DE102013212284A1 - Permanent fixing of dyes on surface of buckskin leather, involves dyeing leather and functionalizing raw material of surface of leather using aqueous solutions, dispersions or emulsions containing polyisocyanates/polyfunctional epoxides - Google Patents

Abstract

Permanent fixing of dyes on a surface of buckskin leather based on polyamide/polyurethane (PU) and polyethersulfone/PU, comprises dyeing a buckskin leather in a known manner and functionalizing raw materials of a surface of the buckskin leather before and/or after dyeing. The functionalizing step is carried out using (a) aqueous solutions, dispersions or emulsions containing polyisocyanates having a molecular weight of 100-5000 g/mol or (b) aqueous solutions, dispersions or emulsions containing polyfunctional epoxides. Permanent fixing of dyes on a surface of buckskin leather based on polyamide/polyurethane (PU) and polyethersulfone/PU, comprises dyeing a buckskin leather in a known manner and functionalizing raw materials of a surface of the buckskin leather before and/or after dyeing. The functionalizing step is carried out using (a) aqueous solutions, dispersions or emulsions containing polyisocyanates having a molecular weight of 100-5000 g/mol, (b) aqueous solutions, dispersions or emulsions containing polyfunctional epoxides or (c) an aqueous solution, dispersion or emulsion containing a mixture of polyisocyanates and polyfunctional epoxides or using acid dyes, metal complex dyes, reactive dyes, disperse dyes or mixtures of cationic functionalizing agent consisting of triazines, polyaziridines, polyethyleneimines, polyacrylamides, polyvinyl amines, polyamines, polyvinyl compounds with N-heterocycles, polyallylamine, and polyallyl with N-heterocycles.

Description

The invention relates to a method for permanent anchoring of dyes on the surface of wild imitation leathers, in particular for dyeing Wild imitation leather, in particular based on Alcantara ^® (polyester / polyurethane = PES / PU) and Amaretta ^® (polyamide / polyurethane = PA / PU) Furthermore, the invention relates to the use of textile auxiliaries for finishing the suede imitations, which bring about a deeper color scheme and achieve a level of authenticity that meets market requirements.

Synthetic suede imitations are made by impregnating nonwoven fabrics of synthetic fibers (eg polyamide, polyester or PAN fibers with polyurethane), which impregnation is carried out in the cross-linking process and after physical-thermal or chemical treatments and suede is a typical Surface lends.

EP 567975 B1 discloses a process for rapid coloration of synthetic composite materials that mimic natural leather, wherein the synthetic composite material is pulled through a dye bath. The dyebath is operated at higher pressure and temperatures> 100 ° C. The strips of the synthetic composite material are mutually performed by the dyebath at a tension of not less than 30 Nw / cm ² .

US 4,756,947 B1 describes a suede imitation with good color fastness due to ultrafine polyamide fibers and a polyurethane containing polyoxyethylene having a molecular weight of 500 to 5000 g / mole.

US 5,876,466 B1 discloses a suede-like artificial leather having good color fastness to light and color fastness to washing and dry cleaning. To this end, the suede imitation contains microfine polyamide fibers and a polyurethane, wherein the suede-like synthetic leather contains, at least on its surface, a dye selected from sulfur dyes, vat dyes and sulfur vat dyes having a benzophenone compound. The raw suede is dyed with the dye previously reduced under basic conditions, or a suede-like artificial leather is immersed in a liquid in which the dye has been reduced by adding a reducing agent under basic conditions. After dyeing, the dye is oxidized to render it insoluble in the water.

JP 2008/240174 A1 relates to a manufacturing method for microbicide-finished suede-like synthetic leather in which micro-acidic leather-dyed suede leather-dyed dyebody is imparted with microbicidal properties. The suede leather obtained by the dyeing process are subsequently treated with a cationic chemical, so that the cationic fractions of the microbicidal agents do not bind with anionic fractions of the dyes. This improves the microbicidal properties, the feel of the handle and the appearance of the imitation suede treated in this way.

DE 102 06 842 A1 discloses a process for dyeing and / or printing textile materials with un-split and / or partially split microfibers and / or microfilaments of synthetic polymers, in particular spunbonded fabrics of 70% by weight PET and 30% by weight PA. For this purpose, inter alia, pretreatment agents which include, inter alia, polyamines, polyamides or polyurethanes used. This pretreatment improves the effect of color depth. An improvement in wet fastness is not achieved.

DE 29 16 672 A1 discloses a process for dyeing, printing and simultaneously finishing textiles made of cellulosic fibers or blends of cellulosic fibers and synthetic fibers with disperse dyes. To this end, methylol and / or methylol ether compounds of urea, cyclic ureas, carbamates or aminotriazines and optionally acidic catalysts are added to the dyeing liquors or the printing pastes.

EP 0 316 730 A2 discloses dyestuff settings for leather dyeing and leather auxiliaries utilizing aliphatic polyamines or polyimines having at least one primary and one secondary amino group as well as water-soluble sulfonic acid group-containing dyes. For suede imitations, these dye settings are not applicable.

WO 2005/010271 A1 discloses the plasma treatment of woven and nonwoven fabrics, textiles, yarns, natural fibers, polymer fibers, inorganic fibers or films, glass or Alcantara. to To improve the wetting ability and hydrophilicity of Alcantara, a cold plasma with CF ₄ as the carrier gas is used.

WO 2005/080669 A1 to improve the depth of shade of polyamide fiber materials such as PA-Meryl microfibers 5-3101, calls aqueous solutions of specific polyamines having at least 2 amino groups and ethylene oxides or propylene oxides.

DE 101 25 843 describes a dyestuff for a dyed or printed nonwoven fabric of un-split and / or split microfibers and / or microfilaments of synthetic polymers containing at least one polyester component and at least one polyamide component and optionally a polyurethane component, such as a non-woven of polyethylene terephthalate and polyamide 66 and a dye on this tailored dyeing process.

US 5,030,243 B1 describes a process for the light stabilization of undyed or dyed PA / PU suede simulants with an aqueous liquid containing light stabilizers.

EP 305 596 A1 discloses dyeing ultrafine polyamide fibers with tannin and a metal salt for the production of artificial leather.

Suede imitations based on polyamide polyurethane are dyed on the basis of polyamide dyeing processes. For this purpose, acid dyes or metal complex dyes but also mixed dyes are used. With such a coloring, however, the polyurethane content of the suede imitation can only be dyed or soiled in pastel shades. For dark shades, the polyurethane paste must be adjusted to a suitable color shade before application to the nonwoven with pigment. However, this method does not replace the dyeing itself, since the PA content must be colored with the respective dye class despite the Vornuancierung with pigments (usually black pigments). Suede imitations based on PET-PU are dyed with disperse dyes. Here, the same applies mutatis mutandis.

• 1. maximal mittlere Farbtiefen erreichbar (oft nur Pastellnuancen)
• 2. 2-fache Kolorierung (Pigmentierung beim Herstellprozess und Ausziehfärbung)
• 3. hohe Losgrößen, damit geringe Flexibilität auf Markt- und Modeanforderungen einzugehen
• 4. erschwerte Nuancierung, Korrekturen von Fehlfärbungen nicht möglich
• 5. eingeschränkte Farbpalette darstellbar
• 6. hohe Färbezeiten, dadurch Schädigung des Materials möglich
• 7. geringe Festigkeiten (Reißfestigkeit, Weiterreißfestigkeit, Scheuerfestigkeit, Abriebverhalten)
• 8. unruhiges Warenbild, schlechte Warenoptik
• 9. harter Warengriff
• 10. hohe Farbstoffbelastung im Abwasser
• 11. Schwankungen im Herstellprozess des Wildleders haben negative Auswirkungen auf das Endresultat und sind irreversibel

These dyeing methods have the following disadvantages

• 1. maximum average color depths achievable (often only pastel shades)
• 2. 2-fold coloration (pigmentation in the production process and exhaust dyeing)
• 3. high lot sizes, so little flexibility to meet market and fashion requirements
• 4. difficult shading, corrections of false color not possible
• 5. Restricted color palette can be displayed
• 6. high dyeing times, thereby damaging the material possible
• 7. low strength (tear strength, tear resistance, abrasion resistance, abrasion behavior)
• 8. restless appearance of goods, poor appearance of goods
• 9. hard fabric handle
• 10. high dye load in the wastewater
• 11. Fluctuations in the production process of suede have negative effects on the final result and are irreversible

There is an increasing demand for suede imitations with appealing and durable staining as well as improved performance properties. Due to the aforementioned disadvantages, the state of the art is not in a position to satisfy this demand only to some extent.

