WO1998038378A1

WO1998038378A1 - Carbamate modified low-molecular polymer compound and the use thereof for after-treatment of dyed or printed cellulose textile material

Info

Publication number: WO1998038378A1
Application number: PCT/CH1998/000071
Authority: WO
Inventors: Uwe Daniel HOLZDÖRFER; Martin Haid; Rainer Braun; Werner Sowoidnich; Viktor Toresan
Original assignee: Textilcolor Ag
Priority date: 1997-02-26
Filing date: 1998-02-23
Publication date: 1998-09-03
Also published as: EP0963478A1; CN1253603A; TR199902509T2; AU5979698A

Abstract

The invention relates to hydroxyethyl carbamate and/or a hydroxypropyl carbamate modified low molecular polymer compound obtained by cross-linking a conversion product of a polycationic amine, obtained by condensation of a primary and/or secondary polyamine with dicyandiamide and by reacting this conversion product with ethylene carbonate or propylene carbonate. The invention also relates to the use of said polymer compounds as after-treatment agents to improve fastness properties, specially wet fastness, of cellulose-containing textile materials dyed or printed using substantive dyes or reactive dyes, wherein colorations or prints exhibiting excellent wet fastness can be obtained.

Description

Carbamate modified low molecular weight polymer compound and its use for the aftertreatment of colored or printed cellulose textile material

The present invention relates to a new low-molecular polymer compound modified with hydroxyethyl and / or hydroxypropyl carbamate, its production and use above all to improve the fastness properties of nouns dyeing and printing on cellulose-containing textile materials, and to processes for improving the fastness properties of substantive dyes and reactive dyes on cellulose material and agents containing a low molecular weight polymeric compound modified with hydroxyethyl and or hydroxypropyl carbamate.

Cellulose fibers can be dyed and printed with a variety of dye types. The sulfur dyes, vat dyes, development dyes, oxidation dyes, pigment dyes, direct dyes and reactive dyes are particularly mentioned in this connection.

Because of their simple and relatively inexpensive method of use, the direct dyes (noun dyes) in particular have become established and have received a large area of application in the dyeing of cellulose fibers, especially since representatives with very good lightfastness can be found in this class of dyes.

On the other hand, however, Celiuiosemien dyed and printed with direct dyes very often have insufficient fastness properties; wet, wash and sweat fastness are mentioned in particular. There was therefore no lack of attempts to reduce or eliminate these disadvantageous properties entirely. In this context, reference is made e.g. to PCT WO 81/02423, which proposes to improve the wet fastness of dyeings on cellulose fibers with direct dyes, reaction products of primary or secondary amines with i.a. Dicyandiamide and N-methylol compounds of ureas, melamines, triazinones, urones, carbamates or acid amides are used.

DE-A-32 03 548 proposes a reaction product or a mixture of such a reaction product as a post-treatment agent to solve this problem polybasic amino compound with an N-methylol compound or with formaldehyde, the dye and the polybasic amino compound in aqueous solution giving a precipitate which, after washing, isolation and drying, is stable in dilute alkalis at a minimum pH of 12 to room temperature. Furthermore, DE-A-3137404 refers to an agent for improving the wet and light fastness of dyeings, especially in light shades, on textiles consisting of cellulose fibers or containing them, consisting of a reaction product of a quaternary polyalkylene polyamine reacted with N-methylol compounds of ureas with melamine , Urethanes, triazinones, urones, carbamates or acid amides and a curing catalyst. DE-A-4131926 describes solutions and dispersions which contain a cycloaliphatic compound with a sterically hindered amino group and which are used as aftertreatment agents! can be used to improve light and wash fastness. DE-A-3609984 describes a process for the treatment of fiber materials using a polymeric compound which is obtained by reacting a reaction product of a dihalohydrocarbon and a polyamine with an epihalohydrin. DE-A-3231059 describes a process for improving the wet fastness properties of direct dyeings on cellulose fibers by treating these dyeings with water-soluble aliphatic dialdehydes, preferably glutardialdehyde, in the customary manner. DE-A-3938918 describes a pretreatment process for dyeing textile material containing nitrogen or hydroxyl or thioi groups by pretreating this textile material with a mixture of polymeric compounds and a textile auxiliary.

DE-A-3217835 finally describes a method for improving the fastness properties of a dye on a hydroxyl group-containing textile material by treating this textile material with a post-treatment agent which is a polymer which, as repeating units, has at least two quaternary ammonium groups, which are represented by alkylene or arylene groups Bridge members are interconnected, optionally containing an N-methylol derivative and a catalyst for crosslinking the N-methylol compound.

Further similar proposals to solve this problem are described in DE-A-3221951, DE-B-855001, DE-A-3330120, DE-B-929642, DE-A-3035940, DE-B-3216913 and DE-B- 3505018 presented. However, none of these suggestions could bring complete satisfaction to this problem.

On the one hand, in many cases a deterioration in other fastness properties, e.g. the light fastness, especially light shades, observed and on the other hand the results obtained are sometimes only temporary. In addition, there are wastewater problems and cost issues and, in isolated cases, a strong color shift.

