EP0828023B1 - Agent for printing or dyeing textile materials - Google Patents

Description

The present invention relates to a process for dyeing or printing textile materials from wool, cotton, regenerated cotton, jute, sisal, polyester, polyamides, polyurethanes, polyacrylonitrile or polypropylene fibers or mixtures thereof using agents which contain polyaspartic acid (PAS). or a derivative thereof. The invention further relates to the use of these agents for dyeing or printing said textile materials.

In the course of dyeings of textile materials made of natural and / or synthetic fibers or in the printing of these textile materials, problems of various kinds frequently occur, for example with regard to levelness, the stability of the liquors or printing pastes or the formation of running wrinkles. In most cases it has been possible to arrive at a satisfactory solution to these problems by adding tools which could be optimized to the problem addressed. Unsatisfactory in most cases, however, is the biodegradability of the aids used, which leads to a heavy burden on the respective wastewater. Examples of aids with poor biodegradability are sulfonated naphthalene-formaldehyde condensates, ethoxylated fatty amines, lignosulfonates, polymers or copolymers of (meth) acrylic acid.

DE-A 4 439 990 discloses leather tanning agents and colorants for dyes which contain, inter alia, polyaspartic acid, its salts and anhydrides.

From US-A 5,408,029 fiber treatment agents are known, which may contain polymers of amino acids, including aspartic acid.

From US-A 5,131,768 refill inks are known which contain, inter alia, polyaspartic acid.

From US-A 3,846,380 a manufacturing method for polyaspartic acid is known, as it can be used in the above-mentioned prior art.

Finally, DE-A-2 253 190 discloses polyamino acid derivatives, processes for their preparation and their use as surfactants, as well as detergents and cosmetics containing these compounds.

It has now been found that successful dyeings or prints can be produced by adding auxiliaries to the dyebaths (baths) or printing pastes which contain PAS or a derivative thereof and optionally other known components. PAS and its derivatives are characterized by excellent biodegradability.

The invention relates to a process for dyeing or printing the textile materials mentioned by treating these textile materials with dyeing liquors or printing pastes which contain dyeing or printing auxiliaries, which is characterized in that these auxiliaries PAS or a derivative thereof and as further component optionally one or more contain the above-mentioned components, wherein the aids in an amount of 0.2 to 10 wt .-%, based on the weight of the goods (weight of the textile materials) are used.

The invention also relates to the use of said agents as auxiliaries for dyeing or printing said textile materials.

The agents to be used in the process according to the invention are characterized above all by their content of PAS or a derivative thereof. As derivatives of the PAS in question as cations Li ^⊕, Na ^⊕, K ^⊕, Mg ^⊕⊕, Ca ^⊕⊕, NH ₄ ^⊕, H ₃ N come above all salts (CH ₂ CH ₂ OH) ^⊕, H ₂ N (CH ₂ CH ₂ OH) ₂ ^⊕ or HN (CH ₂ CH ₂ OH) ₃ ^⊕ included. The manufacture and use of PAS and its derivatives has long been the subject of numerous publications and patents. Reference may be made to J. Org. Chem. 26 (1961), 1084, US 4,839,461 (= EP 256,366), DE-A 2,253,190, US 5,296,578, US 5,288,783, EP 593,187, DE -A 42 21 875, DE-A 49 00 020 and DE-A 43 07 114.

Said US '461 describes the preparation of PAS from maleic anhydride, water and ammonia. Maleic anhydride is converted to the monoammonium salt in an aqueous medium with the addition of concentrated ammonia solution. In a preferred embodiment, PAS is prepared by subjecting maleic ammonium salt to a thermal, optionally continuous, polymerization at 150 to 180 ° C. in a reactor at a residence time of 5 to 300 minutes, and to obtain the obtained polysuccinimide by hydrolysis to give PAS or a salt implemented.

bevorzugt

Zusätzlich können durch geeignete Reaktionsführung und Wahl der Edukte weitere wiederkehrende Einheiten enthalten sein, z. B.

