EP1259672B1 - Crease resistant finishing of cellulose-containing textiles, and laundry post-treatment agents - Google Patents

Abstract

Cellulosic textiles are wrinkleproofed by treating them with aqueous dispersions of C14- to C22-alkylketene dimers and drying them. Also disclosed is a laundry aftertreatment composition comprising from 0.1 to 40% by weight of a C14- to C22-alkylketene dimer as aqueous dispersion, from 0.1 to 50% by weight of at least one fabric conditioner and optionally nonionic surfactants.

Description

The invention relates to a method for anti-wrinkle finishing of cellulosic textiles by treating the textiles with a finishing agent and drying the treated textiles and the use of laundry aftertreatment agents for anti-wrinkle finishing of textiles.

Cellulose-containing textiles are easy-care, for example, by treatment with condensation products of urea, glyoxal and formaldehyde. The equipment takes place during the production of the textile materials. The equipment often uses other additives such as softening compounds. The so refined fabrics have the advantage over the untreated cellulose textiles after the washing process that they have less wrinkles and wrinkles, easier to iron and softer and smoother. But by no means all cellulosic textiles have received such easy care equipment.

WO-A-92/01773 discloses the use of microemulsified aminosiloxanes in fabric conditioners to reduce wrinkling and wrinkling during the washing process (crease arm equipment). At the same time ironing should be facilitated by the use of aminosiloxanes.

From WO-A-98/4772 a process for the pretreatment of textile materials is known wherein a mixture of a polycarboxylic acid and a cationic plasticizer is applied to the textile materials. This achieves a crease protection.

EP-A-0 300 525 discloses fabric softeners based on crosslinkable amino-functionalized silicones which bring about crease protection or an easy-iron effect for the textiles treated therewith.

CH-A-388 246 discloses a process for improving the wet and dry crease resistance of cellulosic textile material in which the fabric is treated with a hot aqueous bath containing a metal salt, in particular a zinc salt, and a crosslinking agent for cellulose. It is mentioned, that the textile material can additionally be treated with a ketene plasticizer.

From US-A-5 028 236 it is known to use alkyl ketene dimers for the hydrophobization of wool and synthetic polyamide fibers.

In DE-A-38 26 769, aqueous alkyl ketene dimer dispersions containing cationic starch as emulsifier are used to improve the surface structure and feel of wool and polyamide carpets.

It is also known to use alkyl ketene dimers or reaction products of alkyl ketene dimers with cationic polymers for surface coverage of fillers, cf. WO-A-92/18695, EP-A-0 451 842 and EP-A-0 445 953. The fillers modified in this way are used, for example, in the production of paper. From US-A-4,241,136 it is known to use alkylketene dimers in admixture with a cationic film-forming polymer for coating glass fibers.

WO-A-96/26318 discloses aqueous dispersions of alkylketene dimers which are used as sizing agents for paper. The alkyl ketene dimer dispersions contain from 1 to 10% by weight of a polymeric protective colloid which is either a copolymer of N-vinylpyrrolidone and at least one quaternized N-vinylimidazole or condensation products obtained by partial amidation of polyethylenimines with monocarboxylic acids followed by Condensation of the partially amidated polyethyleneimines are prepared with at least bifunctional crosslinkers. Aqueous dispersions of alkyl ketene dimers which are stabilized, for example, with the aid of cationic starch and which optionally contain further dispersing aids, such as lignosulfonate, are known engine sizing agents for paper, cf. For example, US-A-4 380 602, US-A-4 654 386, EP-A-0 369 328, EP-A-0 418 015 or EP-A-0 437 764.

The present invention has for its object to provide a method for anti-wrinkle finishing of cellulosic textiles and a means for performing this method.

The object is achieved by a method for anti-wrinkle finishing of cellulosic textiles by treating the textiles with a finishing agent and drying the treated textiles by using as a finishing agent aqueous dispersions of C _{14 to} C ₂₂ -Alkylketendimeren by Emulsifying at least one Alkylketendimeren in the presence of a cationic emulsifier are available.

