DE19744614A1 - Aqueous impregnating liquid for easy-care textile finishing - Google Patents

Abstract

An aqueous impregnating liquid for the easy- care finishing of textiles contains water-dispersible polyurethane and polyalkylene oxide in addition to crosslinkers and other conventional additives. Aqueous easy-care finishing liquid for textiles contains (A) 1-30 wt% water-dispersible polyurethane(s), (B) polyalkylene oxide(s), (C) crosslinker(s), (D) 0.1-15 wt% catalyst(s), (E) 0-15 wt% other textile finishing additives and (F) 0-15 wt% other auxiliary substances (based on solid content). Independent claims are also included for (a) a process for the easy-care finishing of textiles by impregnating the fabric with this liquid and then drying and condensing; (b) easy-care textile fabric treated with this liquid.

Description

The invention relates to an aqueous impregnating liquor for easy maintenance Armor of textile materials, their use, a method of manufacture easy-care textile fabrics and easy-care textile fabrics.

Textile fabric based on cellulose such as cotton or linen nei gene due to the high swellability of cellulose and easy to do the displacement of the fiber structural elements under bending stress strong for shrinking and wrinkling. With the easy care equipment from Cellulose fabrics are made with compounds (the so-called cross-linking ern) treated by the formation of stable, covalently bound bridges cause a cross-linking between the cellulose molecules and thus the Reduce mobility of the fiber structural elements. Get through it Cellulose fabric, the properties of synthetic fibers that are valued No shrinkage or wrinkles.

Usually, the cellulose fabric in swollen or unswollen state in an impregnating liquor which Contains crosslinking agent and a catalyst, impregnated, optionally on a certain residual moisture dried and crosslinked at elevated temperature, where in the case of crosslinking under the action of the acid catalyst OH groups of cellulose takes place. The usual crosslinkers are the N-hydroxy  methyl or N-methoxymethyl derivatives of 5- or 6-membered cyclic Ureas such as 1,3-dimethylol-4,5-dihydroxyethylene urea (DMDHEU) or its methanol-modified derivatives. Find as catalysts acidic metal salts, in particular metal salts which act as Lewis acids, such as Magnesium or aluminum chloride, optionally in the presence of organic Acids such as acetic or citric acid, use.

For the quality of a textile, however, in addition to the easy-care properties The absence of shrinkage and wrinkles also have a high mechanical strength fabric and a soft feel are crucial. The easy-care off Armor of cellulose fabrics is problematic in that the Improvement of the easy-care properties with a reduction in Strength against tensile and bursting forces as well as against abrasion come here. This makes the treated more susceptible to wear Textiles due to later use. The handle is also equipped constant goods are rougher and stiffer than the non-equipped goods.

In F. Reinert, Melliand Textilberichte 1992, page 353 are impregnation liquors with methanol-modified DMDHEU as a low-formaldehyde crosslinker and a mixture of magnesium chloride hexahydrate and acetic acid as catalyze sator revealed. A disadvantage is the strong loss of tensile strength of the treated cotton fabric compared to untreated fabrics.

The object of the invention is to provide an impregnating liquor for easy-care Armor of cellulose fabrics with improved easy-care properties to provide, with which with the improvement of the easy-care-own associated losses in strength are kept within acceptable limits become.  

The object is achieved by an aqueous impregnating liquor containing, based on the solids content

• a) 1 to 30 wt .-% of at least one water-dispersible polyurethane as component A,
• b) 1 to 15% by weight of at least one polyalkylene oxide as component B,
• c) 1 to 30% by weight of at least one crosslinking agent as component C,
• d) 0.1 to 15% by weight of at least one catalyst as component D,
• e) 0 to 15% by weight of other auxiliaries customary in textile finishing than Component E,
• f) 0 to 15% by weight of further auxiliaries as component F.

As component A, the aqueous impregnation liquors according to the invention contain 1 to 30% by weight of a water-dispersible polyurethane. Suitable water-dispersible polyurethanes are made up of

• a1) diisocyanates with 4 to 30 C atoms as monomers A1,
• a2) Diols, of which
  • a21) 10 to 100 mol%, based on the total amount of the diols, have a molecular weight of 500 to 5000 (monomers A21), and
  • a22) 0 to 90 mol%, based on the total amount of the diols, have a molecular weight of 60 to 500 (monomers A22),
  as monomers A2,
• a3) optionally monomers different from monomers A1 and A2 with at least one isocyanate group or at least one opposite Isocyanate groups reactive group, which also has at least one carry a hydrophilic group or a potentially hydrophilic group, whereby the water dispersibility of the polyurethanes is brought about as Monomers A3,  
• a4) optionally other than the monomers A1 to A3 polyvalent compounds with reactive groups, which are alcoholic hydroxyl groups, primary or secondary amino groups or isocyanate groups, as monomers A4 and
• a5) optionally monovalent from monomers A1 to A4 connections with a reactive group that is a alcoholic hydroxyl group, a primary or secondary amino group or an isocyanate group, as monomers A5.