The object of the invention is therefore a process for the refinement of suede imitations, which can dispense with the pre-pigmentation in the dyeing, a permanent anchoring of the dyes and a nuanced and deep dyeing with high performance properties allowed.

According to the invention the object is achieved by a process for the permanent anchoring of dyes on the surface of suede imitations based on polyester (PES) / polyurethane (PU) or polyamide (PA) / polyurethane (PU), wherein the suede imitations are dyed in a known manner, and the surface of the suede imitations is functionalized before or after dyeing with chemical functionalizing agents.

Suede imitations in the sense of the invention are synthetic suede imitations which are produced, for example, by impregnating nonwovens of synthetic fibers (for example polyamide, polyester or PAN fibers with polyurethane), wherein the impregnation in the crosslinking process and after physical-thermal or chemical Treatments are performed and gives the suede a typical surface. The Suede imitations may contain further fiber admixtures, eg microfibers but also modifications in the fiber material or polyurethane.

Particularly suitable for the process of the invention suede imitates based Alcantara ^® and Amaretta ^® is. Alcantara ^® is a suede imitation based on polyester ^® (PES) and polyurethane (PU). Amaretta is a suede imitation made of polyurethane resin (PU) impregnated polyamide microfibers (PA). Both Alcantara ^® and Amaretta ^® are widely used for clothing textiles and also for use textiles.

• a) wässrige Lösungen oder Dispersionen oder Emulsionen, enthaltend Polyisocyanate mit einer Molmasse von 100 bis 5000, bevorzugt 150 bis 1000, ganz besonders bevorzugt 400 bis 900 g/Mol,
• b) oder wässrige Lösungen oder Dispersionen oder Emulsionen, enthaltend polyfunktionelle Epoxide,
• c) oder eine wässrige Lösung oder Dispersionen bzw. Emulsionen enthaltend ein Gemisch aus Polyisocyanaten mit einer Molmasse von 100 bis 5000, bevorzugt 150 bis 1000, ganz besonders bevorzugt 400 bis 900 g/Mol und polyfunktionellen Epoxiden eingesetzt

According to the invention, the functionalization of the surface of the suede imitation raw material and essentially to improve the fastness and dyeing depth before or after dyeing

• a) aqueous solutions or dispersions or emulsions containing polyisocyanates having a molecular weight of 100 to 5000, preferably 150 to 1000, very particularly preferably 400 to 900 g / mol,
• b) or aqueous solutions or dispersions or emulsions containing polyfunctional epoxides,
• c) or an aqueous solution or dispersions or emulsions containing a mixture of polyisocyanates having a molecular weight of 100 to 5000, preferably 150 to 1000, most preferably 400 to 900 g / mol and polyfunctional epoxides used

or functionalizing the surface of the imitation suede raw material prior to dyeing by the use of acid dyes, metal complex dyes, reactive dyes, disperse dyes or mixtures cationic functionalizing agents selected from the group of triazines, polyaziridines, polyethyleneimines, polyacrylamides, polyvinylamines, polyazines, polyvinyl compounds with N Heterocycles, polyallylamines, and polyallyl compounds with N-heterocycles used.

According to an advantageous embodiment of the method according to the invention, the surface of the suede imitation raw material is pretreated with anionic functionalizing agents when using acid dyes, metal complex dyes, reactive dyes, disperse dyes or mixtures thereof with cationic functionalizing agents or when using basic dyes.

The functionalization with cationic auxiliaries is realized by the application of a polycation / polyanion with a high charge density. This functionalization is especially preferred when dyeing PA / PU suede imitations.

Polybases are polyelectrolytes which contain permanent cationic charges in the macromolecule (strong polyelectrolytes, charge = independent of pH) or contain as pro-ionic groups those functional groups which react by reaction with acids to form salts (weak polyelectrolytes, degree of dissociation is pH-dependent) ,

The cationic functionalizers contain aqueous solutions of cationic polyelectrolytes. The cationic polyelectrolytes are selected from the group of triazines, polyaziridines, polyethyleneimines, polyacrylamides, polyvinylamines, polyazines, polyvinyl compounds with N-heterocycles, polyallylamines, polyallyl compounds with N-heterocycles. The positive charge centers may be contained in the main or side chain of the polymer. In addition to their charge activity, polyelectrolytes differ mainly in their molar mass.

As polycations, polymers with N-heteroatom, e.g. Polyaziridines, polyethyleneimines, polyvinylpyridines, polyallylamines, polydiallylamines, polydiallyldimethylammonium chlorides (or other N-substituted polyallyl compounds) or polyvinylamines serve. The weak polyelectrolytic polymers may contain the N-heteroatom as a primary, secondary or tertiary amino function. Polymers with quaternary amine functions belong to the group of strong electrolytes. The heteroatom may also be bonded in the form of heterocyclic aromatic or non-aromatic rings in the polymer.

Furthermore, as a polycation polymers with P-heteroatom are used, such. Polyphosphonium salts formed by copolymerization of vinyl halides with secondary phosphines.

Syntans, polyacrylates, polystyrenesulfonic acids, polyacrylonitriles, polyvinylphosphonic acids or their co-polymers are used as anionic functionalizing agents for the pre-anionization. Furthermore, carboxymethyl-substituted synthetic fiber resins are used.

By modifying with the polymers mentioned functionalities can be generated on the surface of suede imitation, which allow a higher affinity of dye molecules (including Acid dyes, metal complex dyes, mixed dyes, basic dyes) by ionic but also covalent interaction between substrate and dye to produce. The more cationic / anionic centers are present in the macromolecule, the more dye molecules can interact and become more strongly fixed and bound on the surface. The charge density in the polymer can be estimated on the basis of the heteroatom content (sometimes also as a function of the pH).

Rest Beschreibung N, N`, N`` Neutral oder quarternär R H, Methyl, Ethyl, t-Butyl, i-Propyl, H, NH2, Br, Cl, Methyl, Ethyl, t-Butyl, i-Propyl, Phenyl, Benzyl, Acetyl, Carboxymethyl, Sulfonyl, R1, R2 Brom, Sulfatoethylsulfonyl, Chlortriazinyl, Fluortriazinyl, Heterocyklus (R1&R2, Ringschluss) H, NH2, Br, Cl, Methyl, Ethyl, t-Butyl, i-Propyl, Phenyl, Benzyl, Acetyl, Carboxymethyl, Sulfonyl, R3, R4 Brom, Sulfatoethylsulfonyl, Chlortriazinyl, Fluortriazinyl, Heterocyklus (R3&R4, Ringschluss) R5 Methyl, Ethyl, t-Butyl, i-Propyl, Phenyl H, NH2, Br, Cl, Methyl, Ethyl, t-Butyl, i-Propyl, Phenyl, Benzyl, Acetyl, Carboxymethyl, Sulfonyl, R6 Brom, Sulfatoethylsulfonyl, Chlortriazinyl, Fluortriazinyl R7, R8 H, Methyl, Ethyl, t-Butyl, i-Propyl, Heterocyklus (R7&R8, Ringschluss) R9, R11 H, Alkyl, Aryl R10 Alkyl, Aryl, H, Carboxyl, Carboxymethyl, Acetyl H, Br, Cl, NH2, Sulfatoethylsulfonyl, Methyl, Ethyl, t-Butyl, i-Propyl, Phenyl, Carboxymethyl, R12, R13, R14 Sulfonyl, Acetyl As cationic polyelectrolytes, it is advantageous to use polymers having the following monomer units of the general formulas 1 to 5 or triazines of the general formula 7 and also phosphonates of the general formula 6 as effect enhancers. The polymeric phosphorus compound 8 is generated on the basis of vinylogous halogen compounds by reaction with phosphines by subsequent polymerization. A here stands for a phosphonate or phosphinate radical.

