JP2001518573A - Biodegradable binder for dyeing - Google Patents

Abstract

  (57) [Summary] Certain anionic polyurethanes are outstandingly suitable for use as binders in textile and leather coating, dyeing and printing. The polyurethanes are biodegradable. Thus, residues and washings remaining during the dyeing process can be sent to a biological effluent treatment plant.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the use of biodegradable binders for dyeing, in particular for dyeing textiles and leather.

[0002] Completely biodegradable and compostable structural materials
reals of construction will become increasingly important in the future, both in economics and in technology [T. Jopski, Kunststoffe
83 (1993), 10]. The challenge is to produce a plastic that has the required performance capabilities but degrades under the stimulus of a bioactive environment. Start factor (i
A nitrifying factor may be that the backbone of the polymer undergoes microbiological, enzymatic, hydrolytic, photolytic or oxidative degradation at specific sites.
All of the degradation products must be safe and non-toxic in nature and non-accumulative, i.e. they must be completely degraded by microorganisms. until now,
There are three general categories of fully biodegradable and compostable structural materials that have become known: polyesters; plastics based on natural polymers; and other degradable plastics, such as polyvinyl. Alcohol etc. Polyesters include polylactic acid, polyhydroxybutyrate, polyhydroxyvalerate, polycaprolactone and high molecular weight aliphatic polyesters (EP-A-572256). If a sufficiently high molecular weight is to be obtained, the polyesters described in EP-A-572 256 are extended with organic diisocyanates,
This gives the final 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-64 917.

[0003] Biodegradable, thermoplastic polyurethane filaments are disclosed in German Patent C 43
19439. The thermoplastically processable polyurethanes are linear, use bifunctional polyesterdiols and bifunctional polyethylene glycols in the polymer chain configuration, and chain extend hexamethylene diisocyanate and butanediol or hexadiol. Agent (chain extender)
s) (Examples 1 to 3).

[0004] DE-A 195 17 185 and DE 195 20 092 disclose biodegradable compostable products based on hydrophilic polyurethanes, the term "polyurethanes" It also includes polyurethane ureas. These polyurethanes are reaction products of diisocyanates and diols, and also contain diaminosulfonate groups and polyether groups (optionally containing ethylene oxide groups) for the purpose of imparting hydrophilicity to the final product. Incorporate them. Such hydrophilic polyurethanes can be used as a coating material to coat any desired substrate, as an adhesive and / or binder for cellulose when producing nonwovens from cotton and / or hemp or linen, wood, As a high molecular weight binder for sawdust or wood chips, as a film to be included in composite materials when manufacturing biodegradable packaging materials, for the manufacture of sanitary products, such as diapers for babies, Seed dressing (se
useful as binders in the production of pots for plants, as coatings for paper and engine sizing of paper, in the manufacture of sausage hulls, and in the manufacture of cosmetic compositions, as ed dressings. is there. Examples of products that can be made therefrom include flat films, injection molded articles, such as flower pots, beverage containers, food container trays, thermoformed articles, blister packs, blown films or bottles.

[0005] As biodegradability is also becoming increasingly important with textiles, there is a larger area that has not yet been achieved.

[0006] Directly reverse the fabric with a coating or a textile printing paste
When dyeing and coating by a coating or printing method, or when dyeing and coating a textile by an exhaust process with a binder to which a pigment is added, an externally crosslinkable film-forming binder (externally)
crosslinkable film-forming binders)
It is customary to use binders based on, for example, polyurethanes, polyacrylates or butadiene / acrylonitrile copolymers. The mixture of binder and pigment usually contains reactive components which, after the printing stage, cause the binder to crosslink at elevated temperatures and fix the printed or dyed product. It is only such fixing that gives the desired waterfastness that is important, for example, for washing dyed or printed fabrics.

Here, the materials contained in the liquor after dyeing or the washing liquor of the printed fabric, ie the underlying binders and in particular rheological assistants,
nts) was confirmed to be troublesome (refractory). Similarly, the auxiliaries that need to be used in pigment finishing are usually based on troublesome emulsifiers and / or copolymers. However, it is important that such materials exhibit good wetfastnesses in order to achieve satisfactory performance characteristics. In general, good wet fastness is obtained by crosslinking. On the other hand, it was confirmed that the crosslinking deteriorates the biodegradability of the product. The crosslinkers used in binders used in coating and textile printing pastes are usually melamine / formamide condensation products that operate at temperatures above about 120 ° C.

[0008] Ullmanns Encyklopaedie der technischen Chemie, 4th Edition, 2 by W. Berlenbach
2, p. 629, Verlag Chemie, Weinheim 1982, an acid is used as a catalyst when cross-linking by the N-methylol group of the binder is carried out. For 10 to 10 minutes or using dry hot air at 175 ° C. for 30 to 60 seconds.

