EP3122930A1 - Avoidance of textile wrinkles - Google Patents

Abstract

The problem addressed by the invention is that of reducing the wrinkling tendency of a cotton textile or other cellulosic textile by a method that can be applied in the home. This problem was solved by bringing the textile in contact with a shape-memory polymer that has a switching temperature in the range of 20 °C to 60 °C and subsequently increasing the temperature of the textile above the glass transition temperature of the polymer located thereon.

Description

 Avoiding textile wrinkles

The present invention relates to a household practicable process for ironing and / or wrinkle reducing equipment of textiles made of cellulosic material and the use of certain polymers obtainable from norbornene derivatives to reduce crease tendency and to facilitate the ironing of textiles made of cellulosic material.

Textiles made of cellulose, such as cotton or cellulose regenerated fibers (for example Modal or Lyocel) have from the consumer's point of view positive properties in terms of wearing comfort. However, a major disadvantage of these textiles is the slight creasing after washing and drying. This tendency to wrinkle is due to the swelling of the cellulose fibers and their low elastic restoring forces ("bounce") after deformation.

Therefore, it has long been common practice to iron cotton or cellulosic textiles after washing and drying and thus to bring them into the desired shape. For the consumer, however, it would be advantageous to be able to minimize the formation of wrinkles in the context of textile care, which would facilitate the work of ironing or, ideally, would make ironing completely superfluous.

In the textile production one tries with the help of permanent textile equipment by a cross linking of the cellulose molecules among themselves to reduce their tendency to crease. The crosslinking of the cellulose molecules increases the elasticity of the material. The anti-crease equipment is carried out as part of the textile finishing on the raw material. However, crosslinkers used in the textile industry, such as formaldehyde-urea and formaldehyde-melamine combinations, because of their toxicity or the conditions under which they must be used, are not suitable for use in detergents or household use suitable.

Formaldehyde-free crosslinking processes for cellulose are also known, for example from US 2004/0043915 A1 a crosslinking process which is carried out with the aid of hydroxyl-bearing polymer and polycarboxylic acids, in particular butanetetracarboxylic acid (BTCA). From the article by CMWelch in Textile Research Journal, 1988, 480-486 the use of tetracarboxylic acids for crosslinking cellulose fibers is known. These formaldehyde-free approaches of cellulose crosslinking with the aid of polycarboxylic acids may, from a toxicological point of view, be suitable in principle for home use. Unfortunately, the reactions of the carboxyl groups of polycarboxylic acids with the hydroxyl groups of the cellulose leading to esters both require a large amount on catalysts such as triazoles or hypophosphites or phosphites as well as high temperatures. This is not practical for a consumer product.

In another approach, as described for example by M. Hashem, P. Hauser and B. Smith in Textile Research Journal, 2003, 762-766, ion pair bonds are exploited for the crosslinking of the cellulose. Cotton usually has a content of carboxyl groups of about 10 ^{~ 6} mol / g. To get as many ion pair contacts as possible, the cellulose can be treated with chloro or bromoacetic acid to increase the number of its carboxyl groups. Interaction of the carboxylated cellulose with polycations, such as cationized chitosan, can result in ionic crosslinks that reduce the tendency to crease. Without the carboxylation, the effect is too small and carboxylation of cotton textiles with haloacetic acids is not considered for home use.

From the patent application CN 1793483 A there is known a process for producing modified cotton fibers comprising the steps of oxidizing bleached cotton fibers with periodate, removing the oxidizing agent, washing and drying the cellulose fibers, and crosslinking by reaction with an OH and NH 2 groups containing substance such as collagen, chitosan, silk fibroin or sericin.

Shape memory polymers are polymeric stimuli-responsive materials that can alter their shape under the influence of external stimuli such as light, magnetic field or heat. In a heat-controlled shape memory polymer, the permanent shape is usually determined by crystallization or glass transition. The action of mechanical forces can change the shape of the shape memory polymer. As the temperature is raised above a certain switch temperature, these polymers return from their temporarily altered form to their permanent shape.

It has surprisingly been found that the creasing tendency of a cotton or other cellulosic textile (for example regenerated cellulose fiber) can be reduced by contacting with a temperature-controlled shape memory polymer.