Attempts were then made to use reactive dyes to at least solve the problem of wet fastness, since it is known that the dye molecule forms a chemical bond with the cellulose. But here, too, it has proven to be a disadvantage that the cellulose material dyed with reactive dye has to be washed an above average amount in order to remove the non-chemically bound reactive dye and the dye hydrolyzate, which have poor fastness to washing.

Since there is still a great need for colored celiosity materials with direct dyes, one of the objects of the invention was to look for further ways, i.e. to explore further possibilities which, while eliminating the disadvantages indicated above, bring about an improvement, above all, of the fastness to washing, washing and perspiration of dyeings on cellulose fibers or fibers containing hydroxyl groups, and which also withstand repeated washing operations at temperatures above 60 ° C.

The solution to this problem lies in new, low molecular weight polymeric compounds modified with hydroxyethyl and / or hydroxypropyl carbamate.

It has been found that, surprisingly, polymeric compounds which are modified with hydroxyethyl and / or hydroxypropyl carbamate groups bring about an unforeseeable, excellent improvement in authenticity, especially the fastness to washing and perspiration of textile materials dyed or printed with substantive dyes or reactive dyes.

The invention therefore relates to a low molecular weight polymeric compound modified with hydroxyethyl and / or hydroxypropyl carbamate, obtained by crosslinking a reaction product of a polycationic amine, obtained by condensing one primary and / or secondary polyamines with dicyandiamide, characterized in that this reaction product further with a 1, 3-dioxolan-2-one of formula I.

where R is hydrogen or methyl, is reacted.

Of particular importance are low molecular weight polymeric compounds modified with hydroxyethyl and / or hydroxypropyl carbamate, in which the reaction product further with a 1,3-dioxolan-2-one of the formula

CH.-CH— CH,

³ II ²

° -c II '° o

is implemented and in particular those polymeric compounds which contain 5 to 40%, based on the number of functional amine or amide groups of the polyamine, of recurring structural units of the formula

N-CO-0-CH ₂ -CH (R) OH and

C = N-CO-0-CH ₂ -CH (R) OH /

where R is hydrogen or methyl. A modified low molecular weight polymeric compound containing 5 to 40% repeating structural units of the formula is very particularly preferred

, N-CO-0-CH ₂ -CH (CH ₃ ) OH and

C = N-CO-0-CH ₂ -CH (CH ₃ ) OH

obtained by thermal crosslinking of a reaction product of diethylenetriamine with dicyandiamide and ammonium chloride in diethylene glycol by further reacting this reaction product with 4-methyl-1, 3-dioxolan-2-one.

The primary and / or secondary amine is, on the one hand, primarily saturated, open-chain or cyclic amines, such as aliphatic, cycloaliphatic and, on the other hand, also aromatic polyamines with at least one primary or secondary, optionally also tertiary, amino group. Aliphatic, open-chain or cyclic amines and in particular aliphatic, open-chain amines of the formula II are particularly preferred

(left)

in which means:

Ri independently of one another are hydrogen, unsubstituted dC ₁₀ -alkyl or by OH, d-

Mono- or C alkoxy or CN polysubstituted Cι-Cι ₀ alkyl, n is zero or the number range of 1 to 100,

Z independently of one another if n is the number range from 1 to 100, dC ₄ -

Alkylene or CrC ₄ hydroxyalkylene, and X independently of one another if n is the number range from 1 to 100: O, S or NRi with the condition that the polyamine of the formula II contains at least one —NH or —NH ₂ group.

Those amines of the formula II in which:

Ri hydrogen, n zero or the number range from 1 to 30,

Z ethylene, 1, 3-propylene or ß-hydroxypropylene-1, 3, and

X -NR θ or -NH-.

The following amines are mentioned by way of example: ethylenediamine, propanediamines, such as 1,2- and 1,3-diaminopropane, butanediamines, such as 1,4-diaminobutane, 1,6-diaminohexane, N - (- 2-hydroxyethyl) -ethylenediamine, diethylenetriamine ( = 2,2'-diamino-diethylamine), triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, N - ((3-aminopropyl -) - tetramethylene diamine, N, N'-bis (3-aminopropyl) ethylenediamine, dipropylenetriamine, N, N ' - dimethylethylenediamine, N- (ß-hydroxyethyl) -ethylenediamine, 1-amino-3-methylaminopropane, N, N'-bis (3-aminopropyl -) - tetramethylenediamine, di - (- hexamethylene) -triamine and 1 -amino- 3-dimethylamino propane.

Preferred amines are diethylene triamine, triethylene tetramine, tetraethylene pentamine, 2-aminoethyl-3-aminopropylamine, dipropylenetriamine, N, N-bis (3-aminopropyl) methylamine and higher polyethylene or polypropylene or polyhydroxypropylene polyamines, containing up to 8, preferably up to 6 N atoms.

Particularly preferred amines are diethylene triamine, triethylene tetramine and tetraethylene pentamine.