Pigment dyeing with hydrophilic modified polyisocyanates is described, for example, in EP 571 867 and DE-A-4 415 449.

In general, the dyeing materials according to the invention are also effective for use in coating textiles directly and in reverse, provided that only biodegradable components are used, as is known per se. Is a condition. Desired items for coating (desidera
ta) exhibits high flexibility in wet and dry conditions and also has high abrasion resistance and high water and solvent resistance. Therefore, it is necessary to crosslink the binder. Crosslinking agent (active material) for binder (40% strength by weight dispersion)
Is not more than 15% by weight, preferably not more than 10% by weight, particularly preferably not more than 7% by weight, based on the polymer, surprisingly that the coated fabric and the residual Hold.

[0011] Accordingly, one object of the present invention is to overcome the ecological disadvantages of the prior art. More particularly, it allows the residual liquor and washings from the coating and dyeing process to be sent to a biological processing plant and makes the coated, dyed or printed product compostable, i.e. landfilled. Show degradability.

This object is achieved according to the invention by using biodegradable polyurethaneureas, polyesters or polyesteramides.

Accordingly, the present invention relates to textile substrates and non-woven cellulosic (nontextil)
e cellulosic) providing a biodegradable paste for coating, dyeing and printing substrates, comprising: (i) a biodegradable polyurethaneurea, polyester or polyesteramide, (ii) a flow aid, (iii) A pigment or dye that has been finished with a natural source finish, if any, and (iv) a natural based plasticizer.

[0014] Such suitable pastes have a dye content of (i)
Per 40 parts by weight of (i), (ii) no more than 10 parts by weight of mineral and / or natural organic thickeners, (iii) optionally finished with casein and / or albumin Not more than 100 parts by weight of a pigment or dye which may be used, (iv) not more than 30 parts by weight of natural (vegetable or animal) oil or fat, and (v) N-methylol-based or aziridine. It contains up to 25 parts by weight of a cross-linking agent based on epoxide or isocyanate.

The invention furthermore relates to A) a) a1) hexamethylene diisocyanate, or a2) as a binder for dye and / or pigment preparations for dyeing or printing soft substrates, in particular textiles and leather. Up to 60% by weight, based on hexamethylene diisocyanate and mixture a2), of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and / or 4,4'-diisocyanatodicyclohexylmethane And / or a mixture of 1-methyl-2,4 (6) -diisocyanatocyclohexane, and b) b1) (i) adipic acid and / or succinic acid and (ii) a carbon atom number A number average molecular weight of at least one alkanediol of from 2 to 6 of from 500 At least one polyester diol of 000, or b2) up to 32% by weight, based on the total weight of said polyester diol and component b), of 2 to 6 carbon atoms, optionally containing ether groups. mixtures of good alkanediol, and a comprising at diol component, c) c1) formula _{H 2 n (-CH 2) n} -NH (-CH 2) diamino acid salt represented by _m -SO ₃ Me or c2) a mixture of not more than 90% by weight, based on the total weight of the diaminosulphonic acid salt c1) and of component c), of ethylenediamine, comprising: isocyanate-reactive groups (isocy) present in components b) and c)
The diamine component in an amount of from 2 to 50 equivalent%, based on the total amount of anate-reactive), and, optionally, d) a formula of not more than 10% by weight, based on the total amount of components b), c) and d). The hydrophilic polyether alcohols represented by the formula H—X—O—R and, optionally, e) water, which is not included in the calculation of the equivalent ratio of isocyanate groups to isocyanate-reactive groups, A reaction product obtainable by reacting such that the equivalent ratio of the groups is 1: 1 to 2: 1, wherein m and n are independently 2 to 6, and Me is potassium R is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and X is a polyalkylene oxide chain having a number average molecular weight in the range of 88 to 4000. In which the alkylene oxide units, with respect to is and that the remaining ethylene oxide units in the degree of over 40 mol% propylene oxide units, and B. The crosslinking agent for A is 0 to 30% by weight based on A, preferably 0.1 to 2%.
5% by weight is also provided.

The diisocyanate component a) is preferably entirely hexamethylene diisocyanate.

The diol component b) is combined with b1) at least one polyester diol or b2) at least one polyester diol b1) and at least one alkane in an amount of up to 32% by weight, preferably up to 10% by weight. It is composed of any mixture of diols (having 2 to 6 carbon atoms and optionally containing ether groups).

Suitable polyester diols b1) are (i) adipic acid and / or succinic acid and (ii) alkanediols having 2 to 6 carbon atoms and optionally containing ether groups. ), For example ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol and / or 1
The number average molecular weight (which can be calculated from the hydroxyl group content) is from 500 to 10,000, preferably from 1,000 to 2500, based on 2,6-hexanediol. Polyester diols derived exclusively from ethylene glycol and / or 1,4-butanediol as diol are particularly preferred.

