Polymer for the treatment of substrates containing amino and / or amide groups

Abstract

A polymer comprising the repeating units or a salt thereof, or a salt thereof, wherein R 1 independently of one another is -H, -aryl or -alkyl, in particular -CH3 or -C2H5, preferably H; R 2 independently of each other -C 2-8 -alkyl or -Aryl optionally substituted with C 2-20 -alkyl or C 2-20 -alkenyl, or -CH2-CH2-O-Aryl optionally substituted with C 2-20 -alkyl or C 2-20 -alkenyl, preferably -aryl; A is independently an aryl group, in particular -phenyl, -tolyl, -xylyl, or -naphthyl, particularly preferably phenyl, B is independently an aryl group, in particular -phenyl, -tolyl, -xylyl, or -naphthyl, particularly preferably phenyl, which is substituted with, wherein at least 75 mol% of the repeating units W(1) and W(3) are present as at least monovalent salt, preferably as sodium salt, wherein the polymer preferably contains 40-80 mol% W(1), 5-50 mol% W(2), 0.4-10 mol% W(3) and 0-10 mol% W(4) and / or where the preferred molar ratio is W(1):W(2):W(3):W(4)=9-20:1-12:0.1-3:0-3.

Description

[0001] The present invention relates to a partially neutralized polymer and substrates treated therewith.

[0002] Dyed and printed textiles often exhibit unsatisfactory colorfastness. "Colorfastness" refers to the resistance of the dye to external influences such as water, light, or friction. This is particularly the case with dyes using anionic dyes such as acid dyes, pre-metallized dyes, or metal complex dyes, and to a lesser extent with reactive or reduction dyes.

[0003] Many substrates dyed with anionic dyes contain amino or amide groups and are of synthetic or natural origin, such as polyamides or polyamide blends, wool, silk, imitation leather or leather.

[0004] The anionic dye is bound to the substrate by an ionic bond. However, this bond is relatively weak and can lead to fastness issues.

[0005] To ensure color fastness after dyeing, agents are used that enable and promote stable anchoring of the dye molecules to the fibers, thus reducing the likelihood of color loss during wear or washing.

[0006] Colorfastness improvers have been known for a long time. They form ionic bonds with the amino groups of the fibers and create a surface layer, thereby reducing the diffusion of the dye from the treated fiber.

[0007] Well-known aftertreatment agents include so-called "syntans," condensation products of aromatic sulfonic acids and formaldehyde (derivatives). The word "syntan" is a combination of "synthetic" and "tannin," as natural tannins and / or tartar emetic were originally used as aftertreatment agents for anionically dyeable fibers.

[0008] Sulfonated condensation products of phenol, naphthol, bisphenol such as bisphenol A or bisphenol S are also used as color fastness improvers.

[0009] WO 94 / 28231 describes sulfonated naphthol or phenol-formaldehyde condensation products as post-treatment agents for polyamides.

[0010] US Pat. No. 5,574,106 A discloses acrylic copolymers that impregnate nylon carpets and other polyamide products and provide them with stain protection. Their effectiveness as colorfastness improvers is not disclosed.

[0011] The disadvantage of these agents is that the treated substrates tend to yellow due to the phenolic components as a result of UV light, especially sunlight.

[0012] In addition, phenols, bisphenols and formaldehyde are listed as SVHC (substances of very high concern) due to their harmful effects on health and lack of environmental friendliness and are becoming increasingly undesirable.

[0013] To circumvent these problems, WO 95 / 30794 proposes an environmentally friendly composition for anchoring dyes. While this solves the problem of yellowing, it imparts insufficient wash and perspiration fastness.

[0014] The object of the present invention is therefore to overcome the disadvantages of the prior art.

[0015] Surprisingly, it has been found that the polymer or composition of the invention allows the dye to be firmly anchored to a substrate and does not detach or discolor, or only minimally, due to perspiration, frequent washing, steaming, ironing, and / or mechanical friction. Discoloration due to light or UV radiation is just as unobservable as yellowing. Furthermore, the polymer or composition of the invention is free of substances that are hazardous to health, such as phenol, bisphenol, or formaldehyde. The compositions of the invention exhibit good flow and migration properties, good storage stability, and good shear stability.

[0016] Without being bound to any theory, it is assumed that the dye molecules are anchored to the substrate by the polymer of the invention essentially by means of hydrophobic and π-interactions of the aromatic groups.

[0017] In one aspect, the invention is directed to a polymer comprising the repeating units or a salt thereof, or a salt thereof, wherein R 1 independently of one another is -H, -aryl or -alkyl, in particular -CH3 or -C2H5, preferably H; R 2 independently of each other -C 2-8 -alkyl or - Aryl optionally substituted with C 2-20 -alkyl or C 2-20 -alkenyl, or -CH2-CH2-O-Aryl optionally substituted with C 2-20 -alkyl or C 2-20 -alkenyl, preferably -aryl; A is independently an aryl group, in particular -phenyl, -tolyl, -xylyl, or -naphthyl, particularly preferably phenyl, B is independently an aryl group, in particular -phenyl, -tolyl, -xylyl, or -naphthyl, particularly preferably phenyl, which is co-substituted, wherein at least 75 mol% of the repeating units W(1) and W(3) are present as at least monovalent salt, preferably as sodium salt.

[0018] Preferred is R 1 each H. A is preferably a phenyl group. B is preferably a phenyl group which is substituted in particular with. R 2 is preferably -aryl or -CH2-CH2-O-aryl substituted with C 2-20 -alkyl or C 220 -Alkenyl, more preferably -phenyl or -CH2-CH2-O-phenyl substituted with C 2-20 -alkyl or C 2-20 -Alkenyl.

[0019] In a preferred embodiment, R 1in W(1), W(2), W(3) and W(4) each is -H, A is each -phenyl and B is each substituted phenyl, in particular phenyl substituted with -SO3H.

