EP3004312A1

EP3004312A1 - Sulfonate group-containing polymer active ingredients which improve primary detergent power

Info

Publication number: EP3004312A1
Application number: EP14727784.2A
Authority: EP
Inventors: Benoit Luneau; Inga Kerstin Vockenroth; Nicole PLATH; Quang Ngoc TRAN; Trang Phan; Didier Gigmes; Denis Bertin
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2013-06-05
Filing date: 2014-05-23
Publication date: 2016-04-13
Anticipated expiration: 2034-05-23
Also published as: FR3006691B1; FR3006691A1; EP3004312B1; ES2719951T3; WO2014195156A1; PL3004312T3

Abstract

The aim of the invention is to improve the primary detergent power of detergents and cleaning agents, in particular with respect to bleachable and/or enzyme-sensitive soiling. This is substantially achieved by the incorporation of polyesters or polyamides of 5-sulfoisopthalaic acid and a diol and/or a diamine.

Description

The primary washing power improving sulfonate group-containing polymeric agents

The present invention relates to the use of certain sulfonate group-containing polymers to enhance the primary washing power of laundry detergents or cleaners when washing textiles or cleaning hard surfaces against, in particular bleachable or enzyme-sensitive soils, and detergents and cleaners containing such polymers.

In addition to the ingredients indispensable for the washing process, such as surfactants and builder materials, detergents generally contain further constituents which can be summarized under the term washing assistants and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaches, bleach activators and color transfer inhibitors. Such excipients also include substances whose

Presence increases the detergency of surfactants, without them usually have to exhibit a pronounced surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces. Such substances are often referred to as Waschkraftverstärker.

Lin, L.-H., Chiang, C.Y., Liu, H.-J., Chen, K.-M .; J. Appl. Pole. Sci., 2002, 86, 2727-2731 describe emulsion paints with water-soluble polyesters of polyethylene glycol and sulfoisophthalic acid.

Flowable, amphiphilic and nonionic oligoesters are known from international patent application WO 02/18474 A1, which are prepared by reacting one or more dicarboxylic acids with one or more polyol compounds having at least 3 OH groups and one or more water-soluble alkylene oxide addition products of one or more C2 to C4-alkylene oxides to an O to C6 alcohol and optionally one or more diol compounds are available, known as described there for use in cleaning formulations for cleaning hard surfaces, in heavy duty detergents, mild detergents, color detergents,

Gardinenwaschmitteln, Wäscheweichspülern, carpet cleaning and impregnating agents and in hair treatment agents are suitable.

The patent application DE 10 2005 061 058 A1 discloses polyesters of terephthalic acid,

Sulfoisophthalic acid and, optionally, oligomeric alkylene glycols with nonionic

End groups, which can be used as so-called soil release components in detergents and cleaners. Surprisingly, it has been found that certain polyesters or polyamides containing sulfonate groups have particularly good primary washing strength-enhancing properties.

The invention relates to the use of polymers of units of the general formula (I) or (II)

(I) (II) in which independently of one another A is a linear or branched-chain alkylene group having 1 to

12, preferably 2 to 12 carbon atoms,

L is A or a group of the general formula (III),

in which Y is a linear or branched-chain alkylene group having 1 to 6, preferably 2 to 4, carbon atoms,

Y ^{2 is} a linear or branched-chain alkylene group having 1 to 6, preferably 2 to 4, C atoms,

x and z are numbers from 0 to 8, the sum of x + z being in the range of 0 to 8.0, y being a number in the range of 2.0 to 40.0,

R is H or an alkyl group having 1 to 4 C atoms,

R ^{2 is} H or an alkyl group having 1 to 4 C atoms, and

n is a number in the range of 2 to 20,

for strengthening the primary washing power of detergents or cleaners when washing textiles or when cleaning hard surfaces against in particular bleachable or enzyme-sensitive soiling.

The polymers of the general formulas (I) and (II) can be obtained by reacting 5-sulfoisophthalic acid or its alkyl ester derivatives such as dimethyl 5-sulfoisophthalate Na salt with a diol or a diamine. Apart from the units of the general formula (I) or (II), no further units are contained in the polymers; they may have end groups in the form of alkyl ester units, OH groups or NR H groups as a result of the preparation.

The polymeric active ingredient preferably has an average molecular weight (here and below in the case of average molecular weight data: number average) in the range from 500 g / mol to 100 000 g / mol, in particular from 1000 g / mol to 40 000 g / mol.

