WO2017129424A1

WO2017129424A1 - Amphiphilic, carboxyalkylated polyamines as active anticrease ingredient

Info

Publication number: WO2017129424A1
Application number: PCT/EP2017/050712
Authority: WO
Inventors: Doris Dahlmann; Martina Seiler; Martina Hutmacher; Christina RÖLEKE; Karin Kania; Frank Janssen
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2016-01-28
Filing date: 2017-01-13
Publication date: 2017-08-03
Also published as: DE102016201293A1

Abstract

The present invention relates to a washing or cleaning composition for textiles, including at least one surfactant and at least one amphiphilic, carboxyalkylated polyamine as active anticrease ingredient, and to the use of amphiphilic, carboxymethylated polyamines as active anticrease ingredients for textiles. Method of reducing creasing in textiles during washing, characterized in that said amphiphilic, carboxyalkylated polyamine is contacted with the textile, especially as a constituent of a washing or cleaning composition.

Description

"Amphiphilic, carboxyalkylated polyamines as anti-crease agents"

The present invention relates to a washing or cleaning agent for textiles, which comprises at least one surfactant and at least one amphiphilic, carboxyalkylated polyamine as Antiknitterwirkstoff and the use of amphiphilic, carboxyalkylated polyamine as Antiknitterwirkstoff for textiles.

Ironing is a very annoying task, according to consumer surveys. So far, it has not yet been possible to develop a detergent that improves the surface smoothness of clothing after washing to the extent that the ironing is unnecessary.

While in the textile equipment Antiknitterverbindungen are known, the application in the detergent is very limited. In textile finishing, however, the equipment is mainly cellulose-containing textiles during the manufacture of textile materials. The textiles treated in this way have the advantage over the untreated cellulose textiles after the washing process that they have less wrinkles and wrinkles, are easier to iron and are softer and smoother.

Compounds that are used directly in a washing or cleaning agent and there cause a surface smoothness of the textiles in the washing process, are barely known. This is due to the fact that corresponding compounds are either not incorporated into detergents or cleaners, especially if they are liquid, since it leads to instabilities of detergents or cleaning agents, or their effect in the washing process itself is lost. The object of the present invention is now to improve this secondary property in the washing process. Surprisingly, it has been found that the use of certain urethane-based polymers results in a metrologically significant improvement in the surface smoothness of textiles.

In a first subject of the invention, the object underlying the invention is achieved by a washing or cleaning agent for textiles comprising at least one surfactant and additionally at least one amphiphilic, carboxyalkylated polyamine.

An amphiphilic compound consists of a polar (hydrophilic) and an apolar (hydrophobic) moiety. It is preferred according to the invention if the hydrophilic moiety of said polyamine is represented by a carboxyalkylated polyamine moiety and the hydrophobic moiety is represented by at least one hydrocarbon moiety of at least 8 to 20 carbon atoms. A hydrocarbon radical is a structural fragment made up exclusively of carbon and hydrogen. Unless otherwise explicitly defined, a hydrocarbon radical is unsubstituted.

For the purposes of the invention, a polymer is a substance which is composed of a large number of molecules by means of polyreaction, in which one or more types of atoms or atomic groups (so-called constitutive units, basic building blocks or repeating units) are repeatedly arranged next to one another. Such polymer molecules have a molecular weight of at least 1000 g / mol.

In a further subject of the invention, the object underlying the present invention by the use of amphiphilic, carboxyalkylated polyamines, as described in the present application, as Antiknitterwirkstoff for textiles.

In a still further aspect of the invention, the present invention relates to a process for the reduction of wrinkles in textiles during laundering, characterized in that an amphiphilic, carboxyalkylated polyamine as described in the present application, and in particular as a constituent of a washing or cleaning agent with the Brings textile in contact.

Textiles in the context of the present invention comprise textile fibers, the line-shaped textile structures produced therefrom such. B. yarns and threads, the sheet-like textile structures such. As fabrics, knitted fabrics, knitted fabrics, braids, Nähgewirke, nonwovens and felts and the spatial textile structure (body) such. As textile hoses, hosiery or semi-finished textile products for reinforced plastic components as well as those finished goods that are brought using the aforementioned products by packaging, setting up and / or other operations in salable condition for distribution to the processor, the retail or the end user. The textiles may consist of or include any known materials, such as natural or synthetic materials, such as cotton, linen, hemp, polyester, viscose, wool, virgin wool, etc. Preferably, the textile comprises at least one natural material selected for the purposes of the present invention cotton, linen, wool and / or hemp, more preferably cotton or cotton.