1. a) Äpfelsäure-Einheiten der Formel
   
2. b) Maleinsäure- und Fumarsäure-Einheiten der Formel
   

In a preferred embodiment, the PAS contains essentially recurring succinyl units of the following structure:

prefers

In addition, further repeating units can be contained by suitable reaction control and choice of the educts, for. B.

1. a) Malic acid units of the formula
   
2. b) maleic acid and fumaric acid units of the formula
   

The analysis of the chemical structure is preferably carried out with ¹³ C-NMR, FT-IR and after total hydrolysis with HPLC, GC and GC / MS.

In many manufacturing processes, not the pure acids but first the corresponding anhydrides, for example polysuccinimide. Such polymerization products can be converted into a PAA-containing salt by reaction with a base, optionally in the presence of water. This conversion of PSI-containing to PAA-containing polymers is then done in a suitable device by hydrolysis. Preference is given to a pH between 5 and 14 is suitable. In a particularly preferred form, a pH of 7 to 12 is selected, in particular by the addition of a base. Suitable bases are alkali metal hydroxides and alkaline earth metal hydroxides or carbonates such as, for example, sodium hydroxide solution, potassium hydroxide solution, soda or potassium carbonate, ammonia and amines such as triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamines, etc. Particular preference is given to free acids in addition to their Na, K or Ca. salts.

The temperature in the hydrolysis is suitably in a range up to the boiling point of the PSI suspension and preferably at 20 to 150 ° C. The hydrolysis is optionally carried out under pressure.

However, it is also possible to obtain the free polyaspartic acid by purely aqueous hydrolysis or treatment of the salt with acids or acidic ion exchangers. The term "polyaspartic acid" (= PAA) in the present invention also includes the salts unless expressly stated otherwise. The finished product is obtained by drying, preferably spray drying.

Preferred polymers have a molecular weight by gel permeation chromatographic analyzes (from Mw = 500 to 10,000, preferably 700 to 5,000, particularly preferably 1,000 to 4,500). In general, the proportion of the beta-form is more than 50%, preferably more than 70%.

Polysuccinimide which can be used at elevated temperature, preferably at 100 to 240 ° C., if appropriate in the presence of a catalyst, such as in an amount of 0.01 to 1% by weight, can be used as a derivative of PAS in addition to the salts with the abovementioned cations. , based on the PAS, of an acid catalyst, such as sulfuric acid, phosphoric acid, methanesulfonic acid and others occur. However, polysuccinimide is also directly involved in a number of manufacturing processes. In such a case, polysuccinimide may be converted to a salt having one of the above-mentioned cations by reaction with a base, optionally in the presence of water. This transformation happens in Connection to the manufacturing process in a suitable device by hydrolysis. Preference is given here to a pH of between 5 and 14, preferably pH = 7 to 12. Suitable bases for carrying out an alkaline hydrolysis are alkali metal and alkaline earth metal hydroxides or carbonates, for example sodium hydroxide solution, potassium hydroxide solution, soda, potassium carbonate, furthermore ammonia and amines, such as triethylamine, triethanolamine, diethylamine, diethanolamine and ethanolamine.

Further derivatives of PAS which can be used in the process according to the invention are those in which some of the carboxyl groups present in the PAS are present as amides. The preparation of such PAS amides can be carried out from said polysuccinimide with primary or secondary amines (DE-A 22 53 190, EP 274 127, EP 406 623, EP 519 119, US 3,846,380, US 3,927,204, US 4,363. 797). The residual succinimide structures remaining after amide formation can then be converted to free carboxyl or carboxylate groups by the said hydrolytic opening in the presence of bases. In preferred derivatives, from 5 to 50 mol%, preferably from 10 to 35 mol%, of the aspartic acid units present contain such amide structures, while the remaining carboxyl groups are present in the form of carboxylate groups.