The polymer exhibits interactions with anionic surfactants such as in particular linear alkylbenzenesulfonate, which may be due to the formation of a surfactant-polymer aggregate. The effect can be detected by measuring the surface tension, whereby the surface tension is increased by the presence of the polymer. These

Increasing may be due to the formation of a cleaning active aggregate in the solution and therefore less surfactant at the interface.

To determine the aggregation parameter X _ag , the surface tension γ of an aqueous solution of 0.12 g / l of linear C 13 -alkylbenzenesulfonate, as obtainable, for example, under the trade names Disponil® LDBS 55 or Marlon® A360, is in the absence and presence of 0.2 g / l of the polymer and the value in the absence of the polymer is subtracted from the value in the presence of the polymer:

Xag = γι (surfactant + polymer) - γ2 (surfactant)

In this case, the measurement of the surface tension by means of the Du-Noüy ring method, for example using a TE3 ring / plate Tensiometers Lauda (Lauda- Königshofen) are made. For this purpose, a ring of, for example, metal, which is attached to a Torsionskraftmesser so immersed in the surfactant-polymer solution that the ring is below the surface of the solution. The ring is then slowly pulled out of the solution and the force exerted on the measuring ring just before the liquid film breaks off is measured with the torsional force meter. The surface tension can with knowledge of the

Diameter of the ring and the tearing force are calculated.

The measurements are carried out in each case at 25 ° C with adjustment of the measurement solutions to pH 8.5. If the polymer interacts with the surfactant, contact

Aggregation parameter X _ag > 1 mN / m, preferably X _ag > 4 mN / m and in particular in the range of 5 mN / m to 8 mN / m. In all aspects of the present invention, a polymer having an aggregation parameter in these ranges is preferred. Another object of the invention is a method for removing in particular bleachable or enzyme-sensitive soiling of textiles or hard surfaces, in which a detergent or cleaning agent and a said polymeric active ingredient are used. This method can be carried out manually or mechanically, for example by means of a household washing machine or dishwasher. It is possible to apply the particular liquid agent and the active ingredient simultaneously or sequentially. The simultaneous application can be particularly advantageous by the use of an agent containing the active ingredient perform. By bleachable or enzyme-sensitive stains are meant those which are usually at least partially removable from bleaches or with the aid of enzymes.

Bleachable soilings are to be understood as meaning those which are dyed and, after washing, in the presence of a peroxidic bleach and, if appropriate, a

Bleach activator stronger or have at least a lighter shade than after washing without the peroxidic bleaching agent and optionally the bleach activator. The bleachable stains usually contain polymerizable substances, in particular dyes, wherein the dyes are preferably polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds. In addition to removing stains in the colors green, yellow, red or blue, stains in intermediate colors, in particular violet, purple, brown, purple or pink, as well as stains, which are green, yellow, red and violet, come into consideration Purple, brown, purple, pink or blue tint, without essentially being made entirely of this color itself. The colors mentioned can also be light or dark in each case. These are preferably stains, in particular stains of grass, fruits or vegetables, in particular stains by food products, such as spices, sauces,

Chutneys, curries, purees and marmalades, or beverages, such as coffee, tea, wines and juices containing corresponding green, yellow, red, purple, purple, brown, purple, pink and / or blue dyes.

Enzyme-sensitive soiling is to be understood as meaning that after the

Washing in the presence of enzymes are more removed or, if they are colored, have a lighter shade than after washing without the enzyme. Preferably, it is proteinaceous, polysaccharide-containing and / or greasy soils, such as

Eg egg, blood, starch, mannan, grass, or sauces.

The use of the active compounds used according to the invention leads to a significantly better detachment of, in particular, bleachable or enzyme-sensitive soils on hard Surfaces and on textiles, including those of cotton or with a proportion of cotton, as is the case when using compounds known for this purpose so far. Alternatively, significant levels of surfactants can be saved while maintaining soil release capability.

The use according to the invention can be carried out as part of a washing or cleaning process by adding the active ingredient to a washing or cleaning agent-containing liquor or preferably introducing the active ingredient as a constituent of a washing or cleaning agent into the liquor, the concentration of the polymer in the liquor preferably in the range from 0.01 g / l to 0.5 g / l, in particular from 0.02 g / l to 0.2 g / l.

Another object of the invention is therefore a washing or cleaning agent containing a polymer of units of the general formulas (I) or (II).