Alkanediols which may optionally be included as hydroxyl-containing chain extenders (having 2 to 6 carbon atoms and optionally ether groups)
Are of the type exemplified above for the preparation of polyesterdiols.

The diamine component c) may be replaced by c1) a diaminosulfonic acid salt represented by the general formula shown above, or c2) the diaminosulfonic acid salt and ethylenediamine. 9 based on the reactive amino group
0% by weight or less, preferably 70% by weight or less]. A very particularly preferred diaminosulfonic acid salt is N- (2-aminoethyl)
-2-Aminoethanesulfonic acid potassium or sodium salt.

The diamine component c) is generally used in an amount of 1 to 10% by weight, preferably 2 to 5% by weight, based on the weight of component b).

Optional components (optional component)
t) d) encompasses hydrophilic monohydric polyether alcohols of the formula H—X—O—R, wherein R and X are each as defined above.

In such polyether alcohols, R is an aliphatic hydrocarbyl group having 1 to 4 carbon atoms, and X is a polyalkylene oxide chain having a number average molecular weight in the range of 500 to 4000. [Where the alkylene oxide units thereof are ethylene oxide units to a degree of at least 40 mol%, in particular at least 70 mol%, particularly preferably 100 mol%, and for the remainder are propylene oxide units]. Preferred are polyether alcohols.

[0024] Monohydric polyether alcohols of this type are suitable starting materials
The molecule R-OH which is r), such as methanol, n-butanol, n-hexanol or n-dodecanol, is preferably used with ethylene oxide and optionally propylene oxide in the alkylene oxide proportions disclosed hereinabove. Usually occurs when alkylation occurs. The alkylene oxides mentioned herein can be used in mixed and / or sequential form.

When monohydric polyether alcohols d) are used in the process according to the invention, they are used in amounts of not more than 10% by weight, preferably not more than 3% by weight, based on the total amount of components b), c) and d). Use in the amount of

A further component optionally used in the preparation of the urea-group-containing polyurethanes is e) water, which is a component which has been previously formed, especially when the polyurethane is formed.
When the chain extension reaction of the CO prepolymers is carried out in an aqueous medium, particularly when the diamine c) dissolved in water is used in an amount equivalent to or less than the NCO group of the NCO prepolymer, it is used as a reactant. Should be considered.

Other components which are suitable in principle include not only such components but also small amounts of trifunctional compounds such as glycerol or trimethylolpropane,
They can be incorporated in small amounts into the polyesters b1) or can be used in free form as part of component b2). When using such a branching molecule,
In general, it should be supplemented with monofunctional compounds so that a purely arithmetic linear polymer is obtained again.

The preparation of the urea group-containing polyurethanes can be carried out by any desired method using the constituents exemplified above. Preferably, however, component b) and optionally d) and also diisocyanate component a) have an NCO / OH equivalent ratio of 1.5: 1 to 4: 1, preferably 1.8: 1 to 2.5: After the NCO prepolymer is formed using the known prepolymer method of reacting to 1, the NCO prepolymer is reacted with component c) to effect chain extension.

The preparation of this prepolymer is generally carried out at 20 to 150 ° C. in the absence of a solvent.
After working at a temperature of, it is dissolved in a suitable solvent. It will be appreciated that the preparation of the prepolymer can also be carried out directly in a solvent. Suitable solvents include, in particular, solvents which are inert with respect to the isocyanate groups and are miscible with water in any ratio. The solvent used is preferably acetone.

The prepolymer thus prepared is reacted in a second reaction stage with component c) to effect chain extension. In this stage, the equivalent ratio of isocyanate groups in one prepolymer to isocyanate-reactive amino groups in the other component c) is from 1: 1 to 20: 1, preferably from 1.2: 1 to 4: 1. Within the range. The chain extension reaction can be performed in a solution, preferably with acetone, or otherwise in an aqueous medium, in which case the prepolymer is dissolved in an organic solvent. The chain extension reaction can be carried out by combining the solution with component c) in water and mixing thoroughly. This can be achieved by a chain extension reaction involving the reaction of water with the NCO groups contained in the prepolymer as described above. In the preferred two-stage method for preparing a urea group-containing polyurethane described above, the equivalent ratio between the isocyanate groups and the isocyanate-reactive groups in the two reaction stages is determined by:
To be within the scope of the present disclosure in such a way that the overall ratio of isocyanate groups to isocyanate-reactive groups contained in components b) to d) corresponds to the ratio of 1: 1 to 2: 1 given above. select. Water should never be included in the equivalence ratio calculations described above.

The chain extension reaction is generally performed within a temperature range of 20 to 50 ° C.

An alternative method for carrying out this chain extension reaction in the molten state, ie in the absence of solvent or water (
Although a melt dispersion method is also possible in principle, it is never preferred.