The invention therefore relates to a method which can be carried out in the household for the crease-reducing and / or ironing-facilitating finishing of textiles made of cellulose-containing material by contacting with a shape memory polymer which has a switch temperature in the range from 20 ° C. to 60 ° C., especially from 40 ° C to 58 ° C, and subsequently raising the temperature of the fabric above the glass transition temperature of the polymer thereon, for example by using a commercial iron. The cellulosic materials from which the textiles to be treated are made include cotton, regenerated cellulose fibers such as Modal or Lyocel, and blended fabrics of cotton or regenerated cellulose with other fabrics commonly used in clothing such as polyester and polyamide.

After placing the shape memory polymer on a textile of cellulosic material, such as cotton, and then raising the temperature above the glass transition temperature of the shape memory polymer, the polymer, and thereby the textile on which it is placed, gets its permanent shape. Appropriately, the textile is in a desired smooth shape, which, as well as the mentioned temperature increase, for example, by ironing can be achieved. In preferred embodiments of the invention, the textile is ironed following treatment with said polymer with a standard household iron. The tension created when the fabric is worn, combined with the cooling that occurs when the fabric is deposited, can lead to the formation of a so-called temporary shape of the polymer and thus of the textile that supports it, in which the textile may have wrinkles. The washing of the fabrics, possibly combined with the subsequent use of a dryer, raises the temperature of the fabrics above the switch temperature of the polymer, thereby returning to the permanent shape of the shape memory polymer and thus of the fabric bearing it.

The measures of the invention considerably reduce the creasing of textiles made of cellulosic material compared to the untreated starting textiles or a treatment with an aminopolysiloxane.

The assessment of the wrinkle-free effect can be done by measuring the crease recovery angle (KEW) according to DIN 53890: 1972.

The shape memory polymers used according to the invention preferably have a glass transition temperature in the range from 0 ° C to 100 ° C, in particular from 10 ° C to 50 ° C.

Preferably, the textile of cellulosic material at temperatures in the range of 10 ° C to 100 ° C, in particular from 20 ° C to 60 ° C, brought into contact with said polymer. In the event that the permanent shape of the shape memory polymer results only at higher temperatures, the textile is then heated to a correspondingly higher temperature.

The implementation of the invention can be carried out, for example, by bringing textiles made of cellulosic material into contact with an aqueous preparation containing said polymer. This can be done in the context of a normal washing process, which is carried out with the help of a household washing machine or by hand can be done. The said polymer in aqueous liquor is preferably used in the rinsing step, ie after the actual washing step, but can also be used in the washing step. Said polymer may be part of detergents or laundry aftertreatment agents commonly used in such washing processes, such as fabric softeners. The concentration of said polymer in aqueous treatment liquor is in particular in the range from 0.1 g / l to 100 g / l, more preferably 0.5 g / l to 50 g / l. However, said polymer can also be part of a laundry care product, which can be present in particular as a liquid spray product, which, after dilution with water or preferably undiluted, applied to a textile of cellulose-containing material, in particular sprayed on, without having to follow a washing process or the application must be preceded by a washing process immediately.

A further subject of the present invention is therefore a laundry, laundry aftertreatment or laundry care composition containing a shape memory polymer which has a switch temperature in the range of 40 ° C to 60 ° C.

Said polymer is preferably present in amounts of from 0.1% to 5%, more preferably from 0.3% to 2%, by weight in laundry, laundry or laundry care compositions. Said polymer can be present in a liquid or solid agent, whereby the single dosage (for example by a bag packing) of the agent is possible.

Shape memory polymers which are suitable according to the invention can be obtained, for example, by reacting cholic acid (5-norbornene-2-methyl) ester with optionally alkyl-end-capped alkoxylates of 5-norbornene-2-methanol under metathesis conditions. These can be described as described in Macromolecules 2012, pages 1924 to 1930 by means of catalysis by the complex [1, 3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] -dichloro (phenylmethylene) (tricyclohexylphosphine) ruthenium (Grubbs 2nd generation catalyst). It is not essential according to the invention whether the substituent on C2 of the norbornene is in the endo or exo position in the cholic acid (5-norbornene-2-methyl) ester and the polyether derivative of the general formula (I) defined below or whether these are mixtures of endo and exo compounds.

