EP1023486A1

EP1023486A1 - Biodegradable binding agents for dyeing

Info

Publication number: EP1023486A1
Application number: EP98955403A
Authority: EP
Inventors: Harro Träubel; Hanns-Peter Müller; Hans Schulze; Michael Pirkotsch; Norbert Donkels; Hans-Joerg Seiler; Josef Meyer; Rainhard Koch
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1997-10-01
Filing date: 1998-09-18
Publication date: 2000-08-02
Also published as: DE19743457A1; WO1999016958A1; CA2305677A1; JP2001518573A; AU1225799A

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

Biodegradable binders for dyeing

The invention relates to the use of biodegradable binders for dyeing, primarily textiles and leather

Fully biodegradable and compostable materials (BAW) will become more and more important economically and technically in the future (T Jopski, Kunststoffe 83_ (1993), 10) The big challenge is to produce plastics that have the necessary functional moisture, but can be broken down by stimulating a biologically active environment. Triggers can be a microbiological, enzymatic, hydrolytic, light-induced or oxidative breakdown, which attacks a specific point in the main chain of the polymer. All breakdown products must be safe, non-toxic and non-toxic in nature - be cumulative, ie subject to complete microbial degradation. So far, three general categories of BAW have become known: polyesters, plastics based on natural polymers and other degradable plastics, e.g. polyvinyl alcohol.The polyesters include polylactic acid, polyhydroxybutyrate and valerate, polycaprolactone and high molecular weight aliphatic polyester (EP-A 572 256) To achieve high molecular weights, those in the

EP-A 572 256 polyester with organic diisocyanates extended to the end product. The use of thermoplastic polyester urethanes as compostable plastics is described in EP-A 593 975. Thermoplastic processable and biodegradable polyester amides are the subject of EP-A 641 917

Biodegradable, thermoplastic polyurethane filaments are described in DE-PS 4 319 439. The thermoplastically processable polyurethanes are linear, have difunctional polyester diols and difunctional polyethylene glycols built into the polymer chain and are used as hexamethylene diisocyanate and butanediol or hexanediol Chain extender built

(Examples 1 to 3) Biodegradable and compostable moldings based on hydrophilic polyurethanes are known from DE-OS 195 17 185 and 195 20 092, the term “polyurethanes” also comprising polyurethane ureas. These polyurethanes are reaction products of diisocyanates and diols which are used for the purpose of hydrophilizing the The end product also contains built-in residues of diaminosulfonates and, where appropriate, ethylene oxide group-containing polyethers. These hydrophilic polyurethanes can be used as a lacquer for coating any substrates, as an adhesive and / or as a binder for cellulose for the production of nonwovens made of cotton and / or hemp or linen, as a polymeric binder Wood, wood dust or wood shavings, as films in composite materials for the production of biodegradable packaging, for the production of hygiene articles such as baby diapers, as seed dressings for fixing active substances as slow release formulations, as binders for the production of Pfla Net pots can be used as paper coatings and for the mass sizing of paper, for the production of sausage casings and for the production of cosmetic compositions

Manufacture flat foals, injection molded articles such as flower pots, drinking vessels, eating bowls, thermoformed articles, brush packaging, blow molders or bottles

Biodegradability also plays an increasingly important role in textiles - it has not yet been solved in many areas

When dyeing and coating textiles in the direct, reverse, coating or printing process with coating or textile printing pastes or in the exhaust process with pigment-containing binders, the use of externally cross-linkable film-forming binders, for example those on polyurethane, polyacrylate, or

Butadiene / Acrylnitπl-Copolymeπsat-Basis, widespread The mixtures of binder and pigment usually contain reactive compounds that crosslink the binder at a higher temperature after the printing process and can thereby fix the print or color. Only this fixation leads to the desired water fastness, which, for B is important when washing the dyed or printed textiles It has now been shown that the ingredients of residual liquors of the dyeing or washing liquors of the printed textiles, i.e. in particular the underlying binders and rheology aids, are difficult to degrade. The aids necessary for the formation of the pigments are also usually based on poorly degrade emulsifiers and / or copolymers. However, for problem-free use, it is important that the wet fastness of the materials is good Wet fastness properties are generally achieved by crosslinking. On the other hand, crosslinking has been shown to impair the biodegradability of the articles. In practice, melamine / formaldehyde condensation products are used as crosslinkers for the binders used in coating and textile printing pastes, which act above approximately 120 ° C. According to W Berlenbach in Ullmanns Encyklopadie der technical chemistry, 4th edition, vol. 22, p. 629, Verlag Chemie, Weinheim 1982, the crosslinking via N-methylol groups of the binder is catalyzed by acid, it is preferably fixed with dry hot air with exposure times for example 5 to 10 minutes at 140 ° C or 30 to 60 seconds at 175 ° C