When preparing the polyurethanes A, the abovementioned starting materials a), b), c) and optionally d) and / or optionally e) are used in the abovementioned quantitative ratios.

The polyurethanes A are preferably used in the form of an aqueous dispersion. The term `` aqueous dispersion ''
As used herein, this also includes aqueous solutions that may be present when the concentration of hydrophilic centers contained in the urea group-containing polyurethane is sufficient to ensure solubility in water. Such dispersions are often aqueous based, containing not only the dispersed but also dissolved urea group-containing polyurethane.

An aqueous polyurethane dispersion having a structure similar or comparable to the polyurethane A is already disclosed in German Patent Application No. 2 035 732, 2651 506, 195 17
185 and 195 20093.

When such an aqueous dispersion is formed, if the chain extension reaction is carried out in the absence of water, the polyurethane subjected to the chain extension or a solution containing the polyurethane in an organic solvent is used for dispersion. After mixing with water, at least some of the co-solvent used is optionally removed by distillation. When this chain extension reaction is performed in an aqueous medium,
Optionally, water can be further added to form an aqueous dispersion. In this case too, of course, the co-solvent used may be removed by distillation, if desired.

[0037] The total amount of water used is generally such that a dispersion having a concentration of 5 to 60% by weight (preferably a concentration of 20 to 55% by weight) is present.

The polyurethane dispersions can also contain usual auxiliaries. However, it is particularly preferred that such auxiliaries likewise exhibit biodegradability. Such auxiliaries are suitably especially auxiliaries of natural origin, namely gelatin, protein hydrolysates, guar, tragacanth, flour, starch, sawdust, cellulose powder and the like.

Crosslinking agents B include, for example, hydrophilic polyisocyanates, polyfunctional epoxides and carbodiimides as described in DE-A 42 17 716, which are mentioned in DE-A 42 17 716. The contents of the issue are expressly incorporated herein by reference thereto. In addition,
Crosslinking agents B are reactive compounds derived from formaldehyde, such as phenol / formaldehyde and melamine / formaldehyde condensates containing N-methylol groups, such as "Methoden der Organischen Chemie" (Houben-Weyl), Vol. 14/2, Condensates described in the fourth edition, Georg Thieme Verlag, Stuttgart 1963, pages 319 et seq. Such crosslinking results in better water resistance and higher wear resistance, and so on.

Dyes and / or pigments may be added to the mixture of A and B in an amount up to 30% by weight, based on A.

Suitable dyes are alkaline-fixable reactive dyes. They have any color-con
for example, mono- or polyazo, metal complexes azo, anthraquinone, phthalocyanine, formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl, naphthoquinone, pyrenequinone or perylenetetracarbimide sulfo. It may have a residue of a contained organic dye.

Such an alkali-fixable reactive dye preferably has at least one reactive aromatic heterocyclic group and / or less reactive groups of the formula —SO ₂ M. Wherein M = CH ₂ —CH ₂ —OH, CH = CH ₂ or CH ₂ —CH ₂ —V [where V = alkaline-eliminable]
Group, preferably a _{OSO 3 H, SSO 3 H,} OCOCH 3, 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 (the anion is preferably Cl ⁻ )], which reacts with the HO- or NH-containing fiber under dyeing conditions to form a covalent bond.
5- or 6-membered aromatic heterocyclic rings, such as monoazine, diazine or triazine rings, especially pyridine, pyrimidine, pyridazine, pyrazine, thiazine, oxazine or symmetric or asymmetric triazine rings or aromatic carbocyclic rings One or more condensed ring systems, such as the above rings substituted with a quinoline, phthalazine, sinoline, quinazoline, quinoxaline, acridine, phenazine or phenanthridine ring system or with an additional reactive group of vinylsulfone type Those containing at least one reactive substituent attached to the system are preferred.

The reactive substituent on the heterocycle includes, for example, halogen (Cl, Br or F),
Ammonium (hydrazinium, pyridinium, picolinium, include carboxymethyl pyridinium), sulfonium, sulfonyl, azide (-N _3), Chioshiana bets, thioether, oxy ethers, sulfinic acid and sulfonic acid.