[0020] 75 mol-%, preferably 75-99.9 mol-% of the repeating units W(1) and W(3) are present as at least monovalent salt, ie at least singly deprotonated, the sum of W(1) and W(3) being 100 mol-% in total (W(1)+W(3)=100 mol-%).

[0021] The monovalent salt of the repeating unit W(1) is a carboxylate salt. Monovalent salts of the repeating unit W(3) are, for example, sulfates, sulfonates, hydrogen phosphates, or primary phosphonates. Divalent salts of the repeating unit W(3) are, for example, phosphates or secondary phosphonates. The salt-forming cations are, independently of one another, preferably alkali metal ions or alkaline earth metal ions, especially sodium ions.

[0022] It has surprisingly been shown that excellent substantivity can be achieved within the claimed range of salt group concentration in the polymer. Furthermore, the viscosity of the polymer in aqueous solution can be significantly reduced compared to polymers with a salt content below the claimed range.

[0023] The advantageous effect of substantivity achieves outstanding color fastness, and the reduced viscosity facilitates the handling of the polymer in the form of solutions, especially aqueous solutions.

[0024] The polymer preferably contains 40-80 mol%, more preferably 40-70 mol%, more preferably 40-60 mol% or more preferably 50-70 mol%, of repeating units W(1), 5-50 mol%, more preferably 25-50 mol%, or more preferably 10-40 mol%, of repeating units W(2), 1-20 mol%, more preferably 5-20 mol%, more preferably 7-20 mol% or 1-10 mol%, preferably 1-8 mol%, of repeating units W(3) and 0-10 mol%, preferably 0-5 mol%, of repeating units W(4) (with W(1)+W(2)+W(3)+W(4)=100 mol%).

[0025] Accordingly, the molar ratio W(1):W(2):W(3):W(4) is preferably 9-20:1-12:0.1-3:0-3, more preferably 4-6:2.5-5:0.5-2:0-1.

[0026] The polymer preferably contains 35-70 mol%, more preferably 40-70 mol%, even more preferably 50-70 mol% of repeating units of W(2) and W(3) (W(2)+W(3)) based on all repeating units (W(1)+W(2)+W(3)+W(4)=100 mol%).

[0027] It has been shown that the nonpolar repeating units W(2) and W(3), each carrying an aryl group, interact excellently with the dye molecules and stabilize them on the substrate. This effect is thought to be due to π-π interactions.

[0028] At the same time, the dispersibility of the polymers in aqueous media and their interaction with polar substrates, such as amide- and / or amino-containing substrates, can be adjusted by the molar proportions of the repeating units W(1) and W(3) and their degree of deprotonation (≥ 75 mol% salt formation), without counteracting the (desired) nonpolar interactions described above. The polymers of the invention are therefore surprisingly suitable for the uncomplicated treatment of polar substrates in aqueous media with excellent fastness results.

[0029] In a particularly preferred embodiment, the invention is therefore directed to a polymer comprising the repeating units • W(1) or a salt thereof, • W(2), • W(3) or a salt thereof, and • if necessary W(4), wherein at least 75 mol% of the repeating units W(1) and W(3) are present as at least monovalent salt, preferably as sodium salt, and wherein the polymer contains 40-70 mol% W(1), 25-50 mol% W(2), 5-20 mol% W(3) and 0-10 mol% W(4), with the proviso that the polymer contains 35-70 mol%, preferably 40-70 mol%, repeating units of W(2) and W(3) (W(2)+W(3)).

[0030] The polymer of the present invention is preferably water-soluble. In particular, the polymer of the invention is completely soluble in distilled water at 20°C (100-600 g / L), preferably 200-300 g / L.

[0031] The pH of a 30% solution in distilled water at 20°C is preferably 6-7, preferably 6.2-6.5. A 30% solution in distilled water at 20°C preferably has a viscosity of 50-1200 mPas, preferably 50-600 mPas, more preferably 100-300 mPas, measured according to DIN 53019 / ISO 3219. The low viscosity facilitates easy processing and pumpability. The repeating units W(1), W(2), W(3), and optionally W(4) are preferably arranged randomly, alternately, or in blocks in the polymer chain. The polymer according to the invention is preferably a random polymer.

[0032] Another aspect of the invention is a process for producing the polymer described above. The process comprises the steps (a) Providing the monomer solution or dispersion, (b) polymerising the mixture obtained after step (a), (c) neutralising the mixture obtained after step (b) so that at least 75 mol% of the repeating units W(1) and W(3) originating from the monomers M(1) and M(3) are present as at least a monovalent salt, and (d) if necessary, distilling the mixture obtained after step (c).

[0033] R 1 , R 2 , A and B are defined as above.

[0034] Preferred examples of monomer M(3) are sodium styrenesulfonate or sodium vinyltoluenesulfonate.

[0035] Preferred examples of monomer M(4) are ethyl (meth)acrylate, butyl (meth)acrylate, phenyl, benzyl, naphthyl (meth)acrylate and cardanyl (meth)acrylate, preferably cardanyl (meth)acrylate.

[0036] In step (a), the monomers M(1), M(2), M(3) and optionally M(4) are preferably reacted together with water and / or organic solvents, e.g. C 2-8-Alcohol, such as ethanol, glycerin, or isopropanol, glycol, such as butyldiglycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycol esters, esters, such as propylene glycol monomethyl ether acetate, ketone, such as acetone, and / or polyalkylene glycol, in particular polyethylene glycol such as PEG 100-600, preferably PEG 200-300, and propylene glycol, are mixed to form a solution or dispersion. The solution or dispersion can be prepared by methods known to those skilled in the art and includes, for example, stirring or applying high shear forces.

[0037] If necessary, auxiliaries such as surface-active reagents, in particular anionic and / or non-ionic surfactants, can be used to obtain a homogeneous and stable dispersion.