Alkylketene dimers are known. They are mainly used in the form of aqueous dispersions as engine sizing agents for paper. All alkyl ketene dimer dispersions which can be used as sizing agents for paper, which are obtained by emulsifying the alkyl ketene dimers in the presence of a cationic emulsifier, can be used for the process according to the invention. Alkylketene dimers are prepared, for example, from carbonyl chlorides by elimination of hydrogen chloride with tertiary amines. Examples of suitable fatty alkyl ketene dimers are tetradecyldiketene, hexadecyldiketene, octadecyldiketene, eicosyldiketene, docosyldiketene, palmityldiketene, stearyldiketene, oleyldiketene and behenyldiketene. Also suitable are diketenes with different alkyl groups, e.g. Stearylpalmityldiketen, Behenylstearyldiketen, Behenyloleyldiketen or Palmitylbehenyldiketen. Stearyldiketen, Palmityldiketen, Behenyldiketen or mixtures of Stearyldiketen and Palmityldiketen or mixtures of Behenyldiketen and Stearyldiketen are preferably used. The diketenes are contained, for example, in concentrations of up to 60% by weight in the aqueous dispersions. Dispersions containing from 0.1 to 40% by weight, preferably from 0.5 to 25% by weight, of an alkyl ketene dimer in dispersed form are used, for example, for the treatment of cellulose-containing textiles.

In order to obtain stable aqueous dispersions of alkyl ketene dimers, the alkyl ketene dimers are emulsified in the presence of at least one emulsifier or stabilizer. The best known alkyl ketene dimer emulsifier is cationic starch. It is contained in amounts of, for example, from 0.5 to 5% by weight in the aqueous dispersions of the alkylketene dimers. Although any commercially available cationic starch can be used as an emulsifier for alkyl ketene dimers, it is preferred to use those cationic starches which have an amylopectin content of at least 95, preferably 98 to 100%. Such starches can be obtained, for example, by means of fractionation of customary native starches or by breeding measures from plants which produce practically pure amylopectin starch, cf. Günther Tegge, Starch and Starch Derivatives, Behr's Verlag 1984, Hamburg, pp. 157 to 160. Amylopectin starch has a branched structure and has a high degree of polymerization. The molecular weights (number average) are, for example, 200 million to 400 million. For waxy maize starches having an amylopectin content of 99 to 100%, the literature reports average molecular masses (number average) of about 320 million. Of the Cationation degree of the starch is described by means of the degree of substitution (DS). This value represents the number of cationic groups per monosaccharide unit in the cationic starch. The degree of substitution (DS value) of the cationic starches is, for example, 0.010 to 0.150. In most cases it is below 0.045, eg most cationic starches have a degree of substitution (DS) of 0.020 to 0.040. Preferred starches with amylopectin contents of at least 95% are waxy maize starch, waxy potato starch, waxy wheat starch or mixtures of the stated starches in each cationized form. In order for the cationic starches to be effective as an emulsifier, they are usually converted into a water-soluble form.

For this purpose, the starches are subjected to oxidative, enzymatic or hydrolytic degradation in the presence of acids. In addition, thermal degradation is possible, which is possible for example by heating aqueous suspensions of starch. The digestion of the starch is preferably carried out in a jet cooker at temperatures in the range of 100 to 150 ° C.

In the aqueous solutions of degraded cationic starch is then dispersed, for example, C ₁₄ - to C ₂₂ -Alkylketendimere at temperatures above 70 ° C, for example in the range of 70 to 85 ° C. The alkylketene dimers are present at these temperatures as a melt and are dispersed in homogenizers under the action of high shear forces in the aqueous solution of cationic starch. This gives aqueous dispersions of alkyl ketene dimers having an average particle diameter of, for example, 0.5 to 2.5, preferably 0.8 to 1.5 microns. The dispersing of the alkylketene dimers in water may optionally additionally be carried out in the presence of lignosulphonic acid, condensation products of formaldehyde and naphthalenesulphonic acid, polymers containing styrenesulphonic acid groups or the alkali metal and / or ammonium salts of said sulfonic acid group-containing compounds. These substances act as dispersants and stabilize the resulting alkyl ketene dimer dispersions. If such dispersants are used in the preparation of the alkyl ketene dimer dispersions, the amounts are for example 0.01 to 1, preferably 0.02 to 0.2 wt .-%, based on the aqueous dispersions. The content of the aqueous alkyl ketene dimer dispersions of degraded cationic starch is, for example, 0.5 to 5, preferably 1 to 3 wt .-%.

In the preparation of the alkyl ketene dimer dispersions, it is also possible if desired to use other conventional protective colloids which have hitherto been used in the preparation of alkyl ketene dimer dispersions have been used, such as water-soluble cellulose ethers, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, polyamides, polyamidoamines and mixtures of said compounds. The alkylketene dimer dispersions may optionally contain further substances for stabilization, such as C ₁ - to C ₁₀ -carboxylic acids, for example formic acid, acetic acid or propionic acid. The amounts of these additives are for example 0.01 to 1 wt .-%, based on the dispersion. If appropriate, the alkyl ketene dimer dispersions may still contain customary biocides.