Detergents or cleaning agents which contain or are used together with an active substance to be used according to the invention or are 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 ingredient essential to the invention. Preferably, an active ingredient as defined above in amounts of 0, 1 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 5 wt .-% incorporated in detergents or cleaning agents.

Surprisingly, it has been found that such active ingredients positively influence the action of certain other detergent ingredients and, conversely, that the action of the active ingredient is additionally enhanced by certain other ingredients. These effects occur in particular in bleaching agents, in enzymatic active substances, in particular proteases and lipases, in water-soluble inorganic and / or organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates and in synthetic anionic surfactants of the sulfate and sulfonate type, for which reason the use at least one of the said further ingredients is preferred together with the active ingredient to be used according to the invention.

An agent containing or used together with an active ingredient to be used or used in the method of the invention may preferably contain peroxygen bleaching agents, especially in amounts ranging from 5% to 70% by weight, and optionally Bleach activator, especially in amounts ranging from 2 wt .-% to 10 wt .-%, included. 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 perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and Persilicate, which are usually present as alkali salts, especially as sodium salts. Such bleaching agents are in detergents containing an active ingredient according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on total agent, present, in particular percarbonate is used. The optionally present component of the bleach activators comprises the commonly 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, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. The bleach activators can be used to avoid the

Interaction with the per compounds in storage in a known manner coated with coating substances and / or granulated, wherein granulated tetraacetylethylenediamine having mean particle sizes of 0.01 mm to 0.8 mm, granulated 1, 5-diacetyl-2, with the aid of carboxymethylcellulose, 4-dioxohexahydro-1,3,5-triazine, and / or in particulate form

Prefabricated 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 preferred embodiment, an agent according to the invention or used in the context of the invention comprises synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular alkylbenzenesulfonate, fatty alkylsulfate, fatty alkyl ether sulfate, alkyl and / or dialkyl sulfosuccinate, sulfo fatty acid esters and / or sulfo fatty acid salts, in particular in an amount Range from 2% to 25% by weight. The anionic surfactant is preferably selected from the alkylbenzenesulfonates, the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. These are usually not individual substances, but cuts or mixtures. Of these, those are preferred whose proportion of compounds with

longer-chain radicals in the range of 16 to 18 carbon atoms over 20 wt .-% is.

Another embodiment of such agents 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 from 2% by weight to 25% by weight. %. 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 C atoms, preferably 12 to 18 C 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 carboxamides, 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 fatty acid polyhydroxy amides come into consideration. Suitable so-called alkylpolyglycosides for incorporation in the compositions according to the invention are compounds of the general formula (G) n-OR ¹² , 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, arabinose, Include 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 component is glucose because of its good availability. 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 Kokosfettalkylrest, that is, mixtures having substantially R ² = dodecyl and R ² = tetradecyl.

Nonionic surfactant is present in compositions which contain an active ingredient used according to the invention or are used in the context of the use according to the invention, preferably in amounts of from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight. contain amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain lower amounts of up to 5% by weight.

The agents may instead or additionally surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, to which, for example, the already mentioned alkylbenzenesulfonates, in amounts of preferably not more than 20 wt .-%, in particular from 0.1 wt .-% to 18 wt .-%, each based on the total agent included. 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, to call. 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. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. To the appropriate

Sulfonate-type anionic surfactants 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 C -Atomen, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids. Preferred anionic surfactants are also the salts of sulfosuccinic acid esters, which are also known as alkyl sulfosuccinates or

Dialkylsulfosuccinates, 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.

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 in amounts of 0, 1 wt .-% to 5 wt .-% included. 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.

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 polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small proportions of polymerizable substances without carboxylic acid functionality can be included in copolymerized form. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200000 g / mol, that of the copolymers 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 100,000 g / mol. Suitable, although less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as

Vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%. It is also possible to use as water-soluble organic builder substances terpolymers which contain two carboxylic acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C3-C8 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. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C 4 -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, more preferably acrylic acid and / or acrylate, and Maleic acid and / or maleate, and from 5% to 40%, preferably from 10% 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 Methallylsulfonat 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 relative

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, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the above 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 aluminum Mosilikat 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. Crystalline layered silicates which fall under this general formula are described, for example, in European Patent Application EP 0 164 514. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta. And .delta.-sodium disilicates (Na.sub.2Si.sub.20.sup.yH.sub.2O.sub.2) 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 aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali 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 inorganic builder mentioned, further water-soluble or water-insoluble inorganic substances can be used in the compositions which have the properties of the invention

containing active ingredient, used together with this or used in the inventive method to be included. 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 ingredients 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 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular Aminoalkylenphos- phosphonic acids and their salts and up to 2 wt .-%, in particular 0, 1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.