Detergents or cleaning agents in the context of the invention are all types of detergents or cleaners, such as heavy-duty detergents, color detergents, mild detergents, etc. Likewise, the invention also includes fabric softeners. The agents according to the invention (Detergents or cleaning agents) preferably come into contact with the textile during a washing or cleaning process, which includes the fabric softening process.

The washing or cleaning agent according to the invention may be solid or liquid. In particular, it is liquid. For example, these are liquid detergents or fabric softeners. Surprisingly, it has been found that the polyamines according to the invention can be incorporated well into the liquid detergents. Corresponding liquid agents are storage stable. Flocculation or separation is not evident. At the same time results after a washing or cleaning process with the washing or cleaning agent according to the invention a significantly metrological better surface smoothness of the textiles.

A polyamine is an organic compound that carries at least two amino groups.

The amphiphilic, carboxyalkylated polyamine according to the invention preferably carries at least one carboxyalkyl group selected from carboxymethyl and carboxyethyl. Most preferably, said polyamine contains at least one carboxymethyl group. Most preferably, said polyamine carries at least two carboxyalkyl groups, especially at least two carboxyalkyl groups selected from carboxymethyl, carboxyethyl, with at least two carboxymethyl groups being again preferred. Under carboxyalkyl according to the invention, both the acid form and the salt form of the carboxyalkyl understood.

The amphiphilic, carboxymethylated polyamine in the context of the present invention and its individual aspects is preferably an oligomer or polymer having an N-atom-containing backbone with at least two amino groups which i) carries at least two carboxyalkyl groups which are bonded via an N- atom. Atom bind to the polyamine and

ii) carries at least one C8-C22 hydrocarbon radical.

The polyamine, prior to its carboxyalkylation and hydrophobization (i.e., the pure polyamine backbone), has primary amino functions at the terminals (terminus and / or side chains) and preferably both secondary and tertiary amino functions internally; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine.

In one embodiment of the invention, the ratio of primary to secondary amino groups in the polyamine prior to carboxyalkylation and hydrophobization is preferably in the range of 1: 0.5 to 1: 1.5, more preferably in the range of 1: 0.7 to 1: 1. The ratio of primary to tertiary amino groups in the polyamine before the carboxyalkylation is preferably in the range of 1: 0.2 to 1: 1, in particular in the range of 1: 0.5 to 1: 0.8. Preferably, this has Polyamine prior to carboxyalkylation and hydrophobization an average molecular weight in the range of 300 g / mol to 5000 g / mol, in particular from 550 g / mol to 5000 g / mol.

The N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1, 2-propylene groups, 1, 3-propylene groups, and mixtures thereof.

Polyamines bearing ethylene groups as said alkylene group are also referred to as polyethyleneimine or PEI. Carboxyalkylated PEI, in particular carboxymethylated PEI, is a preferred carboxyalkylated polyamine according to the invention.

Very particularly preferred amphiphilic, carboxyalkylated polyamines are disclosed in the document WO 2010/20599 A2. A very particularly preferred amphiphilic, carboxyalkylated polyamine is selected from at least one compound of the formula (I),

wherein

R is a hydrocarbon radical having 12 to 22 carbon atoms,

R ^{2 for} each repeating unit is independently a group -CH ² COOM or -CH 2 CH 2 COOM, in which M stands for H, Na ⁺ , K ⁺ or NH ₄ ⁺ ,

R ³ and R ⁴ independently of one another are H, methyl, 2-hydroxyethyl, a group -CH 2 COOM or a group -CH 2 CH 2 COOM, where M is H, Na ⁺ , K ⁺ or NH ₄ ⁺ ,

p is 0 or 1,

m per repetition unit stands independently for 2 or 3 and

n is 1, 2, 3, 4, 5 or 6.

It is inventively preferred if according to formula (I) p is 1.

It is preferred according to the invention, when according to formula (I) R ² , R ³ and R ^{4 is} a group - CH 2 COOM or -CH 2 CH 2 COOM, where M is H, Na ⁺ , K ⁺ or NH ₄ ⁺ . Most preferably, R ² , R ³ and R ^{4 are} a group -CH 2 COOM in which M is H, Na ⁺ , K ⁺ or NH ₄ ⁺ (in particular wherein M is H or Na ⁺ ).

It is inventively preferred if according to formula (I) m is 3. It is inventively preferred if according to formula (I) n is 2, 3, or 4.

It is inventively preferred if the polyamine according to formula (I) has a molecular weight between 400 g / mol and 2000 g / mol, in particular between 500 g / mol and 1000 g / mol.