1. (a) einem Copolymerisat aus 5 bis 80 Mol.-% N-Vinylpyrrolidon und 95 bis 20 Mol.-% mindestens eines quaternierten N-Vinylimidazols mit einem K-Wert von mindestens 20 (bestimmt nach H. Fikentscher in 0,5 m wäßriger Kochsalzlösung bei einer Polymerkonzentration von 0,1 Gew.-% und einer Temperatur von 25°C) und/oder
2. (b) einem Kondensationsprodukt, das durch teilweise Amidierung von Polyethyleniminen mit Monocarbonsäuren und anschließende Kondensation der teilweise amidierten Polyethylenimine mit mindestens einem bifunktionellen Vernetzer zugänglich ist, wobei die Kondensationsprodukte in 20 gew.-%iger wäßriger Lösung bei 20°C eine Viskosität von mindestens 100 mPas haben,

erhältlich sind.As finishing agents aqueous dispersions of alkyl ketene dimers are used with particular advantage, by emulsifying alkyl ketene dimers in the presence of 1 to 20 wt .-%, based on alkyl ketene dimers, of an emulsifier

1. (A) a copolymer of 5 to 80 mol .-% N-vinylpyrrolidone and 95 to 20 mol .-% of at least one quaternized N-vinylimidazole having a K value of at least 20 (determined according to H. Fikentscher in 0.5 m aqueous Saline solution at a polymer concentration of 0.1% by weight and a temperature of 25 ° C) and / or
2. (B) a condensation product which is accessible by partial amidation of polyethyleneimines with monocarboxylic acids and subsequent condensation of the partially amidated polyethyleneimines with at least one bifunctional crosslinker, wherein the condensation products in 20 wt .-% aqueous solution at 20 ° C has a viscosity of at least 100 mPas have,

are available.

in der

R, R¹, R² =

H, C₁- bis C₄-Alkyl oder Phenyl,

R³ =

H, C₁- bis C₁₈-Alkyl oder Benzyl und

X⊖

ein Anion ist,

Such aqueous dispersions of alkyl ketene dimers are known from WO-A-96/26318. Examples of quaternized N-vinylimidazoles which are suitable as comonomers for the preparation of N-vinylpyrrolidone copolymers are 1-vinylimidazole quaternized with C _{1 to} C ₁₈ -alkyl halides, salts of 1-vinylimidazole with mineral acids such as sulfuric acid or hydrochloric acid, with C ₁ bis-C ₁₈ alkyl halides quaternized 2-methyl-1-vinylimidazole, 3-methyl-1-vinylimidazolium chloride, 3-benzyl-1-vinylimidazolium chloride, 3-ethyl-1-vinylimidazolium methosulfate and 2-methyl-1-vinylimidazolium methosulfate , The copolymers of N-vinylpyrrolidone may also contain several different quaternized N-vinylimidazoles in copolymerized form, for example 1-vinylimidazolium chloride and 2-methyl-1-vinylimidazoliumethosulfate. The quaternized N-vinylimidazoles can be characterized, for example, by the following formula:

in the

R, R ¹ , R ² =

H, C ₁ - to C ₄ -alkyl or phenyl,

R ³ =

H, C ₁ to C ₁₈ alkyl or benzyl and

X .crclbar

is an anion,

The N-vinylpyrrolidone copolymers preferably contain from 20 to 95% by weight of a quaternized N-vinylimidazole of the formula I in copolymerized form. The K value of the copolymers is at least 20 and is preferably in the range from 40 to 80. The K values of the N-vinylpyrrolidone copolymers are determined according to H. Fikentscher in 0.5 M aqueous sodium chloride solution at a polymer concentration of 0.1% by weight. % and a temperature of 25 ° C determined. Preferably used copolymers of N-vinylpyrrolidone contain as comonomer with methyl chloride quaternized vinylimidazole or with methyl chloride quaternized 2-methyl-1-vinylimidazole.

The condensation products which are furthermore preferably suitable as emulsifiers for the preparation of aqueous dispersions of alkylketene dimers can be obtained by reacting partially amidated polyalkylenepolyamines or partially amidated polyethylenimines with crosslinkers. Preferably suitable emulsifiers are those condensation products which are obtainable by a 2-stage reaction of polyethyleneimines with C _{1 to} C ₁₈ monocarboxylic acid to give partially amidated polyethyleneimines and subsequent crosslinking of the partially amidated polyethyleneimines. For the preparation of the partially amidated polyethyleneimines, it is also possible to use, for example, alkyldiketenes, for example stearyldiketene, palmityldiketene, lauryldiketene, oleyldiketene, behenyldiketene or mixtures of diketenes. The polyethyleneimines are partially amidated in the first stage of the process, so that, for example, 0.1 to 90, preferably 1 to 30% of the amidable nitrogen atoms of the polyethyleneimines are present as the amide group. In the amidation no linkage of polyethyleneimine molecules occurs. Such a linkage only occurs in the subsequent reaction of the partially amidated polyethyleneimines with at least bifunctional crosslinkers.