rest description N, N`, N`` Neutral or quaternary R H, methyl, ethyl, t-butyl, i-propyl, H, NH 2, Br, Cl, methyl, ethyl, t-butyl, i-propyl, phenyl, benzyl, acetyl, carboxymethyl, sulfonyl, R1, R2 Bromine, sulfatoethylsulfonyl, chlorotriazinyl, fluorotriazinyl, heterocycle (R1 & R2, ring closure) H, NH2, Br, Cl, methyl, ethyl, t -butyl, i -propyl, phenyl, benzyl, acetyl, carboxymethyl, sulphonyl, R3, R4 Bromine, sulfatoethylsulfonyl, chlorotriazinyl, fluorotriazinyl, heterocycle (R3 & R4, ring closure) R5 Methyl, ethyl, t-butyl, i-propyl, phenyl H, NH 2, Br, Cl, methyl, ethyl, t-butyl, i-propyl, phenyl, benzyl, acetyl, carboxymethyl, sulfonyl, R6 Bromine, sulfatoethylsulfonyl, chlorotriazinyl, fluorotriazinyl R7, R8 H, methyl, ethyl, t-butyl, i-propyl, heterocycle (R7 & R8, ring closure) R9, R11 H, alkyl, aryl R10 Alkyl, aryl, H, carboxyl, carboxymethyl, acetyl, H, Br, Cl, NH 2, sulfatoethylsulfonyl, methyl, ethyl, t-butyl, i-propyl, phenyl, carboxymethyl, R12, R13, R14 Sulfonyl, acetyl

According to an advantageous embodiment, polyethyleneimine is used as the cationic functionalizing agent. The average molar mass X of the polyethyleneimine is: 1000 <= X <= 30,000 g / mol. The Ratio of primary nitrogen to secondary nitrogen to tertiary nitrogen averages 1 to 0.8 to 0.6. The cationic charge density Y is: 10 <= Y <= 20 meq / g (based on the pure substance).

The polyethyleneimine is used as an aqueous solution in a pure concentration of about 0.1 <= X <= 2.0%.

For the cationic functionalization, it is particularly advantageous to use an aqueous solution containing a mixture of polyethyleneimine, polyvinylamine and polydiallyldimethylammonium chloride. The cationic polyelectrolyte mixture contains 50-95% by weight, preferably 70 to 90% by weight of polyethylenimine, 5-30% by weight, preferably 5 to 15% by weight of polyvinylamine and 0.1-30% by weight, preferably 3 to 10% by weight of polydiallyldimethylammonium chloride or its analogues. The mixture with a total concentration within the liquid phase of the pre-cationization of 0.1 to 30% is preferably used.

Preferably, the polyelectrolyte is applied by padding on the suede imitation. Exhaustion, spray application, foam or patch application or a coating are also possible. Also exhaust processes are used.

According to an advantageous embodiment of the method according to the invention, the cationic or cationizable polyelectrolyte is phosphonates, e.g. EDTMP (ethylene diamine tetra (methylene phosphonic acid), HDTMP (hexamethylenediamine tetra (methylene phosphonic acid)) and DTPMP (diethylene triamine penta (methylene phosphonic acid).) The introduction of low molecular weight phosphonates as an additive to the polycationic electrolytes causes an increase in performance (additional fastness improvement). due to the linearization of the chain molecules and by chelation of the hardness formers, the effect enhancement increases with regard to the improvement of the contact fastness / the etching depths The effect enhancement depends on the phosphonate structure and is greater, the higher the N concentration of the polyelectrolyte and the higher its dilution is.

The proportion by weight of the phosphonates in the liquid phase of cationization is between 0.01 and 10% by weight absolute.

The DTPMP has proved to be particularly effective with an absolute concentration (liquor) of 0.5 to 2% by weight.

Advantageously, excess, unfixed functionalizing agent is removed. The removal of excess, unfixed functionalizing agent is preferably carried out by exhaustion before dyeing. In this case, a non-ionic detergent and a special dispersant based on Na sulfonate including sequestering agent is used. Subsequently, a rinse is required.

After the application of the functionalizing agent takes place thermally, physically, mechanically or chemically fixation of the applied functionalizing agent.

According to an advantageous embodiment of the method according to the invention, polyisocyanates from the group of cyanurates (HDI), toluene diisocyanates (TDI), methylene diphenyl diisocyanates (MDI), isophorone diisocyanates or mixtures of these compounds are used before or after dyeing to functionalize the imitation suede raw material stabilized with protective groups could be.

A further advantageous embodiment of the method according to the invention consists in the pretreatment or preimpregnation with blocked polyisocyanates and / or with epoxy compounds. As a result, the wet and dry scrub fastness values can be massively improved. The corresponding agents are applied in aqueous dilute form (solution or dispersion) in a concentration of 10 to 80%.

The following compounds are advantageously used as the polyisocyanate basic body:

The polyisocyanates are protected with protecting groups selected from ε-caprolactam (ε-cap), methyl ethyl ketoxime (MEKO), 3,5-dimethylpyrazole (DMP), 1,2,4-triazole (TRIA), diisopropylamine (DIPA) and diethyl malonate (DEM ) Mistake. The corresponding diol component consists of butanediol or its homologs.

The blocked polyisocyanates are used with a molecular weight of between 100 g / mol and 5000 g / mol in aqueous solution. The pretreatment is carried out continuously, preferably by means of padding process with a liquor pick-up between 30 and 120%, drying between 80 ° C and 150 ° C and a thermal fixation between 100 ° C and 200 ° C with a duration per process step between 30 sec and 4 min. The amount applied is between 0.5 and 8% based on the weight of the product.

Particularly preferred is the pretreatment with an aqueous, with protective groups provided hexamethylene diisocyanate (HDI) solution (as cyanurate). HDI is advantageously provided with MEKO protective groups.

According to a further advantageous embodiment of the method according to the invention, aqueous solutions with polyfunctional epoxide components such as e.g. with or on the basis of glycerol (for example glycerol triglycidyl ether or glycerol glycidyl ether) and / or epichlorohydrin and / or bisphenol derivatives (for example bisphenol S) for pre- or post-treatment. The use of these reactant-crosslinking epoxy compounds leads to an excellent handle in the pre- or post-treatment. The rub fastness values (wet and dry) are improved compared to the reference. The color depth is significantly improved K / S = 111% (compared to 100% as a reference, 2% dye input). The amount applied is between 0.5 and 10% based on the weight of the product.

Advantageously, a Glyceringlycidether emulsion, z. B. Lubricit 1923 used. The pretreatment with the reactant crosslinking epoxy compounds takes place in a padding process. The liquor pick-up is 80 to 100%, this corresponds to about 4% of the product weight, the pad printing is: 0.6 to 1.2 bar, drying at 110 ° C (3-6 minutes) and fixing 170 ° C (2- 4 minutes).

The dyeing process is a modification of the standard process with acid dyes, Metal complex dyes, disperse dyes or mixed dyes (acid dyes plus metal complex dyes). The staining is carried out in the acidic pH range according to the classes of dyes. The temperature and the time depend on the color depth and the bath extract. When dyed with basic dyes, the pH is also slightly acidic (about pH = 5).

Deviating from the known state of the art and this consideration, according to an advantageous embodiment of the invention for dyeing with acid dyes, metal complex dyes, disperse dyes or mixed dyes (acid dyes plus metal complex dyes) additionally a strong retarding leveling agent to improve the levelness, a special anti-wrinkle agent and an acid donor to increase the process safety and pH control used. After staining the dyebath is drained and rinsed Essigsauer. There is a final cleaning of the surface of the colored suede imitation according to the prior art (reductive or oxidative).