Specific examples are the following fiber-reactive groups: 2,4-difluorotriazin-6-yl, 2,4-dichlorotriazin-6
Yl, monohalo-sym-triazinyl groups, especially monochloro- and monofluorotriazinyl groups, which are optionally alkyl, aryl, amino, monoalkylamino, dialkylamino, aralkylamino, arylamino, morpholino, piperidino, pyrrolidino, piperazino , Alkoxy, aryloxy, alkylthio, arylthio, wherein alkyl is preferably optionally substituted C ₁ -C ₄ -alkyl, and aralkyl is preferably optionally substituted phenyl. -C ₁ -C ₄ - alkyl and aryl is preferably phenyl or naphthyl optionally substituted by case, and wherein the suitable substituents in the alkyl group, halogen, hydroxyl, cyano, Dialkylamino, morpho Roh, C ₁ -C ₄ - alkoxy, carboxyl, sulfo or sulfato, and suitable substituents in the phenyl and naphthyl are sulfo, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, carboxyl, halogen , Acylamino, hydroxyl and amino). Also, 2
-Amino-4-fluorotriazin-6-yl, 2-methylamino-4-fluorotriazin-6-yl, 2-ethylamino-4-fluorotriazin-6-yl, 2-isopropylamino-4-fluorotriazine- 6-yl, 2-dimethylamino-4-fluorotriazin-6-yl, 2-diethylamino-4-fluorotriazin-6-yl, 2-β-methoxyethylamino-4-fluorotriazin-6-yl, 2- β-hydroxyethylamino-4-fluorotriazin-6-yl, 2-di- (β-hydroxyethylamino) -4-fluorotriazin-6-yl, 2-carboxymethylamino-4-fluorotriazin-6-yl , 2-di- (carboxymethylamino) -4-fluorotriazin-6-yl, 2-sulfomethyl- Chiruamino -4-fluoro-triazin-6-yl, 2-
β-cyanoethylamino-4-fluorotriazin-6-yl, 2-benzylamino-4-fluorotriazin-6-yl, 2-β-phenylethylamino-4
-Fluorotriazin-6-yl, 2-benzyl-methylamino-4-fluorotriazin-6-yl, 2- (4'-sulfobenzyl) -amino-4-fluorotriazin-6-yl, 2-cyclohexylamino- 4-fluorotriazine-
6-yl, 2- (o-, m-, p-methylphenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m-, p-sulfophenyl) -amino-4-
Fluorotriazin-6-yl, 2- (2 ', 5'-disulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (o-, m-, p-chlorophenyl) -amino-4- Fluorotriazin-6-yl, 2- (o-, 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-5'-sulfophenyl)
-Amino-4-fluorotriazin-6-yl, 2- (2'-methoxy-4'-
Sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (o-,
m-, p-carboxyphenyl) -amino-4-fluorotriazin-6-yl, 2- (2 ', 4'-disulfophenyl) -amino-4-fluorotriazine-
6-yl, 2- (3 ′, 5′-disulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (2′-carboxy-4′-sulfophenyl) -amino-4-fluorotriazine -6-yl, 2- (2'-carboxy-5'-sulfophenyl) -amino-4-fluorotriazin-6-yl, 2- (6'-sulfonaphth-2'-yl) -amino-4-fluoro Triazin-6-yl, 2- (4
', 8'-Disulfonaphth-2'-yl) -amino-4-fluorotriazine-
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-β-hydroxyethyl-N-
Phenyl) -amino-4-fluorotriazin-6-yl, 2- (N-isopropyl-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-6)-
Carbamyl-, N-methyl-N- (2-methylamino-4-chlorotriazine-
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-6-yl, 2- (
o-, m- or p-sulfophenoxy) -4-fluorotriazin-6-yl, 2- (o-, m- or p-methyl- or -methoxy-phenoxy)
-4-fluorotriazin-6-yl, 2-β-hydroxyethylmercapto-
4-fluorotriazin-6-yl, 2-phenylmercapto-4-fluorotriazin-6-yl, 2- (4′-methylphenyl) -mercapto-4-fluorotriazin-6-yl, 2- (2 ′, 4'-dinitrophenyl) -mercapto-4-fluorotriazin-6-yl, 2-methyl-4-fluorotriazine-
6-yl, 2-phenyl-4-fluorotriazin-6-yl and also the corresponding 4-chloro- or 4-bromo-triazinyl groups, and tertiary bases such as trimethylamine, triethylamine, dimethyl-β-hydroxyethylamine , Triethanolamine, N, N-dimethylhydrazine, pyridine, α-,
nicotinic acid or isonicotinic acid, such as β- or γ-picoline, corresponding groups obtained by halogen exchange with sulfinates, especially benzenesulfinic acid or hydrogensulfite, and also di- or trihalopyrimidyl groups For example, 2,4-dichloropyrimidin-6-yl, 2,4,5-trichloro-pyrimidin-6-yl, 4,5-dichloropyrimidin-6-yl, 2,4-difluoropyrimidin-6-yl, , 5-Difluoro-pyrimidin-6-yl, 4-
Fluoro-5-chloropyrimidin-6-yl, 2,4-difluoro-5-chloropyrimidinyl, and also 2,3-dichloroquinoxaline-5-carbonyl and 2,3-dichloroquinoxaline-6-carbonyl are possible. .

It is to be understood that alkali-fixable reactive dyes also include mixtures of reactive dyes of the type described above.