The polyethylenimines used in the condensation have e.g. 10 to 50,000, preferably 100 to 5,000 ethyleneimine units.

Suitable crosslinkers for the preparation of the condensation products are, for example, epihalohydrins, in particular epichlorohydrin and α, ω-bis (chlorohydrins) of polyalkylene glycol ethers and the α, ω-bis (epoxides) of polyalkylene glycol ethers obtainable therefrom by treatment with bases. The chlorohydrin ethers are prepared, for example, by reacting polyalkylene glycols in a molar ratio of 1 to at least 2 to 5 with epichlorohydrin. Suitable polyalkylene glycols are, for example, polyethylene glycol, polypropylene glycol and polybutylene glycols and also block copolymers of C ₂ -C ₄ -alkylene oxides. The average molar masses M _{w of} the polyalkylene glycols are, for example, 200 to 6000 and are preferably in the range from 300 to 2000 g / mol. Other suitable crosslinkers are, for example, α, ω or vicinal dichloroalkanes, for example 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 1,4-dichlorobutane and 1,6-dichlorohexane. Examples of further crosslinkers are the reaction products of at least trihydric alcohols with epichlorohydrin to give reaction products which have at least two chlorohydrin units, for example glycerol, ethoxylated or propoxylated glycerols, polyglycerols having 2 to 15 glycerol units in the molecule and optionally ethoxylated polyhydric alcohols and / or propoxylated polyglycerols. Also suitable as crosslinkers are blocked compounds containing isocyanate groups, for example trimethylhexamethylene diisocyanate blocked with 2,2,3,6-tetramethylpiperidinone-4.

0.001 to 10, preferably 0.01 to 3, parts by weight of an at least bifunctional crosslinker are added per part by weight of the respectively partially amidated polyalkylenepolyamines or polyethyleneimines. The crosslinking of the partially amidated compounds takes place at temperatures of 0 to 200, preferably 50 to 80 ° C. The reaction can be carried out in bulk or preferably in a solvent. Preferred solvent here is water. The crosslinking is preferably carried out in the pH range from 10 to 14, usually from 10 to 12. For this purpose, it may be necessary to add a base or a mixture of bases during the condensation reaction. Suitable bases for this reaction are, for example, sodium hydroxide solution, potassium hydroxide solution, calcium hydroxide, tertiary amines such as triethylamine, triethanolamine or tri-n-propylamine. Sodium hydroxide is preferably used as the base. Particular preference is given to condensation products which are obtained by partial amidation of polyethylenimines having 10 to 50,000 ethyleneimine units with monocarboxylic acids and condensation of the partially amidated polyethyleneimines with epichlorohydrin, α, ω-bis (chlorohydrin) polyalkylene glycol ethers, α, ω-bis (glycidyl) ethers of polyalkylene glycols, α, ω-Dichlorpolyalkylenglykolen, α, ω- or vicinal dichloroalkanes or mixtures thereof are obtainable, wherein 0.01 to 3 wt .-% of a part by weight of a partially amidated polyethyleneimine. Parts of at least one crosslinking agent uses. The crosslinked polyethyleneimines have, for example as a 20 wt .-% aqueous solution at 20 ° C, a viscosity of at least 100 mPas (measured using a Brookfield RVT viscometer).

For the anti-wrinkle finish, preference is given to using those aqueous dispersions of alkyl ketene dimers which contain from 10 to 18% by weight, based on alkyl ketene dimers, of an emulsifier. Preferred emulsifiers are the o.g. Copolymers (a) and the condensation products (b).

The aqueous dispersions of alkyl ketene dimers may additionally contain up to 5% by weight, based on alkyl ketene dimers, of a stabilizer. As a stabilizer are preferably lignosulfonates, quaternary ammonium salts, naphthalenesulfonic acid-formaldehyde condensates, alkyl sulfates, alkyl sulfonates, sulfonated polystyrenes, carboxylic acids, sorbitan esters, polycarboxylic acids having molecular weights of 300 to 20 0000, polyvinyl sulfonates, polyvinyl alcohols, polyamidosulfonic acids, salts of said acid-containing compounds or mixtures of considered compounds.