Very particularly preferred compounds of the formula (I) are sodium cocoamphopolycarboxyglycinates (available as Ampholak 7CX / C from Akzo Nobel), sodium tallowamphopolycarboxyglycinates (available as Ampholak 7TX from Akzo Nobel).

The washing or cleaning agent according to the invention preferably contains amphiphilic, carboxyalkylated polyamine in an amount of from 0.01 to 30% by weight, in particular from 0.05 to 20% by weight, in particular from 0.05 to 10% by weight, in particular from 0, 1 to 5 wt .-%, especially from 0.1 to 4 wt .-%.

Unless otherwise stated, in the present application, the amounts in percent relate to wt .-% based on the total weight of the composition according to the invention. If ranges are specified, then the values in between are to be regarded as disclosed.

The washing or cleaning agent according to the invention may be liquid or solid. Suitable liquid detergents or cleaners comprise at least one surfactant selected from nonionic, anionic and amphoteric surfactants. These additional surfactants are different from the amphiphilic, carboxyalkylated polyamines. Suitable liquid washing or cleaning agents are described, for example, in WO 201 1/1 17079A1, WO 2013 / 186170A1 or WO 2013 / 107579A1, to which reference is hereby expressly made. If the washing or cleaning agent is solid, it comprises one or more washing- or cleaning-active substances, preferably selected from the group of builders, the surfactants, polymers, bleaching agents, bleach activators and enzymes.

The washing or cleaning agent according to the invention preferably has a pH (20 ° C.) in the basic range, ie greater than 7, in particular in the range from greater than 7 to 14, preferably from 7.5 to 12, in particular from 8 to 10 ,

The surfactants for both a solid and for a liquid formulation of the agent according to the invention, as well as further optional constituents, are further elucidated below:

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants. According to the invention, the washing or cleaning agent may comprise one or more of the surfactants mentioned. It particularly preferably comprises at least one or more anionic surfactants (anionic surfactants), which are preferably contained in a proportion of 5 to 50%, in particular from 5 to 35% in the agent according to the invention.

The at least one anionic surfactant is preferably selected from the group comprising C9- to C13-alkylbenzenesulfonates, olefinsulfonates, C12- to cis-alkanesulfonates, ester sulfonates, alk (en) ylsulfates, fatty alcohol ether sulfates and mixtures thereof. It has been found that these sulfonate and sulfate surfactants are particularly suitable for the preparation of stable liquid compositions with yield point. Liquid compositions comprising as anionic surfactant C 9 to C 13 alkylbenzenesulfonates and fatty alcohol ether sulfates have particularly good dispersing properties. Preferred surfactants of the sulfonate type are C9- to C3-alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of C12 to C18 monoolefins with terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are C12 to Cis alkanesulfonates and the esters of sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 to C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 to C 20 oxo alcohols and those Half-ester secondary alcohols of these chain lengths are preferred. From a washing-technical point of view, preference is given to the C 12- to C 16 -alkyl sulfates and C 12- to cis-alkyl sulfates and also C 6 - to C 15 -alkyl sulfates. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also, fatty alcohol ether sulfates, such as the sulfuric acid monoesters of straight-chain or branched C7 to C2i alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9 to Cn alcohols having on average 3.5 moles of ethylene oxide (EO) or C12- to cis-fatty alcohols with 1 to 4 EO, are suitable.

It is preferred that the washing or cleaning agent contains a mixture of sulfonate and sulfate surfactants. In a particularly preferred embodiment, the composition contains C 9- to C 13 -alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant.

In addition to the anionic surfactant, the composition may also contain soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids. The anionic surfactants and the soaps may be in the form of their sodium, potassium or magnesium or ammonium salts. Preferably, the anionic surfactants are in the form of their sodium salts. Further preferred counterions for the anionic surfactants are also the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.

The composition may also comprise at least one nonionic surfactant in addition to the anionic surfactant. The nonionic surfactant includes alkoxylated fatty alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof.

The nonionic surfactant used is preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 5 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C12 to Cw alcohols with 4 EO or 7 EO, C9 to Cn alcohol with 7 EO, C13 to C15 alcohols with 5 EO, 7 EO or 8 EO, C12 to Os Alcohols with 5 EO or 7 EO and mixtures of these. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO (propylene oxide) groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C16 to Cis fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. Particularly preferably, the washing, cleaning, aftertreatment or washing aid contains a C12 to Cis fatty alcohol with 7 EO or a C13 to Ci5 oxo alcohol with 7 EO as a nonionic surfactant.

