, as well-known and proven systems polyphosphates, aminopolyphosphonates, such as. B. EDTMP (ethylenediaminetetramethylenephosphonic acid), DTPMP (diethylenetriaminepentamethylenephosphonic acid) or aminopolycarboxylic acids, such as. B. EDTA (ethylenediaminetetraacetic acid) used.

These known means all show in particular a missing or slow biodegradability. Other weaknesses are still improving iron, copper and manganese binding assets and their not optimal stabilizing effect in bleaching baths and bleaching systems.

WO-A 94/03572, WO-A 94/11099, WO-A 94/25099 are complexing agents according to the following formula (I)

in the
R ¹ and R ^{2 are} H, a C ₁ to C ₈ alkyl or a C ₂ -C ₈ alkenyl, phenyl or benzyl, hydroxyalkyl or hydroxyhalogen alkyl having 1 to 4 carbon atoms,
M denotes hydrogen, alkali metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts,
l, m and n each represent numbers from 0 to 6 and
A _{l is} an alkylene with 2 or 3 carbon atoms, soft unsubstituted or on one, two or all C atoms, single or double with hydroxy, a C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₈ cycloalkylene nyl, aryl, alkylaryl, hetaryl, alkylhetaryl may be substituted,
known, which are used in detergents and cleaning agents. Furthermore, these compounds according to formula (I) mentioned above are known as agents for removing stains (WO-A 95/25159), as viscosity regulators (WO-A 94/11099) or as corrosion inhibitors (WO-A 95/29220).

Taking into account the above problems in pre-, It is aftertreatment and dyeing of textiles or their preliminary stages  Object of the invention, complex image in the mentioned fields of application to provide ner that do not have the disadvantages mentioned. Especially the complexing agents are intended to ensure uniformity when used Allow coloring and have a high biodegradability.

This object is achieved according to the invention by using bis (dicarboxylic acid) diaminoalkylene derivatives of the formula I.

in the
R ¹ and R ^{2 are} H, a C ₁ to C ₈ alkyl or a C ₂ -C ₈ alkenyl, phenyl or benzyl, hydroxyalkyl or hydroxyhalogen alkyl having 1 to 4 carbon atoms,
M denotes hydrogen, alkali metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts,
l, m and n each represent numbers from 0 to 6 and
A _{1 is} an alkylene with 2 or 3 carbon atoms, which is unsubstituted or on one, two or all C atoms, once or twice with hydroxy, a C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₈ cycloalkylene nyl, aryl, alkylaryl, hetaryl, alkylhetaryl may be substituted,
solved in textile dyeing, pre-treatment or post-treatment.

Another aspect of the invention is the provision of a method for Pretreatment, aftertreatment or dyeing of textiles or textile precursors the manufacture or further processing of textiles, which includes the step that containing a treatment bath on the textiles or textile precursors 0.01 to 20 g / l, preferably 0.1 to 10 g / l of the compounds mentioned according to formula (I).

The invention further relates to a pre-treatment, post-treatment or Dye bath for use in the manufacture or processing of Textiles or their precursors, containing 0.01 to 20 g / l, preferably 0.1 up to 10 g / l of a compound of the formula (I) mentioned.

In a preferred embodiment of the use according to the invention, the process according to the invention or the baths according to the invention, the compounds of the formula (I) used are those in which R ¹ and / or R ^{2 is} H and / or —CH ₃ , n and / or m denotes zero, l 1 or 2 and A _{1 are} ethylene, propylene and / or 2-hydroxypropylene groups.

In a particularly preferred embodiment, the compound of the formula (I) mentioned is ethylenediaminodisuccinate (EDDS), (2-hydroxypropylene) - 1,3-diaminodisuccinate (HPDDS) or ethylenediaminodiglutarate (EDDG) [R ¹ = R ² = H; 1 = 2; A ₁ = ethylene] and / or their alkali metal, ammonium and / or substituted ammonium salts. Particularly suitable salts of this type are the sodium, potassium or ammonium salts, in particular the tetrasodium, tetakalium or tetraammonium salt, and also organic tetraamine salts with a tertiary nitrogen atom.