The pigment may be an organic or inorganic pigment. Suitable organic pigments include azo, anthraquinone, thioindigo based pigments as well as other polycyclic pigments such as phthalocyanine, quinacridone, dioxazine, naphthalenetetracarboxylic acid, perylenetetracarboxylic acid or isoindoline pigments, and also metal Complex pigments or laked dyes, such as the sulfo- and / or carboxyl-containing dyes Ca, Mg and Al lakes, and also carbon black, many of which are known, for example, from the second edition of the Color Index . Examples of suitable inorganic dyes are zinc sulfide, ultramarine, titanium oxide, mixed phase (
mixed-phase pigments, for example, cobalt blue, chromium oxide, and chromic acid pigments such as nickel or chromium antimony titanium dioxide, examples of which are Pigment Yellow 53, Pigment Brown.
24.

In particular, pigments that do not contain lead, manganese, cadmium, chromium, etc., that is, do not contain heavy metals, are preferable, and if they exist in a form used by living organisms, they suppress the decomposability.

Examples of particularly suitable pigments are phthalocyanine pigments, for example Pigment Blue
15, an arylamide pigment such as Pigment Green 7;
mono azo pigments, such as Pigment Red 48; Litol pigments, disazo condensed pigments, such as Pigment Red 166; and also carbon black, zinc sulfide and ultramarine.

Such dyes or pigments are not usually added as such to the dyeing pastes or printing pastes, but they are generally used in the form of an aqueous dispersion.
For this purpose, they should be converted mechanically into aqueous dispersions with a finish in a suitable manner. Such finishes substantially coat the dye or pigment, thereby preventing unwanted settling during storage.

Suitable synthetic finishes are oligourethanes having a carbonyl and a hydroxy, as described, for example, in DE-A 41 12 327.
However, natural source finishes are more advantageous with respect to biodegradability. A particularly preferred finish is casein.

A dye and / or pigment is added to the mixture of A and B in an amount of 5% based on the total amount of (A + B).
Not more than 00% by weight, preferably 0.15 to 200% by weight, especially 5 to 150% by weight
It may be added.

It is also possible to add further flow aids to the mixture of A and B in amounts of up to 30% by weight, based on A, such flow aids being of mineral, natural or synthetic organic origin. May be used. Examples of suitable flow aids are alginate, locust bean flour, degradable organic cellulose derivatives and the like, and mineralizable (mineraliz).
able) Inorganic clay, sheet-silicates
And so on.

The mixture of A and B can also contain a plasticizer in an amount up to 50% by weight, based on A. The amount of plasticizer used is preferably only 30% or less. Naturally occurring plasticizers are preferred, but synthetic organic plasticizers are acceptable provided that they are used in an amount up to 20% by weight, based on the plasticizer. Examples of suitable plasticizers are natural fats and oils of plant and animal origin, such as palm oil derivatives (optionally hydrogenated), cow foot oil, castor oil (optionally sulfonated or sulfated). Rapeseed oil (which may be optionally esterified), and the like.

The components A and B can be dispersed in water in the usual manner, but in some cases it is also possible to use organic solvents [thus it is also possible to use, for example, the “benzine emulsification method” which produces oil-in-water emulsions. Is]. However, for environmental reasons, it is preferable to use a printing paste that does not contain benzene. The preparation of such formulations is advantageously carried out with components that do not contain any reactive groups that can interfere with the reaction between the binder and the crosslinker.

It is understood that the preparation of the printing, dyeing and coating pastes can be carried out with further auxiliaries, such as emulsifiers, thickeners, evaporation inhibitors, catalysts, hand improvers, defoamers and the like. I do. Similarly, it is preferable to use a product having a structure that exhibits biodegradability.

The treatment of the textile printing paste is suitably effected by customary printing techniques [eg Ullmanns E
ncyklopaedie der technischen Chemie, 4th edition, Volume 22, pages 565 et seq.
ck ", Verlag Chemie, Weinheim 1982] and also coating techniques [eg Kunststoffhandbuch, Volume 7, Polyurethane, Carl Hanser Verlag, Munich 1993]
As described in [1].

The attached printed matter and coating may be cross-linked at a high temperature, and a relatively low temperature (for example, from room temperature to 100 ° C.) can be used when isocyanate as a cross-linking agent is used. Higher temperatures are not harmful if below. However, in most cases curing conditions of 80 to 100 ° C. (1 to 10 minutes) will give excellent results. Similarly, drying at room temperature for an extended period of time (1-3 days) can provide very good final strength. Staining is padding (pad
This can be performed in a known manner using ding and exhaust methods. In a particular embodiment, a mixture of A and B can be used together with textile and leather dyeing pigments in an aqueous medium.

The percentages and parts in the examples herein below are weight percentages and parts by weight.

