CA2305677A1

CA2305677A1 - Biodegradable binding agents for dyeing

Info

Publication number: CA2305677A1
Application number: CA002305677A
Authority: CA
Inventors: Harro Traubel; Hanns-Peter Muller; Hans Schulze; Michael Pirkotsch; Norbert Donkels; Hans Joerg Seiler; Josef Meyer; Rainhard Koch
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1997-10-01
Filing date: 1998-09-18
Publication date: 1999-04-08
Also published as: AU1225799A; JP2001518573A; WO1999016958A1; DE19743457A1; EP1023486A1

Abstract

Certain anionic polyurethanes are excellently suited for use as binding agents for coating, dyeing and printing textiles and leather. Said polyurethanes are biodegradable. The residual and wash liquors left over from the dyeing process can therefore be conveyed to a biological effluent treatment plant.

Description

Le A 32 400-Foreign CountriesWIM/by/W6/V 13.09.1999 Biodegradable binders for dyein~
This invention relates to the use of biodegradable binders for dyeing, chiefly the dyeing of textiles and leather.
Completely biodegradable and compostable materials of construction will become increasingly important in the future both economically and technically (T.
Jopski, Kunststoffe 83 (1993), 10). The challenge is to produce plastics which have the necessary performance capability yet degrade under the stimulation of a biologically active environment. The initiating factor may be microbiological, enzymatic, hydrolytic, photolytic or oxidative degradation at a specific site in the main chain of the polymer. All the degradation products have to be safe, nontoxic and nonaccumulable in nature, i.e. undergo complete microbial degradation.
Heretofore three general categories of completely biodegradable and compostable materials of construction have become known: polyesters; plastics based on natural polymers; and other degradable plastics, for example polyvinyl alcohol. Polyesters include polylactic acid, polyhydroxybutyrate, polyhydroxyvalerate, polycaprolactone and high molecular weight aliphatic polyesters (EP-A 572 256). To obtain sufficiently high molecular weights, the polyesters mentioned in EP-A 572 256 are extended with organic diisocyanates to form the end product. The use of thermoplastic polyester urethanes as compostable plastics is described in EP-A 593 975.
Thermoplastically processable and biodegradable polyesteramides form part of the subject-matter of EP-A 641 917.
Biodegradable thermoplastic polyurethane filaments are described in DE-C 4 319 439. The thermoplastically processable polyurethanes are linear, have difunctional polyesterdiols and difunctional polyethylene glycols built into the polymer chain, and are constructed using hexamethylene diisocyanate and butanediol or hexanediol as chain extenders (Examples 1 to 3).

Le A 32 400-Foreign Countries DE-A 195 17 185 and 195 20 092 disclose biodegradable and compostable articles based on hydrophilic polyurethanes, the term "polyurethanes" also encompassing polyurethaneureas. The polyurethanes are reaction products of diisocyanates and diols, which to hydrophilicize the end product, also contain built-in radicals of diaminosulfonates and polyethers which optionally contain ethylene oxide groups.
These hydrophilic polyurethanes are useful as coating material for the coating of any desired substrates, as adhesive and/or as binder for cellulose for producing nonwovens from cotton and/or hemp or linen, as polymeric binder for wood, sawdust or wood chips, as films in composite materials for the production of biodegradable packaging, for producing hygiene articles such as, for example, babies' diapers, as seed dressings for immobilizing active substances in the form of slow-release formulations, as binders for the production of plant pots, as coatings for paper and for the engine sizing of paper, for the production of sausage casings and for the production of cosmetic compositions. Examples of products which can be produced therefrom include flat film, injection moldings such as flowerpots, drinking vessels, food Grays, thermoformed articles, blister packs, blown films or bottles.
Biodegradability is also becoming increasingly important in relation to textiles, and there are still large areas where it has not been achieved.
When dyeing and coating textiles with coating or textile print pastes by the direct, reverse, coating or printing process or with pigmented binders by the exhaust process it is common to use externally crosslinkable film-forming binders, for example those based on polyurethane, polyacrylate or butadiene/acrylonitrile copolymer. The mixtures of binder and pigment customarily include reactive compounds which, after the printing step, crosslink the binder at elevated temperature and thereby fix the print or the dyeing. It is only this fixing which provides the desired waterfastness, which is important, for example, in relation to the laundering of the dyed or printed textiles.