[0038] The anionic surfactant preferably comprises at least one phosphate, phosphonate, sulfate, sulfonate, carboxylate, sulfoacetate, sulfosuccinate and / or taurate group. In a further preferred embodiment, the anionic surfactant is selected from mono-, di-(C 4-22 -Alkyl(alkoxy))phosphate, mono-, di-(C 4-22 -alkyl)phosphonate, C 4-22 -Alkylaminophosphonate, C 4-22 -Alkyl (alkoxy) sulfate, secondary alkyl sulfonate, petroleum sulfonate, C 4-22 -Alkylsulfonate, C 4-22 -Alkylarylsulfonate, fatty alcohol ether carboxylate, fatty acid salt, fatty alkyl sulfoacetate, fatty acid amide ether sulfate, fatty alcohol ether carboxylate, nonylphenol ether sulfate, fatty alkyl ether sulfate, C 4-22 -Alkylpolyalkoxylene phosphate and C 4-22 -Alkylpolyalkoxylene sulfate.

[0039] The non-ionic surfactant is preferably an alkoxylation product of fatty acid, fatty acid ester, fatty acid amine, fatty acid amide, fatty alcohol, aliphatic mono-, di- or tri-alcohol, mono-, di- or tri-glyceride, alkylphenol, sorbitan fatty acid and sugar derivatives or trialkylphenol polyalkoxyls or a block copolymer, e.g. poly(ethylene oxide-co-propylene oxide), selected from the group consisting of alkoxylated C9-C 25 -fatty alcohols, alkoxylated C 9-25 -fatty acid amines, alkoxylated C9-C 25 -fatty acid amides, C8-C alkoxylated at the carboxylate function 25 -fatty acids, alkoxylated C8-C 25 -fatty acid esters, alkoxylated C8-C 25 -alkylphenols and alkoxylated mono-, di- or triglycerides of C8-C 25 -fatty acids and / or their esterification products with C8-C 25-fatty acids or trialkylphenyl polyalkoxylene or a block polymer, e.g., poly(ethylene oxide-co-propylene oxide), or fatty alcohol poly(ethylene oxide-co-propylene oxide), and mixtures thereof. The number of alkoxylene groups in the nonionic surfactant is at least 8, preferably 8-85, more preferably 10-85, and most preferably 10-80 repeating units. The alkyl groups can each independently be branched or straight-chain, saturated or unsaturated.

[0040] Preferably, in step (a), 40-80 mol%, more preferably 40-70 mol%, more preferably 40-60 mol% or more preferably 50-70 mol% of M(1), 5-50 mol%, more preferably 25-50 mol% or more preferably 10-40 mol% of M(2), 1-20 mol%, more preferably 5-20 mol%, more preferably 7-20 mol% or 1-10 mol%, more preferably 1-8 mol% of M(3) and 0-10 mol%, more preferably 0-5 mol% of M(4) (with M(1)+M(2)+M(3)+optionally M(4)=100 mol%) are provided as a solution or dispersion.

[0041] Accordingly, the molar ratio M(1):M(2):M(3):M(4) is preferably 9-20:1-12:0.1-3:0-3, more preferably 4-6:2.5-5:0.5-2:0-1.

[0042] The polymerization of the mixture obtained after step (a) in step (b) preferably takes place radically, in particular in the form of a radical solution polymerization. Preferred radical initiators are inorganic persulfates, such as ammonium persulfate, potassium persulfate, sodium persulfate; hydroperoxides, such as cumene hydroperoxide and tert-butyl hydroperoxide; dialkyl peroxides, such as di-tert-butyl peroxide and dicumene peroxide; peroxyesters, such as tert-butyl perbenzoate; diacyl peroxide, such as benzoyl peroxide and lauroyl peroxide; and azo compounds, such as azobisisobutyronitrile and azobisvaleronitrile. The weight fraction of radical initiator, based on the total mass of the polymer, is preferably 3-10 wt.%.

[0043] Particularly preferred is a redox initiator system comprising a combination of a reducing agent, e.g., sodium hypophosphite, sodium pyrosulfite, iron salt, and / or ascorbic acid, and a peroxy compound. Such redox initiator systems ideally result in a short induction time and a homogeneous molecular weight distribution.

[0044] Preferably, chain regulators such as hypophosphite and / or mercaptans such as lauryl mercaptan are also used in the polymerization before or during step (b). The use of chain regulators enables the control of the polymer's molecular weight and polydispersity. The chain regulators are preferably added in a proportion of 0.1-10 wt.%, more preferably 1-7 wt.%, and most preferably 2-3.5 wt.%, based on the total mass of the monomers.

[0045] Furthermore, crosslinking agents such as triallyamine, divinylbenzene and glycidyl methacrylate can also be used, preferably in a proportion of 0.1-12 wt.%, more preferably 0.1-6 wt.%, based on the total mass of the monomers.

[0046] The radical polymerization preferably takes place at elevated temperature, e.g., 30-100 °C, preferably 30-80 °C, preferably with stirring. The conduct of radical polymerization in solution or dispersion is known to those skilled in the art. Step (b) is usually complete when the residual monomer content is <5 wt. %, preferably <2 wt. %.

[0047] The polymer obtained after step (b), in particular the emulsion polymer or solution polymer, is then neutralized. Neutralization is preferably carried out with a base, particularly preferably with an alkali metal hydroxide, such as sodium hydroxide and / or potassium hydroxide or an alkaline earth metal hydroxide, such as magnesium hydroxide, amine, ammonia, or a mixture thereof.

[0048] At least 75 mol% of the repeating units W(1) and W(3) originating from the monomers M(1) and M(3) are present after neutralization as at least a monovalent salt or at least singly deprotonated. The corresponding amount can be calculated either from the starting materials or adjusted by titration measurements.