The polyurethanes (component A) are usually used in the form of their aqueous dispersions. The dispersions generally have a solids content of 10 to 65, preferably 20 to 60% by weight and a viscosity of 10 to 500 mPa.s (measured at a temperature of 20 ° C. and a shear rate of 250 s ^-1 ).

The monomers A1 that are usually used in polyurethane chemistry put into consideration diisocyanates.

Particular mention should be made of diisocyanates X (NCO) ₂ , where X represents an aliphatic hydrocarbon radical having 4 to 12 carbon atoms, a cycloaliphatic or aromatic hydrocarbon radical having 6 to 15 carbon atoms or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms. Examples of such diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethyl cyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane , Trimethylhexanediocyanate, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenylmethane, 2,4'-diisocyanato-diphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis (4-isocyanatocyclohexyl) methane and mixtures consisting of these compounds.

As mixtures of these isocyanates, the mixtures of the particular gene structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane of importance, in particular the mixture of 80 mol% 2.4 diisocya natotoluene and 20 mol% 2,6-diisocyanatotoluene suitable. Furthermore, the Mixtures of aromatic isocyanates such as 2,4 diisocyanatotoluene and / or 2,6-diisocyanatotoluene with aliphatic or cycloaliphatic isocya naten such as hexamethylene diisocyanate or IPDI particularly advantageous, wherein the preferred mixing ratio of the aliphatic to aromatic Isocya nate 4: 1 to 1: 4.

With regard to good film formation and elasticity, A2 appears as diols The higher molecular weight diols A21, which have a molecular weight of about 500 to 5000, preferably from about 100 to 3000.

The diols A21 are in particular polyester polyols which, for. B. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp 62 to 65 are known. Polyester polyols are preferably used, which are obtained by reacting dihydric alcohols with dihydric carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or their mixtures can be used to prepare the polyester polyols. The polycarboxylic acids can be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and optionally, e.g. B. by halogen atoms, substituted and / or unsaturated. Examples include: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylene tetra-hydrophthalic anhydride, glutaric acid, malic acid, fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid anhydride, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid anhydride, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, maleic acid fatty acid, in. Dicarboxylic acids of the general formula HOOC (-CH ₂ ) _y -COOH are preferred, where y is a number from 1 to 20, preferably an even number from 2 to 20, for. B. succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid.

As polyhydric alcohols such. B. ethylene glycol, propane-1,2-diol, propane-1,3-iol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1,5- diol, neopentyl glycol, bis (hydroxymethyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methyl-propane-1,3-diol, methyl pentanediols, also di ethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, di propylene glycol , Polypropylene glycol, dibutylene glycol and polybutylene glycols. Alcohols of the general formula HO- (CH ₂ ) _x -OH are preferred, where x is a number from 2 to 20. Examples include ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dode can-1,12-diol. Neopentyl glycol is also preferred.

Also come polycarbonate diols, such as z. B. by implementing Phosgene with an excess of those as structural components for the poly low molecular weight alcohols called ester polyols can be obtained, into consideration.

Lactone-based polyester diols are also suitable, these being homopolymers or copolymers of lactones, preferably addition products of lactones with terminal hydroxyl groups onto suitable difunctional starter molecules. Preferred lactones are those which are derived from compounds of the general formula HO- (CH ₂ ) _z -COOH, where z is a number from 1 to 20. The Alky lenrest can also have branches. Examples are ε-caprolactone, β-propiolactone, gamma-butyrolactone and / or methyl-ε-caprolactone and mixtures thereof.

In addition, monomers A21 are polyether diols. They are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for. B. in the presence of BF ₃ or by the addition of these compounds where appropriate in a mixture or in succession, to starting components with reactive hydrogen atoms, such as water, alcohols or amines, for. B. water, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 1,2-bis (4-hydroxydiphenyl) propane or aniline available. Polytetrahydrofuran with a molecular weight of 240 to 5000, and especially 500 to 4500, is particularly preferred.

The polyols can also be used as mixtures in a ratio of 0.1: 1 to 9: 1 be used.

The hardness and the modulus of elasticity of the polyurethanes can be increased, if as diols A2, in addition to diols A21, low molecular weight diols A22 with a molecular weight of about 62 to 500, preferably from 62 to 200, can be used.

Above all, the structural components of those for the Production of polyester polyols called short-chain alkanediols sets, the unbranched diols having 2 to 12 carbon atoms and one even number of carbon atoms are preferred. Are also preferred Neopentyl glycol and pentane-1,5-diol.

The proportion of diols is preferably A21, based on the total amount of diols A2 10 to 100 mol% and the proportion of monomers A22, based on the total amount of diols A2 0 to 90 mol%. Especially  the ratio of diols A21 to monomers A22 is preferred 0.2: 1 to 5: 1, particularly preferably 0.5: 1 to 2: 1.