Le A 32 400-Foreign Countries It has now been determined that the ingredients of post-dyeing liquors or of wash liquors of the printed textiles, i.e., the underlying binders and Theological assistants in particular, are refractory. Similarly, the assistants needed to finish the pigments are usually based on refractory emulsifiers and/or copolymers. But for satisfactory performance characteristics it is important that the wetfastnesses of the materials be good. Good wetfastnesses are generally obtained through crosslinking. On the other hand, it has been determined that crosslinking impairs the biodegradability of the articles. The crosslinkers used for the binders used in coating and textile print pastes are customarily melamine/formaldehyde condensation products which act above about 120°C. According to W. Berlenbach in Ullmanns Encyklopadie der tech-nischen Chemie, 4th edition, volume 22, page 629, Verlag Chemie, Weinheim 1982, the crosslinking via N-methylol groups of the binder is catalyzed by acid;
fixing is preferably accomplished using dry hot air for, for example, S to 10 minutes at 140°C
or 30 to 60 seconds at 175°C.
Pigment dyeing with hydrophilic modified polyisocyanates is described for example in EP-B 571 867 and DE-A 4 415 449.
Generally, the coloring materials of the invention are also useful for coating textiles in the direct and reverse process, provided, as is known per se, only biodegradable components are used. Coating desiderata are high flexibility wet and dry and also high abrasion resistance and water and solvent resistance. The binders therefore have to be crosslinked. Surprisingly, the coated textiles and the residual liquors retain their biodegradability when - based on polymer - 15%, preferably 10%, particularly preferably 7%, by weight of crosslinker (active material) on binder (as 40%
strength by weight dispersion) is not exceeded.
It is accordingly an object of the present invention to overcome the ecological disadvantages of the prior art. More particularly, the residual and wash liquors from the coating and dyeing processes shall be dischargeable into a biological treatment Le A 32 400-Foreign Countries plant and the coated, dyed or printed articles shall be compostable, i.e., biodegradable in a landfill.
This object is achieved according to the invention by using biodegradable polyurethaneureas, polyesters or polyesteramides.
The invention accordingly provides biodegradable coating, dyeing and print pastes for textile substrates and nontextile cellulosic substrates, comprising (i) biodegradable polyurethaneureas, polyesters or polyesteramides, (ii) rheological assistants, (iii) pigments or dyes which, if they have been finished, have been finished with finishing agents of natural origin, and optionally (iv) natural-based plasticizers.
Preferred such pastes include per ~0 parts by weight of (i), based on dye content of (i) (ii) up to 10 parts by weight of a mineral and/or natural organic thickener, (iii) up to 100 parts by weight of an optionally casein- and/or albumin-finished pigment or dye, (iv) up to 30 parts by weight of a natural (vegetable or animal) oil or fat, and also (v) up to 25 parts by weight of an N-rnethylol-, aziridine-, epoxide- or isocyanate-based crosslinker.
The invention further provides for the use of A) reaction products obtainable with an equivalents ratio of 1:1 to 2:1 for isocyanate groups to isocyanate-reactive groups from a) a diisocyanate component comprising al) hexamethylene diisocyanate or Le A 32 400-Foreign Countries a2) mixtures of hexamethylene diisocyanate with in total up to 60% by weight, based on mixture a2), of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and/or 4,4'-diisocyanatodicyclohexylmethane and/or 1-methyl-2,4(6)-diisocyanatocyclohexane with b) a diol component comprising b 1 ) at least one polyesterdiol having a number average molecular weight of 500 to 10,000 derived from (i) adipic acid and/or succinic acid and (ii) at least one alkanediol having 2 to 6 carbon atoms or b2) a mixture of such polyesterdiols with up to 32% by weight, based on the total weight of component b), of optionally ether group-containing alkanediols having 2 to 6 carbon atoms, i~
;..) a diamine component in an amount of from 2 to SO equivalents %, based on the total amount of isocyanate-reactive groups present in the components b) and c), comprising cl) diaminosulfonates of the formula H2N (-CH2)n-~ (-CH2)m-S03Me or c2) mixtures of diaminosulfonates cl) with up to 90% by weight, based on the total weight of component c), of ethylenediamine, optionally d) hydrophilic polyether alcohols of the formula H-X-O-R

Le A 32 400-Foreign Countries in an amount of up to 10% by weight, based on the sum total of the components b), c) and d), and also optionally e) water, which does not enter into the calculation of the equivalents ratio of isocyanate groups to isocyanate-reactive groups, where in the formulae mentioned m and n are independently from 2 to 6, Me is potassium or sodium, R is a monovalent hydrocarbon radical having 1 to 12 carbon atoms, and X is a polyalkylene oxide chain of the number average molecular weight range ti-om 88 to 4000 whose alkylene oxide units are ethylene oxide units to a.n extent which is not less than 40 mol% and are propylene oxide units as far as the rest is concerned, and B. 0 to 30%, preferably 0.1 to 25°~0, by weight, based on A, of crosslinker for A
as binders for dye andlor pigment preparations for dyeing or printing flexible substrates, especially textiles and leather.
The diisocyanate component a) is preferably all hexamethylene diisocyanate.
The diol component b) is comprised either of b 1 ) at least one polyesterdiol or b2) of a mixture of at least one polyesterdiol b 1 ) with up to 32%, preferably up to 10%, by weight of at least one optionally ether group-containing alkanediol having 2 to 6 carbon atoms.

Le A 32 400-Foreign Countries Suitable polyesterdiols bl) have a number average molecular weight (computable from the hydroxyl group content) of S00 to 10,000, preferably 1000 to 2500, and are based on (i) adipic acid and/or succinic acid and (ii) optionally ether group-containing alkanediols having 2 to 6 carbon atoms, for example ethylene glycol, diethylene glycol, 1,4-butanediol, neopentylglycol and/or 1,6-hexanediol.
Polyesterdiols prepared using exclusively ethylene glycol and/or 1,4-butanediol as diol are particularly preferred.
The optionally ether group-containing alkanediols of 2 to 6 carbon atoms to be optionally included as hydroxyl-containing chain extenders are those of the just exemplified kind as mentioned for preparing polyesterdiols.
The diamine component c) is comprised either of cl) diaminosulfonates of the abovementioned general formula or of c2) mixtures of such diaminosulfonates with 1 ~ ethylenediamine which is employed, if at all, in amounts of up to 90, preferably up to i 0, equivalents%, based on the isocyanate-reactive amino groups of component c).
Very particularly preferred diaminosulfonates are the potassium or sodium salts of N-('?-aminoethyl)-2-aminoethanesulfonic acid.
The diamine component c) is generally used in an amount of 1 to 10%, preferably 2 to S%, by weight, based on the weight of component b).
The optional formative component d) comprises hydrophilic, monohydric polyether alcohols of the formula H-X-O-R
where R and X are each as defined above.