The low molecular weight polymeric compound modified with hydroxyethyl and / or hydroxypropyl carbamate is water-soluble.

The low molecular weight polymeric compound modified with hydroxyethyl and / or hydroxypropyl carbamate is prepared, for example, by reacting an aliphatic, cycloaliphatic and / or aromatic polyamine, which at least contains a reactive -NH- or -NH ₂ group, with ammonium chloride, dicyandiamide and a 1,3-dioxoian-2-one of the formula I.

wherein R is hydrogen or methyl, optionally in an organic inert solvent at a temperature of 40 ° C to 200 ° C.

Preferred as 1,3-dioxolan-2-one is one of the formula

CH ₃ -CH- -CH ₂

II O

used.

Suitable aliphatic amines are, above all, the amines mentioned above, all of which are known and can be prepared in a known manner.

As cycloaliphatic and aromatic polyamines e.g. called: piperazine, N- (2-aminoethyl) piperazine, 2,2-bis (4-aminocyclohexyl) propane, 1,4-diazabicyclo [2,2,2] octane, 5-amino-1,3. 3-trimethylcyclohexanemethamine (isophoronediamine), 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, o-phenylenediamine, m-phenylenediamine, 2,3-toluenediamine, 3,4- Toluenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-aminobenzylmethylamine, mixtures of isomers of aminobenzyldimethylamine, 4,4'-diamino-diphenylmethane and its isomer mixtures.

These amines are also known and can be prepared in a known manner. Examples of suitable organic inert solvents are: alcohols such as methanol, ethanol, propanols, butanols, octanols, cyclohexanol and methyl cellosolve; Glycols such as ethylene glycol and diethylene glycol (= bis (2-hydroxyethyl) ether); Ethers and glycol ethers such as diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran and mono-, di-, tri- and polyethylene glycol ethers; Ketones - both aliphatic and cycloaliphatic - such as acetone, butanone, ethyl methyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, 2,4-dimethyl-6-heptanone, 2-heptanone, 3-heptanone, cyclopentanone, methylcyclopentanone, cyclohexanone; cyclohexanone Esters such as acetic acid esters, for example ethyl acetate and glycol esters; Nitrogen compounds such as formamide, dimethylformamide, pyridine, hexamethylphosphoric triamide and N-methylpyrrolidone; Sulfur compounds such as carbon disulfide, dimethyl sulfoxide and sulfolane; Nitro compounds such as nitrobenzene; Halogenated hydrocarbons such as dichloromethane, chloroform, 1, 2-dichloroethane, carbon tetrachloride, tri- or tetrachloroethane such as 1, 1, 1 - trichloroethane, ethylene chloride, chlorobenzene and chlorofluorocarbons; Hydrocarbons such as petrol, petroleum ether or other petroleum ether fractions, pentane, hexane, cyclohexane, methylcyclohexane, decalin, terpenes, benzene, toluene and xylenes; also acetonitrile, butyl acetate, and N-methylpyrrolidone.

Polar solvents, especially glycols and glycol ethers and especially diethylene glycol, are particularly preferred.

Mixtures of solvents can also be used.

The only condition is that work is carried out in the absence of additional water.

The overall reaction is carried out in a temperature range from initially 40 ° C. to 100 ° C., preferably 60 ° C. to 100 ° C. and in particular 80 ° C. to 90 ° C. and slowly increasing towards the end of the reaction to a maximum of 200 ° C. as a one-pot process.

The order in which the individual components are added is not critical.

One possibility for the preparation consists, for example, of introducing the organic inert solvent such as diethylene glycol together with ammonium chloride, heating to about 80 ° C. to 90 ° C. and successively the polyamine, for example diethylene triamine, the 1,3-dioxolan-2-one, eg add propylene carbonate and finally dicyandiamide and slowly increase the temperature to about 190 ° C.

Another possibility for the preparation is to submit the organic inert solvent, ammonium chloride and half the amount of dicyandiamide, to heat to about 80 ° C. to 90 ° C. and then in succession the 1, 3-dioxoian-2-one, the remaining half amount Add the dicyandiamide and the polyamine and slowly raise the temperature to about 190 ° C.

The reaction of the diethylenetriamine with ammonium chloride, dicyandiamide and the 1,3-dioxolan-2-one at a temperature of initially around 80 ° C. and after slowly raising the temperature to around 190 ° C. to give the polymeric compound proceeds via various oligomeric intermediates, such as monofunctionalized biguanide hydrochloride and substituted guanidine hydrochloride, the reaction products finally being thermally polymerized.

When reacting dicyandiamide with the amine, the amines can be used in the form of the free base or salt form (e.g. hydrochloride form).