[0049] It has surprisingly been found that by adjusting the salt content of the repeating units W(1) and W(3) in the range of ≥75 mol%, more preferably in the range of 75-99.9 mol%, even more preferably in the range of 80-90 mol%, excellent substantivity is achieved, and the viscosity of the composition is reduced compared to compositions in which less than 75 mol% of the repeating units W(1) and W(3) originating from the monomers M(1) and M(3) are present as salt. This enables excellent effects as well as easier processability and pumpability of the product.

[0050] In an optional step (d), water and / or organic solvent, in particular water and / or organic solvent with a boiling point of ≤100°C under standard conditions, can be distilled off or removed from the mixture obtained after step (c). Typically, organic solvents, in particular organic solvents with a boiling point of ≤100°C under standard conditions, are removed. For concentration or to provide the polymer as a dry powder or granules, the solvent used for the solution or dispersion, in particular water and / or organic solvent, can be partially or completely distilled off in step (d). The composition after step (c) or (d) preferably has a solids content of 15-50 wt.%, preferably 25-40 wt.%, based on the total mass of the resulting mixture.

[0051] A further aspect of the invention is directed to a polymer obtainable by the process described above. This polymer preferably has a pH of 6-7, more preferably 6.2-6.5, measured in a 30% solution of the polymer in distilled water at 20°C. Preferably, the solubility of the polymer at 20°C in distilled water is 100-600 g / L, more preferably 200-300 g / L.

[0052] The present invention is also directed to a composition comprising (A) at least one polymer according to the present invention, (B) Water and possibly a solvent such as C 2-8 -alcohol, glycol, glycol ester, ester, ketone and / or polyalkylene glycol, in particular polyethylene glycol or polypropylene glycol, and (C) optionally comprises one or more additives such as anionic and / or non-ionic surfactant, UV stabilizer or salt such as sodium, aluminum, zinc or magnesium sulfate and / or calcium chloride.

[0053] The salts mentioned under step (C) can further increase the substantivity of the polymers according to the invention, ie the affinity of the polymers to a substrate can be improved.

[0054] Preferably, the composition of the present invention comprises (A) at least one polymer of the present invention, (B) water and optionally an organic solvent such as ethanol, and (C) if necessary, an additive.

[0055] The composition preferably comprises 15-50 wt%, more preferably 25-40 wt%, of component (A) based on the total weight of the composition.

[0056] The composition preferably has a viscosity of 50-1200 mPas, more preferably 50-600 mPas, more preferably 100-300 mPas and most preferably 200-700 mPas at 20 °C measured according to DIN 53019 / ISO 3219, e.g. measured with a Haake viscometer VT3R.

[0057] The composition preferably has a pH in the range of 6-7, more preferably 6.2-6.5, at 20°C.

[0058] The composition can also be diluted with a solvent, for example, water. The solids content of the polymer can preferably be adjusted to 0.5-2 wt.% based on the total mass of the composition.

[0059] The polymer or composition according to the invention is outstandingly suitable for improving the fastness, in particular the colorfastness, e.g., perspiration, washing, light, water, and rubbing fastness, of substrates containing amide and / or amino groups. At the same time, the polymer according to the invention can also be advantageously used as a stain protector. The polymer is also suitable for tanning or retanning leather.

[0060] “Fastness,” particularly “colorfastness,” is understood below to mean the resistance of dyed substrates to physical, chemical, and photochemical influences. “Colorfastness” includes waterfastness, e.g., to salt and chlorinated water, washfastness, perspiration fastness, rubbing fastness, but also lightfastness, i.e., resistance to UV and daylight. Water and washfastness refer to resistance to salt and chlorinated water, as well as to washing at various temperatures in conventional washing solutions. Washfastness can be determined, for example, according to DIN EN ISO 105-C06 A1S (40 °C). Waterfastness can be tested, for example, according to DIN EN ISO 105-E01. Standardized tests according to DIN EN ISO 105-E03 can be used for chlorine bath water fastness.

[0061] Perspiration resistance refers to the resistance to human perspiration, with its acidic and alkaline components. These can attack the dye and lead to discoloration or discoloration. Perspiration resistance can be measured, for example, according to DIN EN ISO 105-E04. Finally, rub resistance refers to the resistance to abrasion caused by mechanical stress.

[0062] The amide- or amino-containing substrates are preferably made of natural or synthetic materials, in particular wool, e.g., sheep's wool, cashmere, mohair, or goat hair, silk, polyamide, such as polyamide 6.0 and polyamide 6.6, polyamide blends, imitation leather, leather, or mixtures thereof. Suitable substrates of the present invention are preferably flexible substrates, such as textile substrates, imitation leather, or leather. In particular, the substrates are textiles, such as fibers, linear structures such as strings, threads, yarns, linen, cords, ropes, threads, woven fabrics, knitted fabrics, nonwovens, cotton wool, semi-finished and finished textile products, and finished goods made therefrom.

[0063] The textiles are used, for example, in the clothing industry, such as sportswear, swimwear, and leisurewear; for home textiles, such as carpets, curtains, upholstery fabrics, or technical textiles, such as protective workwear.

[0064] In a further aspect, the present invention relates to a process for equipping substrates with a polymer according to the present invention or a composition of the present invention comprising the steps (i) providing a polymer as described above in an aqueous solution or aqueous dispersion or a composition as described above, (ii) applying the mixture from step (i) to a substrate, in particular a fibre, a woven fabric, a knitted fabric, a nonwoven fabric, a felt, a braid, an imitation leather or leather and (iii) drying the product obtained after step (ii) at elevated temperature.

[0065] Preferably, the substrate is as described above.

[0066] The aqueous solution or aqueous dispersion in step (i) preferably contains water and optionally an organic solvent such as C 2-8Alcohol, glycol, glycol ester, ester, ketone and / or polyalkylene glycol and preferably contains 0.1-2 wt%, more preferably 0.2-1.5 wt% and most preferably 0.6-1.2 wt% polymer based on the total weight of the aqueous solution or aqueous dispersion or composition.

[0067] Typically, the pH of the aqueous solution or dispersion in step (i) is between 3 and 6.5, preferably between 3 and 5.