Le A 32 400-Foreign Countries _g_ Preference is given to those among such polyether alcohols for which R is an aliphatic hydrocarbyl radical having 1 to 4 carbon atoms, and S X is a polyalkylene oxide chain of the number average molecular weight range from 500 to 4000 whose alkylene oxide units are ethylene oxide units to an extent which is not less than 40 mol%, especially not less than 70 mol% and particularly preferably l00 mol%, and are propylene oxide units as far as the rest is concerned.
Monohydric polyether alcohols of this kind are prepared by conventional alkoxylation of suitable starter molecules R-OH, for example methanol, n-butanol, n-hexanol or n-dodecanol, with the preferred use of ethylene oxide and optionally propylene oxide in the hereinabove disclosed quantitative ratios of the alkylene oxides. The alkylene oxides mentioned can here be used in the form of a mixture and/or in succession.
The monohydric polyether alcohols d) are used in the process of the invention, if at all, in amounts of up to 10%, preferably up to 3%, by weight, based on the sum total of components b), c) and d).
A further optional formative component for preparing the urea group-containing polyurethanes is e) water, which should be considered for use as a reactant in particular when, in the preparation of the polyurethanes, the chain extension reaction of previously prepared NCO prepolymers is effected in an aqueous medium, especially when the diamines c) dissolved in the water are used in subequivalent amounts, based on the NCO groups of the NCO prepolymers.
As well as these formative components, other compounds suitable in principle include trifunctional compounds in minor amounts, for example glycerol or trimethylolpropane, which can either be incorporated into the polyesters bl) in small Le A 32 400-Foreign Countries amounts or be used in free form as part of component b2). The use of such branching molecules generally has to be compensated by means of monofunctional compounds so that, purely arithmetically, linear polymers are again obtained.
The polyurethanes containing urea groups can be prepared from the exemplarily mentioned formative components by any desired process. Preferably, however, the known prepolymer process is used, in such a way that the components b) and optionally d) and also the diisocyanate component a) are reacted using an NCO/OH
equivalents ratio of 1.5:1 to 4:1, preferably 1.8:1 to 2.5:1, to prepare an NCO
prepolymer and this NCO prepolymer is subsequently reacted with the component c) to effect chain extension.
In general, the prepolymer is prepared at temperatures of 20 to 150°C
in the absence of a solvent and is subsequently dissolved in a suitable solvent. It will be appreciated tha.,t the prepolymers can also be formed directly in a solvent. Suitable.
solvents include in particular solvents which are inert toward isocyanate groups and are miscible with water in any proportion. The solvent used is preferably acetone.
The thusly prepared prepolymers are reacted, in the second reaction step, with component c) to effect chain extension. In this step, the equivalents ratio of isocyanate groups in the prepolymers on the one hand to isocyanate-reactive amino groups in component c) on the other is within the range from 1:1 to 20:1, preferably 1.2:1 to 4:1. The chain extension reaction can be earned out in solution, preferably in a solution in acetone, or else in an aqueous medium, by combining the solution of the prepolymers in an organic solvent with a solution of component c) in water with thorough mixing. As already indicated, this may be accompanied by a chain extension reaction involving the reaction of the NCO groups in the prepolymers with the water. In the abovementioned, preferred 2-step process of preparing the urea group-containing polyurethanes, the equivalents ratios between isocyanate groups and isocyanate-reactive groups in the two reaction steps are chosen within the scope of the disclosure in such a way that the overall ratio of isocyanate groups to Le A 32 400-Forei~,n Countries isocyanate-reactive groups in components b) to d) conforms to the above-indicated ratio of 1:1 to 2:1. The water is absolutely excluded from the calculation of the equivalents ratios mentioned.
S The chain extension reaction generally takes place within the temperature range from 20 to 50°C.
A possibility in principle, but in no way preferred, is the alternative of carrying out the chain extension reaction in the melt, i.e., in the absence of solvents and water (melt dispersion process).
To prepare the polyurethanes A, the abovementioned starting materials a), b), c) and optionally d) and/or optionally e) are used in the quantitative ratios mentioned.
1 S The polyurethanes A are preferably used in the form of aqueous dispersions. As used herein, the term "aqueous disperison" shall also encompass aqueous solutions which can be present when the concentration of hydrophilic centers in the urea group-containing polyurethanes is sufficient to ensure solubility in water.
Frequently, the dispersions are aqueous systems comprising not only dispersed but also dissolved urea group-containing polyurethanes.
Aqueous dispersions of polyurethanes in a constitution similar or comparable to the polyurethane A are already known from DE-A 2 035 732, 2 651 506, 195 17 185 and 195 20 093.
To prepare the aqueous dispersions, the chain-extended polyurethanes or their solutions in organic solvents if the chain extension reaction has been carried out in the absence of water are mixed with the dispersing water, followed if appropriate by the distillative removal of at least a portion of any cosolvent used. If the chain extension reaction took place in an aqueous medium, it is possible to add further Le A 32 400-Foreign Countries water if appropriate in order to prepare the aqueous dispersions. In this case, too, it is of course possible to distillatively remove the cosolvent used, if desired.
In general, the total amount of water used is such that dispersions from S to 60%
strength by weight (preferably 20 to 55% strength by weight) are present.
The polyurethane dispersion may include customary assistants. However, particular preference is given to such assistants as are likewise biodegradable. Such assistants are suitably in particular those of natural origin: gelatin, protein hydrolyzates, guar, tragacanth, flour, starch, sawdust, cellulose powder, etc.
The crosslinkers B comprise hydrophilic polyisocyanates, polyfunctional epoxides and carbodiimides as described for example in DE-A 42 17 716; the content of DE-A 42 17 716 in this respect is hereby expressly incorporated herein by reference.
In addition, crosslinkers B can be reactive compounds derived from formaldehyde, for example N-methylol group-containing phenol/formaldehyde and melamine/formaldehyde condensates as described for example in "Methoden der Organischen Chemie" (Houben-Weyl), volume 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, page 319 ff. The crosslinking leads to better water resistance and higher abrasion resistance, etc.
The mixtures of A and B may have added to them up to 30% by weight, based on A, of dyes and/or pigments.
Preferred dyes are alkali-fixable reactive dyes. They may bear any color-conferring moiety, for example residues of a sulfo-containing organic dye of the mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide series.