In particular, the bases on which the organic amine salts are based come re tertiary amines, such as trialkylamines having 1 to 4 carbon atoms in the alkyl radical, such as trimethylamine or triethylamine, and trialkanolamines with 2 or 3 C atoms in the alkanol radical, preferably triethanolamine, tri-n-propanolamine or Triisopropanolamine, in question.

The compounds used according to the invention according to the Formula (I) are mainly used to remove interfering heavy metals such as iron, copper, manganese or zinc or to remove water hardness (Complexation of calcium or magnesium salts). In the Use according to the invention, the compounds according to the genann th formula (I) in amounts of 0.01 to 20 g / l, preferably 0.1 to 10 g / l, in particular 0.5 g to 3 g / l.

Through the use according to the invention in pretreatment, dyeing, over dyeing and post-treatment of the fabrics, the fastness and rubbing and wash fastness as well as the uniformity of the color improved and increased.

The compounds used according to the invention are known by means of Process synthesized. This creates at least 2 asymmetrical C atoms. Depending on the starting substances used, for example naturally occurring chiral substances such as L-aspartic acid, or stereoselectively prepared starting materials or substances present as a racemate, such as D, L-aspartic acid, or achiral compounds such as Maleic acid and the special reaction conditions, such as the use of stereoselective catalysts or chiral auxiliaries, and possibly after the synthesis made separations, such as wise stereoselective crystallization, chromatographic separation, optical Cleavage, optically pure products are obtained in the known processes  or mixtures of optical isomers. With the optical isomers it can are enantiomers, diastereomers or meso compounds.

The effectiveness of the compounds of the formula (I) mentioned as The complexing agent is independent of its stereochemistry; however, it depends Biodegradability strongly depends on the stereochemistry. For example the (S, S) isomer of the above compound EDDS rapidly and completely biodegraded, whereas the racemic mixture only partially biodegradable. That is why they are chiral α-atom (S) -configured compounds of particularly preferred derivatives of Compounds used according to the invention according to the general formula (I).

The compounds used according to the invention are obtained in principle by processes known per se by reacting amino acids (aspartic acid, glutamic acid) with dibromoethane or 2-hydroxydibromopropane to give the degradable (S, S) compounds. The only partially degradable racemates are obtained by reacting maleic anhydride with ethylenediamine to EDDS, glutamic acid with 1,2-dibromoethane to EDDG and by converting maleic anhydride with 2-hydroxy-1,3-dibromopropane to HPDDS [cf. J. Majer et al. [Chem. Zvesti 29 (1975) 44-51]; Neal and Rose: Inorg. Chem. 7 (1% 8) 2405-2412]. Dvorakova et al .: Chem. Zvesti 27 (1973) 313 ff.]
When used in the dye baths according to the invention and before and after treatment baths, the compounds of the formula (I) mentioned are used together with customary dyes and auxiliaries. Vat, reactive, direct, dispersion dyes and mixtures thereof are generally used as dyes. The textiles or textile precursors to be dyed or post-treated are usually woven fabrics, knitted fabrics or knitted fabrics as well as yarns or flakes with fibers of cotton, polyester, cellulose triacetate and mixtures thereof. Fibers and their mixtures of polyamide, wool, polyacrylonitrile, viscose and / or cellulose acetate can also be used.

In addition to the dyes, the dye baths can usually be found in the Textile dyeing used aids such as dispersing, leveling, dyeing accelerators, anti-crease agents, etc. included.

The compounds of formula (I) used according to the invention have their use in the manufacture or processing of textiles or their precursors, in addition to their good biodegradability, are also very low toxicity potential. So shows (S, S) -EDDS in the Zahn-Wellens test biodegradability of <90% under standard conditions (28-day value). In contrast, the biodegradability is more common wisely used ethylenediaminetetraacetic acid under the same conditions less than 10%.