[0068] The mixture is applied to a substrate using methods known to those skilled in the art, such as spraying, padding, dipping, exhausting, brushing, foaming or splashing.

[0069] In the case of textile substrates, the polymer can be applied by forced application or exhaustion. Typically, forced application involves providing a liquor of the desired concentration and applying it to the padder using forced application from an aqueous medium with liquor pickups of 40-100%.

[0070] Typically, the process is adjusted so that about 0.1-2 wt.%, preferably 0.1-1.5 wt.%, more preferably 0.3-1.2 wt.% of the polymer according to the invention is applied based on the dry weight of the substrate.

[0071] Drying of the product obtained according to step (iii) is preferably carried out at 80-140 °C, more preferably at 100-120 °C.

[0072] A further aspect of the present invention is a fiber, a textile, a leather imitation or leather which is finished with a polymer of the present invention or a composition of the present invention or which has been produced by a process of the present invention.

[0073] The present invention is further illustrated by the following examples, but is not limited to them: ExamplesManufacturing example 1:

[0074] In a suitable four-necked flask equipped with a distillation condenser, adjustable stirrer, and internal thermometer, 43 g of water, 0.05 g of diethylenetriaminepenta(methylene)phosphonic acid sodium salt, 5 g of sodium hypophosphite monohydrate, and 70 g of isopropanol are placed. After purging several times with nitrogen, the flask is heated to reflux.

[0075] A solution containing 16.8 g of sodium styrenesulfonate (0.08 mol), 70.5 g of water, 82.5 g of isopropanol, 40.3 g of acrylic acid (0.56 mol), and 59.6 g of styrene (0.57 mol) is metered into the four-necked flask over 4 hours. A solution of 8 g of sodium persulfate in 37 ml of water is also metered into the four-necked flask over 5 hours. The solution is then held at reflux for 1 hour. Following this, 1.85 g of sodium persulfate in 41 g of water is added, and the solution is again held at reflux for 1 hour. The solution is then cooled and treated with 50% sodium hydroxide solution to achieve a degree of neutralization of at least 75 mol%. Vacuum distillation then follows to remove the isopropanol. Water is finally added to obtain a dry matter content of approximately 30%. Production example 2:

[0076] In a suitable four-necked flask equipped with a distillation condenser, adjustable stirrer, and internal thermometer, 43 g of water, 0.05 g of diethylenetriaminepenta(methylene)phosphonic acid sodium salt, 5 g of sodium hypophosphite monohydrate, and 70 g of isopropanol are placed. After purging several times with nitrogen, the flask is heated to reflux.

[0077] A solution containing 16.5 g of sodium styrenesulfonate (0.08 mol), 70.5 g of water, 82.5 g of isopropanol, 39.8 g of acrylic acid (0.55 mol), 58.9 g of styrene (0.56 mol), and 6 g of Cardolite NX 2026 (0.02 mol) is metered into the four-necked flask over a period of 4 hours. A solution of 8 g of sodium persulfate in 37 ml of water is also metered into the four-necked flask over a period of 5 hours. The solution is then refluxed for 1 hour. 1.85 g of sodium persulfate in 41 g of water is then added, and the solution is again refluxed for 1 hour. The solution is then cooled and treated with 50% sodium hydroxide solution to achieve a degree of neutralization of at least 75 mol%. Vacuum distillation then follows to remove the isopropanol. Finally, water is added to obtain a dry matter content of approximately 30%. Example 3: Application technology

[0078] Polyamide 6.6 knitted fabric dyed with Acid Red 426 was post-treated with the preparations from Examples 1 and 2.

[0079] The aftertreatment was carried out using the exhaust process at a liquor ratio of 1:10 for 20 minutes at 70 °C, using the preparations from Examples 1 and 2 at 4% based on the fabric weight. The pH was adjusted to 3 using a formic acid / sodium formate-based buffer system.

[0080] The wash fastness at 40 °C of the post-treated samples was determined according to DIN EN ISO 105-C06 A1S (40 °C) using a multifibre accompanying fabric.

[0081] The assessment of the color change was carried out using a gray scale according to DIN EN 20102-A02.

[0082] The color of the textile samples was evaluated on a scale of 5 to 1 based on the gray scale for color change. The scale ranges from 5 to 1, with 5 representing negligible or no color change and 1 representing significant color change. The results for the preparations from Examples 1 and 2 are listed below: Pattern Color change Not treated 4 Example 1 4-5 Example 2 4-5

[0083] The assessment of bleeding was carried out using a gray scale according to DIN EN ISO 105-A03.

[0084] To assess the bleeding, the treated and untreated accompanying tissue were placed side by side in a single plane and compared using the gray scale. The scale ranges from 5 to 1, with a rating of 5 only being given if there is no difference between the treated and untreated accompanying tissue. A rating of 1 represents a significant difference between treated and untreated accompanying tissue. Accompanying fabric (multifibre) Not treated Example 1 Example 2 Cellulose acetate 4 4-5 4-5 Cotton 1-2 3-4 3-4 Polyamide 6.6 1 3-4 3-4 polyester 4-5 4-5 4-5 Polyacrylonitrile 4-5 4-5 4-5 Wool 3-4 4-5 4-5

[0085] The preparations according to the invention of Examples 1 and 2 thus achieve excellent wash fastness and prevent the bleeding of washed textiles. Comparison example 1:

[0086] A suitable four-necked flask equipped with a distillation condenser, adjustable stirrer, and internal thermometer was charged with 68.25 g of 99% ethanol, 21.75 g of deionized water, and 0.10 g of a 40% solution of the pentasodium salt of diethylenetriaminepentaacetic acid. The flask was purged several times with nitrogen and heated to reflux. A solution of 2.64 g of ammonium persulfate in 15 g of deionized water was added.