Le A 32 400-Foreign Countries The alkali-fixable reactive dyes preferably possess at least one aromatic heterocyclic reactive radical and/or at least one reactive radical of the formula -S02M, where M = CH2-CH2-OH, CH=CH2 or CH2-CH2-V, wherein V = alkali-eliminable radical, preferably OS03H, SS03H, OCOCH3, OP03H2, OS02CH3, SCN, NHS02CH3, C1, Br, F, OCOC6H5, OS02-C6H5, N(CH3)3-anion (anion is preferably Cl-), which under the dyeing conditions reacts with HO- or NH-containing fibers to form covalent bonds. Preference is given to those which contain at least one reactive substituent attached to a S- or 6-membered aromatic heterocyclic ring, for example to a monoazine, diazine or triazine ring, especially a pyridine, pyrimidine, pyr-idazine, pyrazine, thiazine, oxazine or symmetrical or asymmetrical triazine ring, or to such a rzng system which has one or more aromatic carbocyclic rings fused on, for example a quinoline, phthalazine, cinnoline, quinazoline, quinoxaline, acr-idine, phenazine or phenanthridine ring system, or those which are substituted by additional reactive groups of the vinyl sulfone type.
The reactive substituents on the heterocycle include for example halogen (C1, Br or F), ammonium including hydrazinium, pyridinium, picolinium, carboxypyridinium, sulfonium, sulfonyl, azido(-N3), thiocyanato, thioether, oxyether, sulfinic acid and sulfonic acid.
Specific examples are the following fiber-reactive radicals:
2,4-difluorotriazin-6-yl, 2,4-dichlorotriazin-6-yl, monohalo-sym-triazinyl radicals, especially monochloro- and monofluorotriazinyl radicals, which are optionally substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, morpholino, piperidino, pyrrolidino, piperazino, alkoxy, aryloxy, alkylthio, arylthio, where alkyl is preferably optionally substituted C1-C4-alkyl, aralkyl is preferably optionally substituted phenyl-C1-C4-alkyl and aryl is preferably optionally substituted phenyl or naphthyl and where preferred substituents for alkyl Le A 32 400-Foreign Countries are halogen, hydroxyl, cyano, dialkylamino, morpholino, C1-C4-alkoxy, carboxyl, sulfo or sulfato and preferred substituents for phenyl and naphthyl are sulfo, C1-C4-alkyl, C1-C4-alkoxy, carboxyl, halogen, acylamino, hydroxyl and amino.
Also possible are 2-amino-4-fluorotriazin-6-yl, 2-methylamino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluorotriazin-6-yl, 2-dimethyl-amino-4-fluorotriazin-6-yl, 2-diethylamino-4-fluorotriazin-6-yl, 2-f3-methoxy-ethylamino-4-fluorotriazin-6-yl, 2-13-hydroxyethylamino-4-fluorotriazin-6-yl, 2-di-(13-hydroxyethylamino)-4-fluorotriazin-6-yl, 2-carboxymethylamino-4-fluorotriazin-6-yl, 2-di-(carboxymethylamino)-4-fluorotriazin-6-yl, 2-sulfomethyl-methylamino-4-fluorotriazin-6-yl, 2-13-cyanoethylamino-4-fluorotriazin-6-yl, 2-benzylamino-4-fluorotriazin-6-yl, 2-13-phenylethylamino-4-fluorotriazin-6-yl, 2-benzyl-methylamino-4-fluorotriazin-6-yl, 2-(4'-sulfobenzyl)-amino-4-fluorotriazin-6-yl, 2-cyclohexylamino-4-fluorotriazin-6-yl, 2-(0-, m-, p-methylphenyl)-amino-4-fluorotriazin-6-yl, 2-(0-, m-, p-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(2',5'-disul-1 ~ fophenyl)-amino-4-fluorotriazin-6-yl, 2-(0-, m-, p-chlorophenyl)-amino-4-fluorotriazin-6-yl, 2-(0-, m-, p-methoxyphenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-methyl-4'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-methyl-5'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-chloro-4'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-chloro-S'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-methoxy-4'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(0-, m-, p-carboxyphenyl)-amino-4-fluorotriazin-6-yl, 2-(2',4'-disulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(3',S'-disulfo-phenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-carboxy-4'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(2'-carboxy-5'-sulfophenyl)-amino-4-fluorotriazin-6-yl, 2-(6'-sulfonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 2-(4',8'-disulfonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 2-(6',8'-disulfonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 2-(N-methyl-N-phenyl)-amino-4-fluorotriazin-6-yl, 2-(N-ethyl-N-phenyl)-amino-4-fluorotriazin-6-yl, 2-(N-f3-hydroxyethyl-N-phenyl)-amino-4-fluorotriazin-6-yl, 2-(N-iso-propyl-N-phenyl)-amino-4-fluorotriazin-6-yl, 2-morpholino-4-fluorotriazin-6-yl, 2-piperidino-4-fluorotriazin-6-yl, 2-(4',6',8'-trisulfonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 2-(3',6',8'-trisulfonaphth-2'-yl)-amino-4-fluorotriazin-6-yl, 2-(3',6'-disulfonaphth-1'-yl)-amino-4-fluorotriazin-6-yl, N-methyl-N-(2,4-dichlorotriazinyl-Le A 32 400-Foreign Countries 6)-carbamyl-, N-methyl-N-(2-methylamino-4-chlorotriazin-6-yl)-carbamyl-, N-methyl-N-(2-dimethylamino-4-chlorotriazin-6-yl)-carbamyl-, N-methyl- or N-ethyl-N-(2,4-dichlorotriazin-6-yl)-aminoacetyl-, 2-methoxy-4-fluorotriazin-6-yl, 2-ethoxy-4-fluorotriazin-6-yl, 2-phenoxy-4-fluorotriazin-b-yl, 2-(0-, m- or p-sulfo-phenoxy)-4-fluorotriazin-6-yl, 2-(0-, m- or p-methyl- or -methoxy-phenoxy)-4-fluorotriazin-6-yl, 2-13-hydroxyethylmercapto-4-fluorotriazin-6-yl, 2-phenylmercapto-4-fluorotriazin-6-yl, 2-(4'-methylphenyl)-mercapto-4-fluorotriazin-6-yl, 2-(2',4'-di-nitrophenyl)-mercapto-4-fluorotriazin-6-yl, 