The dyeing process according to the invention and / or the dyeing aftertreatment steps can be carried out both continuously and discontinuously will.

The invention is illustrated by the examples listed below explains:  

Manufacturing examples example 1 S'S-EDDS

151 g of L-aspartic acid were at 30 ° C in a solution of 37.2 g NaOH dissolved in 252 g of water and then with 51.6 g of calcium hy hydroxide added. 106 g of dibromoethane were then added to the mixture and heated to 95 ° C. in a closed reactor under a nitrogen atmosphere. The pH was adjusted by adding a total of 89.7 g of 47% by weight NaOH the solution kept at 11.2. After 7 h at 95 ° C was still for Heated to 105 ° C for 1 h. After cooling to room temperature, Diluted 431 g of water and to a pH with 36% by weight hydrochloric acid acidified by 3. 118 g of S, S-EDDS were obtained in crystalline form, correspondingly 71% yield.

Example 2 S'S-EDDG

166 g of L-glutamic acid were at 30 ° C in a solution of 37.2 g of NaOH dissolved in 252 g of water and then with 51.6 g of calcium hydroxide transferred. The mixture was then mixed with 106 g of dibromoethane and heated to 95 ° C. in a closed reactor under a nitrogen atmosphere. By The addition of a total of 89.7 g of 47% by weight NaOH made the pH of the Solution kept at 11.2. After 7 h at 95 ° C., the mixture was still open for 1 h Heated to 105 ° C. After cooling to room temperature, 431 g Diluted water and with 36 wt .-% hydrochloric acid to a pH of 3 acidified. 31 g of S, S-EDDG were obtained in crystalline form, corresponding to 17% Yield.  

Example 3 S'S-HPDDS

151 g of L-aspartic acid were at 80 ° C in a solution of 80 g NaOH dissolved in 300 g of water. The mixture was then 64.5 g 1,3-dichloro-2-propanol added. After 20 h at 80 ° C., the mixture was still open for 1 h Heated to 100 ° C. After cooling to room temperature, it became saturated acidified to a pH of 3 with methanolic hydrochloric acid. Here 38.4 g of S, S-HPDDS were obtained in crystalline form, corresponding to a yield of 21% on aspartic acid.

Examples of use Dyeing polyester fibers example 1

100 g of polyester fibers were in a printing apparatus in 2000 g of water Hardness 20 ° dH with 1 g of Disperse Rad 91 and 4 g of one usual naphthalenesulfonic acid-formaldehyde condensate as dispersant, 4 g of a conventional mixture of aromatic esters and nonionic Surfactants as leveling agents and 1 g / l (calculated on dry weight) of Complexing agent from preparation example 1 added, with acetic acid to pH 4.5 to 5.0, heated to 130 ° C and 60 min at this temperature colored. It was then cooled and washed. You got a complete Men level and intense coloring.

Comparative Example A

The coloring from Example 1 was repeated without complexing agent. Man received a more uneven coloring with only about 65% of the color depth as in Example 1.  

Example 2

100 g polyester fibers were in a printing apparatus in 2000 g water, containing 0.4 g of copper sulfate hexahydrate with 1.5 g of Disper dye se wheel 227 and 2 g of a conventional naphthalenesulfonic acid formaldehyde Condensate as a dispersant and 0.5 g / l of the complexing agent from Her position example 1 added, adjusted to pH 4.5 to 5 with acetic acid, in Heated from 70 ° C to 137 ° C for 30 minutes and dyed at 137 ° C for 45 min. It was then cooled and washed. You got a level and intense bright coloring.

Comparative Example B

The coloring from example 2 was repeated without complexing agent. Man received a color weaker, significantly cloudy and blue color.

Example 3

The coloring was carried out as in Example 2, the water being 1 g Contained ammonium iron (III) sulfate dodecahydrate. The resulting color was completely irrelevant and intense.

Comparative Example C

The coloration from Example 3 without complexing agent fell significantly less color and bluer out.