Advantageously used as a coloring additive: LUBATEX RUN: anti-wrinkling agents and antistatic agents based on hydrophilic polymers and copolymers; SETACID PAS: Acid donor based on formic acid ester; SETAVIN PA / UDP: Leveling agent based on alkylarylsulfonate and alkylamine ethoxylate and ZS-ECOCARRIER CAB: carrier for PES staining.

For suede imitations based on PA / PU, the product properties of the dyed suede imitations with anionic (single fixation) and optionally with cationic fixatives (double fixation) are further increased according to an advantageous embodiment of the method and staining.

Cationic fixatives based on dicyandiamidethylenetriamine condensation product (e.g., Zetesal CPW) and Syntane (Zetesal NR) anionic fixer are used. In the case of Voranionisierung the Doppelfixierschritt can be omitted. In the case of metal complex dyes, it may be possible to dispense with the first post-fixing step (anionic fixation).

Advantageously, a fixative containing an anionic syntan, ZETESAL NR / FRESH / FRESH liq / NT is used for double fixation. As a cationic fixer Zetesal CPW is used. In addition, a treatment with polyisocyanates having a molecular weight of 100 to 5000 g / mol or with a polyurethane size significantly increases the performance characteristics.

In the case of Voranionisierung the fixing step can be omitted, then only lathered and rinsed after staining.

According to an advantageous embodiment of the method according to the invention, the surface of the suede imitation raw material after dyeing is equipped with polysiloxane-containing reactive hydrophilic plasticizers.

eingesetzt.Advantageously, the polysiloxane is an amino-functional polysiloxane of the following formula

used.

The plasticizer Cefasoft MIS containing a microemulsion having an amino-functional polysiloxane compound of the abovementioned formula is particularly preferably used.

According to a further advantageous embodiment of the method according to the invention, the surface of the suede imitation raw material before or after dyeing by a physical plasma method with an atmospheric plasma (DBD plasma method) with a power of the field between 200 and 2000 watts activated and / or with an aqueous Solution containing treated polyisocyanates having a molecular weight of 100 to 5000, preferably 150 to 1000, most preferably 400 to 900 g / mol treated. Advantageously, the surface of the suede imitation raw material is activated prior to dyeing by a physical plasma method using an atmospheric plasma (DBD plasma method). The pretreatment is carried out with N ₂ as a carrier gas. The power of the field is between 200 and 2000 watts, the feed rates go from 10 cm to 20 m / min.

Advantageously, for plasma pretreatment precursors, e.g. TEOS (tetraethyl ortho-silicate) or HMDSO (hexamethyldisiloxane) used.

The raw material thus pretreated is dyed as much as possible while avoiding time delay, ie within 24 hours in a known manner.

Advantageously, timely, i. within 24 h of the DBD plasma pretreatment treatment with chemical functionalizing agents, e.g. Connected blocked polyisocyanates and supplied the thus pretreated goods the dyeing process.

The DBD plasma pretreatment and the combination of plasma pretreatment and treatment with chemical functionalizing agents result in a significant improvement in the authenticity values (rubbing fastness, wet and dry) of the thus pretreated and dyed raw material compared to untreated dyed raw material.

According to a further embodiment of the method according to the invention, the surface of the dyed imitation suede is activated after dyeing by a physical plasma method with an atmospheric pressure plasma (DBD plasma method) with a field strength between 200 and 2000 watts and / or with an aqueous solution containing protective groups provided polyisocyanates having a molecular weight of 100 to 5000, preferably 150 to 1000, most preferably 400 to 900 g / mol or treated with a polyurethane size.

The conditions of the DBD plasma process for aftertreatment correspond to those listed for the pretreatment.

As polyisocyanates used for pretreatment, the compounds used for pretreatment. Particularly preferred is the pretreatment with an aqueous, with protective groups cyanurate hexamethylene diisocyanate (HDI) solution. HDI is advantageously provided with MEKO protective groups.

The aftertreatment is particularly advantageous for suede imitations based on PES / PU suitable. The polyester fibers of this suede imitation can be dyed without pretreatment in the high-temperature dyeing process (HT process) at 120 to 130 ° C.

After a further inventive embodiment of the method according to the invention, the surface of the dyed imitation suede with a polyurethane size, eg. B. a Polycarbonatesterpolyurethan dispersion or a polyester polyurethane dispersion.

Post-treatment by means of DBD plasma and subsequent treatment with polyisocyanates or polyurethane sizes is particularly advantageously suitable for suede imitations based on PES / PU. The polyester fibers of this suede imitation can be dyed without pretreatment in the high-temperature dyeing process (HT process) at 120 to 130 ° C. The dyebath with the raw material is heated.

According to a preferred embodiment of the method according to the invention suede imitation raw material based PA / PU or PES / PU before dyeing with aqueous solutions, emulsions or dispersions containing polyethyleneimine, polyvinylamine or polydiallyldimethyl-ammonium chloride or a mixture of these substances is treated and then dyed in a known manner , Following the dyeing, the product is padded with an aqueous solution containing epoxide and / or a polyisocyanate, dried and fixed. Advantageously, an anionic syntan can then be used together with a silicone plasticizer to improve the fastness.

For a contrasting surface, e.g. for the visualization of logos, pictures or fonts paste-like dispersions containing polyethyleneimine, polyvinylamine or polydiallyldimethylammonium chloride or a mixture of these substances are treated flat or patterned, e.g. Streaked onto the surface of the suede imitation raw material using stencils, printed or sprayed on.

According to a particularly preferred embodiment of the process according to the invention, suede imitation raw material based on PA / PU before dyeing with aqueous solutions, emulsions or dispersions containing polyethyleneimine having an average molar mass X 1000 <= X <= 30000 g / mol, a ratio of primary Nitrogen to secondary nitrogen to tertiary nitrogen of 1 to 0.8 to 0.6 and a cationic charge density Y 10 <= Y <= 20 meq / g (based on the pure substance) used. The polyethyleneimine is treated in a pure concentration Z of about 0.1 <= Z <= 2.0% and then dyed. Following the dyeing, the product is mixed with an aqueous solution containing epoxide and / or a Polyisocyanate padded, dried and fixed. Advantageously, an anionic syntan can then be used together with a silicone plasticizer to improve the fastness.

This process achieves improved color depth and improves dry and wet fastness.

According to another preferred embodiment of the method according to the invention suede imitation raw material based on PES / PU is dyed in a known manner. Following dyeing, the fabric is padded with an aqueous solution containing polyisocyanate and / or a polyfunctional epoxide (e.g., glycerol glycidyl ether, with epichlorohydrin and bisphenol derivatives, e.g., bisphenol S), dried, and fixed. To further improve the fastness of an anionic Syntan is then used together with silicone plasticizer. Particularly preferred is an aqueous solution containing a polyisocyanate (HDI, as cyanurate) and / or as a polyfunctional epoxide, a glycerol glycidyl ether.

The product treated in this way has excellent results in both wet and dry rub fastness tests. The color depth is slightly increased compared to the untreated product.

The process according to the invention makes it possible to bind the dyestuffs to the colored suede imitates by coordinative bonding, bridging and cladding in such a way that a permanent anchoring is achieved.

• 1. Erhöhung der Farbtiefe
• 2. Verbesserung der Kontakt- und Reibechtheit bei vergleichbarer Farbtiefe
• 3. mittlere, brillante und dunkle Farbnuancen erreichbar
• 4. keine Vorpigmentierung notwendig
• 5. beliebige Losgrößen, damit hohe Flexibilität bei geänderten Markt- und Modeanforderungen
• 6. erleichterte Nuancierung, Korrekturen von Fehlfärbungen möglich
• 7. alle Farbnuancen darstellbar
• 8. wirtschaftliche Färbezeiten realisierbar, keine Schädigung des Materials
• 9. sehr hohe Festigkeiten (Reißfestigkeit, Weiterreißfestigkeit, Scheuerfestigkeit, Abriebverhalten)
• 10. ruhiges Warenbild, sehr ansprechende Warenoptik
• 11. weicher Warengriff
• 12. sehr geringe bis keine Farbstoffbelastung (Badauszug über 90%) im Abwasser
• 13. Schwankungen im Herstellprozess des Wildleders werden größtenteils ausgeglichen, die Auswirkungen auf das Endresultat werden minimiert.
• 14. Optimale Kompatibilität der Vorbehandlungsmittel und der Mittel für die Doppelfixierung mit den Rezeptur-Standards.
• 15. Weiterhin werden die Nass- und Trockenreibechtheiten sowie die Anfärbetiefe gleichermaßen signifikant verbessert.