In preferred embodiments of the process according to the invention and of the agents according to the invention, the shape memory polymer is obtained by copolymerization of compounds of the general formula (I) in which R and R ^2, independently of one another, are hydrogen or a methyl group, R ^{3 is} hydrogen or an alkyl group having 1 to 4 carbon atoms and n is a number from 1 to 8, in particular 1 to 4, which can also assume broken values as average value,

with the cholic acid ester of 5-norbornene-2-methanol,

available. Preferred polymers are obtainable by polymerizing the compound of general formula (I) with the cholic acid ester of 5-norbornene-2-methanol in molar ratios ranging from 1: 4 to 4: 1, in particular from 1: 2 to 2: 1.

Another object of the invention is the use of by copolymerization of compounds of general formula (I),

in which R and R ^2, independently of one another, are hydrogen or a methyl group, R ^{3 is} hydrogen or an alkyl group having 1 to 4 carbon atoms and n is a number from 1 to 8, in particular 1 to 4, which can also assume broken values as average value,

polymers obtainable with the cholic acid ester of 5-norbornene-2-methanol to minimize the crease tendency of textiles made of cellulosic material. Another object of the invention is the use of such polymers to facilitate the ironing of textiles made of cellulosic material.

A cumulative effect of the invention results in some, for example 1 to 5, repeated applications of said polymer. The textile need not be ironed after each application of said polymer. Crease recovery angle improves from application to application. This cumulative effect allows the use of lower concentrations of the active ingredient according to the invention. Furthermore, it reduces the risk of damaging a textile by ironing in an undesirable form, for example a fold; Ironing errors can be corrected at the next application. For this reason, a dosage of the active substances essential to the invention which brings about a cumulative effect is preferred.

Detergents, laundry aftertreatment or laundry care products which contain the active ingredient to be used according to the invention or are used together or used in the process according to the invention may contain all customary other constituents of such agents which do not interact in an undesired manner with the active ingredients essential to the invention.

Such agent preferably contains synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1 to 18% by weight, in each case based on the total agent. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants which can be used with particular preference include the abovementioned sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids. The anionic surfactants that can be used also include the salts of sulfosuccinic acid esters, which are also known as alkyl sulfosuccinates or dialkyl sulfates. fosuccinate, and the monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols represent. Preferred sulfosuccinates contain Cs to Cis fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Another synthetic anionic surfactant is alkylbenzenesulfonate in question.

A further embodiment of the compositions comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range of 2 wt .-% to 25 wt .-%.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxylic acid amides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettsäurepolyhydroxyamide into consideration. So-called alkylpolyglycosides which are suitable for incorporation into the compositions according to the invention are compounds of the general formula (G) _n -OR ² , in which R ^{2 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. The glycoside component (G) _n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, Include arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1, 5, in particular between 1, 2 and 1, 4. Preferred monomer building block is because of the good Availability of glucose. The alkyl or alkenyl moiety R ^{2 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can be used to prepare useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a coconut oil alkyl radical, ie mixtures with essentially R ² = dodecyl and R ² = tetradecyl.

Nonionic surfactant is in agents which contain an active ingredient according to the invention or used in the context of the use according to the invention or the method according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with amounts in the upper part of this range are more likely to be found in liquid agents and particulate preferably contain lower amounts of up to 5 wt .-%.

Other optional surface-active ingredients are soaps, suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 12-18 fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably, soap is included in amounts of 0.1 to 5% by weight. In particular, in liquid agents containing an active ingredient according to the invention, however, higher amounts of soap can be contained, usually up to 20 wt .-%.

If desired, the compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.

Among these, esterquats are particularly preferred.

If desired, the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activators, especially in amounts ranging from 2% to 10% by weight. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents containing an active ingredient used in the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15% by weight and particularly preferably from 5 wt .-% to 15 wt .-%, respectively on total means, present, in particular percarbonate is used. The optionally present component of the bleach activators comprises the conventionally used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and Cyanurates, in addition to carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phe- nolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitro rilderivate such as trimethylammoniumacetonitrile salts. To avoid interaction with the peroxygen compounds, the bleach activators may have been coated and / or granulated in a known manner with coating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated by means of carboxymethylcellulose 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.

In a further embodiment, the composition contains water-soluble and / or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.

The agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The molecular weight of homopolymers of unsaturated carboxylic acids is generally intermediate

5000 g / mol and 200000 g / mol, those of the copolymer between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to

100000 g / mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-Cs carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt may be a derivative of a C4-Cs dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. Particularly preferred are vinyl alcohol derivatives which are an ester of short chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid and / or (meth) acrylate to maleic acid and / or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1, and in particular 2: 1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives is. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight. % to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or methallylsulfonate and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, are preferably not suitable as water-insoluble, water-dispersible inorganic builder materials above 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the stated upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding capacity, which can be determined according to the specifications of the German patent DE 24 12 837, is in the range of 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1, 1 to 1: 12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio of Na 2 O: SiO 2 of 1: 1, 9 to 1: 2.8 are preferably added in the course of the production as a solid and not in the form of a solution. Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2 O.sub.x + VH.sub.2O, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na 2 Si 2 O 5-yH 2 O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1, 9 to 2, 1, can be used in compositions which contain an active ingredient to be used according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal silicate, in particular zeolite, is present as an additional builder substance, the content of alkali metal silicate is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2 : 1 and especially 1: 1 to 2: 1. In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the agents containing an active ingredient to be used according to the present invention, used together with it or used in methods of the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the agents may contain other ingredients customary in detergents or cleaners. These optional constituents include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in agents which contain an active substance used according to the invention, up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0, 1% by weight to 2% by weight Complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, and up to 2% by weight, in particular from 0.1% by weight to 1% by weight, of foam inhibitors, the weight proportions in each case referring to the total agent.

Solvents that can be used in particular for liquid agents are, in addition to water, preferably those nonaqueous solvents which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the active compounds used in the invention are usually dissolved or in suspended form.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The usable cellulase may be an enzyme recoverable from bacteria or fungi which has a pH optimum preferably in the weakly acidic to weakly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®. Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.

To the optionally present in particular liquid agents usual enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.

Suitable foam inhibitors include long-chain soaps, in particular behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

The known polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR-) _a OH, also known as a polymeric diol H- (O- (CHR -) _a ) t _> OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -0- (CHR -) _a O- and also polymeric diol units - (0- (CHR ¹¹ -) _a ) bO-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polymers is in the range from 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. The acid underlying the remainder Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, metilitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Preferred diols HO- (CHR-) _a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH 2 -CHR -OH in which R has the abovementioned meaning are particularly preferred. Examples of diol components are ethyleneglycol, 1,2-propyleneglycol, 1,3-propyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol. If desired, the polyesters may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroseloic acid, oleic acid, linoleic acid, linoleic acid, linolenic acid , Eleostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, the 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms can carry, for example, tert-butylbenzoic acid. The end groups may also be based on hydroxymonocarboxylic acids having from 5 to 22 carbon atoms, including, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which include hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units Have molar weights from 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with a substance essential to the invention. The soil release polymers are preferably water-soluble, the term "water-soluble" being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8. Polymers used are preferably polymers However, these conditions have a solubility of at least 1 g per liter, in particular at least 10 g per liter.

In one embodiment of the invention, in particular the laundry care products used as aftertreatment agents may contain additional plasticizer components, preferably cationic surfactants. Examples of fabric softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile saliva.

Suitable examples are quaternary ammonium compounds of the formulas (II) and (III),

R - X ^" (|||); wherein in (II) R and R is an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{2 is} a saturated C ¹ -C ⁴ alkyl or hydroxyalkyl radical, R ^{3 is} either R, R or R ² or is an aromatic radical. X ^" represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these Examples of cationic compounds of the formula (II) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (III) are so-called ester quats. Esterquats are characterized by their good biodegradability and are preferred in the context of the present invention. Here, R ^{4 is} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁵ is H, OH or 0 (CO) R ⁷ , R ⁶ is independently of R ^{5 is} H, OH or 0 (CO) R ⁸ , wherein R ⁷ and R ⁸ are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms having 0, 1, 2 or 3 double bonds, m, n and p may each independently have the value 1, 2 or 3 have. X ^" can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof Preferred compounds are those for R ^5, the group 0 (CO) R ⁷ and for R ⁴ and R ^{7 are} alkyl radicals having 16 to 18 carbon atoms Particular preference is given to compounds in which R ⁶ additionally represents OH for compounds of the formula (III), methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl, methyl ammonium methosulfate or Methyl N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.