[0087] A solution containing 15 g of sodium styrenesulfonate (0.073 mol), 48.2 g of deionized water, 159.25 g of ethanol (99%), 112.5 g of 80% acrylic acid in deionized water (1.249 mol), and 45 g of styrene (0.432 mol) was metered into the four-necked flask over 3 h. A solution of 3.36 g of ammonium persulfate in 20 ml of deionized water was also metered into the four-necked flask over 3.5 h. The solution was then held at reflux for 1 h. The solution was then cooled and treated with a solution of 34.75 g of sodium hydroxide pellets in 150 g of deionized water. Vacuum distillation was then performed to remove ethanol. Deionized water was added to the flask to a net weight of 430 g.

[0088] The dry matter content was approximately 39%. The product is highly viscous.

[0089] After adjusting the dry matter to approximately 30%, the viscosity was 30,000 mPas and the pH was 5.9.

[0090] Molar ratios in the polymer: Sodium styrenesulfonate: 4.16 mol% Acrylic acid: 21.66 mol% Sodium acrylate: 49.54 mol% Styrene: 24.62 mol% Comparison example 2:

[0091] A suitable four-necked flask equipped with a distillation condenser, adjustable stirrer, and internal thermometer was charged with 68.25 g of 99% ethanol, 21.75 g of deionized water, and 0.10 g of a 40% solution of the pentasodium salt of diethylenetriaminepentaacetic acid. The flask was purged several times with nitrogen and heated to reflux. A solution of 2.64 g of ammonium persulfate in 15 g of deionized water was added.

[0092] A solution containing 3 g of sodium styrenesulfonate (0.015 mol), 49.72 g of deionized water, 159.25 g of 99% ethanol, 104.88 g of 80% acrylic acid in deionized water (1.164 mol), and 37.5 g of styrene (0.360 mol) was metered into the four-necked flask over a period of 3 h. A solution of 3.36 g of ammonium persulfate in 20 ml of water was also metered into the four-necked flask over a period of 3.5 h. The solution was then held at reflux for 1 h. The solution was then cooled and treated with a solution of 46.57 g of sodium hydroxide pellets in 150 g of deionized water. Vacuum distillation was then performed to remove ethanol. Deionized water was added to a net weight of 430 g.

[0093] The result was a dry matter content of approximately 34%, a pH value of 7.7 and a viscosity of 400 mPas.

[0094] Production from sodium acrylate monomer is not possible. Therefore, deprotonation was carried out by adding sodium hydroxide.

[0095] Molar ratios in the polymer: Sodium styrenesulfonate: 0.97 mol% Sodium acrylate: 75.63 mol% Styrene: 23.40 mol% Comparison example 3

[0096] 130 g of isopropanol and 35 g of deionized water were placed in a suitable four-necked flask equipped with a distillation condenser, adjustable stirrer, and internal thermometer. The flask was purged several times with nitrogen and heated to 80°C.

[0097] A solution containing 20.7 g of sodium styrenesulfonate (0.100 mol), 45 g of deionized water, 110 g of methacrylic acid (1.278 mol), and 19 g of butyl acrylate (0.148 mol) was metered into the four-necked flask over approximately 2 hours. A solution of 16.6 g of sodium persulfate (0.069 mol) in 60 ml of deionized water was also metered into the four-necked flask over approximately 2 hours. The solution was then held at reflux for 1 hour. 500 g of deionized water was then added to the solution. Vacuum distillation was then performed to remove isopropanol. Distillation continued until an internal temperature of 99–100°C was reached.

[0098] The dry matter content of the sample was approximately 20%, the viscosity was 350 mPas, and the pH value was 1.3 in pure form. The pH value of a 1% solution was 3.5.

[0099] Molar ratios in the polymer: Sodium styrenesulfonate: 6.55 mol% Methacrylic acid: 83.75 mol% Butyl acrylate: 9.70 mol% Comparison example 4

[0100] Starting from Comparative Example 3, butyl acrylate was replaced by styrene in equal quantities.

[0101] 130 g of isopropanol and 35 g of deionized water were placed in a suitable four-necked flask equipped with a distillation condenser, adjustable stirrer, and internal thermometer. The flask was purged several times with nitrogen and heated to 80°C.

[0102] A solution containing 20.7 g of sodium styrenesulfonate (0.100 mol), 45 g of deionized water, 110 g of methacrylic acid (1.278 mol), and 19 g of styrene (0.182 mol) was metered into the four-necked flask over approximately 2 h. A solution of 16.6 g of sodium persulfate (0.069 mol) in 60 ml of water was also metered into the four-necked flask over 2 h. The solution was then held at reflux for 1 h. 500 g of deionized water was then added to the solution. Vacuum distillation was then performed to remove isopropanol. Distillation continued until an internal temperature of 99–100°C was reached.

[0103] The dry matter content of the sample was approximately 20%. The sample was cut-resistant, and viscosity was not measurable. The pH value was therefore determined from a 1% solution and was 3.5. Molar ratios in the polymer: Sodium styrenesulfonate: 6.41 mol% Methacrylic acid: 81.92 mol% Styrene: 11.67 mol% Application technology of the comparison examples:

[0104] The evaluation of the colour change was again carried out using a grey scale according to DIN EN 20102-A02: Pattern Color change Not treated 4 Production example 1 4-5 Comparison example 1 4 Comparison example 2 4 Comparison example 3 4 Comparison example 4 4

[0105] Polyamide 6.6 knitwear dyed with Acid Red 426 was then post-treated with the polymers according to Comparative Examples 1-4. For this purpose, the solids content of the polymers was adjusted with deionized water. The pH was adjusted to 3 using a formic acid / sodium formate-based buffer system.

[0106] The post-treatment was carried out using the exhaust process for 20 minutes at 70 °C. The amount of each preparation used was 4% based on the fabric weight.

[0107] The wash fastness at 40 °C of the post-treated samples was determined according to DIN EN ISO 105-C06 A1S (40 °C) using a multifibre accompanying fabric.