Also suitable for the process according to the invention are those aqueous dispersions of alkyl ketene dimers which are dispersed solely by means of an anionic emulsifier. Suitable anionic dispersants are, for example, condensation products of naphthalene and formaldehyde, condensation products of phenol, phenolsulfonic acid and formaldehyde, condensation products of naphthalenesulfonic acid, formaldehyde and urea, condensation products of phenol, phenolsulfonic acid, formaldehyde and urea and homopolymers of monoethylenically unsaturated carboxylic acids, homopolymers of monoethylenically unsaturated sulfonic acids and copolymers of ( i) hydrophobic monoethylenically unsaturated monomers and (ii) monoethylenically unsaturated carboxylic acids, monoethylenically unsaturated sulfonic acids and monoethylenically unsaturated phosphonic acids. The anionic dispersants are used, for example, in amounts of from 0.05 to 10, preferably from 0.1 to 5,% by weight, based on alkyl ketene dimers. The anionic dispersants can be used both in the form of the free acids and in the form of the alkali metal, alkaline earth metal and / or ammonium salts. The molar mass M _{w of} the condensation products is preferably in the range from 1000 to 30 000. The homopolymers and copolymers have, for example, molecular weights M _w from 800 to 250,000, preferably 1200 to 100,000. Preferred anionic emulsifiers are condensation products of naphthalenesulfonic acid and formaldehyde, homopolymers of acrylic acid and copolymers of isobutene, diisobutene, styrene or mixtures thereof and acrylic acid, methacrylic acid, maleic acid, half ester of Maleic acid or mixtures thereof and the water-soluble salts of such polymers. Preferably used copolymers contain the comonomers in a molar ratio of 1: 1 in copolymerized form.

The invention further provides the use of aqueous dispersions of C _{14 to} C ₂₂ alkyl ketene dimers which are obtainable by emulsifying at least one alkyl ketene dimer in the presence of a cationic emulsifier as finishing agents for anti-wrinkle finishing of cellulose-containing textiles. The aqueous dispersions of alkylketene dimers can be used in different ways. Thus, it is possible, for example, to treat the textiles with the finishing agent in the context of textile production. For example, textiles which have not or only insufficiently been treated with finishing agents may be treated with an aqueous dispersion of alkylketene dimers prior to washing. But it is also possible to treat the textiles after washing with an aqueous dispersion of alkylketene dimers. For this one needs in each case different formulations. The pretreatment employs a fabric laundering pretreatment formulation containing, in addition to a dispersed C _{14 to} C ₂₂ alkyl ketene dimer, from 0.1 to 25% by weight, based on the formulation, of a surfactant.

In the pretreatment, the cellulosic textiles are sprayed, for example, with the aqueous dispersions of alkyl ketene dimers, the amount applied being, for example, 0.01 to 10% by weight, preferably 0.1 to 7, particularly preferably 0.3 to 4% by weight on the weight of the dry textile, can amount. However, the finishing agent can also be applied to the fabric by immersing the fabrics in a bath containing 0.1 to 10% by weight, preferably 0.3 to 5% by weight, of an alkylketene dimer in the form of an aqueous dispersion contains. The textile material is either only immersed in the aqueous dispersion of an alkyl ketene dimer for a short time or can also stay there for a period of, for example, 1 to 30 minutes.

The textiles which have been treated with an aqueous dispersion of at least one alkyl ketene dimer, either by spraying or by dipping, are optionally pressed off and dried. The drying can be carried out in air or in a dryer or by ironing the treated textile hot. By drying the finishing agent is fixed on the fabric. The most favorable conditions for each can be easily determined by means of experiments. The temperatures during drying, including ironing, for example, 40 to 150, preferably 60 to 110 ° C. For ironing is especially the cotton program of the iron. The textiles which have been pretreated by the process described above with an aqueous dispersion of alkyl ketene dimers have excellent wrinkle and wrinkle protection which persists over several washes. Ironing, the textiles after a laundry is often no longer necessary.

The aqueous textile laundry pretreatment formulation consists, for example, of an aqueous dispersion containing 0.1 to 40% by weight, preferably 0.5 to 25% by weight, of alkyl ketene dimer in dispersed form and 1 to 20% by weight, based on alkyl ketene dimer , a nonionic, anionic and / or cationic dispersion adjuvant or stabilizer. In addition, other ingredients such as silicones, preferably silane-containing silicones or silicone surfactants, plasticizers or lubricants such as oxidized polyethylenes or paraffin waxes and oils or plasticizing cationic surfactants in the formulation in an amount up to 25 wt .-%, based on the formulation be. However, a prerequisite is that no incompatibility between the individual components occurs.

If the pretreatment formulation is sprayed onto the fabric, the formulation may additionally contain a spray aid. In some cases, it may also be advantageous to add to the formulation alcohols such as ethanol, isopropanol, ethylene glycol or propylene glycol. Further customary constituents of a textile laundry pretreatment formulation are fragrances and dyes, stabilizers, fiber and color protection additives, viscosity modifiers, soil release additives, anticorrosive additives, bactericides and preservatives in the quantities customary for this purpose.