The overall reaction is shown schematically below using the preferred components:

H ₂ N - (CH ₂ ) ₂ - NH - (CH ₂ -) ₂ - NH ₂ diethylene triamine

[H ₂ N- (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -NH ₂ ] .HCI + NH ₃ diethylene triamine hydrochloride

Dicyandiamide

4-methyl-1,3-dioxolan-2-one

Increase 190 ° C to 200 ° C

tion; Polycondensation)

Low molecular weight, cross-linked polymeric compound (n = approx. 1 to 50) with about 5 to about 40%, based on the number of functional imine or amide groups of the polyethyleneimine recurring structural units of the formula

It is of particular interest that the overall reaction proceeds almost to completely foam-free and that no additional crosslinking catalyst is necessary.

The reaction of diethylenetriamine with dicyandiamide is e.g. known from CH Patent Nos. 253 709, 261 049, 261 050, 261 051, 261 052 and 260 856 and German Patent No. 855 001.

The reaction proceeds with the elimination of ammonia. The molar ratio is generally 0.1 to 1 mol of dicyandiamide per molar equivalent of amine used; the molar ratio is preferably 1 mol of dicyandiamide per molar equivalent of amine used.

The reaction according to the invention is a thermal condensation polymerization. After the addition of all components, the condensation is carried out at a temperature which is slowly increased to about 190 ° C. until the reaction product (polymeric compound) obtained has not yet gelled and is still water-soluble or water-dispersible, i.e. the reaction must be stopped before the reaction product becomes water-insoluble. The duration of the reaction is between 30 minutes and about 3 hours, the reaction product has a dynamic viscosity between 50 and 2000 mPas. . The low molecular weight polymeric compounds modified with hydroxyethyl and / or hydroxypropyl carbamate which are present as viscous liquids are stable in storage and temperature, e.g. for about 6 months at 20 ° to about 50 ° C.

The starting materials are all known and can be prepared by processes known per se. The 1, 3-dioxolan-2-one (ethylene carbonate) and the 4-methyl-1, 3-dioxolan-2-one (propylene carbonate) are also known compounds (cyclic organic carbonates) and can be prepared in a known manner, for example from ethylene oxide or propylene oxide and liquid CO ₂ .

The new polymeric compounds can be purified in a known manner, e.g. by cases with acetone, dialysis or ultrafiltration. This cleaning process enables the water-soluble polymers containing structural units of the formulas mentioned above to be used in extremely pure form, e.g. are obtained as concentrated aqueous solutions which are free or at least essentially free of reaction products and of starting materials or other non-polymeric constituents. The ultrafiltration can be carried out repeatedly, for example two to ten times. Alternatively, the ultrafiltration can also be carried out continuously until the desired degree of purity is reached. A suitable measure for the degree of purity is e.g. the NMR spectrum of the dried polymer in DMSO or the CHN elemental analysis.

The low molecular weight polymeric compounds modified with hydroxyethyl and / or hydroxypropyl carbamate according to the invention are used, above all as aftertreatment agents to improve the fastness properties of cellulosic or hydroxyl group-containing textile materials dyed or printed with substantive dyes or reactive dyes, and in particular as aftertreatment agents of dyes printed and dyed with direct dyes Celiuiosematerialen to improve the wet fastness of the dyes.

Of particular interest is the use of a polymeric compound containing 5 to 40% repeating structural units of the formula

N-CO-0-CH ₂ -CH (CH ₃ ) OH and C = N-CO-0-CH ₂ -CH (CH ₃ ) OH

obtained by thermal crosslinking of a reaction product of diethylenetriamine with dicyandiamide and ammonium chloride in diethylene glycol, by further reacting this reaction product with 4-methyl-1, 3-dioxolan-2-one as a post-treatment agent for improving the fastness to washing and sweating of dyes dyed with direct dyes and / or printed Celiuiosematerialen.

The invention thus also relates to a process for the treatment of fiber materials or cellulose fiber materials containing hydroxyl groups with the polymeric compound according to the invention, which can be obtained by crosslinking a reaction product of a polycationic amine, obtained by condensation of a primary and / or secondary polyamine with dicyandiamide, characterized in that Reaction product further with a 1,3-dioxolan-2-one of the formula I.

R-CH - CH,

^< V °

where R is hydrogen or methyl, is reacted.

The textile material used is, above all, natural or regenerated cellulose, in particular cotton, dyed or printed with noun dyes or reactive dyes, in particular cotton, which, when mixed with other natural and / or synthetic textile material, e.g. natural or synthetic polyamide such as wool, silk, nylon, or e.g. 2 1/2 acetate, triacetate, polyester, polyacrylonitrile or viscose, can be post-treated according to the invention.

Suitable dyes are the dyes known for the cellulose fiber materials mentioned, in particular reactive or direct dyes, for example di- or triphenylmethane dyes, phthalocyanine, acid, oxazine, formazane, indigo, thiazole, 1: 1 or 1: 2 metal complex dyes and in particular azo dyes, such as monoazo, diazo, triazo, tetrazo and polyazo dyes in question.

The customary commercial dyes, such as those used e.g. are known from the Color Index, e.g. C.l. Direct Dyes and C.I. Reactive dyes.

The reactive dyes carry, in addition to 1 to 4 sulfonic acid groups, in particular a mono-, di- or trihalopyrimidinyl or mono- or dihalotriazinyl group as the reactive group.