The agents to be used in the process according to the invention contain from 5 to 100% by weight, preferably from 10 to 50% by weight of PAS, their derivatives (preferably their salts and amides) or mixtures thereof, based on the total weight of the compositions. The amide groups of PAS derivatives contain at the amide nitrogen saturated or unsaturated aliphatic radicals having 2 to 20 carbon atoms, which may be substituted by hydroxyl groups, or cycloaliphatic radicals having 6 to 12 carbon atoms. Examples of such radicals in the amide groups are: hydroxyethyl, hydroxypropyl, butyl, hexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl or cyclohexyl.

The agents to be used in the process according to the invention may contain, in addition to their content of PAS or a derivative thereof, further components. Among the other components are wetting agents, emulsifiers, dispersants or a mixture of several of them, which may be anionic or non-ionic in a known manner. Examples of these are: reaction products of aliphatic, araliphatic or aromatic hydroxyl compounds, carboxylic acids, carboxamides or amines with ethylene oxide, their sulfuric acid half esters or phosphoric acid partial esters, fatty acid esters of mono- or polysaccharides or fatty acid sorbitan esters and their oxyethylation products, C ₁₀ -C ₂₀ -alkanesulfonates, C ₈ -C ₁₂ -alkylbenzenesulfonates, C ₈ -C ₁₈ -alkyl sulfates or phosphates or condensed aromatic sulfonic acids, such as naphthalene-formaldehyde sulfonates. Substances of the type mentioned can also serve as leveling agents. They are known to those skilled in these missions.

Solubilizers as further components are, for example, glycols, mono- to tetraalkylene glycols, their ethers or esters with C ₁ -C ₄ -alcohols or C ₁ -C ₄ -carboxylic acids.

Defoamers as further components are, for example, defoamers containing vegetable oils or mineral oils, in particular propylene oxide-ethylene oxide block polymers.

Occasionally reducing agents, oxidizing agents, reserving agents, pH regulators, complexing agents or more of them may be present in an amount of from 0 to 10% by weight, based on the total weight of the agents to be employed in the process according to the invention, which amounts to the amount PAS and the surfactants mentioned above. The use of such agents is familiar to the skilled worker and described, for example, in Chwala / Anger, Handbuch der Textilhilfsmittel, Verlag Chemie, Weinheim 1977.

The said further components, their production and availability are known as such to the person skilled in the art. Of course, more of the other components mentioned can be used to achieve optimized dyeings or textile prints.

Preferably, at least one of said other components is present. According to the invention, they are present in an amount of 95 to 0% by weight, preferably 90 to 50% by weight, based on the total weight of the compositions according to the invention.

Textile materials which are dyed or printed using the agents to be used in the process according to the invention are wool, cotton or regenerated cotton, as well as jute or sisal.

As synthetic fibers such as polyesters, polyamides, polyurethanes, polyacrylonitrile or polypropylene may be mentioned.

The dyeing or printing of the textile materials is carried out with the dyes suitable for the fibers used, which is basically known to the person skilled in the art. Suitable classes of dyes for this purpose are derived, for example, from the group of acid dyes, sulfo groups-free or sulfo-containing metal complexing agents, reactive dyes, vat dyes, direct dyes, sulfur dyes, cationic dyes, disperse dyes and pigments.

The agents to be used in the process according to the invention are preferably used for dyeing cotton with direct dyes and reactive dyes, dyeing polyester fibers with disperse dyes or dyeing cotton-polyester blends with direct or reactive dyes and disperse dyes. The dyeing or printing of the textile materials mentioned takes place in known processes, such as in the exhaust process, in the continuous process, in the cold pad-stay (KKV) process and others, as well as in the textile printing process known to the person skilled in the art. The amounts of textile auxiliaries to be used in the individual processes, the temperatures to be used, the liquor lengths and concentrations are known to the person skilled in the art. The agents to be used in the process according to the invention are used in an amount of from 0.2 to 10% by weight, based on the weight of the textile material to be dyed or printed.