The washing or cleaning agent may further comprise one or more solvents. These may be water and / or non-aqueous solvents. Preferably, the composition contains water as the main solvent. The composition may further comprise non-aqueous solvents. Suitable non-aqueous solvents include monohydric or polyhydric alcohols, alkanolamines or glycol ethers. Preferably, the solvents selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, Propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents.

The composition according to the invention may further comprise builders and / or alkaline substances. As builders, for example, polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 600 to 750,000 g / mol.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Suitable builders which may be present in the composition according to the invention are, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Organic builders which may furthermore be present in the composition according to the invention are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA) and derivatives thereof and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. However, preference is given to using soluble builders, such as, for example, citric acid, or acrylic polymers having a molar mass of from 1,000 to 5,000 g / mol.

For the purposes of the present invention, alkaline substances or wash alkalis are chemicals for raising and stabilizing the pH of the composition.

In a preferred embodiment, the washing or cleaning agent further comprises at least one enzyme. Suitable enzymes are the enzymes previously mentioned as additives. According to the invention it is also possible that several different enzymes are included. In particular, enzyme granules are contained in a proportion of 4 to 15 wt .-%, preferably from 7 to 12 wt .-%, each based on 100 wt .-% of the total washing or cleaning agent. In a particularly preferred embodiment, the at least one enzyme is present as granules.

The detergents or cleaners according to the invention preferably contain enzymes in total amounts of from 1 × 10 ^-8 to 5% by weight, based on active protein. Preferably, the enzymes are in a total amount of 0.001 to 4 wt .-%, more preferably from 0.01 to 3 wt .-%, even more preferably from 0.05 to 1, 25 wt .-% and particularly preferably from 0, 2 to 1, 0 wt .-% in these detergents or cleaning agents.

In principle, all enzymes known from the state of the art for textile treatment are suitable as enzyme for use as an additive. Preferably, it is one or more enzymes which can develop a catalytic activity as an additive of a detergent, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, xylanase, xanthanase, .beta.-glucosidase, Carrageenase, perhydrolase, oxidase, oxidoreductase and mixtures thereof. Preferred hydrolytic enzymes include, in particular, proteases, amylases, in particular α-amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, β-glucanases, and mixtures thereof. Proteases, amylases and / or lipases and mixtures thereof are particularly preferred, and proteases are particularly preferred. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is in an advanced form under the trade name Alcalase ^® of from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® protease variants derived. Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym ^®, Natalase ^®, Kannase® ^® and Ovozyme ^® from Novozymes, the ^® under the trade names Purafect ^®, Purafect ^® OxP, Purafect Prime, Excellase ^® and Properase.RTM ^® from Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and Protease ^P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and their further developments improved for use in detergents or cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the a-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the enhancements available under the trade names Fungamyl.RTM ^® by the company Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Other advantageous commercial products are for example the Amylase-LT ^®, and Stainzyme® ^® or ultra Stainzyme® ^® or Stainzyme® plus ^®, the latter also from the company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention.

Examples of lipases or cutinases which can be used according to the invention, which are contained in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors, are the lipases which are originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those With the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases which are likewise useful are sold by Amano under the names Lipase ^CE® , Lipase ^P® , Lipase ^B® or Lipase ^CES® , Lipase ^AKG® , Bacillus sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist Brocades preparations M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Depending on the purpose, cellulases may be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement each other in terms of their various performance aspects. These performance aspects include in particular the contributions of the cellulase to the primary washing performance of the composition (cleaning performance), to the secondary washing performance of the composition (anti-redeposition effect or graying inhibition), to softening (tissue effect) or to the exercise of a "stone-washed" effect.A useful fungal, endoglucanase (EC ) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ^®. the products Endolase® ^® and Carezyme ^®, likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG H. insolens DSM 1800. Further commercial products of this company are Cellusoft ^®, Renozyme ^® and Celluclean ^®. Also usable are, for example, the 20 kD eG Melanocarpus that from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^® Other commercial products of AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ^{® is} available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ^® Neutra. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from melanocarpus, in particular melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.