In the case of the aftertreatment of textiles, the use of the aqueous dispersions of alkylketene dimers in the so-called soft or Pflegespülgang after the main wash in the washing of textiles. This treatment can be done both in the completion of the textile materials or in the household laundry. The latter application is preferred.

The concentration of the alkyl ketene dimers in the rinsing liquor is for example 10 to 5000 ppm and is preferably in the range of 50 to 1000 ppm. Ingredients which may be typical for a softener or conditioner may possibly be present in the rinse liquor. The textiles that have been aftertreated in this manner also have a very good crease protection after drying in a tumble dryer, which is associated with the positive effects on ironing described above. The crease protection can be significantly enhanced by a one-time short ironing of the textiles after drying. A similar effect is achieved when the drying of the treated fabric at temperatures of 60 to 180 ° C is carried out in textile production.

In the equipment variants described above, the alkylketene dimers are used e.g. in amounts of 0.01 to 10 wt .-%, based on the weight of the textiles. The finishing agents are preferably added to the rinse cycle of the washing machine during household washing. For example, since the finishing effect wears off after several washes, the finishing equipment is added to the post-rinse bath only after the fourth to sixth washings, thus regaining the original finish quality. The finishing agents can also be added to the post-rinse bath after each wash, and it is also possible to add the finish to the rinse bath after the second, third, fifth, seventh, or tenth wash to re-raise the finish of the fabric to the original level.

1. a) 0,1 bis 40 Gew.-% eines C₁₄- bis C₂₂-Alkylketendimeren als wäßrige Dispersion, die durch Emulgieren des Alkylketendimeren in Gegenwart eines kationischen Emulgators erhältlich ist,
2. b) 0,1 bis 50 Gew.-% eines Weichspülers und
3. c) 0 bis 25 Gew.-% mindestens eines nichtionischen Tensids und Wasser zur Ergänzung auf 100 Gew.-%

enthalten, zur Antiknitterausrüstung von cellulosehaltigen Textilien.The invention also provides the use of laundry aftertreatment agents which

1. a) 0.1 to 40% by weight of a C ₁₄ -C ₂₂ -alkyl ketene dimer as aqueous dispersion obtainable by emulsifying the alkylketene dimer in the presence of a cationic emulsifier,
2. b) 0.1 to 50 wt .-% of a fabric softener and
3. c) 0 to 25 wt .-% of at least one nonionic surfactant and water to supplement to 100 wt .-%

for anti-wrinkle finishing of cellulosic textiles.

1. a) 0,1 bis 40, vorzugsweise 1 bis 25 Gew.-% eines C₁₄- bis C₂₂-Alkylketendimeren als wäßrige Dispersion, die durch Emulgieren des Alkylketendimeren in Gegenwart eines kationischen Emulgators erhältlich ist,
2. b) 0,1 bis 40 Gew.-% mindestens eines kationischen Tensids aus der Gruppe der quartären Diesterammoniumsalze, der quartären Tetraalkylammoniumsalze, der quartären Diamidoammoniumsalze, der Amidoaminoester und der Imidazoliumsalze und gegebenenfalls.
3. c) bis zu 50 Gew.-% mindestens eines nichtionischen Tensids und Wasser zur Ergänzung auf 100 Gew.-%.

The components of the pretreatment formulation described above may also be included in the fabric conditioner of the laundering agent. The fabric softeners contain, for example, amino-functionalized Silicones or other plasticizers, such as cationic surfactants or lubricants. For example, laundry pre-treating agents to be used for the anti-wrinkle finish include

1. a) 0.1 to 40, preferably 1 to 25 wt .-% of a C ₁₄ - to C ₂₂ -Alkylketendimeren as an aqueous dispersion obtainable by emulsifying the alkylketene dimer in the presence of a cationic emulsifier,
2. b) 0.1 to 40 wt .-% of at least one cationic surfactant from the group of diester quaternary ammonium salts, the quaternary tetraalkylammonium salts, the quaternary Diamidoammoniumsalze, the Amidoaminoester and the imidazolium salts and optionally.
3. c) up to 50 wt .-% of at least one nonionic surfactant and water to supplement to 100 wt .-%.

Suitable cationic surfactants which are preferably present in an amount of from 3 to 30 percent by weight in the fabric laundering aftertreatment formulation include, for example, diester quaternary ammonium salts containing two C ₁₁ to C ₂₂ alk (en) ylcarbonyl-oxy (mono-bis pentamethylene) radicals and two C ₁ - to C ₃ alkyl or hydroxyalkyl radicals on the quaternary nitrogen atom and carry as counterion, for example, chloride, bromide, methosulfate or sulfate.