[0108] The assessment of bleeding was carried out using a gray scale according to DIN EN ISO 105-A03.

[0109] To evaluate the bleeding, the treated and untreated accompanying tissue were placed side by side in one plane and compared with the gray scale (see above). Accompanying fabric (multifibre) Not treated Comparison example 1 Comparison example 2 Comparison example 3 Comparison example 4 Production example 1 Cellulose acetate 4 4-5 4-5 4-5 4-5 4-5 Cotton 1-2 2-3 2-3 2 2 3-4 Polyamide 6.6 1 2-3 2-3 2 2 3-4 polyester 4-5 4-5 4-5 4-5 4-5 4-5 Polyacrylonitrile 4-5 4-5 4 4-5 4-5 4-5 Wool 3-4 4-5 4-5 4-5 4-5 4-5

[0110] It has been shown that the composition according to the invention produces significantly better color fastness, in particular wash fastness, on all fabrics tested than the comparison polymers.

[0111] The present invention includes the following points: 1. A polymer comprising the repeating units or a salt thereof, or a salt thereof, wherein R 1 independently of one another is -H, -aryl or -alkyl, in particular -CH3 or -C2H5, preferably H; R 2 independently of each other -C 2-8 -alkyl or -Aryl optionally substituted with C 2-20 -alkyl or C 2-20 -alkenyl, or -CH2-CH2-O-Aryl optionally substituted with C 2-20 -alkyl or C 2-20-alkenyl, preferably -aryl; A is independently an aryl group, in particular -phenyl, -tolyl, -xylyl, or -naphthyl, particularly preferably phenyl, B is independently an aryl group, in particular -phenyl, -tolyl, -xylyl, or -naphthyl, particularly preferably phenyl, which is substituted by, wherein at least 75 mol% of the repeating units W(1) and W(3) are present as at least monovalent salt, preferably as sodium salt. 2. Polymer according to item 1, wherein the polymer contains 40-80 mol% W(1), 5-50 mol% W(2), 0.4-10 mol%, preferably 1-10 mol% W(3) and 0-10 mol% W(4). 3. Polymer according to item 1 or 2, wherein the molar ratio W(1):W(2):W(3):W(4)=9-20:1-12:0.1-3:0-3. 4. Polymer according to any one of the preceding points, wherein R 1 each is -H, A is each -phenyl and B is each -substituted phenyl. 5. Polymer according to any one of the preceding points, wherein the polymer is soluble in 100-600 g / L of distilled water at 20 °C. 6. Polymer according to one of the preceding points, wherein the pH of a 30% solution in distilled water at 20 °C is 6-7, preferably 6.2-6.5 and / or the viscosity of a 30% solution in distilled water 50-600 mPas, preferably 100-300 mPas at 20 °C, measured according to DIN 53019 / ISO 3219. 7. Polymer according to one of the preceding points, wherein the repeating units W(1), W(2), W(3) and optionally W(4) are arranged randomly, alternately or in blocks in the polymer chain. 8. A process for producing a polymer according to any one of items 1-7, comprising the steps (a) Providing the monomer solution or dispersion, (b) polymerising the mixture obtained after step (a), (c) neutralising the mixture obtained after step (b) so that at least 75 mol% of the repeating units W(1) and W(3) originating from the monomers M(1) and M(3) are present as at least a monovalent salt, and (d) if necessary, distilling the mixture obtained after step (c). 9. The process according to item 8, wherein in step (a) water and / or organic solvent, such as C 2-8 -alcohol, glycol, glycol ester, ester, ketone and / or polyalkylene glycol is used as a solvent or dispersant. 10. Process according to any one of points 8-9, wherein in step (a) 40-80 mol% M(1), 5-50 mol% M(2), 0.4-10 mol%, preferably 1-10 mol% M(3), 0-10 mol% M(4) are provided and / or the molar ratio M(1):M(2):M(3):M(4) = 9-20:1-12:0.1-3:0-3 in step (a). 11. Process according to one of points 8-10, wherein in step (b) a radical polymerization is carried out, preferably using radical initiators such as inorganic persulfates such as ammonium persulfate, potassium persulfate, sodium persulfate, hydroperoxides such as cumene hydroperoxide and tert-butyl hydroperoxide, dialkyl peroxides such as di-tert-butyl peroxide and dicumene peroxide, peroxyesters such as tert-butyl perbenzoate, diacyl peroxide such as benzoyl peroxide and lauroyl peroxide and azo compounds such as azobisisobutyronitrile and azobisvaleronitrile. 12. The process according to item 11, wherein the radical initiator is a redox initiator system comprising a combination of a reducing agent, e.g. sodium hypophosphite, sodium pyrosulfite, iron salts and / or ascorbic acid and a peroxy compound. 13. Process according to any one of items 8-12, wherein chain regulators such as hypophosphite and / or mercaptan such as lauryl mercaptan are added before or during step (b). 14. Process according to any one of items 8-13, wherein in step (c) a base, e.g. alkali metal hydroxide, alkaline earth metal hydroxide, amine, ammonia, preferably sodium and / or potassium hydroxide, is added to the mixture obtained after step (b). 15. Polymer obtainable by a process according to any one of items 8-14. 16. Polymer according to item 15, wherein the pH of a 30% solution of the polymer in distilled water at 20°C is 6-7, preferably 6.2-6.5, and / or the solubility of the polymer at 20°C in distilled water is 100-600 g / L, preferably 200-300 g / L. 17. Polymer according to any one of items 1-16, wherein the polymer contains 40-70 mol% W(1), 25-50 mol% W(2), 5-20 mol% W(3) and 0-10 mol% W(4), with the proviso that the polymer contains 30-70 mol%, preferably 35-70 mol%, preferably 40-70 mol%, repeating units of W(2) and W(3) (W(2)+W(3)). 18. Composition comprising (A) at least one polymer according to any one of items 1-7 or 15-17, (B) Water and optionally a solvent, such as C 2-8 -alcohol, glycol, glycol ester, ester, ketone and / or polyalkylene glycol, (C) optionally one or more additives, such as anionic and / or non-ionic surfactant, UV stabilizer or salt such as sodium, aluminum, zinc or magnesium sulfate and / or calcium chloride. 19. Composition according to item 18, comprising 15-50 wt.%, preferably 25-40 wt.%, of component (A) based on the total weight of the composition. 20. Composition according to item 18 or 19, wherein the composition has a viscosity of 50-1200 mPas, preferably 200-700 mPas at 20 °C, measured according to DIN 53019 / ISO 3219. 21. Composition according to any one of items 18-20, wherein the pH of the composition is in the range of 6-7, preferably 6.2-6.5 at 20°C. 22. Use of the polymer according to any one of items 1-7 or 15-17 or of the composition according to any one of items 18-21 for improving the fastness, in particular the color fastness, e.g. perspiration, washing, light, water and rubbing fastness, of amide- and / or amino-group-containing substrates, as stain protection, preferably of carpets, and for tanning or retanning leather. 23. Use according to item 22, wherein the amide- and / or amino-group-containing substrates are dyed and comprise in particular wool, silk, polyamide, such as polyamide 6.0 and polyamide 6.6, imitation leather, leather or mixtures thereof. 24. A process for treating substrates with a polymer according to any one of items 1-7 or 15-17 or a composition according to any one of items 18-21, comprising the steps: (i) providing a polymer according to any one of items 1-7 or 15-17 in an aqueous solution or aqueous dispersion or a composition according to any one of items 18-21, (ii) applying the mixture from step (i) to a substrate, in particular a fibre, a woven fabric, a knitted fabric, a nonwoven fabric, a felt, a braid, an imitation leather or leather, and (iii) drying the product obtained after step (ii) at elevated temperature. 25. A process according to item 24, wherein the aqueous solution or aqueous dispersion in step (i) comprises water and optionally organic solvent, such as C 2-8-alcohol, glycol, glycol ester, ester, ketone and / or polyalkylene glycol and preferably contains 0.1-2 wt%, more preferably 0.2-1.5 wt% and most preferably 0.6-1.2 wt% polymer based on the total weight of the aqueous solution or aqueous dispersion. 26. A process according to item 24 or 25, wherein the application according to step (ii) is carried out by spraying, padding, dipping, exhausting, brushing, foaming or padding processes. 27. A process according to any one of items 24-26, wherein step (iii) is carried out at 80-140 °C, preferably 100-120 °C. 28. Fibre, textile, imitation leather or leather finished with a polymer according to any one of items 1-7 or 15-17 or with a composition according to any one of items 18-21 or obtainable by a process according to any one of items 24-27. QUOTES CONTAINED IN THE DESCRIPTION