The dyeing or printing of hydroxyl-containing textile material from e.g. Vegetable material, for example of cellulose, such as cotton, with the direct dyes or reactive dyes can be carried out by conventional methods which are known for direct or reactive dyes. The cotton can be padded or printed using the pull-out method, the printing method, from a short or long fleet.

Dyes on blended fabrics of cotton with synthetic fibers can also be aftertreated if fiber mixtures have been dyed with direct or reactive dyes.

The aftertreatment of the dyeings and prints according to the invention takes place after the dye has been fixed, the dyed or printed textile being dried or post-treated in a moist state, and it must be ensured that there is sufficient penetration of the goods.

The aftertreatment of the dyed or printed textile material according to the invention is carried out according to methods of the padding process known per se, such as the heat-setting, pad-dry, pad-roll or pad-steam process with or without intermediate drying or else after the block-cold dwell carried out. It can also be aftertreated in the exhaust process from a short or long liquor (e.g. 1: 5 to 1:50). The dyed or printed textile is mainly post-treated at temperatures of 20-100 ° C, advantageously at 20-60 ° C and a pH of 5-11, preferably 6-8 for 5-60 minutes. A preferred aftertreatment is carried out in an acetic acid bath for about 30 minutes at 40 ° C. in a liquor ratio of 1:10, the aftertreated fabric subsequently being rinsed with cold water and then dried.

The amounts in which the low molecular weight polymeric compounds modified with hydroxyethyl and / or hydroxypropyl carbamate according to the invention are used primarily depend on the color depth of the fixed dyeings. They are in the range of about 0.5 to 3.0%, preferably 1.5 to 2.0%, based on the weight of the goods.

With the help of the aftertreatment, a fixation of the direct or reactive dye is achieved, which brings about an excellent improvement, especially of the fastness to washing, washing and sweating, by the dyed textile materials even in the case of alkaline, repeated washes at temperatures between about 40 ° C and 80 ° C, especially above 60 ° C.

It is possible to dye pure cellulose of all common types as well as blended fabrics of cellulose fibers with other native or synthetic fibers, true to color, with direct dyes or reactive dyes.

The post-treated dyeings are further distinguished by good overall fastness properties, for example by the color, the shine, the feel of the goods, the wash-and-wear behavior, the alkali fastness, the acid fastness, the chlorine fastness, the fastness to ironing, the fastness to exhaust gases and the fastness to rubbing are retained unchanged or are improved.

Simultaneous use of an aid in the aftertreatment is also possible. Suitable auxiliaries are those which are used in dyeing, padding or printing, such as known plasticizers, grip agents, wetting agents and water repellents. For example, the simultaneous use of one Anti-crease product in the aftertreatment to further improve the fastness properties.

The new process is therefore basically suitable for improving the authenticity of all commercially available direct and reactive dyeings on cellulose fibers; the cationic part of the low molecular weight polymeric compound modified with hydroxyethyl and / or hydroxypropyl carbamate forms with the anionic part of the dye (sulfonic acid) a poorly soluble, enlarged molecule, which, due to the new carbamate structure, above all significantly improves the wet fastness properties.

It is emphasized that all direct and reactive dyeings are fundamentally improved in their fastness properties, especially fastness to washing and sweating.

Another object of the invention relates to a method for improving the fastness properties of a direct dye or a reactive dye on a hydroxyl-containing textile material, characterized in that the dyed or printed hydroxyl-containing textile material is aftertreated with a low molecular weight polymeric compound modified with hydroxyethyl and / or hydroxypropyl carbamate, the polymeric compound is a reaction product of a polycationic amine, obtained by condensation of a primary and / or secondary amine with dicyandiamide and a 1,3-dioxolan-2-one of the formula I.

R-CH— CH,

° -c II '° E (I)

where R is hydrogen or methyl.

As a particularly preferred 1,3-dioxolan-2-one compound, propylene carbonate comes into consideration owing to its very good fastness improvement. This method is used in particular to improve the fastness to washing and sweating on a cellulose material dyed and / or printed with direct dyes or reactive dyes by this cellulose material with a polymeric compound containing 5 to 40% repeating structural units of the formula

N-CO-0-CH ₂ -CH (CH ₃ ) OH and

C = N-CO-0-CH ₂ -CH (CH ₃ ) OH

obtained by thermal crosslinking of a reaction product of diethylenetriamine with dicyandiamide and ammonium chloride in diethylene glycol, by further reacting this reaction product with 4-methyl-1, 3-dioxolan-2-one.

Finally, the invention also relates to an agent for the treatment of fiber materials containing hydroxyl groups, in particular cellulose, characterized in that it contains a low molecular weight polymeric compound modified with hydroxyethyl and / or hydroxypropyl carbamate, which is obtained by crosslinking a reaction product of a polycationic amine obtained by condensation a primary and / or secondary polyamine with dicyandiamide, by this reaction product further with a 1, 3-dioxolan-2-one of the formula I

R-CH— CH,

° ¹ y '(I)

II

O where R is hydrogen or methyl, is reacted.