In a preferred embodiment, the agents contain the additional plasticizer components in amounts of up to 35% by weight, preferably from 0.1 to 25% by weight, more preferably from 0.5 to 15% by weight and especially from 1 to 10 Wt .-%, each based on the total agent.

In addition to the aforementioned components, the agents may contain pearlescing agents. Pearlescing agents give the textiles an extra shine and are therefore preferably used in mild detergents. Examples of suitable pearlescing agents are: alkylene glycol esters; fatty acid; partial glycerides; Esters of polybasic, optionally hydroxysubstituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms; Ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms, fatty acids and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Furthermore, liquid agents may additionally contain thickeners. To increase consumer acceptance, the use of thickening agents has proven particularly useful in gel-type liquid detergents. Naturally derived polymers which can be used as thickening agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethyl cellulose hydroxyethyl and -propylcellulose, and polymeric polysaccharide thickeners such as xanthan gum; In addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable. In a preferred embodiment, the textile care agents according to the invention contain thickeners, preferably in amounts of up to 10% by weight, more preferably up to 5% by weight, in particular from 0.1 to 1% by weight, in each case based on the total composition ,

Furthermore, the agents may additionally contain odor absorbers and / or color transfer inhibitors. In a preferred embodiment, the agents optionally contain from 0.1% to 2%, preferably from 0.2% to 1%, by weight of color transfer inhibitor which in a preferred embodiment of the invention comprises a vinylpyrrolidone polymer, Vinylimidazole, vinylpyridine-N-oxide, or a copolymer of these. Useful are, for example, polyvinylpyrrolidones having molecular weights of from 15,000 to 50,000, as well as polyvinylpyrrolidones having molecular weights over 1 000 000, in particular from 1 500 000 to 4 000 000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxylic acid amides, polyesters containing polyesters containing pyrrolidone groups and polyamides, grafted polyamidoamines, polyamine -N-oxide polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives off hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, wherein also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used. Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.

Preferred deodorizing substances are metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms and / or a rosin acid with the exception of the alkali metal salts and any desired mixtures thereof. A particularly preferred unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms is ricinoleic acid. A particularly preferred rosin acid is abietic acid. Preferred metals are the transition metals and the lanthanides, in particular the transition metals of Groups Villa, Ib and IIb of the Periodic Table, and lanthanum, cerium and neodymium, particularly preferably cobalt, nickel, copper and zinc, most preferably zinc. The cobalt, nickel and copper salts and the zinc salts are similarly effective, but for toxicological reasons, the zinc salts are to be preferred. It is advantageous and therefore particularly preferred to use as deodorizing substances one or more metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate. Cyclodextrins, as well as mixtures of the abovementioned metal salts with cyclodextrin, preferably in a weight ratio of from 1:10 to 10: 1, particularly preferably from 1: 5 to 5: 1 and in particular from 1, also prove to be suitable further deodorizing substances in the sense of the invention. 3 to 3: 1. The term "cyclodextrin" includes all known cyclodextrins, ie both unsubstituted cyclodextrins with 6 to 12 glucose units, in particular alpha-, beta- and gamma-cyclodextrins and also their mixtures and / or their derivatives and / or mixtures thereof.

The preparation of solid compositions used according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, with enzymes and any further thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the preparation of inventive compositions with increased Bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all components - optionally one layer at a time - in a mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric presses or rotary presses, with pressing forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN. Particularly in the case of multilayer tablets, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are predominantly introduced via the metering device, for example the washing machine, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.

Liquid or pasty compositions in the form of common solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients that can be given in bulk or as a solution in an automatic mixer.

In a particularly preferred embodiment, the agents are present, preferably in liquid form, as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.

The funds can be packed, for example, in foil bags. Pouches made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or hand basin, possible. The film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature. There are numerous processes in the prior art for producing water-soluble detergent portions, which are basically also useful in the context of the present invention. The best known methods are the tubular film processes with horizontal and vertical sealing seams. Also suitable for the production of film bags or dimensionally stable detergent portions is the thermoforming process (thermoforming process). However, the water-soluble envelopes need not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.