Furthermore, in particular for the removal of certain problem soiling, further enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-splitting enzymes and β-glucanases. The Bacillus subtilis Glucanase is available under the name Cereflo ^® from Novozymes. According to the invention particularly preferred hemicellulases are mannanases, which are marketed under the trade names man Away ^® by the company Novozymes or Purabrite ^® by the company Genencor. The pectin-destroying enzymes in the context of the present invention are also counted enzymes with the designations pectinase, pectate lyase, pectin esterase, pectin methoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectin esterase, pectin-pectin hydrolase, pectin-polymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin-polygalacturonase, Endo-polygalacturonase, poly-a-1, 4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1, 4-a-galacturonidase, exopolygalacturonase, poly (galacturonate) hydrolase, exo-D-galacturonase, exo-D Galacturonanase, exopoly-D-galacturonase, exo-poly-o galacturonosidase, exopolygalacturonosidase or exopolygalacturanosidase. Examples in this regard, suitable enzymes for example, under the name Gamanase ^®, Pektinex AR ^®, X-Pect ^® or Pectaway ^® by the company Novozymes, UF under the name Rohapect ^®, Rohapect TPL ^®, Rohapect PTE100 ^®, Rohapect MPE ^®, Rohapect MA available plus HC, Rohapect DA12L ^®, Rohapect 10L ^®, Rohapect B1 L ^® by the company AB Enzymes and under the name Pyrolase® ^® by the company Diversa Corp., San Diego, CA, United States.

Of all these enzymes, particular preference is given to those which have been stabilized per se with respect to oxidation in a comparatively stable manner or, for example, via point mutagenesis. Among the above-mentioned commercial products Everlase ^® and Purafect ^® OxP as examples of such proteases and Duramyl ^® are particular to cite as an example of such a-amylase.

It is preferred that an optical brightener stilbenedisulfonic acids as an additive from the substance classes of distyrylbiphenyls, the stilbenes, the 4,4 ^{^{'diamino-2,2',}} coumarins, the dihydroquinolinones, the 1, 3-diaryl pyrazolines, naphthalimides of, benzoxazole systems, benzisoxazole systems, benzimidazole systems, heterocyclic substituted pyrene derivatives, and mixtures thereof. These classes of optical brighteners have high stability, high light and oxygen resistance, and high affinity for fibers.

Particularly good and stable, the following optical brightener, which consists of the group consisting of disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulfonate, disodium 2,2 '- bis (phenyl-styryl) disulfonate, 4,4'-bis [(4-anilino-6- [bis (2-hydroxyethyl) amino] -1, 3,5-triazin-2-yl) amino] stilbene 2,2,2'-disulfonic acid, hexasodium 2,2 '- [vinylenebis [(3-sulphonato-4,1-phenylene) imino [6- (diethylamino) -1, 3,5-triazine-4,2-diyl ] imino]] bis (benzene-1, 4-disulfonate), 2,2 '- (2,5-thiophenediyl) to [5-1, 1 -dim are selected to incorporate as an additive. Both the powdered and the liquid detergent or cleaning agent may contain one or more other components described in the prior art, such as optical brighteners, complexing agents, bleaching agents, bleach activators, antioxidants, enzyme stabilizers, antimicrobial agents, graying inhibitors, anti-redeposition agents, pH adjusters , Electrolytes, detergency boosters, vitamins, proteins, foam inhibitors and / or UV absorbers.

A laundry softener according to the invention as an embodiment of a laundry detergent or cleaning agent comprises conventional laundry softeners, such as one or more fabric softening compounds, fragrance compositions and other additives such as alcohols, amphoterols, nonionic surfactants, pH buffers, enzymes, fungicides or antioxidants.

A fabric softener usually comprises a fabric softening compound. It is preferred that the fabric softening compound is selected from the group of quaternary ammonium compounds, polysiloxanes, fabric softening clays and mixtures thereof. These compounds are effective and commercially available fabric softening compounds.

Furthermore, it is particularly advantageous that the fabric softener contains a quaternary ammonium compound as fabric softening compound. It is particularly preferred that the quaternary ammonium compound is a compound of the following general formula (B):

in which

R ^{4 is} an aliphatic alk (en) yl radical having 1 1 to 21 carbon atoms with 0, 1, 2 or 3

Double bonds and / or optionally with substituents;

R ⁵ is H, OH or O (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 alk (en) ylrest having 1 1 to 21 carbon atoms with 0, 1, 2 or 3 Double bonds is,

m, n and p can each independently have the value 1, 2 or 3 and

X ^" may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these anions.

In fabric softeners which contain quaternary ammonium compounds and in particular mono-, di- and / or triesters of fatty acids with alkanolamines as fabric-softening compounds achieved a particularly strong increase in viscosity by a Ci6-fatty material, which is contained in a preferred embodiment in the final product according to the invention.

The pH of the fabric softener is preferably in the range from 1 to 6, particularly preferably from 1.5 to 3.5.

In addition, the laundry softener usually also comprises a thickener, for example a cationic acrylic polymer.