Advantages of the method according to the invention

• 1. increase the color depth
• 2. Improvement of contact and rubbing fastness with comparable color depth
• 3. medium, brilliant and dark shades achievable
• 4. no prepigmentation necessary
• 5. Any lot sizes, so high flexibility with changed market and fashion requirements
• 6. easier shading, corrections of false color possible
• 7. all shades can be displayed
• 8. economic dyeing times feasible, no damage to the material
• 9. very high strengths (tear strength, tear resistance, abrasion resistance, abrasion behavior)
• 10. calm goods image, very attractive appearance of goods
• 11. soft goods handle
• 12. very low to no dye load (bath extract over 90%) in the wastewater
• 13. Fluctuations in the production process of the suede are largely compensated, the effects on the final result are minimized.
• 14. Optimum compatibility of the pretreatment agents and the double fixation means with the formulation standards.
• 15. Furthermore, the wet and dry rubbing fastnesses as well as the dyeing depth are significantly improved.

Reference to subsequent embodiments, the invention will be explained in more detail. The following commercial products were used: CEFAPAD WAT: Wetting agent based on carboxylic acid sulphonates TISSOCYL DLF: detergent based on fatty alcohol polyglycol ether ZS-DYESET RFT / RFT conc: disperser and leveler based on polyacrylates, naphthalenesulfonates and phosphonates CEFATEX ENN: Silicone-based deaerator LUBATEX RUN: anti-wrinkle and antistatic agents based on hydrophilic polymers SETACID PAS: Acid donor based on carboxylic acid ester SETAVIN PA / UDP: Leveling agent based on alkylarylsulfonate and alkylamine ethoxylate ZETESAL NR / FRESH / FRESH liq / NT: Anionic fixative based on a phenol-formaldehyde condensate (Syntane) and mesitol-formaldehyde condensate ZETESAL CPW / TCS: Cationic fixer for the double-fixation process based on dicyandiamidethylenetriamine condensation product CEFASOFT SMA / MIS / (MC): silicone emulsion, nonionic (macro and micro) ANTHYDRIN SC / SCE: fluorocarbon resins (C6), slightly cationic Biobac ZS: Bactericide based on quaternary N compounds Polappret PU-DM: cross-linked polyurethane; Rubbing resistance improvement, improvement of the grip Lubricit 1923: Epoxy crosslinker based on glycerine glycidyl ether ZS-ECOCARRIER CAB: ecological carrier for PES staining SETAVIN PE: PES leveling and dispersing agent based on fatty acid ethoxylate SETACID A40: pH buffer for setting a defined acidic pH

EMBODIMENT 1: Equipment of imitation suede PA-PU 60% / 40%, dyeing with acid dye in shade violet

As a cationic functionalizer, polyethyleneimine having an average molar mass of X 1000 <= X <= 30000 g / mol, a ratio of primary nitrogen to secondary nitrogen to tertiary nitrogen of 1 to 0.8 to 0.6 and a cationic charge density Y 10 < = Y <= 20 meq / g (based on the pure substance) used. The polyethyleneimine is used in a pure concentration Z of about 0.1 <= Z <= 2.0%.

The functionalizing agent was used in a process variant DTPMP with an absolute concentration (liquor) of 1% by weight.

The raw material is 30 g / l with the aforementioned polycation once with DTPMP additive and once without padding, subsequently dried / fixed. On the dyeing machine type Soft flow, the thus pretreated product is washed with 0.5 g / l TISSOCYL DLF (nonionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, followed by rinsing. The staining bath is mixed with the running wrinkle preventer (LUBATEX RUN), the deaerator (CEFATEX ENN), the retarding leveling agent (SETAVIN UDP), the acid dye (2% Nylosan Violet FBL), and the acid donor (SETACID PAS). After cooling, drained and rinsed. To improve the authenticity, an anionic syntan (ZETESAL FRESH liq) is used. It is followed by another rinse. The next step is drying the goods, the final equipment comes with a cation. Aftertreatment agent (30 g / l ZETESAL CPW) is carried out together with silicone softener (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS).

Result:

• • Increased color depth by 85% compared to standard technique (colorimetric rating with Datacolor 550).

Ausführungsbsp. 1: Violet (2% Nylosan Violet FBL) Color strength [%]  Difference brightness dL standard procedures  100  reference Simple method (without DTPMP)  176.0  -7.3 Procedure with DTPMP  185.3  -8.7

• • In addition, the fabric surface is visually more even.

Exemplary Embodiment 2: Suede Imitation PA-PU 60% / 40 /%, Dyeing with Metal Complex Dye in Color Black (8.9% Metal Complex Dye)

The raw material is padded with 30 g / l of polycation according to Example 1, subsequently dried / fixed. On the dyeing machine type Soft flow, the thus pretreated product is washed with 0.5 g / l TISSOCYL DLF (nonionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, followed by rinsing. The staining is treated with antifouling agent (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP), the 1: 2 metal complex dye (6.5% Selmalan Black S-MRL conc + 2.4% Selmalan Yellow S-2G), the acid donor (SETACID PAS) is added as a further addition. After cooling, drained and rinsed. To improve the authenticity, an anionic syntan (ZETESAL FRESH liq) is used. It is followed by another rinse. The next step is the drying of the product, the final finishing is carried out with a cationic post-treatment agent (30 g / l ZETESAL CPW) together with silicone softener (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS).

Result:

• • Compared to the standard procedure, a 305% shade was achieved.

Ausführungsbsp. 2: Black (8.9% metal complex dyes) Color strength [%]  Difference brightness dL standard procedures  100  reference Single method (without phosphonate)  384.5  -19.7 Method with phosphonate additive  405.0  -21.1

• • Furthermore, the look and feel is significantly improved, the tear and tear resistance also.

Exemplary Embodiment 3 Imitation Suede PA-PU 60% / 40%, Dyeing with Metal Complex Dye in Color Black (Comparison of Dye Insertion and Fastnesses for the Same Color Depth)

On the dyeing machine type Soft flow pretreated / cationized product according to Example 1, washed without DTPMP additive with 0.5 g / l TISSOCYL DLF (nonionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) 20 min, followed by rinsing , The staining is mixed with anti-wrinkle agent (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP), the 1: 2 metal complex dye (8%) to be dosed, as further addition of the acid donor (SETACID PAS). After cooling, drained and rinsed. To improve the authenticity, an anionic syntan (ZETESAL FRESH liq) is used. It is followed by another rinse. The next step is drying the goods.

According to a process variant, a final equipment with a cationic. Aftertreatment agent (30 g / l ZETESAL CPW) is carried out together with silicone softener (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS).

Result:

• • Compared to the standard procedure (target: same color depth) 75% dye could be saved.
• • Furthermore, the fastnesses were significantly improved.