Furthermore, methods for producing water-soluble capsules of polyvinyl alcohol or gelatin are known, which in principle offer the possibility to provide capsules with a high degree of filling. The methods are based on introducing the water-soluble polymer into a shaping cavity. The filling and sealing of the capsules takes place either synchronously or in successive steps, in which case the filling of the capsules takes place through a small opening in the latter case. The capsules are filled, for example, by a filling wedge, which is arranged above two drums rotating against each other, which have spherical half-shells on their surface. The drums carry polymer bands that cover the hemispherical cavities. At the positions where the polymer band of one drum coincides with the polymer tape of the opposite drum, a seal takes place. In parallel, the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelhalbschalenkavitäten. A process for the preparation of water-soluble capsules, in which initially the filling and then the sealing takes place, is based on the so-called Bottle-Pack ^® method. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.

The shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof , Blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and Clariant L648. The water-soluble thermoplastic used to prepare the portion may additionally optionally contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers, exhibit. It is preferred if the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol -1, preferably from 1 1 .000 to 90,000 gmol ^-1 , more preferably from 12,000 to 80,000 gmol ^-1 and especially from 13,000 to 70,000 gmol ^-1 is located. It is further preferred if the thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight of the water-soluble polymeric thermoplastic.

Examples

Example 1: Synthesis of a shape memory polymer a) Preparation of the cholic acid ester of 5-norbornene-2-methanol

2.04 g of 5-norbornene-2-methanol, 6.71 g of cholic acid and 0.2 g of 4-dimethylaminopyridine were dispersed in 40 ml of dichloromethane under a nitrogen atmosphere. The solution is cooled to 0 ° C and 3.77 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride are added. The mixture was stirred at room temperature for 17 hours. The organic phase was washed with 50 ml of hydrochloric acid (0.1 M), 50 ml of NaHCCb solution (10% by weight) and 3 times with 50 ml of saturated NaCl solution. The organic phase was dried and the solvent removed. The residue was purified by flash chromatography (silica gel / ethyl acetate). b) Preparation of methoxytriethylene glycol p-toluenesulfonate

19.85 g of p-toluenesulfonyl chloride were dissolved in 100 ml of pyridine under a nitrogen atmosphere. At room temperature, 18.99 g of triethylene glycol monomethyl ether was added over 15 minutes. The mixture was cooled to 0 ° C and stirred with cooling through an ice bath overnight. The reaction mixture was washed with 100 ml of water, 100 ml of hexane and 100 ml of ethyl acetate. The remaining organic phase was neutralized with 1 g hydrochloric acid (2 M) and then with 25 ml of water is separated again. The solution was dried and the solvent removed. c) Preparation of the 5-norbornene-2-methyl-trioxyethylenemethoxy ether

1.35 g of sodium hydride were dispersed in 170 ml of dimethylformamide under a nitrogen atmosphere. 4.35 g of 5-norbornene-2-methanol were added dropwise. The solution was stirred for 10 minutes at room temperature and then heated to 60 ° C for one hour. A solution of 14.86 g of TosO (CH 2 CH 2 O) 3 CH 3 prepared in step b) in 20 ml of dimethylformamide was added dropwise at room temperature. The solution was stirred at room temperature for 10 minutes and then at 60 ° C overnight. 200 ml of water were added and the aqueous phase was extracted 3 times with 130 ml of ethyl acetate. The combined organic phases were washed with 200 ml NaHCOb solution (10% by weight) and 3 times with saturated NaCl solution. The solution was dried and the solvent removed. d) Preparation of the polymer

2 g of NTEG prepared in step c), 3.81 of NCA prepared in step a) and 6 mg of Grubbs catalyst (2nd generation) were dissolved in 30 ml of tetrahydrofuran, degassed in an ultrasound bath and 3

Stirred at 25 ° C for hours. By addition of hexane, the polymer was precipitated. The monomer ratio in the finished polymer was 1: 1. Its glass transition temperature (determined by DSC) was 55 ° C.

Example 2: Test

A solution of the polymer prepared in Example 1 in tetrahydrofuran (1 weight percent) was sprayed onto cotton fabric (type "Stella Royal" from the manufacturer Brenneth) to give a liquid uptake of 100% of the weight of the fabric ironed with a domestic iron (temperature setting three points).