Quaternary diesterammonium salts are furthermore, in particular, those which have a C ₁₁ - to C ₂₂ -alk (en) ylcarbonyl-oxy-trimethylene radical which, at the middle C atom of the tri-methylene group, has a C ₁₁ - to C ₂₂ -alk ( en) carries ylcarbonyl-oxy radical, and have three C ₁ - to C ₃ alkyl or hydroxyalkyl radicals on the quaternary nitrogen atom and carry as counterion, for example, chloride, bromide, methosulfate or sulfate.

Quaternary tetraalkylammonium salts are in particular those which have two C ₁ - to C ₆ -alkyl radicals and two C ₈ - to C ₂₄ -alk (en) yl radicals on the quaternary nitrogen atom and as counterion, for example, chloride, bromide, methosulfate or Wear sulfate.

Quaternary diamidoammonium salts are in particular those containing two C ₈ to C ₂₄ -alk (en) ylcarbonylamino-ethylene radicals, a substituent selected from hydrogen, methyl, ethyl and polyoxyethylene with up to 5 oxyethylene units and as a fourth radical have a methyl group on the quaternary nitrogen atom and carry as counterion, for example, chloride, bromide, methosulfate or sulfate.

Amidoamino esters are, in particular, tertiary amines which have, as substituents on the N atom, a C ₁₁ - to C ₂₂ -alk (en) ylcarbonylamino (mono- to trimethylene) radical, a C ₁₁ - to C ₂₂ -alk (en) ylcarbonyl radical. oxy (mono- to trimethylene) radical and carry a methyl group.

Imidazolinium salts are in particular those which in the 2-position of the heterocycle a C ₁₄ - to C ₁₈ -alk (en) ylrest, at the neutral N-atom of a C ₁₄ - to C ₁₈ -alk (en) yl-carbonyl- (oxy or amino) -ethylene radical and on the positive charge-carrying N atom carry hydrogen, methyl or ethyl, counterions here are, for example, chloride, bromide, methosulfate or sulfate.

The textile laundry aftertreatment formulation may also contain the usual additives in fabric softeners in the usual amounts, e.g. nonionic surfactants, fragrances and dyes, stabilizers, fiber and color protective additives, viscosity modifiers, soil release additives, anti-corrosive additives, bactericides and preservatives.

Examples

The percentages in the examples mean wt .-%, unless otherwise stated in the context.

The following equipment was used: Equipment A

1% aqueous dispersion of a C ₁₆ / C ₁₈ -alkylketene dimer and cationic waxy maize starch (N content 0.063%) in a weight ratio of 6: 1.5.

Finishing equipment B

1% aqueous dispersion of a C ₁₆ / C ₁₈ -alkylketene dimer and modified polyethyleneimine in a weight ratio of 6: 1. The modified polyethylenimine was prepared by mixing 258 g of anhydrous polyethyleneimine containing 420 ethyleneimine units with 43.7 g of valeric acid and heating to a temperature of 150 to 180 ° C for 8 hours while continuously distilling off water from the reaction mixture. After cooling, the reaction product was taken up in water and the solids content of the solution adjusted to 25%. One then gave 75 g of a 22% aqueous solution of a bis (chlorohydrin) polyethylene oxide with 10 ethylene oxide units and heated the reaction mixture until the viscosity (measured at 20 ° C and a concentration of 21.6%) was 790 mPas.

Equipment C

1% aqueous dispersion of a C _{16 /} C ₁₈ -alkylketene dimer and cationic waxy maize starch (N content 0.33%) in a weight ratio of 6: 1.5.

Example 1 to 3

Cotton fabrics of the size indicated in Table 1 with a basis weight of 160 g / m ² were sprayed on both sides with the finishing agents A, B, and C, so that the application amount was 2%, based on the respective weight of the dry textile, and then hot-ironed in a slightly damp state, using the cotton program of the iron.