Preferably, the cationic acrylic polymer is in the form of solid particles. The particles are preferably spherical particles, which in particular have a spherical shape. The average particle size (average volume diameter) of the solid particles is in particular in the range of 100 to 900 μιη, preferably in the range of 200 to 800 μιη, more preferably in the range of 250 to 750 μιη. If the solid particles are in spherical form, the diameter of the sphere corresponds to the particle size. For all other spherical forms, the particle size corresponds to the size of the particles with the greatest spatial extent. The particle size can be determined by means of scanning electron micrographs (SEM).

The cationic acrylic polymer is hygroscopic. With a particle size of 100 μιη or less, in particular of 200 μιη or less, especially of 250 μιη or less so much water can be accumulated on the surface of the particles that a stable suspension is no longer obtained. Rather, it then comes to a swelling of the cationic acrylic polymer, so that after mixing with a suspending agent according to the invention no meterable suspension, but a highly viscous, rubbery mass is obtained. On the other hand, if the particle size is more than 900 μm, these large and therefore also heavy particles can sediment faster than particles having a size of 900 μm or less, in particular of 800 μm or less, especially of 750 μm or less.

Suitable cationic acrylic polymers which can be used as thickeners according to the invention are described, for example, in WO 03/102043 A1 on pages 1 to 4, to the content of which reference is made in their entirety. The cationic acrylic polymers of the invention are therefore preferably made

a) a water-soluble ethylenically unsaturated monomer or a mixture of these monomers which comprise at least one cationic monomer,

b) at least one crosslinking agent in an amount of more than 50 ppm, based on the weight of the compound a), and

c) at least one chain Überträg he

educated. The cationic monomer preferably corresponds to a compound according to the following compound (I)

in which independently

Ri is hydrogen or methyl,

R2 is hydrogen or O to C4-alkyl,

R 3 is C 1 -C ₄ -alkylene,

R4, R5 and R6 are each independently hydrogen or O to C4 alkyl,

X -O- or -NH- and

Y is Cl, Br, I, hydrogen sulfate or methosulfate

represent.

The respective alkyl groups may be linear or branched.

The crosslinking agent b) preferably comprises at least two ethylenically unsaturated units. Suitable preferred crosslinking agents are divinylbenzene, tetraallylammonium chloride, allyl acrylates and allyl methacrylates, diacrylates and dimethacrylates of glycols and polyglycols, butadiene, 1,7-octadiene, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid, Ν, Ν'-methylenebisacrylamide and polyol polyallyl ethers such as polyallylsucrose and pentaerythritol triallyl ether , Particularly preferred crosslinking agents are

Tetraallylammonium chloride, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid and Ν, Ν'-methylenebisacrylamide. Very particular preference is given to tetraallylammonium chloride and Ν, Ν'-methylenebisacrylamide as crosslinking agent. It is also possible to use mixtures of the crosslinking agents.

In a preferred embodiment, the cationic acrylic polymer comprises at least one crosslinking agent b) in a proportion of 50 to 1200 ppm, preferably 500 to 1000 ppm and more preferably 700 to 900 ppm, each based on the weight of component a).

The chain transfer agent c) is preferably selected from the group comprising mercaptans, malic acid, lactic acid, formic acid, isopropanol and hypophosphites. The content of chain transfer agent c) is preferably from 10 to 50,000 ppm, preferably from 100 to 10,000 ppm, in each case based on the weight of component a). In a particularly preferred embodiment, the cationic acrylic polymer is formed from the formula (Ia) shown below as a cationic monomer:

in which independently

Ri is hydrogen or methyl,

R2 is hydrogen or methyl,

R 3 is C ₁ -C ₂ -alkylene and

Y Cl, Br or l

represent and

i) the at least one crosslinking agent is selected from the group consisting of divinylbenzene, tetraallylammonium chloride, allyl acrylates and allyl methacrylates, diacrylates and dimethacrylates of glycols and polyglycols, butadiene, 1,7-octadiene, allylacrylamides and allylmethacrylamides, bisacrylamidoacetic acid, Ν, Ν ' -Methylenbisacrylamid and Polyolpolyallylether, and in an amount of 50 to 1200 ppm, preferably in an amount of 50 to 1000 ppm, more preferably in an amount of 700 to 900 ppm, each based on the weight of component a), and

ii) at least one chain transfer agent selected from the group consisting of malic acid, lactic acid, formic acid, isopropanol and hypophosphites in an amount of 1,000 to 9,000 ppm, preferably in an amount of 2,000 to 5,000 ppm, each based on the weight of Component a) is included.