The properties exhibited by the products tested in the examples herein below were evaluated on the following qualitative scale:

[0060]

[Table 1]

[0061] Using examples the following ingredients:

[0062]

[Table 2]

[0063]

[Table 3]

Preparation of Polyurethane Urea Dispersion: 170 g of a mixture of 1,6-hexanediol and neopentyl glycol in a weight ratio of 1.9: 1 and a polyester diol having a molecular weight of 1700 produced from adipic acid were used. Is degassed at 120 ° C. under reduced pressure for 60 minutes. 0.2 ml of benzoyl chloride are added to the batch under nitrogen and 30.1 g of hexamethylene diisocyanate are added all at once. NCO after stirring at 120 ° C. for 30 minutes
The content is 3.2%. The prepolymer was dissolved in 500 g of acetone at 50 ° C., and the solution was cooled to room temperature.
Mix with high speed agitation with a mixture of 1.51 g of ethylenediamine and 20 g of water. After stirring for 15 minutes, 300 g of water are added and acetone is added to 140 g.
Remove up to 60 ° C. under millibar. The amount of the distillation residue is 505 g. Dilution is performed using 11 g of water to obtain a 40% concentration thin white polyurethaneurea dispersion.

[0065]

[Table 4]

Example 1-6

[0067]

[Table 5]

Example 7-10

[0069]

[Table 6]

[0070]

[Table 7]

[0071]

[Table 8]

[0072] dyeing using a brush cleaning test brush cleaning test and printed matter of washing fastness (washfastn
ess) can be tested. The degree of wear can be used as a measure of the degree of crosslinking of the binder.

After fixing the dyed and printed fabric sample (about 10 × 20 cm), 2.5 g of Catile soap (“green soap”)
/ G of anhydrous sodium carbonate at 2 g / l of sequestrant (eg Trilon B)
Is placed in a 2 g / l mixture for about 10 minutes at 80 ° C., then stretched and hard Perlo
Brush with a n-hand brush at a constant pressure (1 kg). Typically, 50 double strokes are performed.

Thereafter, the sample is rinsed and dried. The pigment abrasion of this brushed sample is compared to the original unbrushed sample. If no pigment abrasion is observed, the binder can be considered completely crosslinked. Decay test of Example 18-21

[0075]

[Table 9]

[0076]

[Table 10]

The printing paste was applied on a release paper with a knife to form a film therefrom. This film was subjected to the following composting test.

The films to be tested were first dried to constant weight at 80 ° C. and then clamped to 6 × 6 cm slide frames. From composter to compost
After taking out t) and filling it in a plastic ball having a depth of 2 cm, the film was embedded therein. Each of the filled boxes was incubated in a 60 ° C. incubator for 4 weeks. As a result of determining the amount of water loss by weight loss, it was good. During the incubation, the pH of the compost was measured once a week. In each case the batch was stopped after 4 weeks, the film was removed and cleaned, 8
After drying to constant weight at 0 ° C., pictures were taken. The weight loss of the film was determined through re-weighing immediately after drying.

In the poisoned control, the compost was dried at 105 ° C. and then the evaporated water was replaced by a 1% strength HgCl ₂ solution. This poison loading control, the film before entering the said compost mixture, entering is it to HgCl ₂ solution, dried and placed in the venom added compost. Incubation of this control batch was performed in the same manner as the other batches.

In the microbial active batch, the cellulose filter used in the parallel test of the film was used.
If it disappears completely in the same manner as Lum but remains intact in the poisoned control,
Una film was classified as a degradable film.result a) Film Example 18-20 Complete Decomposition 21 No Decomposition Printed matter (test similar to film composting test) b) CO Vlisco Example 18 Full Decomposition 19 Full Decomposition 20 Some Decomposition 21 No Decomposition c) COnit Example 18 Greatly decomposed 19 Slightly decomposed 20 Slightly decomposed 21 Not decomposedExample 22 (Fabric coating) Polyurethane urea dispersion is 1000 g and EUKANOL Schwarz is 1
Approximately 80 g (wet) of release paper with a mixture of 6 g Emulgator VA at 00 g
Condition) / m^TwoCoating to become. After passing through a drying tunnel at 80-110-125 ° C., 100 g of the polyurethane urea dispersion was used for EUKANOL Schwa.
rz is 55 g and Emulgator VA is 12 g. ^Two (Wet state) and apply cotton fabric on top. After drying the coated dough at 135 ° C., it could be peeled off the release paper.

A coating was applied in a similar manner to the bonded cellulose fiber nonwoven using a polyurethaneurea dispersion in a conventional manner.

The coating showed the required fastness in the sense of Flexometer and adhesion and showed biodegradability. Examples 23 and 24 relating to biodegradation of printing pastes Printing pastes 23 (prior art) and 24 (invention) were prepared by adding
After a time, the biodegradability test (BOD-5, method: LCK 55K by Lange)
uevette test) for 5 days.