The pigment coloring with hydrophilically modified polyisocyanates is described for example in EP-PS 571 867 and in DE-OS 4 415 449

In general, the color compositions according to the invention are also suitable for coating textiles in the direct and reverse process, provided that, in a manner known per se, only biodegradable components are used. When coating, high flexibility, wet and dry, as well as high abrasion resistance and water and solvent resistance are required. Therefore, the binders have to be crosslinked. Surprisingly, the coated textiles and the remaining liquors retain their biodegradability if - based on polymer - 15. preferably 10 and, particularly preferably, 7% by weight of crosslinking agent (active material) on binder (as a 40% by weight dispersion) does not exceed

The object of the invention was therefore to overcome the ecological disadvantages of the prior art. In particular, the residual and washing liquors from the coating and dyeing processes should be fed to a biological clarification system. The coated and colored or printed articles can be compostable, ie biodegradable in a landfill

According to the invention, this object is achieved by using biodegradable polyurethane ureas, polyesters or polyester amides

The invention thus relates to biodegradable coating, color and printing pastes for textile substrates and non-textile cellulosic substrates containing

(i) biodegradable polyurethane ureas, polyesters or polyester amides,

(ii) rheology aids,

(iii) pigments or dyes which, if they have been formed, are formed with shaping agents of natural origin and, if appropriate, (iv) plasticizers on a natural basis

Preferred such pastes contain per 40 parts by weight of (i), based on the solids content of (i),

(ii) up to 10 parts by weight of a mineral and / or a natural organic thickener,

(iii) up to 100 parts by weight of a pigment or dye, optionally formed with casein and / or albumin, (iv) up to 30 parts by weight of a natural (vegetable or animal) oil or fat and (v) up to 25 parts by weight of a crosslinking agent on N- Methylol, aziridine, epoxy or isocyanate based

Another object of the invention is the use of

A in compliance with an equivalent ratio of isocyanate groups to isocyanate group-reactive groups of 1 1 to 2 1 obtainable reaction products a) a diisocyanate component consisting of

al) hexamethylene diisocyanate or

a2) mixtures of hexamethylene diisocyanate with a total of up to 60% by weight, based on mixture a2), l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane and / or 4,4'-diisocyanatodicyclohexylmethane and / or 1- methyl-2,4 (6) -diisocyanatocyclohexane with

b) a diol component consisting of

bl) at least one polyester diol with a number average molecular weight of 500 to 10,000 from (i) adipic acid and / or succinic acid and (ii) at least one alkanediol with 2 to 6 carbon atoms or

b2) a mixture of such polyester diols with up to 32% by weight, based on the total weight of component b), of alkane diols with 2 to 6 carbon atoms which may have ether groups,

c) a diamine component in an amount of 2 to 50 equivalent%, based on the total amount of the groups present in components b) and c) which are reactive towards isocyanate groups, consisting of

cl) diamino sulfonates of the formula

H ₂ N (-CH ₂ ) _n -NH (-CH ₂ ) _m -SO ₃ Me

or

c2) Mixtures of diaminosulfonates cl) with up to 90% by weight, based on the total weight of component c), of ethylenediamine, if appropriate d) hydrophilic polyether alcohols of the formula

H-X-O-R

in an amount of up to 10% by weight, based on the sum of components b), c) and d) and, if appropriate

e) water which is not included in the calculation of the equivalent ratio of isocyanate groups to groups which are reactive toward isocyanate groups,

being in the formulas mentioned

m and n independently of one another for numbers from 2 to 6,

Me for potassium or sodium,

R stand for a monovalent hydrocarbon radical with 1 to 12 carbon atoms and

X is a number average molecular weight polyalkylene oxide chain of

88 to 4000 means whose alkylene oxide units consist of at least 40 mol% of ethylene oxide units and the rest of propylene oxide units and

B 0 to 30, preferably 0.1 to 25% by weight, based on A, crosslinking agent for A.

as a binder for dye and / or pigment preparations for dyeing or printing flexible substrates, in particular textiles and leather

The diisocyanate component a) preferably consists exclusively of hexamethylene diisocyanate The diol component b) consists either of bl) at least one polyester diol or b2) of a mixture of at least one polyester diol bl) with up to 32, preferably up to 10% by weight of at least one alkane diol, which may have ether groups, and has 2 to 6 carbon atoms

Suitable polyester diols b1) are those having a number average molecular weight of 500 to 10,000, preferably 1,000 to 2,500, based on (i) adipic acid and / or succinic acid and (ii) alkane diols with ether groups, which can be calculated from the hydroxyl group content, with 2 up to 6 carbon atoms, such as, for example, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and / or 1,6-hexanediol polyester diols, in the production of which only ethylene glycol and / or 1,4-butanediol have been used as the diol are particularly preferred

