EP0828023A2 - Agent for printing or dyeing textile materials - Google Patents

Abstract

An agent for dyeing or printing natural and/or synthetic fibre textiles contains polyaspartic acid (I) or its derivative and optionally wetting agent, emulsifier, levelling agent, dispersant, reducing agent, oxidant, solvent aid, antifoam, resist agent, pH regulator and/or chelating agent. Also claimed is a method of dyeing or printing these textiles by treatment with a dye liquor or printing paste containing this agent and the use of the agent as ancillary in dyeing and printing.

Description

The present invention relates to agents for dyeing or printing textile materials from natural or synthetic fibers or mixtures thereof, the by content of polyaspartic acid (PAS) or a derivative thereof Marked are. The invention further relates to a method for dyeing or printing on these textile materials using the inventive Agents and the use of these agents for dyeing or printing the mentioned textile materials.

In the course of dyeing textile materials from natural and / or synthetic Fibers or when printing on these textile materials occur frequently Problems of various kinds, for example with regard to equality, the Stability of the liquors or printing pastes or the formation of creases. In the In most cases it has been possible to add aids to the subject Problem could be optimized to a satisfactory solution to get these problems. In most cases, however, this is unsatisfactory Biodegradability of the tools used, which leads to a strong Pollution of the respective wastewater leads. Examples of tools with poor biodegradability are sulfonated naphthalene-formaldehyde condensates, oxyethylated fatty amines, lignin sulfonates, polymers or copolymers the (meth) acrylic acid.

It has now been found that successful dyeings or prints are produced can be, if one of the dye baths (liquors) or printing pastes aids adds the PAS or a derivative thereof and optionally other known ones Components included. PAS and its derivatives are characterized by an excellent biodegradability.

The invention accordingly relates to agents for dyeing or printing textile materials from natural or synthetic fibers or mixtures of the two Contain polyaspartic acid (PAS) or a derivative thereof and as another Component optionally wetting agents, emulsifiers, leveling agents, dispersing agents, Reducing agents, oxidizing agents, solubilizers, defoamers, Reserving agents, pH regulators, complexing agents or more thereof.

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

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

The agents according to the invention are characterized above all by their content of PAS or a derivative thereof. The most suitable derivatives are salts of PAS, the cations Li ^⊕ , Na ^⊕ , K ^⊕ , Mg ^⊕⊕ , Ca ^⊕⊕ , NH ₄ ^⊕ , H ₃ N (CH ₂ CH ₂ OH) ^⊕ , H ₂ N (CH ₂ CH ₂ OH) ₂ ^⊕ or HN (CH ₂ CH ₂ OH) ₃ ^⊕ contain. The production and use of PAS and its derivatives has long been the subject of numerous publications and patents. For this, reference is made to J. Org. Chem. 26 (1961), 1084, US 4,839,461 (= EP 256 366), DE-A 22 53 190, 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.

The said US '461 describes the production of PAS from maleic anhydride, Water and ammonia. Maleic anhydride is in an aqueous medium with the addition of concentrated ammonia solution in the monoammonium salt transformed. In a preferred embodiment, PAS prepared that maleic acid monoammonium salt preferably at 150 to 180 ° C in a reactor with a residence time of 5 to 300 minutes one thermal, optionally continuously carried out polymerization and the polysuccinimide obtained by hydrolysis to PAS or a salt implement it.

bevorzugt

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

prefers

a) Äpfelsäure-Einheiten der Formel

b) Maleinsäure- und Fumarsäure-Einheiten der Formel

In addition, further recurring units can be contained by suitable reaction control and choice of the starting materials, e.g. B.

a) Malic acid units of the formula

b) Maleic acid and fumaric acid units of the formula

The chemical structure is preferably analyzed using ¹³ C-NMR, FT-IR and, after total hydrolysis, using HPLC, GC and GC / MS.

In many manufacturing processes, the pure acids do not fall first the corresponding anhydrides, for example polysuccinimide. Such Polymerization products can optionally be reacted with a base be converted into a PAA-containing salt in the presence of water. This Conversion of PSI-containing to PAA-containing polymers then takes place in a suitable device by hydrolysis. A pH value is preferred suitable between 5 and 14. A pH value is in a particularly preferred form chosen from 7 to 12, in particular by adding a base. Suitable bases are alkali and alkaline earth metal hydroxides or carbonates such as Sodium hydroxide solution, potassium hydroxide solution, soda or potassium carbonate, ammonia and amines such as Triethylamine, triethanolamine, diethylamine, diethanolamine, alkylamines etc. Especially In addition to free acids, preference is given to their Na, K or Ca salts.

The temperature in the hydrolysis is suitably in a range including 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, by purely aqueous hydrolysis or treatment of the Salt with acids or acidic ion exchangers to free polyaspartic acid receive. The term "polyaspartic acid" (= PAA) in the present context Invention also the salts, unless expressly stated otherwise. The Finished product is obtained by drying, preferably spray drying.