The printing paste 24 exhibits a high rate of biodegradation as expected and a comparable application property profile.
)showed that.

[0084]

[Table 11]

[0085]

[Table 12]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP , KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventor Schjürze, Hans Germany 51061 Cologne Wolfskaul 4 (72) Inventor Pirkocille, Michael Day of the Federal Republic of Germany-51381 Reefel Kusen-Ryutzenkirchenasiut Lath 367 (72) Inventor Donkels, Norbert Day of the Federal Republic of Germany-41068 Moncheng Ratbatha Rhermondasiutlase 198 (72) Inventor Zeiler, Hans-Yelg D-51375 Reefel Kusen-Mölspräuchäichtüller Se 38 (72) Inventor Maia , Josef, Federal Republic of Germany -47809 Krefeld-Butzischdonk 8 (72) Inventor Kotzho, Reinhardt Federal Republic of Germany -51065 Cologne Ripnikassyutlase 12 F term (reference) 4H057 AA01 BA07 BA15 CA32 CA34 CA36 CA38 CB03 CB04 CB08 CB09 CC02 DA01 DA21 FA17 GA04 GA07 HA01 JA10 JB03 4J034 BA06 BA07 BA08 CA02 CA04 CA05 CA15 CA17 CB01 CB03 CB04 CB07 CC03 CC08 CD04 CD09 CD18 CE01 DA01 DB03 DB07 DF16 DF20 DG03 DG04 DG09 HA14 HC17 HC22 HC46 HC52 HC61 HC64 HC67 HC71 HC73 JA02 JA14 JA42 QA01 QA05 QC05 RA07

Claims (6)

[Claims] 1. A biodegradable paste for coating, dyeing and printing on textile substrates and non-woven cellulosic substrates, comprising: (i) a biodegradable polyurethane urea, polyester or polyester amide; (ii) a flow aid. (Iii) a pigment or dye that has been finished with a natural source finish if finished, and optionally (iv) a natural based plasticizer. Consisting of paste. 2. Based on the dye content of (i), per 40 parts by weight of (i), up to 10 parts by weight of mineral and / or natural organic thickener, (iii) casein and Not more than 100 parts by weight of pigments or dyes finished with albumin; (iv) not more than 30 parts by weight of natural (vegetable or animal) oils or fats; and (v) N-methylol based 2. The paste according to claim 1, which comprises a crosslinker based on pyridine, aziridine, epoxide or isocyanate in an amount of not more than 25 parts by weight. 3. A) a) a1) hexamethylene diisocyanate, or a2) a mixture with hexamethylene diisocyanate a2) as a binder for dye and / or pigment preparations for coating, dyeing and printing soft substrates. 60% by weight or less of 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane and / or 4,4′-diisocyanatodicyclohexylmethane and / or 1-methyl- A mixture of 2,4 (6) -diisocyanatocyclohexane, a diisocyanate component comprising: b) b1) (i) adipic acid and / or succinic acid; and (ii) at least one of 2 to 6 carbon atoms. At least one having a number average molecular weight of 500 to 10,000 made from alkanediol B2) a mixture of up to 32% by weight, based on the total weight of said polyester diol and of component b), of an alkanediol optionally containing 2 to 6 carbon atoms and optionally containing ether groups. and a diol component comprising at, c) c1) formula _{H 2 n (-CH 2) n} -NH (-CH 2) diamino acid salt represented by _m -SO ₃ Me or c2,) diamino sulfonates c1) And 90% by weight or less of ethylenediamine, based on the total weight of component c), comprising from 2 to 50% by weight, based on the total amount of isocyanate-reactive groups present in components b) and c). Amount of the diamine component and, optionally, d) a hydrophilic polyether alcohol of the formula H—X—O—R in an amount of not more than 10% by weight, based on the total amount of components b), c) and d). E) water, which is not taken into account in the calculation of the equivalent ratio of isocyanate groups to isocyanate-reactive groups, and the equivalent ratio of isocyanate groups to isocyanate-reactive groups is from 1: 1 to 2: 1. Wherein m and n are independently 2 to 6, Me is potassium or sodium, and R is 1 to 12 carbon atoms. And X is a polyalkylene oxide chain having a number average molecular weight in the range of 88 to 4000, wherein the alkylene oxide units are ethylene oxide units to a degree of 40 mol% or more. And for the remainder are propylene oxide units], and B.I. The use of 0 to 30% by weight, based on A, of a crosslinking agent for A. 4. Use according to claim 3, wherein the crosslinking agent B is present in an amount of 0.1 to 25% by weight, based on A. 5. The use according to claim 3, wherein said crosslinking agent B is selected from the group consisting of polyisocyanates, polyfunctional epoxides, carbodiimides and compounds containing N-methylol groups. 6. Use according to claim 3 for coating, dyeing and printing textiles or leathers.