[0000] This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions. Cited patent literature

[0000] WO 94 / 28231

[0009] US 5,574,106 A

[0010] WO 95 / 30794

[0013]

Claims

[1] A polymer comprising the repeating units, or a salt thereof, or a salt thereof, wherein R 1 independently of one another is -H, -aryl or -alkyl, in particular -CH3 or -C2H5, preferably H; R 2 independently of each other -C 2-8 -alkyl or -Aryl optionally substituted with C 2-20 -alkyl or C 2-20 -alkenyl, or -CH2-CH2-O-Aryl optionally substituted with C 2-20 -alkyl or C 2-20 -alkenyl, preferably -aryl; A is independently an aryl group, in particular -phenyl, -tolyl, -xylyl, or -naphthyl, particularly preferably phenyl, B is independently an aryl group, in particular -phenyl, -tolyl, -xylyl, or -naphthyl, particularly preferably phenyl, which is co-substituted, wherein at least 75 mol% of the repeating units W(1) and W(3) are present as at least monovalent salt, preferably as sodium salt, wherein the polymer preferably contains 40-80 mol% W(1), 5-50 mol% W(2), 0.4-10 mol% W(3) and 0-10 mol% W(4) and / or where the preferred molar ratio is W(1):W(2):W(3):W(4)=9-20:1-12:0.1-3:0-3. [2] Polymer according to claim 1, wherein R 1 each is -H, A is each -phenyl and B is each -substituted phenyl. [3] Polymer according to one of the preceding claims, wherein the polymer is soluble in distilled water at 20 °C to 100-600 g / L and / or wherein the pH of a 30% solution in distilled water at 20 °C is 6-7, preferably 6.2-6.5 and / or the viscosity of a 30% solution in distilled water is 50-600 mPas, preferably 100-300 mPas at 20 °C, measured according to DIN 53019 / ISO 3219. [4] Composition comprising (A) at least one polymer according to any one of claims 1-3, (B) Water and optionally a solvent, such as C 2-8 -alcohol, glycol, glycol ester, ester, ketone and / or polyalkylene glycol, (C) optionally one or more additives, such as anionic and / or non-ionic surfactant, UV stabilizer or salt such as sodium, aluminum, zinc or magnesium sulfate and / or calcium chloride, wherein the composition preferably comprises 15-50 wt.%, preferably 25-40 wt.%, of component (A) based on the total weight of the composition. [5] Composition according to claim 4, wherein the composition has a viscosity of 50-600 mPas, preferably 100-300 mPas at 20°C, measured according to DIN 53019 / ISO 3219 and / or wherein the pH of the composition is in the range of 6-7, preferably 6.2-6.5 at 20°C. [6] Fiber, textile, imitation leather or leather finished with a polymer according to any one of claims 1-3 or with a composition according to any one of claims 4-5. [7] Fiber, textile, imitation leather or leather according to claim 6, which contains amide and / or amino groups, and which is preferably dyed and in particular comprises wool, silk, polyamide, such as polyamide 6.0 and polyamide 6.6, imitation leather, leather or mixtures thereof.