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

The preferably present enzymes are in particular 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 usable lipase can for example

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, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm

commercially available. The usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly 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 under the name Pyrolase® from Diversa Corp., San Diego, CA, USA available.

The customary enzyme stabilizers present, if appropriate, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali 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, especially behenine, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes, and mixtures thereof which, in addition, are microfine, optionally silanated or otherwise

hydrophobized silica may contain. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

The preparation of solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the preparation of inventive compositions having an 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 agents according to the invention in tablet form, which may consist of single-phase or multiphase, monochrome or multicolor and in particular of one or more layers, in particular two layers, it is preferable to use all of them

Components - optionally one layer each - mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric presses or

Rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN. Particularly in the case of multilayer tablets, it may 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 square or cuboid shaped tablets, which predominantly over the

Dosing device, for example, the dishwasher are introduced, is dependent on the geometry and the volume of this metering device. Exemplary preferred

Embodiments have a footprint of (20 to 30 mm) x (34 to 40 mm), in particular 26 x 36 mm or 24 x 38 mm.

Liquid or pasty compositions according to the invention in the form of customary solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

In a preferred embodiment, an agent which is incorporated into the active ingredient to be used according to the invention is liquid and contains 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight, of nonionic surfactant, 2% by weight. % to 30% by weight, in particular 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular 2% by weight to 12.5% by weight of soap, 0, 5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1, 5 wt .-%, in particular 0, 1 wt .-% up to 1% by weight complexing agent for heavy metals, such as phosphonate, and in addition to optionally contained enzyme, enzyme stabilizer, dye and / or fragrance, water and / or water-miscible solvent.

In a further preferred embodiment, an agent in which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular from 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% by weight .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic builder, up to 10 wt .-%, in particular 2 wt .-% to 8 wt. % water-soluble organic builder, 10% to 25% by weight synthetic anionic surfactant, 1% to 5% by weight nonionic surfactant and up to 25% by weight, especially 0.1% by weight to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate. Examples

Example 1: Preparation of Polymers Preparation of Polymer P1:

A mixture of 0, 133 mol of 1, 4-butanediol, 0.065 mol of dimethyl-5-sulfoisophthalate sodium salt and

1 g of titanium isopropoxide (2% by weight, based on the monomers) was added while passing argon through

Heated to 200 ° C for 2 hours. Subsequently, 0.065 mol of dimethyl 5-sulfoisophthalate sodium salt was added and the reaction mixture was stirred for 2 hours at 240 ° C. The

Reaction mixture solidified 30 minutes after the addition of the dimethyl 5-sulfoisophthalate sodium salt. It was taken up in 600 ml of distilled water, insolubles were filtered off and the product was precipitated by addition of acetone, filtered off and dried at 60 ° C. for 2 days.

Preparation of polymer P2:

A mixture of 0.0505 mole of 1, 8-octanediol, 0.025 mole of dimethyl 5-sulfoisophthalate sodium salt and 1 g of titanium isopropyloxide (1.5% by weight based on the monomers) was added while bubbling with argon for 2 hours heated to 220 ° C. Subsequently, 0.025 mol of dimethyl 5-sulfoisophthalate sodium salt was added and the reaction mixture was stirred for 1 hour at 220 ° C. The reaction mixture became solid. It was taken up in 600 ml of distilled water, the product was precipitated by addition of acetone, filtered off and dried.

Preparation of polymer P3:

A mixture of 0.134 mol of 1,4-diaminobutane, 0.30 mol of dimethyl 5-sulfoisophthalate sodium salt and 2.5 g of resorcinol (5% by weight based on the monomers) was added while bubbling with argon for 4 hours heated to 200 ° C. The reaction mixture was washed 3 times with 800 ml of ethanol, then taken up in 300 ml of distilled water, insoluble matter was filtered off and the product was precipitated by addition of acetone, filtered off and dried.

Preparation of Polymer P4:

A mixture of 0.108 mole of 1, 8-diaminooctane, 0.105 mole of dimethyl 5-sulfoisophthalate sodium salt and 2.25 g of resorcinol (5% by weight based on the monomers) was added while bubbling with argon for 2 hours heated to 190 ° C. The reaction mixture was washed 3 times with 800 ml of ethanol, then taken up in 300 ml of distilled water, insoluble matter was filtered off and the Product precipitated by addition of acetone, filtered off, washed with ethanol and dried at 60 ° C for 2 days.