In order to improve the water dispersibility of the polyurethanes, the Polyurethanes in addition to the monomers A1, A2 and A4 from the com components A1, A2 and A4 different monomers A3, at least an isocyanate group or at least one against isocyanate groups reactive group and moreover at least one hydrophilic group or a group that can be converted into a hydrophilic group (potentially hydrophilic group), wear, built. The following text uses the term "hydrophilic groups or potentially hydrophilic groups" with "(potentially) hydrophilic groups ". The (potentially) hydrophilic groups react with isocyanates much more slowly than the functional groups of the monomers that are used to build the main polymer chain.

The proportion of components with (potentially) hydrophilic groups in the Total amount of components A1, A2, A3 and A4 is generally dimensioned so that the molar amount of the (potentially) hydrophilic groups, based on the amount by weight of all monomers A1 to A4, 30 to 1000, is preferably 50 to 500 and particularly preferably 80 to 400 mmol / kg.

The (potentially) hydrophilic groups can be nonionic or are preferably (potentially) ionic hydrophilic groups.

Polyethylene in particular comes as nonionic hydrophilic groups glycol ether from preferably 5 to 100, preferably 10 to 80 ethylene oxide re recovery units, into consideration. The content of polyethylene oxide units is generally 0 to 15, preferably 0 to 10 wt .-%, based on the amount by weight of all monomers A1 to A4.  

Preferred monomers with nonionic hydrophilic groups are Reaction products from a polyethylene glycol and a diisocyanate, the carry a terminally etherified polyethylene glycol residue. Such Diisocya Nates and methods for their production are in US 3,905,929 and US 3,920,598.

Ionic hydrophilic groups are mainly anionic groups like that Sulfonate, the carboxylate and the phosphate group in the form of their alkali tall or ammonium salts and cationic groups such as ammonium group pen, especially protonated tertiary amino groups or quaternary ammoni regroup.

Potentially ionic hydrophilic groups are primarily those that stand out simple neutralization, hydrolysis or quaternization reactions in the let the above-mentioned ionic hydrophilic groups be transferred, e.g. B. Carboxylic acid groups, carboxylic acid anhydride groups or tertiary amino groups pen.

(Potentially) ionic monomers A3 are e.g. B. in Ullmann's Encyclopedia of technical chemistry, 4th edition, volume 19, pp. 311-313 and for example in DE-A 14 95 745 described in detail.

The (potentially) cationic monomers A3 include, above all, monomers tertiary amino groups of particular practical importance, for example: Tris (hydroxyalkyl) amines, N, N'-bis (hydroxyalkyl) alkylamines, N-hydroxyal kyl-dialkylamines, tris (aminoalkyl) amines, N, N'-bis (aminoalkyl) alkylamines, N-aminoalkyl dialkylamines, the alkyl radicals and alkanediyl units these tertiary amines independently of one another from 2 to 6 carbon atoms exist.  

These tertiary amines are either with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids or by reaction with suitable quaternizing agents such as C ₁ - to C ₆ alkyl halides or benzyl halides, for. B. the bromides or chlorides in the ammonium salts.

Usually come as monomers with (potentially) anionic groups aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids and sulfonic acids are considered which have at least one alcoholic hydroxyl wear group or at least one primary or secondary amino group. Bis (hydroxyalkyl) carboxylic acids are preferred, especially those with 4 to 10 Carbon atoms as also described in US-A 3,412,054. Tertiary bis (hydroxyalkyl) carboxylic acids are particularly preferred, especially 2,2-dimethylol propionic acid.

Corresponding dihydroxysulfonic acids and dihydroxy are also suitable phosphonic acids such as 2,3-dihydroxypropanephosphonic acid.

Otherwise, dihydroxyl compounds with a molecular weight are suitable over 500 to 10,000 with at least 2 carboxylate groups derived from the DE-A 39 11 827 are known.

Suitable monomers A3 with amino groups reactive toward isocyanates are amino carboxylic acids such as lysine, β-alanine, the adducts of aliphatic diprimary diamines with α, β-unsaturated carboxylic acids and sulfonic acids mentioned in DE-A 20 34 479. Such connections obey, for example, the general formula I.

H ₂ NR-NH-R'-X (I)

in which R and R 'independently of one another are a C ₁ to C ₆ alkanediyl unit, preferably ethylene, and X is COOH or SO ₃ H. Particularly preferred compounds of the formula I are N- (2-aminoethyl) -2-aminoethcarboxylic acid and the N- (2-aminoethyl) -2-aminoethanesulfonic acid or the corresponding alkali metal salts, Na being particularly preferred as the counterion.

The adducts of the aliphati mentioned above are also particularly preferred diprimeric diamines on 2-acrylamido-2-methylpropanesulfonic acid, such as they z. B. are described in DE-A 19 54 090.

Also monofunctional carbon or sulfonic acids such as isocyanate e.g. B. glycolic acid or taurine are suitable.