Ausführungsbsp. 3: Black Same color strength  standard procedures  Procedure without cationic fixation Method with cationic fixation Recipe dyes  12% Lanasyn Black SRL 3% Lanasyn Black SRL 3% Lanasyn Black SRL Saving [%]  reference  75%  75% Authenticity level dry rub ISO 105-X12 2-3  3-4  4 Authenticity level wet rub ISO 105-X12 1  2  2-3 Authenticity level heavy water ISO 105-E01 , bleed to PA 2-3  4  4

Embodiment 4: Imitation suede PA-PU 60% / 40%, dyeing with reactive dye in color Brillantrot (7% reactive dye of the brand Eriofast)

The raw material is padded with 30 g / l of polycation without DTPMP additive according to Example 1, subsequently dried / fixed. On the dyeing machine type Soft flow, the thus pretreated product is washed with 0.5 g / l TISSOCYL DLF (nonionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, followed by rinsing. The staining is mixed with anti-wrinkle agent (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP), the reactive dye solution (3.8% Eriofast Red 2B + 3.2% Eriofast Yellow R), as further addition takes the acid donor (SETACID PAS) and calcium chloride. After cooling, drained and rinsed. To improve the authenticity, an anionic syntan (ZETESAL FRESH liq) is used. There are 3 more rinses. The next step is to dry the product, the final finish is carried out with a cationic post-treatment agent (20 g / l ZETESAL CPW) together with silicone softener (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS).

Result:

• • Compared to the standard procedure, a 156% shade was achieved.

Ausführungsbsp. 4: Brilliant Red (7% reactive dyes) Color strength [%]  Difference brightness dL standard procedures  100  reference Method according to exemplary embodiment 4  255.5  -12.6

• • An identical level of authenticity has been achieved compared to the standard procedure.

Ausführungsbsp. 4: Brilliant red (7% reactive dye) Waterfastness heavy ISO 105-E01 rub fastness staining PA / color change dry wet standard procedures  4-5 / 5 4-5 3-4  2-3 Method according to exemplary embodiment 4  4-5 / 5 4-5 3-4  2-3

Embodiment 5: Imitation suede PA-PU 60% / 40%, Vorkationisieren by forced application spraying, then drying and overdye in dark blue shade for the purpose of patterning (design light / dark).

The raw material 60% PA / 40% PU is with a thickened (natural-based thickener) paste, which in addition to the thickener also contains 10 parts by weight polycation according to Embodiment 4, printed or sprayed. It can be applied both over the entire surface as well as pattern-like (eg a logo) by means of appropriate templates. After drying / fixing, the goods are dyed. The corresponding differently cationically charged surfaces create a contrast. The dyeing was carried out with 5% Isolan Blue 3GL with the already mentioned in Examples 1 and 3 methods and tools.

Result:

• • Contrast difference was 114% compared to non-cationized area.

Ausführungsbsp. 5: spray application, then overdye in dark blue shade for patterning purposes Color strength [%]  Contrast difference [%] standard procedures  100  reference Method according to exemplary embodiment 5  213.5  113.5

Embodiment 6: 100% PES nonwoven fabric, coated with PU, without or with CEFAPAD ALE-SD in the polyurethane coating paste, dyeing with 5% mixed dye in anthracite

For the production of suede imitation, solidified PES fleece is coated in two embodiments with different polyurethane pastes. The coating paste 1 contains 50 parts of POLAPPRET PU-DM, 5 parts of POLAPPRET VIB, 5 parts of native-based thickener, and the remainder is water. The coating paste 2 contains 50 parts POLAPPRET PU-DM, 5 parts POLAPPRET VIB, 3 parts polycation according to embodiment 1, 5 parts native-based thickener, the rest is water.

After coating, the product is dried, subsequently condensed, 30s Gesamtkondensierzeit at final temperature.

On the dyeing machine type Soft flow, the thus pretreated goods are washed with 0.5 g / l TISSOCYL DLF (non-ionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, followed by rinsing. The staining is mixed with anti-wrinkle agent (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP), 5% black mixed dye (5% metal complex / reactive), as further addition of the acid donor (SETACID PAS) , After cooling, drained and rinsed. To improve the authenticity, an anionic syntan (ZETESAL FRESH liq) is used.

It is followed by another rinse. The next step is drying the goods, the final equipment comes with a cation. Aftertreatment agent (30 g / l ZETESAL CPW) is carried out together with silicone softener (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS).

Result:

• • The product treated and dyed with coating paste 2 has a 88% higher color depth compared to the product treated and dyed with coating paste 1.

Ausführungsbsp. 6: PES nonwoven coated with different PU pastes, anthracite coloration Color strength [%]  Difference brightness dL PU coating  100  reference PU coating with polycation  188  -18.8

Embodiment 7: Suede Imitation PES-PU 60% / 40%

• a) Metallkomplexfarbstoff in Farbe Grau
• b) Dispersionsfarbstoff (gut egalisierender Farbstoff) in Farbe Rot
• c) Metallkomplexfarbstoff in Farbe Grau und Dispersionsfarbstoff (gut egalisierender Farbstoff) in Farbe Rot

Dyeing with

• a) metal complex dye in gray
• b) Disperse dye (good leveling dye) in red color
• c) metal complex dye in color gray and disperse dye (good leveling dye) in red color

A PES-PU imitation leather (60% / 40 /%) is treated without or with polycation according to Example 1 (without DTPMP additive). The treatment with 30 g / l polycation is done by padding, followed by drying and fixing.

In the partial test a) the goods are dyed with a metal complex dye type Isolan Gray S-GL (2%) according to the known process for metal complex dyes.

Result:

• • The metal complex dye predominantly colors the PU portion of the imitation leather. The pre-cationized product has a 56% higher color depth than the one without.

Ausführungsbsp. 7: Sub-experiment a), metal complex color gray Color strength [%]  Difference brightness dL standard procedures  100  reference Method according to exemplary embodiment 7  156.4  -6.64

In sub-experiment b) the fabric is dyed with a disperse dye type leveling dye (2% Dianix Red CC) with the auxiliaries CEFATEX ENN, SETAVIN PE and SETACID SN for 30 min. This is followed by an alkaline-reductive post-purification.

Result:

• • The product cationized with polycation has a 13% higher color depth than the one without.

Ausführungsbsp. 7: sub-experiment b), dispersion color red Color strength [%]  Difference brightness dL standard procedures  100  reference Method according to exemplary embodiment 7  113.4  -3.14

In sub-experiment c) the product is treated with a metal complex dye type Isolan Gray S-GL (2%) and a disperse dye type leveling dye (2% Dianix Red CC) at 130 ° C with the auxiliary agents CEFATEX ENN, SETAVIN PE, SETAVIN UDP and SETACID SN Dyed for 30 minutes. This is followed by an alkaline-reductive post-purification.

Result:

• • The product pre-cationized with polycation has a 32% higher color depth than the one without.

Ausführungsbsp. 7: sub-experiment c), metal complex color gray + dispersion color red Color strength [%]  Difference brightness dL standard procedures  100  reference Method according to exemplary embodiment 7  131.7  -6.04

Embodiment 8: Imitation suede PA-PU 60% / 40%, pre-anionization, dyeing with cationic (basic) dye combination in red color (3.4% basic dyes of the brand Maxilon)

The raw material is padded with 50 g / l Syntan at a liquor pick-up of 70% (anionized), followed by drying for 3 min. On the dyeing machine type Soft flow, the thus pretreated product is washed with 0.5 g / l TISSOCYL DLF (nonionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) at 60 ° C. for 20 min, followed by rinsing. The staining is started in advance with running-fold inhibitor (LUBATEX RUN), SETAVIN MSN (precipitation inhibitor, leveling agent, dispersing agent), the basic dyes (3.0% Maxilon Red GRL-BR + 0.3% Maxilon Yellow GRL + 0.1% Maxilon Blue GRL) as a solution, as another Addition of the acid donor (SETACID PAS). After cooling, drained and rinsed. For post-washing, the special dispersant ZS-DYESET RFT is used at 2 g / l. It is followed by another rinse. The next step is drying the goods.

Result:

• • Compared to the standard procedure, a 58% tint has been achieved.

Ausführungsbsp. 8: red (pre-anionization, staining with 3.4% basic dyes) Color strength [%]  Difference brightness dL standard procedures  100  reference Method according to exemplary embodiment 8  158  -4.6

EMBODIMENT 9: Suede imitation PA-PU 60% / 40% finishing, dyeing with Nuance Purple Acid using a polymer blend

The raw material is padded once with polycation according to Example 1 and according to another method with 30 g / l polycation of polyethyleneimine, polyvinylamine and DADMAC in the ratio: 90 to 5 to 5% (mass fractions), subsequently dried / fixed.