Preparation of Polymer P5:

A mixture of 0.071 mol Jeffamine 600 (general formula (III) with Y = Y ² = isopropyl, y ^" 9, (x + z) ^" 3.6, NH 2 end groups), 0.079 mol dimethyl 5-sulfoisophthalate sodium Salt and 1 g titanium isopropoxide (1, 5 wt .-% based on the monomers) was heated while passing argon at 220 ° C for 8 hours. The reaction mixture was taken up in distilled water, the product was precipitated by addition of acetone, filtered off, dissolved in water, precipitated again by addition of acetone, filtered off and dried under vacuum.

Preparation of polymer P6:

A mixture of 0.071 mol Jeffamine 900 (General formula (III) with Y = Y ² = isopropyl, y ^"12.5, (x + ^z)" 6, NH 2 - terminal groups), 0.079 mol of dimethyl 5-sulfoisophthalate sodium- Salt and 1 g titanium isopropoxide (1, 5 wt .-% based on the monomers) was heated while passing argon at 220 ° C for 8 hours. The reaction mixture was taken up in distilled water, the product was precipitated by addition of acetone, filtered off, dissolved in water, precipitated again by addition of acetone, filtered off and dried under vacuum.

Preparation of Comparative Polymer V1:

A mixture of 0.0505 mole of polyethylene glycol (PEG 300), 0.025 mole of dimethyl 5-sulfoisophthalate sodium salt and 1 g of titanium isopropyl oxide was heated to 220 ° C while bubbling with argon for 2 hours. Then, 0.025 mol of dimethyl 5-sulfoisophthalate sodium salt was added, and the reaction mixture was stirred at 220 ° C for 8 hours. The reaction mixture was taken up in distilled water and a pH of 7-8 was adjusted by adding 0.2 M NaOH. The crude product was taken up in ethanol, insolubles were filtered off and the solvent was removed on a rotary evaporator. The product was dried under vacuum.

Preparation of Comparative Polymer V2:

A mixture of 0.0505 mole of polyethylene glycol (PEG 1000), 0.025 mole of dimethyl-5-sulfoisophthalate sodium salt and 1 g of titanium isopropyl oxide was heated to 220 ° C while bubbling with argon for 2 hours. Then, 0.025 mol of dimethyl 5-sulfoisophthalate sodium salt was added and the reaction mixture was stirred at 220 ° C for 8 hours. The

Reaction mixture was taken up in distilled water by addition of 0.2 M NaOH a pH of 7-8 was set. The crude product was taken up in ethanol,

Insolubles were filtered off and the solvent was removed on a rotary evaporator. The product was dried under vacuum.

Example 2: Determination of the Aggregation Parameter X _ag

At 25 ° C using a Lauda TE3 ring / plate tensiometer

Surface tension γ of an aqueous solution of 0.2 g / l linear alkylbenzene sulphonate (LAS; Disponil® LDBS 55) adjusted to pH 8.5. The measurement was repeated with otherwise identical solutions, but additionally containing 0.2 g / l of each polymer to be examined. The aggregation parameter X _ag was determined by subtracting the measurement of the system without polymer from that of the system with polymer.

Xag = γι (surfactant + polymer) - γ2 (surfactant)

The polymers P2 and V1 prepared in Example 1 were tested. The aggregation parameters given in Table 1 below were determined:

Table 1: Aggregation parameters of the surfactant-polymer systems

Example 3: Detergent

Table 2: Detergent compositions (in% by weight)

A B C D E F G H

C 9-13 -alkylbenzenesulfonate, Na salt 9 10 6 7 5 15 15 9

C12-18 fatty alcohol with 7 EO 8 9 6 7 5 6 1 1 10

C12-14 fatty alcohol sulphate with 2EO - - 8 7 10 2 2 5

C12-18 fatty acid, Na salt 4 3 3 3 4 2 4 7

Citric acid 2 3 3 2 2 2 2 3 Sodium hydroxide 3 3 2 3 3 3 3 4

Boric acid 1 1 1 1 1 1 1 1

Enzymes (amylase, protease, cellulase) + + + + + + + +

Perfume 1 0.5 0.5 1 1 1 1 1

Propanediol - - - - - 5 5 -

Ethanol 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 5

PVA / maleic acid copolymer 0.1 - 0.1 - - - - -

Optical brightener - 0, 1 - 0.1 0.2 0.2 0.2 0.2

Opacifier 0.2

Phosphonic acid, Na salt 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Invention-essential polymer 2 2 2 2 2 2 2 2