The chain extender optionally containing hydroxyl groups and optionally containing ether group-containing alkane diols with 2 to 6 carbon atoms are those of the type just mentioned, as mentioned for the preparation of polyester diols

The diamine component c) consists either of cl) diaminosulfonates of the general formula already mentioned above or from c2) mixtures of such diaminosulfonates with ethylenediamine, which, if at all, in amounts of up to 90, preferably up to 70 equivalent%, based on the Amino groups of component c) which are reactive toward isocyanate groups are used. Particularly preferred diaminosulfonates are the potassium or sodium salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid

The diamine component c) is generally used in an amount of 1 to 10, preferably 2 to 5% by weight, based on the weight of component b) The optional structural component d) is a hydrophilic, monohydric polyether alcohol of the formula

H-X-O-R

in which

R and X have the meanings given above

Such polyether alcohols are preferred for which

R represents an aliphatic hydrocarbon radical having 1 to 4 carbon atoms and

X represents a polyalkylene oxide chain in the number average molecular weight range from 500 to 4,000, in which at least 40, in particular at least 70 and particularly preferably 100 mol% of the alkylene oxide units present, ethylene oxide units and the remaining alkylene oxide units represent propylene oxide units

Such monohydric polyether alcohols are prepared by known alkoxy preparation of suitable R-OH starter molecules such as, for example, methanol, n-butanol, n-hexanol or n-dodecanol, with preferred use of ethylene oxide and optionally propylene oxide in the quantitative ratios of the alkylene oxides disclosed above The alkylene oxides mentioned can be used as a mixture and / or in succession

The monohydric polyether alcohols d) are used in the process according to the invention, if at all, in amounts of up to 10, preferably up to 3% by weight, based on the sum of components b), c) and d) As a further structural component which may be considered in the production of the urea group-containing polyurethanes, e) water is to be mentioned, which is to be considered as a reactant in particular when the chain extension reaction to be carried out in the last stage in the preparation of the polyurethanes is carried out in the last stage NCO prepolymers are carried out in an aqueous medium, in particular when the diamines c) dissolved in the water are used in amounts which are less than the equivalent, based on the NCO groups of the NCO prepolymers

In addition to these structural components, trifunctional compounds in minor amounts are also possible in principle, such as glycerol or trimethylolpropane, which can either be incorporated in small quantities into the polyester bl) or used in free form as part of component b2) branching molecules must generally be compensated for by monofunctional compounds, so that, purely mathematically, linear polymers again result

The production of the urea groups-containing polyurethanes from the structural components mentioned by way of example can be carried out by any process. However, the known prepolymer process is preferably used, in such a way that components b) and, if appropriate, d) and diisocyanate component a) are adhered to NCO / OH equivalent ratio of 1.5 1 to 4 1, preferably 1.8.1 to 2.5 1, an NCO prepolymer is produced and this is then reacted with component c) with chain extension

The prepolymer is generally prepared without solvent at temperatures of 20 to 150 ° C. and then dissolved in a suitable solvent. Of course, the prepolymers can also be formed directly in a solvent. Solvents which are inert to isocyanate groups and can be mixed with water without limit Consideration Acetone is preferably used as the solvent. The prepolymers prepared in this way are reacted with component c) in the second reaction stage with chain extension. Here, the equivalent ratio of isocyanate groups of the prepolymers on the one hand to amino groups of component c) which are reactive toward isocyanate groups is on the other hand 1 1 to 20 1, preferably 1.2 1 to 4 1. The chain extension reaction can occur in

Solution, preferably in acetone solution, or also in an aqueous medium such that the solution of the prepolymers in organic solvent is combined with a solution of component c) in water with intensive mixing. As already indicated, a chain extension reaction may also be carried out Reaction of the NCO groups of the prepolymers with the water In the above-mentioned, preferred two-stage preparation of the urea group-containing polyurethanes, the equivalent ratios between isocyanate groups and groups which are reactive towards isocyanate groups in the two reaction stages are chosen within the scope of the disclosure such that the total ratio of isocyanate groups to one another Isocyanate groups reactive groups of

Components b) to d) correspond to the ratio of 1 1 to 2 1 given above. The water is in no way included in the calculation of the equivalent ratios mentioned

The chain extension reaction generally takes place within the temperature range of 20 to 50 ° C

In principle possible, but by no means preferred, the chain extension reaction can also take place in the melt, i.e. in the absence of solvents and water (melt dispersion method)

To prepare the polyurethanes A, the starting materials a), b), c) and optionally d) and / or optionally e) mentioned above are used in the proportions mentioned