2-methyl-4-fluorotriazin-6-yl, 2-phenyl-4-fluorotriazin-6-yl and also the corresponding 4-chloro- or 4-bromo-triazinyl radicals and the corresponding radicals obtained by halogen exchange with tertiary bases such as trimethylamine, triethylamine, dimethyl-13-hydroxyethylamine, triethanolamine, N,N-dimethylhydrazine, pyridine, a-, 13- or y-picoline, nicotinic acid or isonicotinic acid, sulfinates, especially benzenesulfinic acid or hydrogen sulfite, and also di- or trihalopyrimidinyl radicals, such as 2,4-dichloropyrimidin-6-yl, 2,4,5-trichloro-pyrimidin-6-yl, 4,5-dichloropyrimidin-6-yl, 2,4-difluorop~~-imidin-6-yl; 4,5-difluoro-pyrimidin-6-yl, 4-fluoro-5-chloropyrimidin-6-yl, 2.4-difluo;-o-5-chloropyrimidinyl and also 2,3-dichloroquinoxaline-5-carbonyl and 2,3-dichloroquinoxaline-6-carbonyl.
Alkali-fixable reactive dyes are also to be understood as including mixtures of reactive dyes of the abovementioned kind.
The pigments can be organic or inorganic. Suitable organic pigments are those of the azo, anthraquinone, thioindigo series, as well as other polycyclic pigments, for example of the phthalocyanine, quinacridone, dioxazine, naphthalenetetracarboxylic acid, perylenetetracarboxylic acid or isoindoline series and also metal complex pigments or laked dyes such as Ca, Mg and Al lakes of sulfo- and/or carboxyl-containing dyes, and also carbon black, of which a large number are known from Color Index, 2°d edition, for example. Examples of suitable inorganic dyes are zinc sulfides, ultramarine, titanium oxides, mixed-phase pigments such as nickel or Le A 32 400-Foreign Countries chromium antimony titanium dioxide, cobalt blue, chromium oxides and chromate pigments; examples thereof are Pigment Yellow 53, Pigment Brown 24.
Particular preference is given to pigments which are free of lead, manganese, cadmium, chromium, etc., i.e., free of heavy metals, which, if they are present in bioavailable form, inhibit the degradability.
Examples of particularly preferred pigments are phthalocyanine pigments, such as Pigment Blue I5, Pigment Green 7, arylamide pigments such as Pigment Yellow 83, Pigment Yellow 17, monoazo pigments such as Pigment Red 48, lithole pigments, disazo condensations pigments such as Pigment Red 166, and also carbon blacks, zinc sulfides and ultramarines.
The dyes or pigments are customarily not added as such to the dye or print paste, but 1 S they are generally used in the form of aqueous dispersions. To this end, they have to be mechanically converted in a suitable manner into the aqueous dispersion with the aid of f.nishing agents. The finishing agents substantially enrobe the dyes :
or pigments and so prevent undesirable sedimentation in storage.
Suitable synthetic finishing agents are carbonyl- and hydroxy-bearing oligourethanes as described for example in DE-A 41 12 327. However, finishing agents of natural origin have the advantage of biodegradability. A particularly preferred finishing agent is casein.
The mixtures of A and B may have up to 500%, preferably 0.15 to 200%, especially 5 to 150%, by weight of dye and/or pigments, based on the sum (A + B), added to them.
The mixtures of A and B may further have added to them up to 30% by weight, based on A, of rheological assistants, which can be of mineral, natural organic or synthetic organic origin. Examples of preferred rheological assistants are alginates, carob bean Le A 32 400-Foreign Countries flour, the organic, degradable cellulose derivatives, ete., and inorganic, mineralizable clays, sheet-silicates, etc.
The mixtures of A and B may also include up to 50% by weight, based on A, of plasticizers. Preferably, only up to 30% of plasticizes is used. Plasticizers of natural origin are preferred, although up to 20% by weight, based on the plasticizers mentioned, of synthetic organic plasticizes are tolerated. Examples of preferred plasticizers are the natural oils and fats of vegetable and animal origin such as palm oil dervatives, which are optionally hydrogenated, neatsfoot oil, optionally sulfonated or sulfatic castor oil, optionally esterified rapeseed oil, etc.
The components A and B can be dispersed in water in a conventional manner, optionally through the use of organic solvents (thus, for example, by the "benzine emulsion process", whereby oil-in-water emulsions are formed). For reasons of 1S environmental compatibility, however, the use of benzine-free print pastes is preferred. The formulation is advantageously prepared without the use of components having reactive groups which might interfere with the reaction between binder and crosslinker.
The print, dyeing and coating pastes, it will be appreciated, may be prepared using further assistants, for example emulsifiers, thickeners, evaporation inhibitors, catalysts, hand improvers, antifoams. Preference is likewise given to the use of products which have such a structure that they are biodegradable.
The textile print pastes are suitably processed using the customary methods of printing technology; cf. for example Ullmanns Encyklopadie der technischen Chemie, 4'h edition, volume 22, page 565 ff. "Textildruck", Verlag Chemie, Weinheim 1982, and also of coating technology, as are described, for example in Kunststoffhandbuch, volume 7, Polyurethane, Carl Hanser Verlag, Munich 1993.