If monomers with potentially ionic groups are used, converting them to the ionic form before, during, but preferably after the isocyanate polyaddition. The are particularly preferably Carboxylate groups in the form of their salts with an alkali ion or a Ammonium ion as counter ion.

Monomers A4, which are different from monomers A1 to A3, generally serve for crosslinking or chain extension. There are generally more than dihydric non-aromatic alcohols, amines with 2 or more primary and / or secondary amino groups and compounds gene in addition to one or more alcoholic hydroxyl groups or carry several primary and / or secondary amino groups.

Polyamines with 2 or more primary and / or secondary amino groups are mainly used when the chain extension or Ver Wetting should take place in the presence of water, as amines usually react with isocyanates faster than alcohols or water. It is common  then required if aqueous dispersions of cross-linked polyurethanes or high molecular weight polyurethanes may be desired. In such In some cases, the procedure is to prepare prepolymers with isocyanate groups provides, this dispersed quickly in water and then by adding Compounds with several amino groups reactive towards isocyanates chain extended or networked.

Suitable amines are generally polyfunctional amines of Molecular weight range from 32 to 500, preferably from 60 to 300 g / mol, which are at least two primary, two secondary or one primary and one contain secondary amino group. Examples include diamines such as Di aminoethane, diaminopropanes, diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (Isophoronediamine, IPDA), 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclo hexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamines such as Diethylenetriamine or 1,8-diamino-4-aminometlylylctane.

The amines can also be in blocked form, e.g. B. in the form of correspond the ketimines (see e.g. CA-1 129 128), ketazines (see e.g. the US-A 4 269 748) or amine salts (see US-A 4 292 226) can be used.

Mixtures of di- and triamines are preferably used, especially preferably mixtures of isophoronediamine and diethylenetriamine.

Alcohols with a higher valence than 2, which are used for the adjustment of a certain degree of branching or networking can serve, z. B. Trimethylolpropane, glycerin or sugar.  

For the same purpose can also be used as monomers A4 and trivalent tetravalent isocyanates are used. Commercially available connections are for example the isocyanurate or the biuret of hexamethylene diisocyanate.

Monomeric AS, which may also be used, are monoisocyanas te, monoalcohols and mono-primary and secondary amines. In general their proportion is a maximum of 10 mol%, based on the total molar amount of the monomers. These monofunctional compounds usually carry further functional groups such as olefinic groups or carbonyl groups and serve to introduce functional groups into the polyurethane, which are the dispersion or the crosslinking or other polymer analogs Enable implementation of the polyurethane. Consider this Monomers such as isopropenyl-α, α-dimethylbenzyl isocyanate (TMI) and esters of Acrylic or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl metha crylate.

It is well known in the field of polyurethane chemistry how that Molecular weight of the polyurethanes by choosing the proportions of each other reactive monomers and the arithmetic mean of the number of reactive functional groups can be set per molecule.

Normally, the monomers A1, A2, A3, A4 and A5 and their respective molar amounts are chosen so that the ratio x: y with
x) the molar amount of isocyanate groups and
y) the sum of the molar amount of the hydroxyl groups and the molar amount of the functional groups which can react with isocyanates in an addition reaction
0.5: 1 to 2: 1, preferably 0.8: 1 to 1.5: 1, particularly preferably 0.9: 1 to 1.2: 1. The ratio x: y is very particularly preferably as close as possible to 1: 1.

In addition to the monomers A1, A2, A3 and A4, monomers with only a reactive group generally in amounts up to 15 mol% before adds up to 8 mol%, based on the total amount of monomers A1, A2, A5 and A4 used.

The monomers A1 to A4 used usually carry an average of 1.5 to 2.5, preferably 1.9 to 2.1, particularly preferably 2.0 isocyanate groups or functional groups with isocyanates in an addition reaction can react.

The polyaddition of the monomers A1 to A4 generally takes place after the known methods, preferably the so-called acetone method or the so-called prepolymer mixing process, for example from the DE-A-44 18 157 are known, is used.

The general procedure is to start with an inert solution organic solvents a prepolymer or the polyurethane (component A) produces and then the prepolymer or the polyurethane in Water dispersed. In the case of the prepolymer, the reaction takes place at Polyurethane by reaction with the water or by a subsequent added amine (monomer A4). Usually the solvent completely or partially removed by distillation after dispersion.

Hydrophobic auxiliaries that may be difficult to homogenize in the finished dispersion are to be distributed, such as phenol condensation resins from aldehydes and phenol or phenol derivatives or epoxy resins and  further z. B. in DE-A 39 03 538, DE-A 43 09 079 and DE-A 40 24 567 mentioned polymers, which in polyurethane dispersions for example as Liability improvers can be used according to the two above Written methods described the polyurethane or the prepolymer be added before the dispersion.

The polyurethanes generally have a Shore A hardness of at most 90, preferably from a maximum of 80, particularly preferably from 30 to 70. The Shore A hardness is determined according to DIN 53 456.