The polyurethanes A are preferably used in the form of aqueous dispersions. The term "aqueous dispersion" used in the context of the invention is also intended to contain water include solutions which can be present if the concentration of hydrophilic centers in the urea group-containing polyurethanes is sufficiently high to ensure that they are insoluble in water. Often, the dispersions are aqueous systems which have both dispersed and dissolved urea groups Polyurethanes included

Aqueous dispersions of polyurethanes of a constitution similar or comparable to the polyurethanes A are already known from DE-OS 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 had been carried out in the absence of water, are mixed with the dispersing water, whereupon the distillative removal, if appropriate, of at least some of the auxiliary solvent which may be used is followed

If the chain extension reaction was carried out in an aqueous medium, further water can optionally be added to prepare the aqueous dispersions. In this case too, the auxiliary solvent used can of course also be removed by distillation if desired

In general, the total amount of water used is such that 5 to 60% by weight (preferably 20 to 55% by weight) dispersions are present

The polyurethane dispersion can contain customary auxiliaries, but particularly preferred are those auxiliaries that are also bioabbarable. Such auxiliaries are, above all, those of natural origin such as gelatin, protein hydrolyzates, guar, tragacanth, flour, starch, wood flour, cellulose powder, etc

Crosslinkers B include hydrophilic polyisocyanates, multifunctional epoxides and

Carbodiimides, as described, for example, in DE-OS 42 17 716, are hereby expressly referred to the relevant content of DE-OS 42 17 716. taken. Also suitable as crosslinking agent B are reactive compounds derived from formaldehyde, such as, for example, phenol / formaldehyde and melamine / formaldehyde condensates containing N-methylol groups, as described, for example, in "Methods of Organic Chemistry" (Houben-Weyl), Vol. 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, page 319 ff. The crosslinking leads to better water resistance and higher abrasion resistance etc.

Up to 30% by weight, based on A, of dyes and / or pigments can be added to the mixtures of A and B.

Preferred dyes are alkali-fixable reactive dyes. You can use any coloring part, such as Residues of a sulfo-containing organic dye of mono- or polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, , Pyrenequinone or perylene tetracarbonimide series wear.

The alkaline fixable reactive substances preferably have at least one aromatic-heterocyclic reactive radical and / or at least one reactive radical of the formula -SO ₂ M, in which

M = CH ₂ -CH ₂ -OH, CH = CH ₂ or CH ₂ -CH ₂ -V, where V = alkaline eliminable residue, preferably OSO ₃ H, SSO3H, OCOCH3, OPO ₃ H ₂ , OSO ₂ CH ₃ , SCN , NHSO ₂ CH ₃ , Cl, Br, F, OCOC ₆ H ₅ , OSO ₂ -C ₆ H ₅ , N (CH ₃ ) ₃ anion (anion is preferably Cl "), which under the staining conditions with the OH or

NH-group-containing fibers react to form covalent bonds. Those which contain at least one reactive substituent bound to a 5- or 6-membered aromatic-heterocyclic ring, for example to a monoazine, diazine or triazine ring, in particular a pyridine, pyrimidine, Pyridazine, pyrazine, thiazine, oxazine or asymmetrical or symmetrical triazine ring, or to such a ring system which has one or more fused aromatic-carbocyclic Has rings, for example a chinohn, phthalazine, cinno n, quinazo n, quinoxaline, acπdin, phenazine or phenanthπdin ring system, or those which are substituted with additional reactive groups of the vinyl sulfone type

The reactive substituents on the heterocycle include, for example, halogen (Cl, Br or F), ammonium including hydrazinium, pyπdinium, picohnium, carboxy-pyπdinium, sulfonium, sulfonyl, azιdo- (N ₃ ), rhodanido, thiol ether, oxyether, sulfonic acid and sulfonic acid

The following fiber-reactive radicals may be mentioned in detail

2,4-Difluorotπazιnyl-6-, 2,4-Dιchlortπazιnyl-6-, monohalogen-sym-tπazinyl residues, especially monochloro and monofluorotπazinyl residues, which are optionally substituted by alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, morpholino,

Pφeπdino, pyrrohdino, piperazino, alkoxy, aryloxy, alkylthio, arylthio are substituted, alkyl preferably being optionally substituted Ci-Czj-ATkyl, aralkyl preferably optionally substituted phenyl-C j -C4-alkyl and aryl preferably optionally substituted phenyl or naphthyl and wherein preferred substituents for alkyl halogen, hydroxy, cyano, dialkylamino, morpholino,