On the dyeing machine type Soft flow, the thus pretreated product is washed with 0.5 g / l TISSOCYL DLF (nonionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, followed by rinsing. The staining is mixed with anti-wrinkle agent (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP), the acid dye (2% Nylosan Violet FBL), and the acid donor (SETACID PAS) as further addition. After cooling, drained and rinsed. To improve the authenticity, an anionic syntan (ZETESAL FRESH liq) is used. It is followed by another rinse. The next step is the drying of the product, the final finishing is carried out with a cationic post-treatment agent (30 g / l ZETESAL CPW) together with silicone softener (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS).

Result:

• • Compared to the process with polyethyleneimine, the use of the mixture results in an increased color depth of about 10% (colorimetric evaluation with Datacolor 550).

Ausführungsbsp. 9: Violet (2% Nylosan Violet FBL) Color strength [%]  Difference brightness dL standard procedures  100  reference Process with pure polyethyleneimine as functionalizing agent  185.3  -8.7 Method using a polymer mixture  195.1  -9.1

Embodiment 10: Imitation suede PES-PU 60% / 40% pretreatment and then dyeing with disperse dye (good leveling dye) in red color

A PES-PU imitation leather (60% / 40%) is pretreated with a polyisocyanate having a molecular weight of 890 g / mole based on HDI cyanurate (with MEKO protecting groups). The treatment is done by padding, followed by drying and fixing. However, there is a handle stiffening, but no yellowing was observed, the application was completely uniform and stain-free.

The fabric is dyed with a disperse dye (2% Dianix Red CC) in the exhaust process with the aid CEFATEX ENN, SETAVIN PE, LUBATEX RUN, ZS-DYESET RFT, ZS-ECOCARRIER CAB and SETACID A40) for 45 min at 130 ° C. After a first rinsing bath, an alkaline-reductive after-cleaning and two further rinsing baths are carried out.

Result:

• • The product pretreated with polyisocyanate has a performance profile improved by 1 grade compared to the untreated product in both the wet and dry scrub test.
• • Achieved a comparable color depth.

Embodiment 11: Imitation suede PES-PU 60% / 40% pretreatment and then dyeing with disperse dye (good leveling dye) in red color

A PES-PU imitation leather (60% / 40%) is pretreated by means of DBD plasma. The pretreatment is carried out with N ₂ as a carrier gas. The power of the field is between 200 and 2000 watts.

The product is padded within the next 24 h with a polyisocyanate having a molecular weight of 730 g / mol based on MDI (with protective group: ε-caprolactam), dried and fixed. There is a handle stiffening, but no yellowing was observed, the application was completely uniform and stain-free.

The subsequent dyeing in the exhaust process was carried out with a disperse dye (2% Dianix Red CC) with the aid CEFATEX ENN, SETAVIN PE, LUBATEX RUN, ZS-DYESET RFT, ZS-ECOCARRIER CAB and SETACID A40 min at 130 ° C. After a first rinsing bath, an alkaline-reductive after-cleaning and two further rinsing baths are carried out.

Result:

• • The product pretreated with DBD and polyisocyanate has a performance profile improved by at least 1 note compared to the untreated product in both the wet and dry scrub test.
• • Furthermore, the color depth increases by about 20% compared to untreated goods.

Embodiment 12: Imitation suede PES PU 60% / 40% pretreatment and then dyeing with disperse dye (good leveling dye) in red color

A PES PU imitation leather (60% / 40%) is pretreated by means of an epoxy crosslinker (the Lubricit brand). Foulardier and drying and fixing conditions correspond to the embodiment 11. There is no yellowing and grip stiffening, but the product has a greasy, greasy handle after pretreatment. However, this is reflected in the color and the product has a pleasant soft touch.

The coloring also takes place as in the exemplary embodiment 11.

Result:

• • The pre-treated product has similar values to the untreated product in both the wet and dry scrub test.
• • The color depth increases by about 30% compared to the untreated product and there is no grip stiffening.

Embodiment 13: Suede Imitation PA-PU 60% / 40% pretreatment with polyisocyanate and subsequent dyeing with metal complex dye in black (8.9% metal complex dye)

The raw material is padded with polyisocyanate (TDI, 150 g / mol, MEKO blocked), subsequently dried / fixed. On the dyeing machine type Soft flow, the thus pretreated product is washed with 0.5 g / l TISSOCYL DLF (nonionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, followed by rinsing. Staining is supplemented with antifouling (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP) containing 1: 2 metal complex dye (6.5% Selmalan Black S-MRL conc + 2.4% Selmalan Yellow S 2G), the acid donor (SETACID PAS) is added as further addition. After cooling, drained and rinsed.

Result:

• • Contrast difference was 115% compared to non-pretreated area. The rub fastness values improve by half a note (both wet and dry) compared to the untreated reference.

Embodiment 14: Suede Imitation PA-PU 60% / 40% Pretreatment and Dyeing with Metal Complex Dye in Color Black (8.9% Metal Complex Dye)

The raw material is treated with plasma and padded with polyisocyanate based on isophorone (MW: 400 g / mol, as diethyl malonate) within the next 24 hours. On the dyeing machine type Soft flow, the thus pretreated product is washed with 0.5 g / l TISSOCYL DLF (nonionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, followed by rinsing. Staining is supplemented with antifouling (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP) containing 1: 2 metal complex dye (6.5% Selmalan Black S-MRL conc + 2.4% Selmalan Yellow S 2G), the acid donor (SETACID PAS) is added as further addition. After cooling, drained and rinsed.

Result:

• • The contrast difference was plus 85% compared to the non-pretreated area.
• • The rub fastness values improve by one note (both wet and dry) compared to the untreated reference.

Embodiment 15: Imitation suede PES PU 60% / 40% dyeing with disperse dye (good leveling dye) in red color and subsequent aftertreatment

The raw material is dyed with a disperse dye (2% Dianix Red CC) in the exhaust process with the aid CEFATEX ENN, SETAVIN PE, LUBATEX RUN, ZS-DYESET RFT, ZS-ECOCARRIER CAB and SETACID A40 min at 130 ° C. After a first rinsing bath, an alkaline-reductive after-cleaning and two further rinsing baths are carried out.

Following the dyeing, the product is padded with a polyisocyanate (MDI uretdione, dimethylpyrazole, MW: 850 g / mol), dried and fixed. It enters a grip reinforcement.

Result:

• • The polyisocyanate aftertreated product has excellent results in both wet and dry rub fastness tests. In the dry the grade is 4.5-5 and in the wet the grade is 4.5.
• • The color depth is slightly increased compared to the untreated product, but there is a grip stiffening.

Embodiment 16: Imitation suede PES-PU 60% / 40% dyeing with disperse dye (good leveling dye) in red color and subsequent aftertreatment

The dyeing is carried out as in the embodiment 15.

The dyed fabric is aftertreated by means of DBD plasma and padded with polyisocyanate (HDI cyanurate, MW: 850 g / mol) within the next 24 h. The padding process is carried out as in Example 15. The DBD plasma treatment was carried out as indicated in Example 11.

Result:

• • The treated with DBD plasma and polyisocyanate goods has excellent rub fastness. In the dry the grade is 5 and in the wet the grade is 4.5-5.
• • The color depth is slightly increased compared to the untreated product, but there is a grip stiffening.

Embodiment 17: Imitation suede PES-PU 60% / 40% dyeing with disperse dye (good leveling dye) in color red and subsequent aftertreatment

The dyeing is carried out as in the embodiment 15.

The dyed fabric is padded once with PU size Impranil DLC and once with PU size Impranil DLF. The padding process is carried out as in the embodiment 15.

Result:

• • The color depth of the finished product is slightly increased compared to the untreated product.
• • Dry dry rub values improve by about 1.5 grades compared to untreated stock, but the improvements are very wet. It comes to a grip reinforcement.