The same applies analogously to the polymeric compound on average as was said at the beginning about the polymeric compound.

The following examples serve to explain the invention. Unless expressly stated otherwise, it contains quantities, weights and temperatures are given in degrees Celsius. The examples are not intended to limit the invention in any way, for example to the scope of the examples.

Example 1: 100.0 g of bis (2-hydroxyethyl) ether and 107.0 g [2.00 mol] of ammonium chloride are placed in a reaction vessel at 20 ° C. and heated to 90 ° C. 206.3 g [2.00 mol] of 2,2'-diamino-diethylamine are added dropwise with stirring in the course of 30 minutes and, after the ammonia elimination has ended, the mixture is stirred at 90 ° C. for 15 minutes.

Then 10.2 g [0.10 mol] of 4-methyl-1, 3-dioxolan-2-one are added dropwise and 168.2 g [2.00 mol] of dicyandiamide are added. The mixture is heated within 120 minutes with a linear temperature gradient from 90 ° C to 180 ° C.

After the ammonia elimination has slowed, stirring is continued at 180 ° C. for 180 minutes. The polymer melt is cooled to 130 ° C., diluted with 285.0 g of distilled water and, after cooling to 25 ° C., is adjusted to a pH of 5.30 by adding 21.6 g of hydrochloric acid 32%. The total amount of ammonia released is 106.0 g [6.22 mol]. The result is 792.3 g of a slightly viscous, clear polymer solution.

The dynamic viscosity is 75 mPas.

5 g of the polymer solution thus obtained are introduced into 100 ml of 2-propanol using a laboratory disperser. The polymer precipitates out, is filtered off with suction, rinsed with 50 ml of 2-propanol and dried at 110 ° C. for 24 hours.

The elemental analysis corrected:

41.6% carbon, 6.9% hydrogen, 33.1% nitrogen, 18.4% chlorine as chloride.

The 400 MHz ¹ H NMR spectrum in hexadeutero DMSO with the addition of D ₂ O to suppress free amino groups shows the following signal chain (δ [ppm]):

4.08 / 3.85 / 3.83 / 3.82 / 3.80 / 3.78 / 3.77 / 3.69 / 3.53 / 3.52 / 3.50 / 3.46 / 3, 44 / 3.43 / 3.27 / 2.11 / 2.01 / 1, 98/1, 07/1, 05/1, 02 /. Example 2: 100.0 g of bis (2-hydroxyethyl) ether and 107.0 g [2.00 mol] of ammonium chloride are placed in a reaction vessel at 20 ° C. and heated to 90 ° C. 206.3 g [2.00 mol] of 2,2'-diamino-diethylamine are added dropwise with stirring in the course of 30 minutes and, after the ammonia elimination has ended, the mixture is stirred at 90 ° C. for 15 minutes.

Then 40.8 g [0.40 mol] 4-methyl-1, 3-dioxolan-2-one are added dropwise and 168.2 g [2.00 mol] dicyandiamide are added. The mixture is heated within 140 minutes with a linear temperature gradient from 90 ° C to 180 ° C.

After the ammonia elimination has slowed, the mixture is stirred at 180 ° C. for 60 minutes. The polymer melt is cooled to 130 ° C, diluted with 280.0 g of distilled water and after cooling to 25 ^C C by the addition of 18.8 g of 32% hydrochloric acid to a pH value of 5.31 adjusted. The total amount of ammonia released is 102.6 g [6.02 mol]. The result is 818.5 g of a slightly viscous, clear polymer solution which slightly opalesces after 24 hours.

The dynamic viscosity is 50 mPas.

5 g of the polymer solution thus obtained are precipitated and dried analogously to Example 1.

Corrected by elementary analysis:

41.8% carbon, 7.0% hydrogen, 33.6% nitrogen, 17.6% chlorine as chloride.

The 400 MHz n H-NMR spectrum in hexadeutero DMSO with the addition of D ₂ O to suppress free amino groups shows the following signal chain (δ [ppm]):

4.03 / 3.88 / 3.83 / 3.82 / 3.80 / 3.79 / 3.77 / 3.68 / 3.53 / 3.52 / 3.51 / 3.46 / 3, 45 / 3.43 / 3.29 / 3.27 / 3.26 / 1, 97/1, 06/1, 03/1, 02.

EXAMPLE 3 100.0 g of bis (2-hydroxyethyl) ether, 64.2 g [1.20 mol] ammonium chloride and 50.5 g [0.60 mol] dicyandiamide are placed in a reaction vessel at 20.degree. on Heated 180 ° C and stirred at 180 ° C for 2 hours. The mixture containing guanidine hydrochloride is cooled to 130 ° C. 70.5 g [0.80 mol] of molten 1,3-dioxolan-2-one are added dropwise and 168.2 g [2.00 mol] dicyandiamide are introduced. 206.3 g [2.00 mol] of 2,2'-diamino-diethylamine are added dropwise with stirring in the course of 5 minutes. The mixture is heated within 120 minutes with a linear temperature gradient from 90 ° C to 170 ° C. After 120 minutes at 170 ° C, the ammonia elimination is complete.