Dyeing potyester / cellulose blended fabrics Example 4

100 g of a mixed fabric made of polyester and cellulose (1: 1) were in a pressure apparatus in 1500 g water of hardness 10 ° dH with 1.5 g one usual naphthalenesulfonic acid-formaldehyde condensate as a dispersant,  2 g of a conventional polyacrylate as a protective colloid, 1.5 g of the complexing agent from preparation example 1, 1.5 g of the dye Disperse Blue 148 and 1.5 g of the dye Vat Blue 4 added, with acetic acid to pH 4.5 to Set 5.0, heated to 130 ° C and dyed at this temperature for 60 min. The mixture was then cooled to 80 ° C. and at this temperature as usual Treated for 15 min with sodium hydroxide solution and sodium dithionite. Then was stained for 15 to 20 min at 50 to 60 ° C. You got one perfectly level and intense coloring.

Comparative Example D

The coloring from example 4 was repeated without complexing agent. Man received a more uneven and 40% weaker shade.

Dyeing cotton Example 5

Bleached cotton jersey was 1: 20 in one Laboratory cup bath colored. The dye liquor with a water hardness of 20 ° dH contained 2 g / l of Vat Blue 4 dye, 18 ml / l sodium hydroxide solution (38 ° Bé), 6 g / l sodium dithionite and 1 g / l of the complexing agent from Example 1. Das Staining vessel was placed in the heating bath at 25 ° C and at 60 ° C heated, then dyeing at this temperature for 45 minutes. Subsequently was the coloring in the usual way by oxidizing, rinsing and soaping completed.

A level and true-to-color dyeing was obtained.  

Comparative Example E

The coloring from example 5 was repeated without complexing agent. Man got an irregular, spotty coloring with only about 20% of the color depth like in Example 5.

Dyeing polyester Example 6

100 g of polyester fibers are in a printing apparatus in 2000 g of water, containing 1 g of ammonium iron (III) sulfate dodecahydrate, with 2.5 g of the color Disperse Blue 148, 4 g of a commercially available naphthalenesulfonic acid Formaldehyde condensate as a dispersant and 1 g (calculated on Troc weight) of the complexing agent from Example 1, with acetic acid pH 4.5-5 adjusted, heated to 130 ° C and 60 min at this temperature colored. It was then cooled and washed.

A completely level and intensive coloring was obtained.

Comparative Example F

The coloring from example 6 was repeated without complexing agent. Man got a cloudy and reddish color.

Example 7

The coloring was carried out as in Example 6, but with 2 g of color Disperse Red 60 and 0.4 g copper sulfate hexahydrate. You got one completely level and intense red coloring.

Comparative Example G

The coloring from example 7 was repeated without complexing agent. Man got a color weaker, cloudy and blue color.  

Use of the complexing agents in the bleaching liquor Example 8

100 g of cotton knitwear were in a printing apparatus in 2000 g of what water with a hardness of 10 ° dH with 6 ml / l hydrogen peroxide (35% by weight), 2 g / l caustic soda, 1 g / l nonionic surfactant and 2 g / l (calculated on Dry weight) of the complexing agent from Preparation Example 1 added Heated at 100 ° C and bleached at 100 ° C for 60 minutes. After that it became like washed and rinsed as usual. A bleached knitted fabric was obtained a degree of whiteness (measured according to Berger with a spectroflash 500 Company ICS-Texunion) of 75.

Comparative Example H

With the same working method, but without complexing agents in the bleaching liquor, you got a whiteness (Berger) of 69, a significantly lower one White effect.