Embodiment 18: Imitation suede PES PU 60% / 40% dyeing with disperse dye (good leveling dye) in red color and subsequent aftertreatment

The raw material is dyed with a disperse dye (2% Dianix Red CC) in the exhaust process with the aid CEFATEX ENN, SETAVIN PE, LUBATEX RUN, ZS-DYESET RFT, ZS-ECOCARRIER CAB and SETACID A40 min at 130 ° C. After a first rinsing bath, an alkaline-reductive after-cleaning and two further rinsing baths are carried out. Following the dyeing, the product is padded with an epoxide (Lubricit), dried and fixed. To improve the authenticity, an anionic syntan (ZETESAL FRESH liq) is used. There are 3 more rinses.

Result:

• • The Lubricit aftertreated product has excellent results in both wet and dry rub fastness tests. In the dry the grade is 5 and in the wet the grade is 4.5.
• • The color depth is slightly increased compared to the untreated product

EMBODIMENT 19 Suede Imitation PA-PU 60% / 40 /%, Dyeing with Metal Complex Dye in Color Black (8.9% Metal Complex Dye)

On the dyeing machine type Soft flow, the product is washed with 0.5 g / l TISSOCYL DLF (non-ionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, followed by rinsing. Staining is supplemented with antifouling (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP) containing 1: 2 metal complex dye (6.5% Selmalan Black S-MRL conc + 2.4% Selmalan Yellow S 2G), the acid donor (SETACID PAS) is added as further addition. After cooling, drained and rinsed.

The dyed fabric is pretreated with a polyisocyanate having a molecular weight of 890 g / mol based on HDI (with protective groups MEKO). The treatment is done by padding, followed by drying and fixing.

• • Die mit Polyisocyanat nachbehandelte Ware besitzt hervorragende Reibechtheiten. Im Trockenen zeigt sich die Note 5 und im Nassen zeigt sich die Note 5.
• • Die Farbtiefe verstärkt sich leicht im Vergleich zur unbehandelten Ware.

To improve the authenticity, an anionic syntan (ZETESAL FRESH liq) is used. It is followed by another rinse. The next step is the drying of the product, the final finishing is carried out with a cationic post-treatment agent (30 g / l ZETESAL CPW) together with silicone softener (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS).

• • The treated with polyisocyanate goods has excellent rub fastness. In the dry the grade is 5 and in the wet the grade 5 is shown.
• • The color depth is slightly increased compared to the untreated product.

Embodiment 20 Equipment of suede imitation PA-PU 60% / 40%, dyeing with acid dye in shade violet

The raw material is padded with a polycation comparable to Example 1, subsequently dried / fixed.

On the dyeing machine type Soft flow, the thus pretreated product is washed with 0.5 g / l TISSOCYL DLF (non-ionic detergent) and 2 g / l ZS-DYESET RFT (special dispersant) for 20 min, hereinafter rinsed. The staining is mixed with anti-wrinkle agent (LUBATEX RUN), deaerator (CEFATEX ENN), a retarding leveling agent (SETAVIN UDP), the acid dye (2% Nylosan Violet FBL), and the acid donor (SETACID PAS) as further addition. After cooling, drained and rinsed. Following the dyeing, the product is padded with an epoxide (Lubricit) and a polyisocyanate (HDI), dried and fixed. To improve the authenticity, an anionic syntan is then used together with silicone plasticizer (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS). There are 3 more rinses.

Result:

• • Compared to the reference, the color depth is improved by 60% (colorimetric rating with Datacolor 550).
• • Compared to the reference, the dry and wet fastness are excellent. Both dry and wet rub fastness ratings are 4.5 to 5.
• • No grip hardening.

Embodiment 21 Suede imitation finish PES-PU 60% / 40%; Dyeing with disperse dye (good leveling dye) in red and subsequent aftertreatment

The raw material is dyed with a disperse dye (2% Dianix Red CC) in the exhaust process with the aid CEFATEX ENN, SETAVIN PE, LUBATEX RUN, ZS-DYESET RFT, ZS-ECOCARRIER CAB and SETACID A40 min at 130 ° C. After a first rinsing bath, an alkaline-reductive after-cleaning and two further rinsing baths are carried out. Following the dyeing, the product is padded with a polyisocyanate (HDI, MW: 850 g / mol) and an epoxide (Lubricit), dried and fixed. For further improvement of authenticity, an anionic syntan is then used together with silicone plasticizer (20 g / l CEFASOFT SMA and 20 g / l CEFASOFT MIS). There are 3 more rinses

Result:

• • The product treated with polyisocyanate has excellent results in both the wet and dry scrub test. In the dry as well as in the wet the grade 5 shows.
• • The color depth is slightly increased compared to the untreated product,
• • No grip hardening

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The 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

• EP 567975 B1 [0003]
• US 4756947 B1 [0004]
• US 5876466 B1 [0005]
• JP 2008/240174 A1 [0006]
• DE 10206842 A1 [0007]
• DE 2916672 A1 [0008]
• EP 0316730 A2 [0009]
• WO 2005/010271 A1 [0010]
• WO 2005/080669 A1 [0011]
• DE 10125843 [0012]
• US 5030243 B1 [0013]
• EP 305596 A1 [0014]

Cited non-patent literature

• ISO 105-X12 [0088]
• ISO 105-X12 [0088]
• ISO 105-E01 [0088]
• ISO 105-E01 [0090]

Claims (8)

Process for the permanent anchoring of dyes on the surface of suede imitations based on PA / PU and PES / PU, wherein the suede imitations are dyed in a known manner and the surface of the suede imitation raw material is functionalized before or after dyeing, characterized in that the functionalization of the Surface of suede imitation raw material before or after dyeing a) aqueous solutions or dispersions or emulsions containing polyisocyanates having a molecular weight of 100 to 5000 g / mol, b) or aqueous solutions or dispersions or emulsions containing polyfunctional epoxides, c) or a aqueous solution or dispersions or emulsions containing a mixture of polyisocyanates having a molecular weight of 100 to 5000 g / mol and polyfunctional epoxides are used or that for functionalizing the surface of the suede imitation raw material before dyeing in the application of acid dyes, metal complex dyes, reactive dye fumes, disperse dyes or mixtures of cationic functionalizers selected from the group of triazines, polyaziridines, polyethyleneimines, polyacrylamides, polyvinylamines, polyazines, polyvinyl compounds with N-heterocycles, polyallylamines, and polyallyl compounds with N-heterocycles. A method according to claim 1, characterized in that polyisocyanates from the group of cyanurates (HDI), toluene diisocyanates (TDI), methylene diphenyl diisocyanates (MDI), isophorone diisocyanates or mixtures of these compounds are used for the functionalization. A method according to claim 2, characterized in that the functionalization after dyeing with an aqueous, provided with protective groups HDI cyanurate solution. A method according to claim 1, characterized in that an aqueous solution containing polyethylenimine polyvinylamine or polydiallyldimethylammonium chloride or a mixture of these substances is used as the cationic functionalizing agent. A method according to claim 4, characterized in that the cationic functionalizing agent additionally contains low molecular weight phosphonates selected from EDTMP, DTPMP or HDTMP or their analogues. A method according to claim 1, characterized in that additionally before or after dyeing the surface of the imitation suede is activated by a physical plasma method with an atmospheric plasma (DBD plasma method) with a power of the field between 200 and 2000 watts. Method according to one of claims 1 to 6, characterized in that the surface of the suede imitation raw material is pretreated in the application of basic dyes with anionic functionalizing agents and that the anionic functionalizing agents aqueous solutions, dispersions or emulsions of polyelectrolytes selected from Syntanen, polyacrylates, polystyrenesulfonic acids , Polyacrylnitrilaten, polyvinyl phosphonic acids, polyacrylamides or their co-polymers or carboxymethyl-substituted synthetic fiber resins or mixtures of these classes of substances. Method according to one of claims 1 to 7, characterized in that the surface of the suede imitation raw material is equipped in the post-treatment step with polysiloxane-containing reactive hydrophilic plasticizers.