The polymer melt is cooled to 115 ^C C, diluted with 330.0 g of distilled water and adjusted after cooling to 25 ° C by the addition of 55.2 g of 32% hydrochloric acid to a pH value of 5.30.

The total amount of ammonia removed is 102.8 g [6.04 mol]. The result is 942.2 g of a slightly viscous, clear polymer solution.

The dynamic viscosity is 420 mPas.

Corrected by elementary analysis:

42.9% carbon, 6.7% hydrogen, 37.4% nitrogen, 13.0% chlorine as chloride.

3.79 / 3.78 / 3.76 / 3.75 / 3.73 / 3.49 / 3.48 / 3.47 / 3.46 / 3.44 / 3.42 / 3.41 / 3, 39 / 3.37 / 3.25 / 3.21 / 3.06 / 3.04 / 1, 03/1, 01 /.

Example 4: 50 g of boiled and bleached cotton fabric are separated in a liquor ratio 1:10 with 0.3 g / l of a conventional wetting agent based on an isotridecyl alcohol-8-ethoxylate and 3% dye Cl Direct Red 79 (in each of 3 laboratory dewatering cup dyeing machines). Cl 29065) of the formula

wetted at 40 ° C for 20 minutes. The dye bath is heated for 45 minutes with 1 ⁰ C / minute to 95 ° C. After the final dyeing temperature has been reached, 20 g / l of sodium chloride are added and the mixture is treated at 95 ° C. for a further 60 minutes. The dyeings are then freed of excess dye by rinsing with water at 40 ° C. and rinsing twice with cold water.

The 3 dyeings are then aftertreated for 30 minutes at 40 ° C. in an acetic acid bath with a pH of 5.5 and 3% (based on the substrate) of the respective polymer of Examples 1, 2 and 3 in a liquor ratio 1:10.

Finally, it is rinsed with cold water and the dyed cotton fabric is dried.

In all 3 cases, dyeings result as can be seen from Table 1, the washfastness of which is significantly improved in comparison to an untreated (untreated) fabric.

Table 1 :

Example 5

50 g of boiled and bleached cotton fabric are separately separated in a liquor ratio of 1:10 in each of 4 laboratory swab cup dyeing machines, each with 0.3 g / l of a conventional wetting agent based on an isotridecyl alcohol 8-ethoxylate and a) 1% dye C.I. Direct Blue 71 (C.L. 34140) of the formula

b) 1% dye C.I. Direct Red 80 (C.L. 35780) of the formula

c) 1% dye C.I. Direct Yellow 106 (C.L. 40300) of the formula

respectively.

d) 4% dye C.I. Direct Black 22 (C.L. 35435) of the formula

wetted at 40 ° C for 20 minutes. The dyeing temperature is 1 ° C / min for 45 minutes. heated to 95 ° C. After the final dyeing temperature has been reached, 10 g / l of sodium chloride are added and the mixture is treated at 95 ° C. for a further 60 minutes. The dyeings are then freed from excess, adhering dye by rinsing with water at 40 ° C. and rinsing twice with cold water.

Half of the dyed cotton fabric is then post-treated for 30 minutes at 40 ° C. in an acetic acid bath with a pH of 5.5 and 2% of the polymer of Example 1 in a liquor ratio of 1:10.

Finally, it is usually rinsed with cold water and the dyed cotton fabric is dried. (The untreated stains served as a reference for determining the fastness to washing and perspiration).

In all 4 cases, compared to the untreated (untreated) dyeings, dyeings which, as can be seen from Tables 2, 3, 4 and 5, have improved fastness to washing and sweating; the nuance remains unchanged in all cases.

Table 2

Table 3

Table 4

Table 5

Claims

claims

1. Hydroxyethyl and / or hydroxypropyl carbamate modified low molecular weight polymeric compound, obtained by crosslinking a reaction product of a polycationic amine, obtained by condensation of a primary and / or secondary polyamine with dicyandiamide, characterized in that this reaction product is further combined with a 1,3-dioxoian 2-one of formula I.

where R is hydrogen or methyl, is reacted.

2. Hydroxyethyl and / or hydroxypropyl carbamate modified low molecular weight polymeric compound according to claim 1, characterized in that the reaction product further with a 1,3-dioxolan-2-one of the formula

CH ₃ -CH— CH, O, 0

II 0 is implemented.

3. Hydroxyethyl and / or hydroxypropyl carbamate modified low molecular weight polymeric compound according to claims 1 and 2, characterized in that these 5 to 40%, based on the number of functional imine or amide groups of the polyamine, repeating structural units of the formula

N-CO-0-CH ₂ -CH (R) OH and C = N-CO-0-CH, -CH (R) OH /

where R is hydrogen or methyl.