Le A 32 400-Foreign Countries The applied prints and coatings can be crosslinked at elevated temperatures, isocyanate crosslinkers permitting the use of relatively low temperatures (for example room temperature to 100°C), but higher temperatures of up to 170°C are not harmful either. However, curing conditions of 80 to 100°C (1 to 10 minutes) will give excellent results in most cases. Similarly, drying at room temperature for a prolonged period (1-3 days) can be used to obtain a very good final strength.
Dyeings can be carried out in known manner by the padding and exhaust process. A
particular embodiment provides that the mixtures of A and B can be used together with pigment for dyeing textiles and leather in an aqueous medium.
Percentages and parts in the examples hereinbelow are by weight.
The properties of the products tested in the examples hereinbelow were appraised on the following qualitative scale:
Appraisal Abbreviation similar a a little superiorw+

a little inferiorw-somewhat superiore+

somewhat inferiore-superior +
inferior -distinctly superior d+
distinctly inferior d-significantly superior b+
significantly inferior b-Le A 32 400-Foreign Countries Examples The following components were used:
~ACRACONZ BN 20% strength dispersion of the ammonium salt of a lightly crosslinked acrylic acidlacrylamide copolymer in an isoparaffinic hydrocarbon; Bayer AG

~ACRAFIx MF melamine/formaldehyde condensate, Bayer AG

~ACRAFIX ML modified melamine resin ~ACRAMIN O/W emulsion of paraffin oils, esters and Weichmacher ACN silicone oils ~ACRAMIN PUD Ol 40% strength aqueous polyurethane dispersion, Bayer AG

~ACRAMIN aqueous pigment formulation based on Cu Marine Blau FBC phthalocyanine 1 SO% and oxazine (P.V.23)/Dystar ~ACRAMIN ALV~I 40% strength aqueous dispersion of an acrylonitrile/butyl acrylate/styrene/acrylic acid emulsions copolymer (83:8:4:3 parts); Bayer AG

~ACRAMIN Weich- aqueous microemulsion of a silicone oil macher SID

~Bayderm FIX CIN modified aliphatic polyisocyanate, Bayer AG

~Bentone EW sheet-silicate ~Dialgin HV sodium alginate (Diamalt) ~Emulgator L 42% strength aqueous emulsifier solution (Bayer AG) OEmulgator VA 46% strength aqueous emulsifier solution (Bayer AG) ~Emulgator WN 90% strength aqueous solution of an ethylene oxide polyether started on a phenolic component having an average molecular weight of about 900 (Bayer AG) OO Natrosol MR hydroxyethylcellulose (Hercules Powder) ~RESPUMIT BA 2000 silicone-free, biodegradable nonionic foam suppressant Le A 32 400-Foreign Countries based on natural oil ~RESPUMIT SD silicone oil ~Solvesso 100 aromatic hydrocarbon mixture (bp. 163-181C) from Esso Chemie, Cologne thickener solution 4% strength aqueous solution of a cellulose derivative (~Natrosol MR from Hercules Powder) polyurethaneurea 40% strength aqueous dispersion obtainable by the process dispersion indicated hereinbelow Le A 32 400-Foreign Countries Preparation of the polyurethaneurea dispersion:
170 g of a polyesterdiol of molecular weight 1700, formed from adipic acid and a mixture of 1,6-hexanediol and neopentylglycol in a weight ratio of 1.9:1, are degassed under reduced pressure at 120°C for 60 minutes. Under nitrogen, 0.2 ml of benzoyl chloride and, in one go, 30.1 g of hexamethylene diisocyanate are added to the batch. After stirring at 120°C for 30 minutes, the NCO content is 3.2%. The prepoly~rner is dissolved in 500 g of acetone at 50°C, the solution is cooled to room temperature, and is admixed with a mixture of 9.7 g of a 50°.'°
strength aqueous solution of AAS salt, 1.51 g of ethylenediamine and 20 g of water by rapid stirring.
After 15 minutes of stirnng, 300 g of water are added, and the acetone is removed at up to 60°C and 140 mbar. The distillation residue amounts to 505 g.
Dilution with 11 g of water provides a 40% strength thin white polyurethaneurea dispersion.

Le A 32 400-Foreign Countries Pigments EUKANOL colors'~>
~EUKANOL Orange contains Pigment Orange 34 & Pigment Brown 24 and also 15.6% of casein solution in water ~EUKANOL Schwarz contains Pigment Black 7 and also 15.6%
of casein solution in water OEUKANOL Blau N contains Pigment Blue 60 and also 12%
of casein solution in water ~AC:12AMIN Orange azo pigment preparation based on Pigment FG Orange 034 *) designations of pigment type from Colour Index.

Le A 32 400-Foreign Countries Examples 1-6 Batch: 1 2 3 4 5 6 Water 100 80 70 197 177 787 ~ACRACONZ BN 20 ~Emulgator WN 5 5 5 S S S

~Emulgator VA 3 3 3 3 3 3 ~ACRAMIN PUD O1 150 1 SO 1 SO 150 150 150 ~ACRAMIN-Marineblau 20 FBC 1 SO%

~EUKANOL Blau N 6.5%130 130 130 130 130 Pigm.

~Dialgin HV 4% 597 597 X97 ~Bentone EW 3% 500 500 ~ ~P.ESPLTMIT SD 5 5 5 5 5 S

~ACRAMIN- 20 20 20 Weichmacher ACN ~

~BAYDERM FIX CIN 10 10 20 10 10 10 Batch size: 1000 g Le A 32 400-Forei,~n Countries Examples 7-10 Batch 7 8 9 10 Water 197 187 187 187 ~Emulgator WN 5 S 5 5 ~Emulgator VA 3 3 3 3 ~ACRAM1N PUD O1 150 150 150 150 ~EUKANOL Blau N 130 130 130 130 6.5% Pigm.