With the aid of the agents to be used in the process according to the invention, extremely stable dyebaths and, in turn, dyeings having excellent levelness and brilliance are obtained. In addition, the formation of running wrinkles is reduced or completely avoided. Corresponding advantages are also obtained in textile printing. Here, the non-environmentally friendly polyacrylate used otherwise as a thickener in dyeing or printing auxiliaries can be completely or partially replaced by the agent to be used in the process according to the invention.

The agents to be used in the process according to the invention have excellent biodegradability and therefore contribute to a reduction in the wastewater load of textile factories. In the case of the partial or complete replacement of polyacrylate obtained further low viscose dyeing liquors.

example 1

100 g of bleached cotton yarn were dyed in a cross-dyeing apparatus at a liquor ratio of 1:10 at 80 ° C using a dyeing liquor containing per liter 4 g Reactive Green 021 and 2 g of the adjuvant described below. After a dyeing time of 10 minutes, 80 g of sodium chloride were added, after a further 30 minutes 5 g of sodium bicarbonate and, after 30 minutes, finally 10 g of sodium carbonate. The staining was completed in another 60 minutes. A dyeing of excellent levelness was obtained and there were no filtrations visible on the bobbin.

The auxiliary used consisted of an aqueous solution containing 12% of the sodium salt of PAS and 10% of the sodium salt of a sulfonated naphthalene-formaldehyde condensation product.

Example 2

Cotton knit fabric having a basis weight of 250 g / m ² was dyed in the manner described in Example 1 using Reactive Blue 116 instead of the dyestuff mentioned therein.

A blue color of excellent levelness was obtained. The dyeing liquors used had a very good stability, as a result of which no smears were produced in the dyeing apparatus and thus no stains on the dyed material.

Example 3

Bleached cotton gabardine having a basis weight of 260 g / m ² was dyed by the pad cold pad process at a liquor pick-up of 80% using a liquor which was 30 g in Reactive Green 021, 2.5 g PAS, 2 g a commercial wetting agent (eg a reaction product of isotridecanol with 6 moles of ethylene oxide), 20 g of sodium carbonate and 3 g of sodium hydroxide solution of 38 ° Be contained. The residence time of the material in the wet state was 48 hours. After washing, a green color of excellent levelness was obtained, in addition, no so-called edge or end effluent was observed.

Example 4

A fabric of cotton / polyester (80:20) was dyed on a Baumfärbeapparat in the liquor ratio 1:14 by the two-bath method. The first bath contained besides 0.385% (based on textile material) Disperse Yellow 042 and 1.9% Disperse Blue 060 1 g / l of the PAS amide described below as dispersing agent and 0.5 g / l of a commercially available leveling agent (eg a 1 : 1-mixture of stearic acid x6 EO and nonylphenol x10 EO). The staining was started at 80 ° C. With a heating rate of 1 ° C / min was heated to 130 ° C and dyed at this temperature for 45 min. It was then dyed with a second bath at 80 ° C, which initially contained 2.0 g / l of the PAS amide solution described below and after 10 minutes 0.0096% (based on textile material) Reactive Yellow 111 and 3.319% Reactive Green 021 were added. After every 30 minutes, 80 g / l of sodium chloride, 2 g / l of sodium carbonate and finally 4 ml / l of sodium hydroxide solution (38 ° Be) were added successively to the dyebath. After another half hour, a coloration of perfect areal quality was obtained. Due to the high stability of the dyeing liquors, filtrations were avoided in the inner layers of the tree coloring.

The PAS amide used was prepared by heating 48.4 parts of polysuccinimide and 40.5 parts of oleylamine in 103 parts of N-methylpyrrolidone at 130 to 135 ° C and stirred for 5 hours at this temperature. After cooling to 90 to 95 ° C were set to 295 parts of water and 28 parts of 50% sodium hydroxide solution and stirred for about 1 hour at 95 to 100 ° C after. About 500 parts of a 20% strength solution of the PAS amide were obtained as a slightly turbid solution, which could be converted into a clear solution by a clarification filtration.