The treated tissue samples were washed for comparison with untreated tissue samples of the same size and ballast tissue with a liquid detergent at 40 ° C in an automatic household washing machine (load between 1.5 and 3.0 kg) and then dried in a drum dryer. The washing and drying was carried out five times in succession. For use came a standard washing or. Standard drying program (program color wash 40 ° C or program cupboard dry). After the fifth cycle, the tissue samples were scored visually according to the AATCC Test Method 124, where the grade 1 indicates that the tissue is very creased and has many wrinkles, while the score 5 is awarded for wrinkle and wrinkle-free tissue. The fabric samples treated with finishing agents A, B and C received scores between 3 and 4. In contrast, the scores for the untreated fabric samples ranged from 1 to 1.5, cf. Table 1. Table 1 BW ¹⁾ (40 cm x 40 cm) load 1.5 kg BW (40 cm x 40 cm) load 3.0 kg BW (40 cm x 80 cm) load 1.5 kg untreated 1 1 1 A 3.5 3 3 B 4 4 4 C 3.5 3 3.5 ¹⁾ BW: cotton

Of the individual tissue samples, the dry wrinkle recovery angle according to DIN 53890 was determined after five washing cycles. The larger the recovery angle, the more effective the dispersion. The results obtained are shown in Table 2. Table 2 BW (40 cm x 40 cm) load 1.5 kg Crease recovery angle Σ (chain & shot) untreated 104 ° A 137 ° B 152 ° C 143 °

Claims (12)

1. A process for wrinkleproofing cellulosic textiles by treating the textiles with a finish and drying the treated textiles, which comprises using a finish comprising aqueous dispersions of C₁₄- to C₂₂-alkylketene dimers that are obtainable by emulsifying at least one alkylketene dimer in the presence of a cationic emulsifier.
2. The process according to claim 1 wherein the aqueous dispersions of alkylketene dimers used are obtainable by emulsifying alkylketene dimers in the presence of cationic starch as emulsifier.
3. The process according to claim 1 or 2 wherein the cationic emulsifier used is a cationic starch having an amylopectin content of not less than 95% by weight.
4. The process according to claim 1 wherein the aqueous dispersions of alkylketene dimers used are obtainable by emulsifying alkylketene dimers in the presence of from 1 to 20% by weight, based on alkylketene dimers, of an emulsifier comprising

   (a) a copolymer formed from 5-80 mol% of N-vinylpyrrolidone and 95-20 mol% of at least one quaternized N-vinylimidazole and having a K value of not less than 20 (determined by the method of H. Fikentscher in 0.5 m aqueous sodium chloride solution at a polymer concentration of 0.1% by weight and 25°C) and/or

   (b) a condensation product obtainable by partial amidation of polyethyleneimines with monocarboxylic acids and subsequent condensation of the partially amidated polyethyleneimines with at least one bifunctional crosslinker, the condensation products having a viscosity of not less than 100 mPas in 20% by weight aqueous solution at 20°C.
5. The process according to claim 4 wherein the aqueous dispersions of alkylketene dimers include from 10 to 18% by weight, based on alkylketene dimers, of an emulsifier.
6. The process according to any of claims 1 to 5 wherein the aqueous dispersions of the alkylketene dimers additionally include up to 5% by weight, based on alkylketene dimers, of a stabilizer.
7. The process according to claim 6 wherein the stabilizer used is selected from ligninsulfonates, quaternary ammonium salts, naphthalenesulfonic acid-formaldehyde condensates, alkyl sulfates, alkylsulfonates, sulfonated polystyrenes, carboxylic acids, sorbitan esters, polycarboxylic acids having molar masses of from 300 to 20,000, polyvinylsulfonates, polyvinyl alcohols, polyamidosulfonic acids, salts of the acid compounds mentioned or mixtures thereof.
8. The use of aqueous dispersions of C₁₄- to C₂₂-alkylketene dimers that are obtainable by emulsifying at least one alkylketene dimer in the presence of a cationic emulsifier, as finishes for wrinkleproofing cellulosic textiles.
9. The use according to claim 8 wherefor the alkylketene dimers are used in amounts of from 0.1 to 10% by weight, based on the weight of the textiles.
10. The use according to claim 8 or 9 wherefor the finishes are added to the final rinse bath in the washing machine in a domestic laundering process.
11. The use of laundry aftertreatment compositions comprising

    a) from 0.1 to 40% by weight of a C₁₄- to C₂₂-alkylketene dimer as aqueous dispersion which is obtainable by emulsifying the alkylketene dimer in the presence of a cationic emulsifier

    b) from 0.1 to 50% by weight of a fabric conditioner and

    c) from 0 to 25% by weight of at least one nonionic surfactant and water ad 100% by weight, for wrinkleproofing cellulose textiles
12. The use of laundry aftertreatment compositions comprising

    (a) from 0.1 to 25% by weight of a C₁₄- to C₂₂-alkylketene dimer as aqueous dispersion, which is obtainable by emulsifying the alkylketene dimer in the presence of a cationic emulsifier

    (b) from 0.1 to 40% by weight of at least one cationic surfactant from the group of the quaternary diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary diamidoammonium salts, the amidoaminoesters and the imidazolinium salts and optionally

    (c) up to 50% by weight of at least one nonionic surfactant and water ad 100% by weight,
    for wrinkleproofing cellulose textiles