~Natrosol MR 4% 250 250 167 333 ~Bentone EW 3% 250 250 333 167 ~RESPLTMIT SD 5 5 5 5 ~BAYDERM FIX C1N 10 . 20 20 20 Batch size: 1000 g Appraisal relating to batch 7 Film properties Print dried 5 min at 80C

Brush wash ( 100) + + +

Rubfastness wet ( 1 Ox) ~ e+ ~ e+ ~ +

Film properties Print dried and fixed 5 min at 150C

Brush wash ( 100 x) w+ w+ e+

Rubfastness wet (10 x) e+ ~ e+ ~ a Le A 32 400-Forei,~n Countries Examples 11-17 Batch 11 12 13 14 15 16 17 Water 187 167 147 167 147 167 147 ~Emulgator WN 5 5 5 5 S 5 5 ~Emulgator VA 3 3 3 3 3 3 3 ~ACRAMIN PUD O1 150 1 SO 1 150 150 150 150 SO

~EUKANOL Blau N 130 130 130 130 130 130 130 6.5% Pigm.

~Natrosol HR 4% 333 333 333 333 333 333 333 ~Bentone EW 3% 167 167 167 167 167 167 167 '~RESPUMIT SD 5 5 5 5 5 5 5 Soybean oil 20 40 Sunflower oil 20 40 Castor oil 20 40 ~BAYDERM FIX CIN 20 20 20 20 20 20 20 Batch size 1000 g Le A 32 400-Foreign Countries Appraisal relating to batch 11 Film properties Print 5 min dried at Rubfastness wet w- w+ w+ w+ w- e-(10 x) Color yield ~ ~ w+ w+ w+ e+ w+ w+
( ~ ~ ~ ~

Film properties Print dried and fixed min at Rubfastness wet e+ a a w- a w-(10x) Hand a a a a a a Hand after 1 x w+ w+ w+ w+ w+ w+
Household wash Hand after 3 x w+ e+ e+ + + +
Household wash Brush wash test The washfastness of dyeings and prints can be tested using the brush wash test. The abrasion can serve as a measure of the degree of crosslinking of the binder.
A sample (ca. 10 x 20 cm) of the dyed and printed fabric is after fixing placed into a mixture of 2.5 g/1 of Castile soap ("green soap"), 2 g/1 of anhydrous sodium carbonate, and 2 g/1 of sequestrant (e.g., ~Trilon B) at 80°C for about 10 minutes, then stretched and brushed with a hard Perlon handbrush using constant pressure ( 1 kg). Normally, 50 double strokes are performed.

Le A 32 400-Foreign Countries Thereafter, the sample is rinsed and dried. The pigment abrasion of the brushed sample is compared with the unbrushed original sample. If no pigment abrasion is visible, the binder can be considered fully crosslinked.
Examples 18-21 of rotting tests Batch 18 19 20 21 Water 105 115 85 804 - - _ ~ACRACONZ BN 28 ~Emulgator WN 5 5 5 3 ~Emulgator VA 5 5 S 3 ~ACRAMIN ALW 120 Polyurethaneurea dispersion200 200 200 ~ACRAMIN-Marineblau 20 a FBC 1 ~0%
i ~EUKANOL Blau N 6.5% 130 130 130 ' I Pig.
~

~Natrosol MR 4% 1 SO 150 150 ~Bentone EW 3% 350 350 350 ~RESPLTMIT SD 5 5 5 2 ~ACRAMIN 10 Weichmacher SID

Sunflower oil 50 20 50 ~ACRAFIX ML 10 ~BAYDERM FIX CIN 20 20 1000 g Print on Zimmer sample table (round sleeve) CO (Vlisco) R. 10/P.3/G. 40 CO knit R.16/P.5/G. 40 Le A 32 400-Foreign Countries Woven cotton (CO Vlisco) Batch 18 19 20 21 Film properties Print dried and fixed 5 min at Rubfastness dry (10 a w+ w+ comparison x) CO knit S
Batch 18 19 20 21 Film properties Print dried and fixed 5 min at Rubfastness dry (10x) e+ e+ e+ comparison The print pastes were knife-coated onto release paper and films prepared therefrom.
The films were subjected to the following composting test:
The films to be tested were first dried at 80°C to constant weight and then clamped into 6 x 6 cm slide frames. Compost from a composter was packed into plastic bowls 2 cm deep and the films embedded therein. The filled boxes were each incubated for 4 weeks at 60°C in an incubator. Water losses were determined via the weight loss and were made good. During incubation, the pH of the compost was measured once a week. After 4 weeks in each case, a batch was discontinued, and the films were removed, cleaned, dried at 80°C to constant weight and photographed.
Directly after drying, the weight loss of the films was determined by renewed weighing.