The dyeing could be carried out with equal success if 2 g / l of an agent consisting of 12% of a sulfonated naphthalene-formaldehyde condensation product, 10% polyaspartic acid sodium salt and 78% water were used instead of this PAS amide in the reactive dyebath duration.

Claims (11)

1. Process for dyeing or printing textile materials composed of wool, cotton, regenerated cotton, jute, sisal or polyester, polyamide, polyurethane, polyacrylonitrile or polypropylene fibres or mixtures thereof, characterized in that these textile materials are treated with dyeing liquors or printing pastes containing, as auxiliaries, polyaspartic acid or a derivative thereof and one or more further components such as wetting agents, levelling agents, dispersing agents, reducing agents, oxidizing agents, solubilizers, defoamers, resist agents, pH regulators, complexing agents and the auxiliaries are used in an amount of 0.2 to 10% by weight, based on the weight of the textile materials to be printed or to be dyed.
2. Process according to Claim 1, characterized in that derivatives of polyaspartic acid comprise salts containing Li^⊕, Na^⊕, K^⊕, Mg^⊕⊕, Ca^⊕⊕, NH₄ ^⊕, H₃N (CH₂CH₂OH)^⊕, H₂N(CH₂CH₂OH)₂ ^⊕ or HN (CH₂CH₂OH) ₃ ^⊕ as cations, or polysuccinimide.
3. Process according to Claim 1, characterized in that the polyaspartic acid contains recurring succinyl units of the structure

   

   preferably

   

   
4. Process according to Claim 1, characterized in that the polyaspartic acid contains further recurring units such as

   a) malic acid units of the formula

   

   or

   b) maleic acid and furmaric acid units of the formula

   

   through suitable reaction management and choice of starting materials.
5. Process according to Claim 1, characterized in that the further components are present in an amount of 90 to 50% by weight based on the total weight of the compositions according to the invention.
6. Process according to Claim 1, characterized in that the textile material is bleached cotton yarn and the dyeing liquor contains Reactive Green 021 or Reactive Blue 116, the sodium salt of polyaspartic acid and the sodium salt of a sulphonated naphthalene-formaldehyde condensation product.
7. Process according to Claim 1, characterized in that the polyaspartic acid used is essentially a β-polyaspartic acid having a molecular weight of 500 to 10 000, understood as weight average.
8. Process according to Claim 1, characterized in that the polyaspartic acid derivatives used are those in which a portion of the carboxyl groups present in the polyaspartic acid are present as amides.
9. Process according to Claim 1, characterized in that reaction products of aliphatic, araliphatic or aromatic hydroxy compounds, carboxylic acids, carboxylic acid amides or amines with ethylene oxide, sulphuric acid half esters or phosphoric acid partial esters thereof, fatty acid esters of mono- or polysaccharides or fatty acid sorbitan esters and oxyethylation products thereof, C₁₀-C₂₀-alkanesulphonates, C₈-C₁₂-alkylbenzenesulphonates, C₈-C₁₈-alkyl sulphates or phosphates or condensed aromatic sulphonic acids, such as naphthalene-formaldehyde-sulphonates, are used as wetting agents, emulsifiers or dispersing agents.
10. Process according to Claim 1, characterized in that the dyeing liquors or printing pastes contain dyestuffs from the group of acid dyestuffs, metal complex substances which are free from sulpho groups or contain sulpho groups, reactive dyestuffs, vat dyestuffs, direct dyestuffs, sulphur dyestuffs, cationic dyestuffs, disperse dyestuffs and pigments.
11. Use of polyaspartic acid or a derivative thereof and one or more components such as wetting agents, levelling agents, dispersing agents, reducing agents, oxidizing agents, solubilizers, defoamers, resist agents, pH regulators, complexing agents in an amount of 0.2 to 10% by weight based on the weight of the textile materials to be printed or to be dyed, characterized in that these are used in dyeing liquors or printing pastes for dyeing or printing textile materials composed of wool, cotton, regenerated cotton, jute, sisal or polyester, polyamide, polyurethane, polyacrylonitrile or polypropylene fibres or mixtures thereof.