4. Hydroxyethyl and / or hydroxypropyl carbamate modified low molecular weight polymeric compound according to claims 1 to 3, characterized in that the primary and / or secondary polyamine is an aliphatic, cycloaliphatic or aromatic polyamine.

5. Hydroxyethyl and or hydroxypropyl carbamate modified low molecular weight polymeric compound according to claim 4, characterized in that the primary and / or secondary polyamine is an aliphatic, open-chain or cyclic polyamine.

6. Hydroxyethyl and / or hydroxypropyl carbamate modified low molecular weight polymeric compound according to claim 5, characterized in that the aliphatic polyamine is an aliphatic, open-chain polyamine of the formula II

in which means:

Ri independently of one another hydrogen, unsubstituted d-Cio-alkyl or C ₁ -C 8 -alkyl which is mono- or polysubstituted by OH, dC -alkoxy or CN, or zero, or the number range from 1 to 100

Z independently of one another if n is the number range from 1 to 100, d-d-

Alkylene or dC ₄ -hydroxyalkylene, and

X is independent of one another if n is the number range from 1 to 100: O, S or

NR, with the condition that the polyamine of formula II at least one -NH- or -NH ₂

Group contains.

7. Hydroxyethyl and / or hydroxypropyl carbamate modified low molecular weight polymeric compound according to claim 6, characterized in that the aliphatic, open-chain polyamine of the formula II is one in which:

Ri hydrogen, n zero or the number range from 1 to 30,

Z ethylene, 1, 3-propylene or ß-hydroxypropylene-1, 3, and

8. Hydroxyethyl and / or hydroxypropyl carbamate modified low molecular weight polymeric compound according to claim 7, characterized in that the aliphatic, open-chain polyamine of the formula II is diethylene triamine, triethylene tetramine and tetraethylene pentamine.

9. Hydroxypropyl carbamate modified low molecular weight polymeric compound containing 5 to 40% repeating structural units of the formula

, N-CO-0-CH ₂ -CH (CH ₃ ) OH and

C = N-CO-0-CH ₂ -CH (CH ₃ ) OH

10. A process for the preparation of a low molecular weight polymeric compound modified with hydroxyethyl and / or hydroxypropyl carbamate by reacting an aliphatic, cycloaliphatic and / or aromatic polyamine which contains at least one reactive -NH- or -NH ₂ group with ammonium chloride, dicyandiamide and a 1st , 3-dioxolan-2-one of the formula I R-CH— CH ₂ (|)

II o wherein R is hydrogen or methyl, optionally in an organic inert solvent at a temperature of 40 ° C to 200 ° C.

11. The method according to claim 10, characterized in that as 1, 3-dioxolan-2-one such one of the formula

is used.

12. The method according to claims 10 and 1 1, characterized in that one works in an organic inert solvent and as such a glycol or glycol ether is used.

13. The method according to claim 12, characterized in that a glycol is used as the organic inert solvent.

14. The method according to claim 13, characterized in that the glycol is diethylene glycol.

15. The method according to claims 10 to 14, characterized in that the temperature is slowly increased to 190 ° C to 200 ° C after the addition of all components.

16. Use of the low molecular weight polymeric compound modified with hydroxyethyl and / or hydroxypropyl carbamate according to claims 1 to 9 or of the low molecular weight polymeric compound obtained with hydroxyethyl and / or hydroxypropyl carbamate modified as aftertreatment agent to improve the fastness properties of Nouns or reactive dyes dyed or printed cellulose-containing or hydroxyl-containing textile materials.

17. Use according to claim 16, as aftertreatment agent of colored and / or printed Celiuiosematerialien with direct dyes or with reactive dyes.

18. Use of the low-molecular-weight polymer compound modified with hydroxypropyl carbamate according to claim 9 as an aftertreatment agent to improve the fastness to washing and sweating of dyed and or printed with direct dyes Celiuiosematerialien.

19. A method for improving the fastness properties of a dye on a hydroxyl group-containing textile material, characterized in that the colored or printed hydroxyl group-containing textile material is aftertreated with a low-molecular polymer polymer compound modified with hydroxyethyl and or hydroxypropyl carbamate, the polymeric compound being a reaction product of a polycationic amine, obtained by condensation of a primary and / or secondary amine with dicyandiamide and a 1, 3-dioxolan-2-one of formula I.

R-CH - CH,

II ²

° ^ c II '° o where R is hydrogen or methyl.

20. The method according to claim 19 for improving the fastness to washing and sweating on a cellulose material dyed and / or printed with direct dyes or reactive dyes, characterized in that this cellulose material is aftertreated with a polymeric compound according to claim 9.

21. The method according to claim 19, characterized in that the 1,3-dioxolan-2-one of the formula I is one of the formula

is.

22. The after-treated according to claims 19 to 21 hydroxyl-containing textile material.

23. Agents for the aftertreatment of fiber materials containing hydroxyl groups, which are dyed or printed with direct or reactive dyes, characterized in that it contains a low-molecular polymer compound modified with hydroxyethyl and / or hydroxypropyl carbamate as described in claims 1 to 9.