The aqueous impregnants according to the invention contain as component B. liquor 1 to 15 wt .-% of at least one polyalkylene oxide. Polyalkylene oxides are known per se. They can be obtained by adding Ethylene oxide or propylene oxide on starter components with active water substance such as water, alcohols or amines. Known starter components are Ethylene glycol, 1,2- and 1,3-propylene glycol, oligomeric polyalkylene oxides, Glycerin, pentaerythritol, sugar or aniline. Ethylene or propylene oxide can be used alone, in a mixture or in stages, where Homopolymers, statistical copolymers or block copolymers with any variable proportion of ethylene oxide units can be obtained. Prefers are statistical ethylene oxide-propylene oxide copolymers with a proportion of Ethylene oxide units of ≦ 5%, particularly preferably ≦ 40%. Suitable polyalkylene oxides have a molecular weight of 500 to 10,000 on. Polyalkylene oxides with a molecular weight of are preferred 1500 to 8000, particularly preferably used from 2000 to 6000. Under the molecular weight is always in the present application understood number average molecular mass. Suitable polyalkylene oxides have generally from 30 to 80 ° C, preferably from 50 to 70 ° C. The cloudy Practice point is the temperature point at which when heating the aqueous  Polyalkylene oxide solution turbidity of the liquid takes place by segregation and is determined according to DIN 539 174.

The aqueous impregnation liquor 1 according to the invention contains component C up to 30% by weight of a crosslinker. Suitable crosslinkers are in Petersen, Handbook of Fiber Science and Technology Volume II Part A (1983), page Called 217 to 247. Suitable crosslinkers are, for example, N-hydroxy methyl and N-alkoxymethyl derivatives of acyclic ureas such as Mono- and dihydroxymethyl urea and their alkyl derivatives such as mono- and dime thoxymethyl urea, N-methyl-N'-methoxymethyl and hydroxymethyl urea substance, N, N'-dimethyl-methoxymethyl or hydroxymethyl urea, N-dime thyl-N'-methoxymethyl or hydroxymethyl urea and trimethoxymeth yl urea. O-hydroxyalkylated or alkoxyalkylated are also suitable Carbamates such as hydroxymethyl carbamate or methoxyethyl carbamate and the additionally N-alkyl or N-alkoxyalkyl-substituted derivatives such as hydroxy methylated methyl, ethyl and isopropyl carbamates or hydroxymethylated 2-methoxyethyl carbamate, also hydroxymethylated biscarbamates such as hy doxymethylated 1,4-butanediol biscarbamate. N-hydroxy are also suitable methylated or N-alkoxymethylated carboxamides such as hydroxymethy Formated, acetamide or acrylamide or the dimethoxymethylde derivatives of formamide, acetamide, β-methoxypropionic acid amide, stearylamide and glycidamide.

N-hydroxymethylated and N-alkoxymethylated are also suitable Derivatives of cyclic ureas, the derivatives of 5- and 6-membered cyclic ureas are preferred. Suitable 5-membered Cyclic urea derivatives are derived from ethylene urea (imidazolidinone 2) and are, for example, dihydroxymethyl or dlmethoxymethylethyl lenurea, dihydroxymethyl or dimethoxymethyl-4,5-dihydroxyethylene urea or dimethoxyethylene urea, monohydroxymethyl and dime  thoxymethylhydantoin and tetrahydroxyacetylene diurea. Suitable 6- limb cyclic urea derivatives are derived from propylene urea (2-oxo hexahydropyrimidine) and are, for example, dihydroxymethyl and Dialkoxymethylpropyleneurea, dihydroxymethyl- and dialkoxymethyl-5- methyl propylene urea, dihydroxymethyl and dialkoxymethyl-5,5-dimethyl propylene urea, dihydroxymethyl and dialkoxymethyl 5-hydroxypropylene urea or dihydroxymethyl- and dialkoxymethyl-4-hydroxy (methoxy) -5,5- dimethyl propylene urea.

The hydroxymethyl derivatives mentioned can by reacting the ent get talking nitrogenous starting compound with formaldehyde are, the corresponding alkoxymethyl derivatives by subsequent Ver etherification with an alcohol, partial or complete etherification the hydroxymethyl groups formed is possible. The partial or full Derivatives that are permanently etherified are free of formaldehyde because of their lower content preferably used. Of the alkoxymethylated derivatives are the methoxymethyl derivatives obtained by etherification with methanol are particularly preferred.

Hydroxymethylated and alkoxymethy are also suitable as crosslinkers gated derivatives of aminotriazines, such as the derivatives of melamine (2,4,6- Triamino-1,3,5-triazine), which is obtained by reacting melamine with 1-6 mol Formaldehyde and optionally partial or complete etherification of the Hydroxymethyl groups formed, preferably with methanol, accessible are.

Preferred component C are the hydroxymethyl and methoxyme thyl derivatives of 5-membered cyclic ureas used, especially preferably 1,3-dimethylol-4,5-dihydroxyimidazolidinone-2 (DMDHEU) and  whose accessible by partial or complete etherification with methanol Lichen methyl derivatives.