Water at 100

Example 4: Washing Tests

Household washing machines (Miele® W 1514) were loaded with 3.5 kg of clean accompanying laundry as well as cotton and dirt ballast with standardized stains (A: Pigment / Sebum; B: Pigment / Oil; C: Blood; E: Cocoa). 75 ml of the detergent C listed in Example 3 with one of the polymers prepared in Example 1 were metered in and washed at 40.degree. After hanging drying and mangling of the test textiles, their whiteness was determined spectrophotometrically (Minolta® CR200-1). Table 3 below shows the differences between the remission values for the otherwise identically composed detergent without the polymer as mean values from 4 determinations and the errors in the 4-fold determination (LSD). Positive values indicate an improvement, negative values mean a worsening of stain removal.

Table 3: Wash results (Angabi

Soiling \

A B C D

polymer

V1 -1, 7 0.3 3.2 1, 2 P1 nb 1,2 5,4 1y

P2 0.1 1.3 5.7 1.1

P3 nb 1.7 5.6 1.0

P5 0.0 1.7 7.1 1.3

P6 nb 1.5 7.0 1.2

LSD 1.6 1.3 3.9 1.3

nb: not determined

The detergents with an active ingredient to be used according to the invention overall showed a significantly better primary washing performance than an otherwise identically composed agent which did not contain any or any other polymer in their place.

Claims

claims

1. Use of polymers of units of the general formula (I) or (II)

(I) (Ii) in which independently of one another A is a linear or branched-chain alkylene group

1 to 12, in particular 2 to 12 C atoms,

L is A or a group of the general formula (III),

in which Y is a linear or branched-chain alkylene group having 1 to 6, in particular 2 to 4, carbon atoms,

Y ^{2 is} a linear or branched-chain alkylene group having 1 to 6, in particular 2 to 4, C atoms,

x and z are numbers from 0 to 8, the sum of x + z being in the range of 0 to 8.0,

y is a number in the range of 2.0 to 40.0,

R is H or an alkyl group having 1 to 4 C atoms,

R ^{2 is} H or an alkyl group having 1 to 4 C atoms, and

n is a number in the range of 2 to 20,

to enhance the primary washing power of washing or cleaning agents when washing textiles or when cleaning hard surfaces against soiling.

2. Use according to claim 1, characterized in that it is in the

Stains to bleachable or enzyme-sensitive stains is. Use according to claim 1 or 2, characterized in that the polymer is added to a washing or cleaning agent-containing liquor or incorporated as part of a detergent or cleaning agent in the fleet.

Method for removing in particular bleachable or enzyme-sensitive

Soiling of textiles or hard surfaces, where a wash or

Cleaning agent and a polymer of units of general formula (I) or (II)

1 to 12, in particular 2 to 12 C atoms,

L is A or a group of the general formula (III),

y is a number in the range of 2.0 to 40.0,

R is H or an alkyl group having 1 to 4 C atoms,

R ^{2 is} H or an alkyl group having 1 to 4 C atoms, and

n is a number in the range of 2 to 20,

be used.

5. The method according to claim 4, characterized in that it is carried out manually or mechanically, in particular by means of a household washing machine or dishwasher.

6. The method according to claim 4 or 5, characterized in that the concentration of the polymer in the liquor in the range of 0.01 g / l to 0.5 g / l, in particular from 0.02 g / l to 0.2 g / l lies.

7. washing or cleaning compositions containing a polymer of units of the general

Formula (I) or (II)

1 to 12, in particular 2 to 12 C atoms,

L is A or a group of the general formula (III),

y is a number in the range of 2.0 to 40.0,

R is H or an alkyl group having 1 to 4 C atoms,

R ^{2 is} H or an alkyl group having 1 to 4 C atoms, and

n stands for a number in the range of 2 to 20. Composition according to claim 7, characterized in that it contains the polymer in amounts of 0, 1 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 5 wt .-%.

Use according to one of claims 1 to 3, method according to one of claims 4 to 6, or agent according to claim 7 or 8, characterized in that the polymer has an average molecular weight in the range of 500 g / mol to 100000 g / mol, in particular of 1000 g / mol to 40,000 g / mol.

10. Use, method or means according to any one of the preceding claims, characterized in that the polymer has an aggregation parameter X _ag > 1 mN / m, in particular X _ag > 4 mN / m.