C \ -C4 ~ alkoxy, carboxy, sulfo or sulfato and preferred substituents for phenyl and naphthyl sulfo, -C -C4 alkyl, -C -C4 alkoxy, carboxy, halogen, acylamino, hydroxy and amino are to be mentioned further 2- Amιno-4-fluor-tπ- azιnyl-6, 2-methylamιno-4-fluorotπazιnyl-6, 2-ethylamιno-4-fluorotπazιnyl-6, 2-isopropylamιno-4-fluorotπazιnyl-6, 2-dimethylamιno- 4-fluorotazazyl-6, 2-dimethylamino

4-fluor-tπazιnyl-6, 2-ß-methoxy-ethylamιno-4-fluor-tπazιnyl-6, 2-ß-hydroxyethyl-amιno-4-fluor-tπazιnyl-6, 2-Dι- (ß-hydroxyethylamιno) - 4-fluoro-tπazιnyl-6, 2-

Carboxymethylamin-4-fluor-tπazιnyl-6, 2-Dι- (carboxymethylamιno) -4-fluor-tπ- azιnyl-6, 2-Sulfomethyl-methylamιno-4-fluor-tπazιnyl-6, 2-ß-cyanoethylamιno-4- fluoro-tπazιnyl-6, 2-benzylamιno-4-fluoro-tπazιnyl-6, 2-ß-phenylethylamιno-4-fluoro-tπazιnyl-

6, 2-benzyl-methylamιno-4-fluoro-tπazιnyl-6, 2- (4'-sulfobenzyl) -amιno-4-fluoro-tπ-azιnyl-6, 2-cyclohexylamιno-4-fluoro-trιazmyl-6, 2nd - (o-, m-, p-methylphenyl) -amιno-4- fluorotriazinyl-6, 2- (o-, m-, p-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2 ', 5'-disulfophenyl) amino-4-fluoro- triazinyl-6, 2- (o-, m-, p-chlorophenyl) amino-4-fluoro-tri-azinyl-6, 2- (o-, m-, p-methoxyphenyl) amino-4-fluoro- triazinyl-6, 2- (2'-methyl-4'-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (2'-methyl-5'-sulfophenyl) amino-4-fluoro-triazinyl- 6, 2- (2'-chloro-4'-sulfophenyl) amino-4-fluorotriazinyl-6, 2- (2'-chloro-5'-sulfophenyl) amino-4-fluorotriazinyl- 6, 2- (2'-methoxy-4'-sulfophenyl) amino-4-fluoro-tri-azinyl-6, 2- (o-, m-, p-carboxyphenyl) amino-4-fluoro-triazinyl- 6, 2- (2 ', 4'-disulfophenyl) amino-4-fluoro-triazinyl-6, 2- (3 ^l , 5'-disulfophenyl) amino-4-fluoro-triazinyl-6, 2- (2'-Carboxy-4'-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (2'-carboxy-5'-sulfophenyl) amino-4-fluoro-triazinyl-6, 2- (6 ^, -Sulfonaphthyl- (2 ')) - amino-4-fluoro-triazinyl-6, 2- (4', 8'-

Disulfonaphthyl- (2 ')) - amino-4-fluoro-triazinyl-6, 2- (6', 8'-disulfonaphthyl- (2 ')) - amino-4-fluoro-triazinyl-6, 2- (N- Methyl-N-phenyl) -amino-4-fluoro-triazinyl-6, 2- (N-ethyl-N-phenyl) -amino-4-fluoro-triazinyl-6, 2- (N-ß-hydroxyethyl-N- phenyl) amino-4-fluoro-triazinyl-6, 2- (N-iso-propyl-N-phenyl) amino-4-fluoro-triazinyl-6, 2-morpholino-4-fluoro-triazinyl-6, 2 -Piperidino-4-fluorotriazinyl-6, 2- (4 ', 6', 8'-trisulfonaphthyl- (2 ')) - amino-4-fluorotriazinyl-6, 2- (3', 6 ', 8 ^, -Trisulfonaphthyl- (2 ')) - amino-4-fluorotriazinyl-6, 2- (3', 6'-disulfonaphthyl- (l ')) - amino-4-fluorotriazinyl-6, N- Methyl-N- (2,4-dichlorotriazinyl-6) -carbamyl-, N-methyl-N- (2-methylamino-4-chlorotriazinyl-6) -carbamyl-, N-methyl-N- (2-dimethylamino -4-chlorotriazinyl-6) -carbamyl-, N-methyl- or N-ethyl- N- (2,4-dichlorotriazinyl-6) -aminoacetyl-, 2-methoxy-4-fluorotriazinyl-6, 2- Ethoxy-4-fluoro-triazinyl-6, 2-phenoxy-4-fluoro-triazinyl-6, 2- (o-, m- or p-sulfophenoxy) -4-fluoro-triazinyl-6, 2- (o-, m- or p-methyl- or -Methoxy-phenoxy) -4- fluorotriazinyl-6, 2-ß-hydroxyethylmercapto-4-fluorotriazinyl-6, 2-phenylmercapto-4-fluorotriazinyl-6, 2- (4'-methylphenyl) mercapto-4-fluorotriazinyl-6 - (2 ', 4'-Dinitrophenyl) -mercapto- 4-fluorotriazinyl-6, 2-methyl-4-fluorotriazinyl-6, 2-phenyl-4-fluorotriazinyl-6 and the corresponding 4-chlorine - or 4-bromo-triazinyl residues and the corresponding by halogen exchange with tertiary bases such as trimethylamine, triethylamine, dimethyl-ß-hydroxyethylamine, triethanolamine, N, N-dimethylhydrazine, pyridine, α-, ß- or γ-picoline, nicotinic acid or isonicotinic acid, sulfinates, especially benzenesulfinic acid or hydrogen sulfite, and residues obtainable as well as di- or trihalopyrimidinyl residues, such as 2,4-dichloropyrimidinyl-6, 2,4,5-trichloropyrimidinyl-6, 4,5-dichloropyrimidinyl-6, 2,4 -Difluoropyrimidinyl-6-, 4,5-difluoropyrimidinyl-6-, 4-fluoro-5-chloropyrimidinyl-6-, 2,4-difluoro-5-chloropyrimidinyl and 2,3-dichloroquinoxaline-5-carbonyl and 2,3-dichloroquinoxaline-6-carbonyl