The aqueous impregnants according to the invention contain as component D. liquor 0.1 to 15 wt .-% of a catalyst. Suitable catalysts are in Petersen, Handbook of Fiber Science and Technology Volume II Part A, Pages 205 to 217. Generally used as catalysts Acids or latent acids are used, i.e. substances or mixtures of substances, which already react as acids in the impregnation solution or their acidic ones Properties in the heat, for example when performing the Vernet development step. Suitable catalysts are acidic metal salts such as the chlorides, nitrates, sulfates, phosphates or tetrafluoroborates of Magnesi um, calcium, zinc and aluminum, such as magnesium chloride, Calcium chloride, zinc (II) chloride, zinc (II) nitrate, magnesium nitrate, aluminum chloride and zinc (II) tetrafluoroborate.

Also suitable as catalysts are organic acids such as acetic acid, Hydroxyacetic acid, oxalic acid, tartronic acid, citric acid or maleic acid.

The metal salts and the organic acids can be used on their own are set, but a mixture of a metal salt and is preferred an acid used.

The ammonium salts of mineral are also suitable as catalysts acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid or of organic acids like oxalic acid, the salts of organic amines like Methylamines and ethanolamines, for example the hydrochlorides of Monomethylamine, mono-, di- and triethanolamine or 2-amino-2-ethyl-1- propanol.  

Suitable catalysts are also aluminum chlorohydroxide [Al ₂ (OH) ₅ Cl], preferably in a mixture with phosphoric acid, and magnesium dihydrogen phosphate or boric acid.

Acidic metal salts are preferably used as component D in the impregnating liquors according to the invention in a mixture with organic acids, particularly preferably a mixture of magnesium chloride hexahydrate and / or NaBF ₄ and acetic acid and / or citric acid.

The aqueous impregnation solutions according to the invention can be used as component E. 0 to 15% by weight of other auxiliaries customary in textile finishing contain. Aids in textile finishing are, for example, in Ull mann's Encyclopedia of Industrial Chemistry, Volume II Part A, page 305 called up to 315. Aids that are common in textile finishing are for example handle variators ("hand builders"), plasticizers, hydropho Beer or oleophobic agents and flame retardants.

The aqueous impregnation liquors according to the invention can be used as component F. 0 to 15% by weight of other auxiliaries such as surfactants, emulsifiers and ent foamer included.

The solids content of the aqueous impregnation liquors according to the invention is generally 2 to 40% by weight, preferably 4 to 30% by weight, particularly preferably 6 to 20% by weight. The solids content is the proportion of the total of components A to F on the total weight of the impregnation liquor.

The textile material in the impregnation liquor becomes an easy-care finish soaked. This is followed by a customary finishing process, at for example dry crosslinking, wet crosslinking or wet crosslinking. Each According to the chosen method, the fiber is largely cross-linked  in the de-swollen state (dry crosslinking) or in part (wet ver wetting) or completely water-swollen state (wet cross-linking).

The easy-care equipment is preferably carried out with the device according to the invention ß aqueous impregnation liquor by dry crosslinking. This will be Textile material treated with a padding impregnating liquor. Also Impregnation from a long liquor is possible, e.g. B. Fleet ratio 1:20, 20th min at room temperature. After soaking in the impregnation liquor the textile to a liquor absorption of 30 to 150%, preferably 55 to 100% squeezed. The% figures relate to those given by the Increase in the weight of the impregnation liquor, based on the weight of the untreated textile. Then it is determined on a residual moisture dried. The temperature during the drying step is generally 100 to 140 ° C, preferably 110 to 120 ° C. The Residual moisture of the textile after the drying step is generally up to 15%, preferably 5 to 12%, particularly preferably 6 to 8% Water. The percentages relate to the total weight of the imprä textile fabric. The crosslinking is generally increased Temperature carried out, preferably at 130 to 220 ° C, especially before pulls at 140 to 190 ° C, for a period of 10 sec to 20 mm, preferably 20 sec to 5 min.

Suitable textile materials for easy care equipment with the invent Aqueous impregnating liquor according to the invention are textile materials on the basis of cellulose such as cotton, linen or viscose. It can be the un spun fibers or the yarn before processing into a textile fabrics are treated. The easy-care equipment is preferably provided on a textile fabric. Textile fabrics are, for example, hurt, knitted or Knitted fabric or textile fleece. The textile fabrics can only be made from Cellulose fibers exist or synthetic fibers such as polyester, polyamide,  Polyacrylonitrile and polyurethane fibers contain, in proportions up to 80 % By weight can be added. Textile fabrics are particularly preferred 100% cotton like cotton poplin.