Preferred polymers have a molecular weight according to gel permeation chromatography Analyzes (from Mw = 500 to 10,000, preferably 700 to 5,000, particularly preferably 1,000 to 4,500). In general, the share of beta form at more than 50%, preferably at more than 70%.

In addition to the salts with the above-mentioned cations, PAS can be used as a derivative Polysuccinimide can be used, which at elevated temperature, preferably at 100 to 240 ° C, optionally in the presence of a catalyst, such as in a Amount of 0.01 to 1% by weight, based on the PAS, of an acid catalyst, such as sulfuric acid, phosphoric acid, methanesulfonic acid and others. However, polysuccinimide also falls in a number of manufacturing processes immediately. In such a case, polysuccinimide can be reacted with a base, optionally in the presence of water, in a salt with one of the cations mentioned above are transferred. This transformation happens in Connection to the manufacturing process in a suitable device Hydrolysis. A pH between 5 and 14 is preferred, preferably pH = 7 to 12. Suitable bases for carrying out an alkaline hydrolysis are Alkali and alkaline earth metal hydroxides or carbonates, such as sodium hydroxide solution, Potash lye, soda, potassium carbonate, ammonia and amines, such as Triethylamine, triethanolamine, diethylamine, diethanolamine and ethanolamine.

Other derivatives of PAS that can be used according to the invention are those in which a Part of the carboxyl groups present in the PAS are present as amides. The The preparation of such PAS amides can be carried out using the polysuccinimide mentioned 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 after The remaining succinimide structures remaining after the amide formation can subsequently be used through said hydrolytic opening in the presence of bases into free Carboxyl or carboxylate groups are converted. In preferred derivatives contain 5 to 50 mol%, preferably 10 to 35 mol% of the aspartic acid units present such amide structures, while the remaining carboxyl groups are in the form of carboxylate groups.

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

In addition to their PAS or a derivative thereof, the agents according to the invention can contain further components. The other components include wetting agents, emulsifiers, dispersants or a mixture of several of them, which can be anionic or nonionic in a known manner. Examples are reaction products of aliphatic, araliphatic or aromatic hydroxy compounds, carboxylic acids, carboxylic acid amides or amines with ethylene oxide, whose Schwefelsäurehalbester or phosphoric acid partial esters, fatty acid ester of mono- or polysaccharides or fatty acid sorbitan ester and oxyethylation products thereof, C ₁₀ -C ₂₀ alkanesulfonates, C ₈ -C ₁₂ alkyl benzene sulfonates, 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 the art for these uses.

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

Occasionally, reducing agents, oxidizing agents, Reserving agents, pH regulators, complexing agents or several of them in one Amount of 0 to 10 wt .-%, based on the total weight of the invention Medium, present what is the amount of PAS and the above Surfactants is taken into account. The skilled worker is familiar with the use of such agents and for example in Chwala / Anger, Handbuch der Textilhilfsmittel, Verlag Chemie, Weinheim 1977.

The other components mentioned, their manufacture and availability are as those known to the person skilled in the art. Of course, to achieve optimized dyeings or textile prints also several of the others mentioned Components are used.

At least one of the other components mentioned is preferably located in front. According to the invention, they are in an amount of 95 to 0% by weight, preferably 90 to 50% by weight, based on the total weight of the agents according to the invention, in front.

Textile materials dyed using the agents according to the invention or are printed, are fiber materials made of loose fibers, ridges, weaving or Hosiery or nonwovens in the form of natural or synthetic Fibers or their mixtures. Examples of natural fibers are wool, Silk, linen, cotton or regenerated cotton, as well as jute or sisal called. Examples of synthetic fibers are those made of polyesters, polyamides, Polyurethanes, polyacrylonitrile or polypropylene called.

The dyeing or printing of the textile materials is carried out with the used ones Dyes suitable fibers carried out, which the person skilled in the art is known. Suitable classes of dyes for this originate, for example, from Group of acid dyes, sulfo-free or sulfo-containing Metal complexes, reactive dyes, vat dyes, direct dyes, sulfur dyes, cationic dyes, disperse dyes and the pigments.

The agents according to the invention are preferably used when dyeing Cotton with direct dyes and reactive dyes when dyeing polyester fibers with disperse dyes or when dyeing cotton-polyester mixed articles used 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 block-cold residence (KKV) procedures and others, as well as within the framework of the Textile printing processes known to those skilled in the art. The ones to be used in the individual procedures Amounts of textile auxiliaries, the temperatures to be used, the Fleet lengths and concentrations are known to the person skilled in the art. The invention Agents are in an amount of 0.2 to 10 wt .-%, based on the Weight of the textile material to be dyed or printed.

With the help of the agents according to the invention, dyebaths are outstandingly stable and in turn colorations with excellent levelness and brilliance receive. In addition, the formation of creases is reduced or completely avoided. Corresponding advantages are also obtained with textile printing. Here can be used as a thickener in dyeing or printing aids, non-environmentally friendly polyacrylate in whole or in part by the inventive Funds to be replaced.