Alkaline fixable reactive dyes are also understood to mean mixtures of reactive dyes of the type mentioned above

The pigments can be organic or inorganic in nature. Suitable organic pigments are those of the azo, anthraquinone and thioindigo series, as well as other polycyclic pigments, e.g. from the phthalocyanine, quinacridone, dioxazine, naphthalene tetracarboxylic acid, perylene tetracarboxylic acid or isoindoline series and

Metal complex pigments or lacquered dyes such as Ca, Mg, Al lacquers of dyes containing sulfonic acid and / or carboxylic acid groups, and carbon black, a large number of which are known, for example, from Color Index, 2 editions. Suitable inorganic pigments are, for example, zinc sulfides, ultramarine , Titanium oxides, mixed phase pigments such as nickel or chromium antimony titanium dioxide, cobalt blue,

Chromium oxides and chromate pigments, examples include Pigment Yellow 53, Pigment Brown 24

Pigments which are free of lead, manganese, cadmium, chromium etc. are particularly preferred, that is to say free of heavy metals which, if they are bioavailable, hinder their degradability

Particularly preferred pigments are, for example, phthalocyanine pigments such as Pigment Blue 15, Pigment Green 7, arylamide pigments such as Pigment Yellow 83, Pigment Yellow 17, monoazo pigments such as Pigment Red 48, lithol pigments, disazo condensation pigments such as Pigment Red 166, and carbon blacks, zinc sulfides and ultramarine

Usually, the dyes or pigments are not added to the color or printing paste as such, but are generally used as aqueous dispersions. To do this, they must be mechanically converted into the aqueous dispersion in a suitable manner with the aid of forming agents. The forming agents coat the Dyes or pigments largely and thus prevent unwanted sedimentation during storage

Suitable synthetic shaping agents are carbonyl and hydroxyl group-bearing oligourethanes, as are described, for example, in DE-OS 41 12 327

Forming agents of natural origin, however, have the advantage of biodegradability. A particularly preferred forming agent is casein

The mixtures of A and B can contain up to 500, preferably 0.15 to 200, in particular 5 to 150% by weight of dyes and / or pigments, based on the total

(A + B) can be added

Up to 30% by weight, based on A, of rheology aids can furthermore be added to the mixtures of A and B, which can be of mineral, natural organic or synthetic organic origin. Preferred rheology aids are, for example, alginates, locust bean flour, the organic, degradable cellulose derivatives etc. or inorganic, mineralisable clays, layered silicates etc

The mixtures of A and B can also contain up to 50% by weight, based on A, of plasticizers. Preferably only up to 30% plasticizers are used

Plasticizers of natural origin are preferred, with up to 20% by weight, based on the plasticizer mentioned, of synthetic organic plasticizers being preferred. Preferred plasticizers are, for example, the natural oils and fats of vegetable and animal origin, such as palmol derivatives, which are optionally hardened, claw oil, optionally sulfonated or sulfatic castor oil, optionally esterified rapeseed oil, etc

Components A and B can, as usual, be dispersed in water, optionally using organic solvents (for example in the so-called "gasoline emulsion process", after which oil-in-water emulsions are formed)

For reasons of environmental compatibility, however, the use of petrol-free printing pastes is preferred do without components with reactive groups that could interfere with the reaction between the binder and the crosslinking agent

Other auxiliaries, such as, for example, emulsifiers, thickeners, evaporation inhibitors, catalysts, grip improvers, anti-foaming agents, can of course be used to produce the printing, ink and coating pastes. Products which are biodegradable due to their structure are also preferably used.