Use of the complexing agent in the desizing fleet Example 9

A twill fabric made of raw cotton of 310 g / m ² , finished with water-soluble starch derivatives, was impregnated with a liquor of 70 ° C and a liquor absorption of approx. 100% (corresponding to a liquor ratio of approx. 1: 1), the 5 g / 1 l of a conventional nonionic surfactant and 3 g / l of complexing agent from preparation example 1 and had been adjusted to a pH of 8.5, treated, then washed twice with hot and twice with cold. Thereafter, peroxide bleaching was carried out in a steaming device at 100 ° C for 15 minutes. The bleaching liquor applied with a liquor pickup of 125% (corresponding to a liquor ratio of 1: 1.25) contained 40 g / l hydrogen peroxide (35% by weight), 15 g / l caustic soda, 1 g / l 10 times oxyethylated nonylphenol and 5 g / l commercial bleach stabilizer (Mg-containing stabilizer based on phosphonic acid and polyacrylate). After washing and drying, a bleached cotton fabric with a Berger degree of whiteness of 83 and a DP value of 2060 was obtained (DP value = average degree of polymerization; measure of fiber damage; the higher the values, the less the damage. The value became viscosimetric determined in copper cuoxam solution).

Comparative Example 9

With the same working method, but without complexing agent in the desizing brisk, became a lower whiteness (Berger) of 76 and a lower Obtained DP value of 1750.

Use of the complexing agent in the bleaching liquor Example 10

A desized cotton-nettle fabric of 150 g / m ² was impregnated with a liquor pick-up of 100% and bleached in a steaming device at 100 ° C. for 15 minutes. The applied bleaching liquor had been prepared with water at 10 ° dH and contained 40 ml / l hydrogen peroxide (35% by weight), 13 g / l caustic soda, 1 g / l of a conventional nonionic ethoxylate and 3 g / l of the complexing agent from preparation example 1. After washing and drying, a bleached fabric with a degree of whiteness (Berger) of 80 and a DP value of 2100 resulted.

Comparative Example J

With the same working method, but without complexing agents in the bleaching liquor, became a lower whiteness (Berger) of 75 and a lower DP value preserved from 1800.

Claims (6)

1. Use of bis (dicarboxylic acid) diaminoalkylene derivatives of the formula I.
in the
R ¹ and R ^{2 represent} H, a C ₁ -C ₈ -alkyl or a C ₂ -C ₈ -alkenyl, phenyl or benzyl, hydroxyalkyl or hydroxyhalogenoalkyl having 1 to 4 carbon atoms,
M denotes hydrogen, alkali metal, ammonium or substituted ammonium in the corresponding stoichiometric amounts,
l, m and n each represent numbers from 0 to 6 and
A _{1 is} an alkylene with 2 or 3 carbon atoms, which is unsubstituted or on one, two or all C atoms, once or twice with hydroxy, a C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ cycloalkyl or C ₃ -C ₈ cycloalkenyl, aryl, alkylaryl, hetaryl, alkyl ketaryl radical may be substituted,
as a complexing agent in textile dyeing, pre-treatment or post-treatment. 2. Use according to claim 1, wherein in the compound of the formula (I) R ¹ and / or R ^{2 is} H and / or -CH ₃ , n and m are zero, l 1 or 2 and A _{1 are} ethylene, propylene or 2- Are hydroxypropylene. 3. Use according to claim 1 or 2, wherein as a compound according to Formula (I) ethylene diaminodisuccinate (EDDS), (2-hydroxypropylene) -1,3- diaminodisuccinate (HPDDS) or ethylenediaminodiglutarate (EDDG) and / or their alkali metal, ammonium or substituted ammonium salts be used. 4. Use according to any one of the preceding claims, wherein the Compounds of formula (I) in amounts of 0.01 to 20 g / l, preferably as 0.1 to 10 g / l, particularly preferably 0.5 to 3 g / l used will. 5. Process for pre-treatment, post-treatment or dyeing of textiles or Textile preliminary stages in textile production or textile further processing, comprehensively the step that on the textile or Textilvor stage a treatment bath containing 0.01 to 20 g / l, preferably 0.1 up to 10 g / l, particularly preferably 0.5 to 3 g / l of the compound according to of formula (I) is allowed to act.   6. Pre-, post-treatment or dye baths for use in manufacturing provision or further processing of textiles or their preliminary stages, containing 0.01 to 20 g / l, preferably 0.1 to 10 g / l, especially before adds 0.5 to 3 g / l of a compound according to formula (I).