Le A 32 400-Foreign Countries In the poisoned control, the compost was dried at 105°C and the water which had evaporated was then replaced with a 1 % strength HgCl2 solution. Before being introduced into the compost mixture, the films for the poisoned control were placed in the HgCl2 solution, dried and then introduced into the poisoned compost.
The control batch was incubated in the same way as the other batches.
A film was classified as degradable when it completely vanished in the microbially active batches in the same way as a cellulose film used in a parallel test and remained intact in the poisoned control.
Result a) Films Examples 18-20 fully degraded 21 no degradation Prints (test analogous to the film composting test) b) CO Vlisco Examples 18 fully degraded 19 fully degraded 20 somewhat degraded 21 no degradation Le A 32 400-Foreign Countries c) CO knit Examples 18 substantially degraded 19 slightly degraded 20 slightly degraded 21 no degradation Beispiel 22 (textile coating) A release paper is coated with about 80 g wet/m2 of a mixture of 1000 g of polyurethaneurea dispersion, 100 g of ELTKANOL Schwarz and 6 g of Emulgator VA. After passing through a drying tunnel at 80°-110°-125°C the adhesive coating of 100 g of polyurethaneurea dispersion, 55 g of EUKANOL Schwarz and 12 g of Emulgator VA is applied in a thickness of 150 g/m2 wet, and a cotton fabric is laminated thereto. After drying at 135°C, the coated fabric was removable nom the release paper.
A cellulose fiber nonwoven bonded with polyurethaneurea dispersion in a conventional manner was provided with a coating in a similar manner.
The coated products had the requisite fastnesses in terms of Flexometer and adhesion; the products proved to be biodegradable.
Examples 23 and 24 concerning the biodegradation of print pastes The print pastes 23 (prior art) and 24 (inventive) were subjected to the biodegradability test for five days (BOD-S, method: LCK 55 Kuvette test from Lange) four hours after being prepared.

Le A 32 400-Foreign Countries Print paste 24 exhibited the expected high degradability rate coupled with a comparable application property profile.
Example 23 24 Water 816 175 ~ACRACONZ BN 26 ~Emulgator WN 3 5 ~Emulgator VA 3 5 ~ACRAMIN ALW 120 Polyurethaneurea dispersion 120 ~ACRAMIN Orange FG 10 . ~EUKANOL Orange 130 ~Natrosol MR 4% 150 ~Bentone EW 3%

~RESPLTMIT SD 2 ~ --~RESPUMIT BA 2000 5 ~ACRAMIN Weichmacher SID 10 Rapeseed oil 50 ~ACRAFIX ML 10 ~BAYDERMFIX CIN ( 10 ' Ash 1000C 0.0012/ 0.016/
0.0017 0.016 BOD 7.62 240 ' BOD in % 4.3 56.7 Print on Zimmer sample table (rotary screen) Print dried and fixed at 150°C for 5 min Le A 32 400-Foreign Countries Batch: ~ 23 24 Fabric: Hilden cheesecloth Film properties Brush wash ( 100x) e-Rubfastness dry ( w-10x) Rubfastness wet (10x) e-Fabric: CO knit Film properties Brush wash (50x) e-Rubfastness dry (lOx) e-Rubfastness wet (lOx) e-

Claims

We claim:

1. Biodegradable coating, dyeing and print pastes for textile substrates and nontextile cellulosic substrates, comprising (i) biodegradable polyurethaneureas, polyesters or polyesteramides, (ii) rheological assistants, (iii) pigments or dyes which, if they have been finished, have been finished with finishing agents of natural origin, and optionally (iv) natural-based plasticizers.

2. Pastes according to claim 1, which include per 40 parts by weight of (i), based on dye content of (i) (ii) up to 10 parts by weight of a mineral and/or natural organic thickener, (iii) up to 100 parts by weight of a casein- and/or albumin-finished pigment or dye, (iv) up to 30 parts by weight of a natural (vegetable or animal) oil or fat, and also (v) up to 25 parts by weight of an N-methylol-, aziridine-, epoxide- or isocyanate-based crosslinker.

3. The use of A) reaction products obtainable with an equivalents ratio of 1:1 to 2:1 for isocyanate groups to isocyanate-reactive groups from a) a diisocyanate component comprising a1) hexamethylene diisocyanate or a2) mixtures of hexamethylene diisocyanate with in total up to 60% by weight, based on mixture a2), of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and/or 4,4'-diiso-cyanatodicyclohexylmethane and/or 1-methyl-2,4(6)-diiso-cyanatocyclohexane with b) a diol component comprising b1) at least one polyesterdiol having a number average molecular weight of 500 to 10,000 derived from (i) adipic acid and/or succinic acid and (ii) at least one alkanediol having 2 to 6 carbon atoms or b2) a mixture of such polyesterdiols with up to 32% by weight, based on the total weight of component b), of optionally ether group-containing alkanediols having 2 to 6 carbon atoms, c) a diamine component in an amount of from 2 to 50 equivalents %, based on the total amount of isocyanate-reactive groups present in the components b) and c), comprising c1) diaminosulfonates of the formula H2N(-CH2)n-NH(-CH2)m-SO3Me or c2) mixtures of diaminosulfonates c1) with up to 90% by weight, based on the total weight of component c), of ethylenediamine, optionally d) hydrophilic polyether alcohols of the formula -34-~

H-X-O-R
in an amount of up to 10% by weight, based on the sum total of the components b), c) and d), and also optionally e) water, which does not enter into the calculation of the equivalents ratio of isocyanate groups to isocyante-reactive groups, where in the formulae mentioned m and n are independently from 2 to 6, Me is potassium or sodium, R is a monovalent hydrocarbon radical having 1 to 12 carbon atoms, and X is a polyalkylene oxide chain of the number average molecular weight range from 88 to 4000 whose alkylene oxide units are ethylene oxide units to an extent which is not less than 40 mol% and are propylene oxide units as far as the rest is concerned, and B. 0 to 30% by weight, based on A, of crosslinker for A
as binders for dye and/or pigment preparations for coating, dyeing and printing flexible substrates.

4. A use according to claim 3, wherefor crosslinker B is present in an amount of 0.1 to 25% by weight, based on A.

5. A process according to either of claims 3 and 4, wherefor said crosslinker B is selected from the group consisting of polyisocyanates, polyfunctional epoxides, carbodiimides and compounds containing N-methylol groups.

6. A use as claimed in any of claims 3 to 5 for coating, dyeing and printing textiles or leather.