The usual methods of are suitable for processing textile printing pastes

Printing technology, see, for example, Ullmann's Encyklopadie der technical chemistry, 4 ed., Vol. 22, pp 565 ff "Textile Printing", Verlag Chemie, Weinheim 1982, as well as the coating technology, as described, for example, in the plastics handbook, Volume 7, Polyurethane, Carl Hanser Verlag, Munich 1993, are described.

The applied prints and coatings can be crosslinked at elevated temperatures, whereby isocyanate crosslinkers allow the use of relatively low temperatures (e.g. room temperature up to 100 ° C), but also higher temperatures of up to 170 ° C are not harmful With curing conditions of 80 to 100 ° C (1 to 10 minutes), however, excellent results can be achieved in most cases. Very good final strength can also be achieved by drying at room temperature for a long time (1-3 days). Staining can be carried out in a known manner in the padding and exhausting process According to a special embodiment, the mixtures of A and B can be used together with pigment for the dyeing of textiles and leather in an aqueous medium

The percentages in the following examples relate to the weight, parts are parts by weight

When evaluating the properties of those tested in the examples below

Products were based on the following qualitative evaluation standard Rating abbreviation similar ä little better w + little less w- somewhat better e + somewhat less e- better + less clearly better d + significantly less d- significantly better b + significantly less b-

Examples

The following components were used:

Production of the polyurethane urea dispersion

170 g of a polyester diol of molecular weight 1700 from adipic acid and a mixture of 1,6-hexanediol and neopentyl glycol in a weight ratio of 1.9 l are degassed for 60 minutes at 120 ° C. in vacuo

0.2 ml of benzoyl chloride and 30.1 g of hexamethylene diisocyanate added in one pour. After stirring for 30 minutes at 120 ° C., the NCO content is 3.2%. The prepolymer is dissolved in 50 g of acetone at 50 ° C., cooled to room temperature and given with rapid stirring, a mixture of 9.7 g of a 50% aqueous solution of AAS salt and 1.51 g of ethylenediamine and 20 g of water to form the acetone solution

15 minutes of stirring are mixed with 300 g of water and the acetone is removed at 60 ° C. and 140 mbar. The distillation residue remains 505 g. After dilution with 11 g of water, a 40%, low viscosity, white polyurethane urea dispersion is obtained

Pigments EUKANOL colors ^*)

") Designations of the pigment type from the Color Index.

Examples 1-6

Batch quantity: 1000 g

Examples 7-10

Evaluation of approach 7

Examples 11-17

Assessment of approach 11

Burst wash test

The wash fastness of dyeings and prints can be checked using the burst wash test. Abrasion can serve as a measure of the degree of crosslinking of the binder

A sample (approx. 10 x 20 cm) of the dyed and printed fabric is then fixed in a mixture

2.5 g / 1 Marseille soap ("green soap"),

2 g / 1 anhydrous soda and

2 g / 1 sequestering aid (e.g. B ^® Trilon B)

soaked at 80 ° C for about 10 minutes, then stretched and brushed with a hard Perlon hand brush with constant pressure (1 kg). Normally you do 50 double strokes The sample is then rinsed and dried. The pigment abrasion of the brushed sample is compared with the unburbished original sample. If no pigment abrasion can be seen, the binder can be regarded as fully cross-linked

Examples 18-21 for rotting tests

Print on room - tee table (round sleeve)

CO (Vlisco) R 10 / P 3 / G 40 CO knitted fabric R 16 / P 5 / G 40

Goods: CO knitted goods

The printing pastes were worked on release paper and films were made from them. The films were subjected to the following composting test:

The films to be tested were first dried to constant weight at 80 ° C. and then clamped in 6 × 6 cm slide frames. Compost from a composting plant was filled 2 cm high in plastic trays and the films were placed in it. The filled boxes were incubated in an incubator for 4 weeks at 60 ° C. Water losses were determined and compensated for by weight loss. The pH of the compost was measured once a week during the incubation. After 4 weeks each batch was stopped, the films removed, cleaned, dried to constant weight at 80 ° C. and photographically immediately after drying, the weight loss of the films was determined by weighing again

In the poisoned control, the compost was dried at 105 ° C., the evaporated water was then replaced by 1% HgC ^ solution. The films for the poisoned control were placed in the HgCl ₂ solution before being introduced into the compost mixture , dried and then placed in the poisoned compost. The control batch was incubated in exactly the same way as the other batches

A film was said to be degradable if it disappeared completely in the microbially active batches and the cellulose film used in a parallel test and was retained in the poisoned control