The agents according to the invention have excellent biodegradability and therefore contribute to reducing the wastewater load of textile companies at. In the event of partial or total replacement of polyacrylate one continues to use less viscous dyeing liquors.

example 1

100 g of bleached cotton yarn were in a cheese package in the Liquor ratio 1:10 dyed at 80 ° C using a dye liquor, those per liter of 4 g of Reactive Green 021 and 2 g of that described below Aid included. After a dyeing time of 10 minutes, 80 g of sodium chloride added, after a further 30 minutes 5 g of sodium bicarbonate and after 30 Finally, 10 g of sodium carbonate in minutes. The color was changed in another 60 Minutes completed. A coloration of excellent levelness was obtained, and no filtering could be seen on the coil.

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

Example 2

Cotton knitwear with a basis weight of 250 g / m ² was dyed in the manner described in Example 1, using Reactive Blue 116 instead of the dye mentioned there.

A blue color of excellent levelness was obtained. The used Dyeing liquors had very good stability, which meant that there was no smearing in the dyeing machine and thus no stains appeared on the colored material.

Example 3

Bleached cotton gabardine with a basis weight of 260 g / m ² was dyed by the block-cold dwelling process with a liquor pick-up of 80%, using a liquor which contained 30 g of Reactive Green 021, 2.5 g of PAS, 2 g in liters a commercially available 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 at 38 ° Be. The residence time of the material in the wet state was 48 hours. After washing out, a green color of excellent levelness was obtained, in which no so-called edge or end drain was observed.

Example 4

A cotton / polyester fabric (80:20) was placed on a tree dyeing machine dyed in a liquor ratio of 1:14 using the two-bath process. The first bath contained 0.385% (based on textile material) of Disperse Yellow 042 and 1.9% Disperse Blue 060 1 g / l of the PAS amide described below as Dispersant and 0.5 g / l of a commercial leveling agent (e.g. a 1: 1 mixture from stearic acid x6 EO and nonylphenol x10 EO). The coloring was started at 80 ° C. With a heating rate of 1 ° C / min Heated 130 ° C and dyed at this temperature for 45 min. Then was with a second bath colored at 80 ° C, the first 2.0 g / l of the below PAS amide solution described and after 10 minutes 0.0096% (based on textile material) Reactive Yellow 111 and 3.319% Reactive Green 021 were added. After every 30 min the dye bath was then successively 80 g / l sodium chloride, 2 g / l sodium carbonate and finally slowly 4 ml / l sodium hydroxide solution (38 ° Be) added. After another half an hour a color of perfect surface levelness was obtained. Due to the high The stability of the dye liquors were filtered off in the inner layers of the Tree staining avoided.

The PAS amide used was prepared by mixing 48.4 parts of polysuccinimide and 40.5 parts oleylamine in 103 parts N-methylpyrrolidone to 130 heated to 135 ° C and stirred for 5 hours at this temperature. After this Cooling to 90 to 95 ° C was 295 parts of water and 28 parts of 50% Sodium hydroxide solution and stirred at 95 to 100 ° C for about 1 hour. There were receive approx. 500 parts of a 20% solution of the PAS amide as a slightly cloudy solution, which could be converted into a clear solution by clarification filtration.

The coloring could be carried out with the same success if you put in place of this PAS amide in the reactive dye bath used 2 g / l of an agent which consists of 12% a sulfonated naphthalene-formaldehyde condensation product, 10% polyaspartic acid Na salt and 78% water.

Claims (6)

Means for dyeing or printing textile materials from natural or synthetic fibers or mixtures of both, containing polyaspartic acid (PAS) or a derivative thereof and as a further component optionally wetting agents, emulsifiers, leveling agents, dispersing agents, Reducing agents, oxidizing agents, solubilizers, defoamers, reserving agents, pH regulators, complexing agents or more thereof. Agent according to claim 1, characterized in that the further component (s) in an amount of 95 to 0% by weight, preferably 90 to 50% by weight, based on the total weight of the compositions. Agent according to at least one of claims 1 and 2, characterized in that that as a derivative of polyaspartic acid one of its salts, you Amide or its anhydride is used. Agent according to at least one of claims 1 to 3, characterized in that that as a polyaspartic acid essentially a β-polyaspartic acid with a molecular weight of 500 to 10,000, understood as Weight average, is used. Process for dyeing or printing textile materials from natural or synthetic fibers or mixtures of both by treatment these textile materials with dyeing liquors or printing pastes, the dyeing or Contain printing aids, characterized in that these aids Polyaspartic acid (PAS) or a derivative thereof and as others Component optionally wetting agents, emulsifiers, leveling agents, dispersing agents, Reducing agents, oxidizing agents, solubilizers, defoamers, Reserving agents, pH regulators, complexing agents or more of these, the auxiliaries in an amount of 0.2 to 10 % By weight, based on the weight of the goods, are used. Use of the agent according to at least one of claims 1 to 4 as Aid for dyeing or printing textile materials natural or synthetic fibers or mixtures of both.