By treatment with the impregnating liquor according to the invention easy-care textile fabrics obtained, which are characterized by a particularly good Wrinkle recovery, defined by a particularly high dry crease rate angle, mark. The dry crease recovery angle is a measure of the crease recovery ability of a textile fabric during wear. He is determined according to DIN 53 890. The easy-care according to the invention Textile fabrics show untreated, but otherwise identical textile fabrics weave an increase in crease recovery of generally ≦ 10%, preferably ≦ 30%, particularly preferably ≦ 45%. The increases The recovery capacity can be 55% or more. Against over otherwise identical textile fabrics treated with an impregnating liquor which do not contain components A and B (with the same content on components C and D), the crease recovery ability of the invention contemporary textile fabric by at least 10%, preferably 10 to 50%, particularly preferably 15 to 25% increased. For example, a tree points wool poplin with an initial crease recovery of 146 ° (the untreated Tissue) after treatment with the impregnating liquor according to the invention a dry crease recovery angle of generally ≦ 180 °, preferred ≦ 200 °, particularly preferably ≦ 215 °, in particular ≦ 230 °.

The improvement in wrinkling behavior is surprisingly low Decrease in mechanical strength. The mechanical strength is determined by sizes such as tear resistance, tear resistance (simple strip pull attempt) and loss of abrasion characterized.  

The easy-care textile fabrics according to the invention are characterized by a Slight decrease in tear through compared to untreated textile fabrics consistency. The tear resistance is primarily characterized by embrittlement of the fabric and is a measure of the susceptibility to wear of a fabric for later use. The tear resistance corresponds to the force that lets a incised tissue sample tear. It will go to Elmen Dorf, DIN 53 862. The decrease in the tear resistance of the textile fabric according to the invention is compared to untreated, but otherwise same textile fabric in general ≦ 40%, preferably ≦ 30%, particularly preferred ≦ 25%.

The easy-care textile fabrics according to the invention are also distinguished due to low tear resistance losses compared to untreated textile fabrics out. The tensile strength of a textile fabric is its resistance in Moment of tearing and is in the simple strip tensile test DIN 53 857 determined. The tensile strength loss of the textile ge according to the invention webe is compared to the loss of tensile strength of untreated, however otherwise the same textile fabrics ≦ 30%, preferably ≦ 25%, particularly preferably ≦ 20%.

The easy-care textile fabrics according to the invention are also distinguished from low abrasion losses. The loss of abrasion is caused by the % weight loss caused by mechanical abrasion. He is after AATCC 93-1970 with an abrasion tester - the Accelorotor. The Accelorotor consists essentially of a metal cylinder, the inner wall is designed with a rubbing material and in the one Two-bladed propeller rotates. The tissue sample is made by the turns of the propeller hurled into the metal cylinder and bending, abrasive, rubbing, bumping, stretching and squeezing Exposed to forces. The amount of abrasion loss is also from that  grinding material, the number of revolutions and the duration of the spin ganges determined. The abrasion loss of the textiles according to the invention is compared to the abrasion loss otherwise identical textiles, which with an Imprä gnier liquor are treated that does not contain components A and B (at same content of components C and D), significantly reduced, in all common by at least 10%, preferably by at least 20%, particularly preferably by at least 25%. The be. According to the Accelorotor method agreed loss of abrasion of a cotton poplin treated according to the invention when using emery paper P320 as a rubbing material, a speed of 3000 rpm and a duration of 3 min in general ≦ 20%, preferably ≦ 17%, particularly preferably ≦ 15%, especially ≦ 13%.

The soft feel of the textile fabrics according to the invention is also advantageous.

The invention is illustrated by the examples below.

example 1

The easy-care treatment of a cotton poplin with a surface weight of 130 wind is done by soaking in an impregnation liquor, which is made by mixing

• - 50 g of an aqueous solution of a modified with methanol DMDHEU (1,3-dimethoxymethyl-4,5-dihydroxyethylene urea) with a solids content of 70% by weight (Fixapret® CL from BASF AG, Ludwigshafen, DE) as a networker,
• - 10 g magnesium chloride hexahydrate and
• 0.5 g of a 60% by weight aqueous acetic acid as catalyst,  
• - 48 g of an aqueous solution of a polyester-polyurethane dispersion with a Shore A hardness of 50 and a solids content of 40 % By weight (Perapret® PU from BASF AG, Ludwigshafen, DE),
• - 30 g of an aqueous solution of a polyalkylene oxide of ethylene and Propylene oxide with a cloud point of 60 ° C and a solid Ge content of 50% by weight (Siligen® FA from BASF AG, Ludwigshafen, DE),
• - 2 g of a nonionic surfactant (isodecanol with 3-5 ethylene oxide in units) with a solids content of 90% by weight (Kieralon® Jet-B conc. from BASF AG, Ludwigshafen, DE)

and make up to 1 liter with water, squeeze onto a liquor holder from 75%, drying to 6% residual moisture and condensation for 4 min at 150 ° C. The equipped cotton poplin will then be the subjected to application testing.

Comparative Example 1

Like example 1, but the impregnation liquor contains only the crosslinker (50 g Fixapret CL) and the catalyst (10 g magnesium chloride hexahydrate and 0.5 g of 60% by weight aqueous acetic acid).