Strips of 5 cm in length (in the warp direction) and 2 cm in width were cut from the fabric thus treated. On each strip was about 1 mg of polymer. The strips were glued with an adhesive strip so that a leg of 1 cm width remained freely foldable. For the loading phase, the thigh was folded over the edge of the tape and held down with a slide (glass plate) weighted at 1 kg. After 30 minutes loading time in the oven at 70 ° C, the weight and slide were removed and the strip left for the recovery phase at room temperature. After 30 minutes, the recovery angle was measured (EW1). This was followed by another 30 minutes recovery time, half of the strips again at 70 ° C in the drying oven, the second half of the strips at room temperature, before again the recovery angle (EW2 70 ° C, EW2 RT) was read. For comparison, the recovery angles of untreated cotton strips were measured under the same conditions. The values given in the table below (in °, averages of duplicate determinations) were obtained.

EW1 EW2 70 ° C EW2 RT

 treated 63.75 77.5 71, 25

untreated 42.5 57.5 60 It can be seen that the coating with the polymer leads to an increase in the recovery angle and thus a reduction in the crease tendency. In the case of untreated cotton, there is almost no difference between room temperature and 70 ° C in the second recovery phase. In contrast, treatment with the polymer shows an improvement of about 9% in recovery at 70 ° C compared to recovery at room temperature.

Claims

claims

Anspruch [en] A method of ironing and / or wrinkle reducing equipment of cellulosic fabric fabrics by contacting with a shape memory polymer having a switch temperature in the range of 20 ° C to 60 ° C and subsequently raising the temperature of the fabric the glass transition temperature of the polymer thereon.

2. The method according to claim 1, characterized in that the shape memory polymer is used in an aqueous liquor, in which the concentration of shape memory polymer called polymer in the range of 0, 1 g / l to 100 g / l, in particular of 0.5 g / l to 50 g / l.

3. The method according to claim 1, characterized in that the shape memory polymer is part of a laundry care product, which is applied after dilution with water or undiluted to the textile.

4. A laundry, laundry aftertreatment or laundry care composition comprising a shape memory polymer having a switch temperature in the range of 20 ° C to 60 ° C.

5. Composition according to claim 4, characterized in that it contains the shape memory polymer in amounts of 0.1 wt .-% to 5 wt .-%, in particular from 0.3 wt .-% to 2 wt .-%.

6. The method according to any one of claims 1 to 3 or means according to claim 4 or 5, characterized in that the shape memory polymer by copolymerization of compounds of general formula (I),

in which R and R ^2, independently of one another, are hydrogen or a methyl group, R ^{3 is} hydrogen or an alkyl group having 1 to 4 carbon atoms and n is a number from 1 to 8, which can also assume broken values as an average value,

 with the cholic acid ester of 5-norbornene-2-methanol.

7. Use of by copolymerization of compounds of general formula (I), in which R and R ^2, independently of one another, are hydrogen or a methyl group, R ^{3 is} hydrogen or an alkyl group having 1 to 4 carbon atoms and n is a number from 1 to 8, which can also assume broken values as an average value,

 polymers obtainable with the cholic acid ester of 5-norbornene-2-methanol to minimize the crease tendency of textiles made of cellulosic material.

8. Use of by copolymerization of compounds of general formula (I),

in which R and R ^2, independently of one another, are hydrogen or a methyl group, R ^{3 is} hydrogen or an alkyl group having 1 to 4 carbon atoms and n is a number from 1 to 8, which can also assume broken values as an average value,

 polymers obtainable with the cholic acid ester of 5-norbornene-2-methanol to facilitate the ironing of textiles made of cellulosic material.

9. A method or composition according to claim 6 or use according to claim 7 or 8, characterized in that in the polymer of general formula (I) n is a number from 1 to 4, and / or the polymer by polymerization of a compound of general formula (I) and the cholic acid ester of 5-norbornene-2-methanol in molar ratios in the range of 1: 4 to 4: 1, in particular 1: 2 to 2: 1 is available.

10. A method or use according to any one of the preceding claims, characterized in that the textile is ironed after treatment with the shape memory polymer with a conventional household iron.