A washing or cleaning agent according to the invention preferably comprises the amphiphilic, carboxyalkylated polyamine according to the invention in an amount of from 0.01 to 30% by weight, in particular from 0.05 to 20% by weight, in particular from 0.05 to 10% by weight. %, in particular from 0, 1 to 5% by weight, especially from 0, 1 to 4 wt .-%. It has been found that a lower proportion of said polyamines does not lead to the desired effect both in the fabric softener and in other washing or cleaning agents. Although an excess of polyamine does not affect the cleaning or fabric softening performance of the corresponding agents. However, an increase in the desired Antiknitterwirkung and easy-ironing effect (ironing aid) is not observed, so in particular a proportion of 0, 1 to 10 wt .-% seems sufficient to obtain the desired effect. Particularly preferably, a content of 5% by weight or less is sufficient. In a further embodiment, the object underlying the present invention is provided by the use of amphiphilic, carboxyalkylated polyamines as described in the present application as anti-crease agent for textiles. Surprisingly, it has been shown that the polyamines described lead to the desired effect.

In yet another embodiment, the present invention relates to a process for reducing wrinkles in fabrics during laundering which comprises characterizing an amphiphilic, carboxyalkylated polyamine as described in the present application, and in particular as a constituent of a washing or cleaning composition with the Brings textile in contact. In contrast to Antiknitterwirkstoffen described in the prior art, a pretreatment with the inventive compositions is not possible. Rather, the present invention makes it possible to stably incorporate the amphiphilic, carboxyalkylated polyamines of the invention into a detergent or cleaning agent which includes fabric softeners. At the same time as cleaning, textiles are finished with the Antiknitterwirkstoff.

According to the invention, bringing into contact with the automated cleaning of textiles, especially in a washing machine. However, it is also possible to bring the washing or cleaning agent either directly with the textiles in manual cleaning or first to prepare an aqueous solution of the washing or cleaning agent (wash liquor) and bring this wash with the textile in contact. A special reaction time of the amphiphilic, carboxyalkylated polyamine on the textile is surprisingly not necessary.

In the following embodiment, the present invention is carried out by way of example in a non-limiting manner. In the context of the present invention, all previously described and also preferred embodiments or the features described in each case can also be combined individually. Moreover, in the context of the present invention, the term "comprising" also covers the alternative in which the products / methods / uses, with respect to which the term "comprising" is used, consist exclusively of the elements which subsequently exist. Examples:

Embodiment 1: Composition of the detergent

Laundry loads of textiles (cotton fabric) were put together. Washing load 1 was washed with a reference liquid detergent (formulation 1, comparative example).

The same procedure was followed with wash load 2 and wash load 3. Washing load 2 was washed with the liquid detergent according to Formulation 1 with the addition of 0.5% of an amphiphilic, carboxymethylated polyamine from the raw material Ampholak 7CX / C (Formulation 2, according to the invention) and washing load 3 with the liquid detergent according to Formulation 1 with the addition of 0.5 % By weight of an amphiphilic, carboxymethylated polyamine from the raw material Ampholak 7TX (formulation 3, according to the invention).

These fabrics were each washed separately at 40 ° C (in the Easy Care program) in a standard washing machine from Miele. There were 5 washes done. After 3 washes, it was dried overnight.

The following table describes the three formulations. The information is given in% by weight

Composition Recipe 1 Recipe 2 Recipe 3

(according to the invention) (according to the invention)

Cio-13-alkylbenzenesulfonic acid and 5.7% 5.7% 5.7%

Fatty alcohol ether sulfate with 2 mol

ethylene oxide

C13-15 alkyl ethers with 7 moles 3.3% 3.3% 3.3%

ethylene oxide

Builder (citric acid and 0.43% 0.43% 0.43%

phosphonates)

Sodium hydroxide 0.6% 0.6% 0.6%

Pa l m e rn o nts 0.5% 0.5% 0.5%

Glycerine 0.5% 0.5% 0.5%

Sodium chloride 1, 8% 1, 8% 1, 8%

Enzymes (protease, amylase, 0.4% 0.4% 0.4%

Cellulase, lipase)

Boric acid 0.5% 0.5% 0.5%

Sodium cocoamphopolycarboxy - 0.5% glycinate Sodium Tallowamphopolycarboxy- 0.5

glycinate

Further additions 0.49% 0.49% 0.49

(Preservative, defoamer,

opt. Brightener, dye, perfume)

Water rest rest rest

Embodiment 2: Measuring Method

The frictional resistance of the fabrics after washing was determined. This test method is used to determine the resistance that opposes a textile surface rubbing by a friction body.

test conditions:

Sample width 100 mm

Sample length 250 mm

Test length (friction path) 200 mm

Weight of the friction body 2920 g (hanger

Test speed 500 mm / min

Test direction horizontally

For measurement, a Zwick Z010 and a commercial iron (2920 g) were used. The Teflon friction body was centered at the end of the test sample. By starting the tensile tester, the friction body was moved to the other end of the test sample.