Comparative Example 2

An untreated cotton poplin is examined.  

Application test

There are the dry crease recovery angle, the tear work, the tear strength and the loss of abrasion determined.

The dry crease recovery angle is determined in accordance with DIN 53 890 on 50 mm long and 20 mm wide test specimens. The examinee is like this folded that the folded end of the strip has a length of 10 mm and that the fold is perpendicular to the longitudinal edges of the fabric strip. The folded specimen is placed between two glass plates and with one Weight of 1 kg for 30 minutes. The one after the discharge forming angle is measured after 30 min. The specified dry crease recovery angle is the sum of the corresponding angles in Warp and weft.

The determination of the ripping work is done on a falling pendulum DIN 53 862.

The tensile strength is determined in a simple strip tensile test according to DIN 53 857 on 50 cm wide and 200 cm long test objects.

The abrasion loss (in% by weight) was determined on a Accelorotor by spinning 10.10 large tissue for 3 minutes samples in a metal lined with P 320 as a friction material cylinder at 3000 rpm.

The table summarizes the results of the application test together.  

Comparative Example 3

Like example 1, but the impregnation liquor contains no polyalkylene oxide. The treated cotton poplin usually shows an intolerable hard grip.  

table

Claims (10)

1. Containing aqueous impregnation liquor for easy-care finishing of textile materials, based on the solids content,

• a) 1 to 30% by weight of at least one water-dispersible polyurethane as component A,
• b) 1 to 15% by weight of at least one polyalkylene oxide as component B,
• c) 1 to 30% by weight of at least one crosslinking agent as component C,
• d) 0.1 to 15% by weight of at least one catalyst as component D,
• e) 0 to 15% by weight of further auxiliaries customary in textile finishing as component E,
• f) 0 to 15% by weight of further auxiliaries as component F.

2. Aqueous impregnation liquor according to claim 1, characterized in that the polyurethane (component A) is composed of

• a1) diisocyanates with 4 to 30 C atoms as monomers A1,
• a2) Diols, of which
  • a21) 10 to 100 mol%, based on the total amount of the diols, have a molecular weight of 500 to 5000 g / mol (monomers A21), and
  • a22) 0 to 90 mol%, based on the total amount of the diols, have a molecular weight of 60 to 500 g / mol (monomers A22),
  as monomers A2,
• a3) if appropriate, monomers different from monomers A1 and A2 with at least one isocyanate group or at least one group which is reactive toward isocyanate groups and which also carry at least one hydrophilic group or a potentially hydrophilic group, thereby causing the water-dispersibility of the polyurethanes as monomers A3,
• a4) optionally, other than the monomers A1 to A3 ne polyvalent compounds with reactive groups, which are alcoholic hydroxyl groups, primary or secondary amino groups or isocyanate groups, as monomers A4 and
• a5) optionally monomers different from the monomers A1 to A4 with a reactive group which is an alcoholic hydroxyl group, a primary or secondary amino group or an isocyanate group, as monomers A5.

3. Aqueous impregnation liquor according to claim 1 or 2, characterized records that the polyurethane (component A) has a Shore A hardness of has a maximum of 80. 4. Aqueous impregnation liquor according to one of claims 1 to 3, characterized in that the polyalkylene oxide (component B) has one or both of the following features:

• - molecular weight 1500 to 10,000
• - Content of ethylene oxide units ≧ 5 mol%.

5. Aqueous impregnation liquor according to one of claims 1 to 4, characterized characterized in that the polyalkylene oxide has a cloud point in water has between 30 and 80 ° C. 6. Aqueous impregnation liquor according to one of claims 1 to 5, characterized characterized in that 1,3-dimethylol-4,5- as crosslinker (component C) dihydroxyimidazolidinone-2 (DMDHEU) and / or its partial or fully methylated derivatives are used. 7. Process for easy care finishing of a textile fabric by Im impregnate the textile fabric with an impregnating liquor, drying and Condensing, characterized in that the textile fabric with a Impregnation liquor is impregnated according to one of claims 1 to 6. 8. Easy-care textile fabric that is treated with an impregnating liquor according to a of claims 1 to 6 is treated. 9. Paint easy-care textile fabric according to claim 8 with the following characteristics:

• - The crease recovery ability is increased by at least 30% compared to the crease recovery ability of an untreated, but otherwise identical textile fabric;
• - The tear resistance (measured as tear strength) is less than 30% less than the tear resistance of an untreated, but otherwise identical textile fabric;
• - The tensile strength is reduced by less than 25% compared to the tensile strength of an untreated but otherwise identical textile fabric;
• - The abrasion loss compared to the abrasion loss of an otherwise identical textile fabric, but which has been treated with an impregnating liquor which does not contain components A and B at the same content of components C and D, is reduced by at least 25%.

10. Use of an impregnating liquor according to one of claims 1 to 6 for the production of easy-care textile materials.