Result a) Movies

Examples

18-20 completely degraded

21 no dismantling

Prints (test analogous to the film composting test)

b) CO Vlisco

Examples

18 completely dismantled

19 completely dismantled

20 somewhat reduced

21 no dismantling c) CO knitted fabric

Examples

18 largely dismantled

19 little degraded

20 little degraded

21 no dismantling

Example 22 (textile coating)

Spread about 80 g wet / m ^{2 of} a mixture of 1000 g polyurethane urea dispersion, 100 g EUKANOL black and 6 g VA emulsifier on a release paper. After passing through a drying tunnel of 80 ° -1 10 ^o -125 ° C, the adhesive line consisting of 100 g polyurethane urea dispersion, 55 g EUKANOL black and 12 g emulsifier VA is applied in a thickness of 150 g / m ² wet and a cotton fabric is laminated. After drying at 135 ° C, the coated fabric could be removed from the release paper.

In an analogous manner, a cellulose fiber nonwoven bonded with polyurethane urea dispersion in a known manner was provided with a coating.

The coated products had the required fastness properties in flexometer and adhesion; the products proved to be biodegradable.

Examples 23 and 24 for biodegradation of the printing pastes

Printing pastes 23 (prior art) and 24 (paste according to the invention) were subjected to the biodegradability test for five days four hours after production (BOD-5, method: LCK 55 cuvette test from Lange).

The printing paste 24 showed the expected high degradability rate with a comparable application properties.

% Ash 1000 ° C 0.0012 / 0.016 / 0.0017 0.016

COD value 179 427

BOD value mg / 1 7.62 240

BOD value in% 4.3 56.7

Print on room tee table (round stencil) Print dried and 5 min. fixed at 150 ° C.

Claims

claims

1 Biodegradable coating, color and printing pastes for textile substrates and non-textile cellulosic substrates containing (l) biodegradable polyurethane ureas, polyesters or polyester amides, (n) rheological aids,

(m) pigments or dyes, which - if they are formed - are formed with shaping agents of natural origin, and optionally (iv) plasticizers on a natural basis

2 pastes according to claim 1, per 40 weight (l), based on the dye content of (l),

(n) up to 10 parts by weight of a mineral and / or a natural organic thickener,

(in) up to 100 parts by weight of one formed with casein and / or albumin

Pigments or dye, (iv) up to 30 parts by weight of a natural (vegetable or animal) oil or fat and (v) up to 25 parts by weight of a crosslinker on N-methylol, azidine,

Contain epoxy or isocyanate base

3 Use of

A) while maintaining an equivalent ratio of isocyanate groups to isocyanate-reactive groups of 1 1 to 2 1 available reaction products

a) a diisocyanate component consisting of

al) hexamethylene diisocyanate or a2) Mixtures of hexamethylene diisocyanate with a total of up to

60% by weight, based on mixture a2), l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and / or 4,4'-diisocyanatodicyclohexylmethane and / or l-methyl-2 , 4 (6) -diiso-

5 cyanatocyclohexane with

b) a diol component consisting of

bl) at least one polyester diol with a number average molecular weight of 500 to 10,000 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 polyester diols with up to 32% by weight, 15 based on the total weight of component b), of alkane diols with 2 to 6 carbon atoms which may have ether groups,

c) a diamine component in an amount of 2 to 50 equiv. 20 lent%, based on the total amount of the groups present in components b) and c) which are reactive towards isocyanate groups, consisting of

cl) diamino sulfonates of the formula

25

H ₂ N (-CH ₂ ) _n -NH (-CH ₂ ) _m -SO ₃ Me

or

30 c2) mixtures of diaminosulfonates cl) with up to 90% by weight, based on the total weight of component c), of ethylenediamine, if appropriate d) hydrophilic polyether alcohols of the formula

H-X-O-R

in an amount of up to 10% by weight, based on the sum of components b), c) and d), and if appropriate

being in the formulas mentioned

m and n independently of one another for numbers from 2 to 6,

Me for potassium or sodium,

R stand for a monovalent hydrocarbon radical with 1 to 12 carbon atoms and

X denotes a polyalkylene oxide chain in the number average molecular weight range from 88 to 4000, the alkylene oxide units of which consist of at least 40 mol% of ethylene oxide units and the remainder of propylene oxide units and

B 0 to 30% by weight, based on A, crosslinker for A

as a binder for dye and / or pigment preparations for coating, coloring and printing flexible substrates

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

5. Use according to claims 3 and 4, according to which the crosslinking agent B is selected from the series of polyisocyanates, multifunctional epoxides, carbodiimides, compounds containing N-methylol groups.

6. Use according to claims 3 to 5 for coating, dyeing and printing of textiles or leather.