The distance traveled was then included in a force / length change diagram.

With this method you can directly determine the surface smoothness of a textile. The less force needed to move the iron over the fabric, the smoother the surface of the fabric.

The measurement results are shown graphically and in tabular form below, where "tissue new" means the values of the textiles immediately after purchase (without a washing process). "Formulation 1" are fabrics washed by conventional means according to Formulation 1; The same applies to the measured values labeled "Formulation 2" and "Formulation 3" which were each obtained with the composition according to the invention.

Tissue new Recipe 1 Recipe 2 Recipe 3

Mean [cN] 184.4 270.7 217.0 214, 1 The tissues treated with the formulations according to the invention show a resistance similar to that of the unwashed tissues, whereas with conventional detergents a greater force is necessary. This indicates a high resistance, more creases and less smooth fibers of the tissues. With the amphiphilic, carboxyalkylated polyamines according to the invention, a reduced wrinkling of tissue as well as a simpler ironing is thus possible.

Claims

Patent claim:

1. washing or cleaning agent for textiles comprising at least one surfactant and additionally at least one amphiphilic, carboxyalkylated polyamine.

2. washing or cleaning agent for textiles according to claim 1, characterized in that said polyamine carries at least two carboxyalkyl groups.

3. washing or cleaning agent for textiles according to one of claims 1 or 2, characterized in that said polyamine is an oligomer or polymer having an N-atom containing backbone having at least two nitrogen atoms, which i) carries at least two carboxyalkyl groups, which bind to the polyamine via an N atom and

ii) carries at least one C8-C22 hydrocarbon radical.

4. washing or cleaning agent for textiles according to one of claims 1 to 3, characterized in that said polyamine contains at least two carboxyalkyl groups selected from carboxymethyl, carboxyethyl, wherein at least two carboxymethyl groups are preferred.

5. washing or cleaning agent for textiles according to one of claims 1 to 4, characterized in that the amphiphilic, carboxyalkylated polyamine is selected from at least one compound of formula (I),

wherein

R is a hydrocarbon radical having 12 to 22 carbon atoms,

R ³ and R ⁴ independently of one another are H, methyl, 2-hydroxyethyl, a group --CH 2 COOM or a group -CH 2 CH 2 COOM, where M is H, Na ⁺ , K ⁺ or NH ₄ ⁺ ,

p is 0 or 1,

m per repetition unit stands independently for 2 or 3 and

n is 1, 2, 3, 4, 5 or 6.

6. washing or cleaning agent for textiles according to one of claims 1 to 5, characterized in that according to formula (I) p is 1.

7. washing or cleaning agent for textiles according to one of claims 1 to 6, characterized in that according to formula (I) R ² , R ³ and R ^{4 is} a group -CH 2 COOM or - CH 2 CH 2 COOM, wherein M is H, Na ⁺ , K ⁺ or NH ₄ ⁺ stands.

8. washing or cleaning agent for textiles according to one of claims 1 to 7, characterized in that according to formula (I) R ² , R ³ and R ^{4 is} a group -CH 2 COOM, wherein M is H, Na ⁺ , K ⁺ or NH ₄ ⁺ is.

9. washing or cleaning agent for textiles according to one of claims 1 to 8, characterized in that according to formula (I) m is 3.

10. washing or cleaning agent for textiles according to one of claims 1 to 9, characterized in that according to formula (I) n is 2, 3 or 4.

1 1. washing or cleaning agent for textiles according to one of claims 1 to 10, characterized in that it contains amphiphilic, carboxyalkylated polyamine in an amount of 0.01 to 30 wt .-%, in particular from 0.05 to 20 wt. %, in particular from 0.05 to 10 wt .-%, in particular from 0.1 to 5 wt .-%, especially from 0.1 to 4 wt .-%., Contains.

12. washing or cleaning agent for textiles according to one of claims 1 to 10, characterized in that it is basic and has a pH greater than 7, in particular in the range of greater than 7 to 14, preferably from 7.5 to 12, in particular from 8 to 10.

13. Use of amphiphilic, carboxyalkylated polyamines as defined in any one of claims 1 to 10, as Antiknitterwirkstoff for textiles.

14. A process for the reduction of wrinkles in textiles during washing, characterized in that one defines an amphiphilic, carboxyalkylated polyamine as in any one of claims 1 to 7 and 9 and in particular as a constituent of a washing or cleaning agent according to any one of claims 1 to 12 in contact with the textile.