WO2001046377A1 - Agent for treating substrates - Google Patents

Abstract

The invention relates to an agent for treating substrates which contains bleaching agents and/or surfactants and optionally contains solvents. Said agent is characterized in that it exhibits an antidilutive behavior.

Description

 Agents for the treatment of substrates

The present invention relates to agents for the treatment of substrates which can be used for the pretreatment or aftertreatment of soiled textiles or as a washing additive or also for the treatment of hard surfaces, and to a pretreatment or aftertreatment process for textile washing.

Textiles often have stubborn stains that cannot be completely removed by washing with a commercially available detergent. These stains are usually treated directly in the home with a so-called pretreatment agent. These are usually surfactant compositions that are offered in the form of sprays, pastes or liquids. Such agents are applied directly to the stains and left there until they are washed. The stains are pre-dissolved by this pretreatment and finally removed in the main washing process.

Common pretreatment agents are pastes containing surfactants, which show good cleaning performance on greasy stains, but whose cleaning effect is not always satisfactory compared to bleachable stains such as tea or coffee. Products containing bleach, which are known from the prior art as low-viscosity products, are more expedient for the removal of pliable soils. Commercial products have a viscosity of up to approximately 1,200 mPa ^* s.

Intensive stain pretreatment, for example mechanically with the aid of a sponge or a brush, is difficult when using pasty agents, since the product is generally applied directly to the stain and is difficult to distribute from there. These products are often first diluted with water and then used for pretreating laundry. On the other hand, the viscous products containing bleach are distributed very quickly over the textile or fabric, so that a higher dosage is required in order to be able to apply sufficient agents to the soiling itself. Hard surfaces also often have stubborn stains that must be pretreated before normal cleaning to allow these stains to be removed completely. Here, too, there is the problem that paste-like agents are difficult to distribute, while low-viscosity agents run quickly over the entire surface and do not remain on the area to be pretreated.

The object of the present invention was to provide an agent for treating substrates which can be used as a pre-treatment and / or after-treatment agent in textile washing, for treating stains on textile surfaces and for treating stains on hard surfaces. The agent should have a good cleaning effect against both greasy and bleachable soiling and at the same time be easy to apply to the soiling and also be suitable for mechanical stain pretreatments.

Surprisingly, it has been found that compositions which contain bleaching agents and / or surfactants and, if appropriate, other customary constituents, have a good cleaning action against fatty and bleachable stains and can also be used well for mechanical pretreatment of stains if they have a shear-thinning behavior. When applied, the composition liquefies so that it can be easily distributed and can also penetrate into textile fabrics. As soon as the application of the composition to the substrate ends, the viscosity increases again, i.e. the fluidity decreases and the composition remains on the treated substrate without flowing.

The present invention accordingly relates to an agent for the treatment of substrates containing surfactants and / or bleaching agents and optionally solvents, which is characterized in that it exhibits a shear-thinning behavior.

For the purposes of the present invention, substrates are textiles, textile surfaces and any hard surfaces, such as floor coverings, wall and furniture surfaces and any surfaces of household objects, e.g. Metal, plastic and porcelain.

According to the invention, the agent exhibits shear thinning behavior. This means that the viscosity of the agent is reduced when exposed to shear. The shear thinning behavior can be pseudoplastic or thixotropic, ie as soon as the action stops from shear forces, the original viscosity is restored immediately (pseudoplastic behavior) or with a time delay (thixotropic behavior).

In one embodiment, the agents according to the invention are used for the pretreatment of soiled textiles or as a washing additive. In further embodiments, however, they can also be used as a heavy-duty detergent, for washing in a washing machine or by hand, as a detergent booster and as a household cleaner for hard surfaces, such as in wet rooms or in the kitchen, as a dishwashing detergent, as a toilet cleaner or for carpet cleaning.

The term "pretreatment of soiled textiles" used here means that the aqueous composition is applied to the soiled fiber and is left there before the textile fiber is washed. To increase the cleaning effect, the soiling can also be treated mechanically, for example by Rubbing and distributing the composition according to the invention, if appropriate in aqueous dilution, with a sponge or a brush or by simply rubbing textile surfaces against one another The aqueous composition can also be applied to the textile substrate together with sufficient water to moisten the textile.

The term “washing” here means the usual cleaning process for textiles with at least one surfactant using a washing machine or simply by hand.

The expression "treatment of hard surfaces" means that customary of the above-mentioned surfaces, as they usually occur in the home, can be (pre) treated with the agent according to the invention in order to remove stubborn stains. The pretreatment can be carried out with a sponge or a brush or other auxiliary means. The treatment with the composition according to the invention can be followed by a conventional cleaning.

The agents contain bleaching agents and / or surfactants as essential components.

Preferred bleaching agents are H ₂ O and compounds which provide H ₂ O ₂ in water, such as sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate or ent speaking percarbonate salts, persilicate, peroxypyrophosphates, persulfates, such as monopersulfate, urea peroxyhydrate, citrate perhydrates, organic peroxides and peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid, phthalimino acids or diperoxydodecandis. H ₂ 0 ₂ is particularly preferably used.

The bleaching agent component can be present in the agents according to the invention in an amount of 0.1 to 35% by weight, based on the total agent, preferably 0.5 to 15% by weight and particularly preferably 1 to 10% by weight his.

In order to achieve an improved bleaching effect when used as a textile treatment agent at temperatures of 60 ° C. and below, and in particular in laundry pretreatment, bleach activators can be incorporated into the detergent tablets. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 20 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine (DADHT), acylated glycolurils, in particular 1, 3,4.6 - Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids (acetyl) -AC, such as triethyl-acetic acid such as triethyl , Carboxylic anhydrides and their derivatives, in particular phthalic anhydride, isatoic anhydride and / or succinic anhydride, carboxylic acid amides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, isopropenylacetate, 2,5-diacetoxy-2,5-di-diacetoxy and Enol esters as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam and N-acetylcaprol. Hydrophilically substituted acyl acetates and acyl lactams can also be used. Nitride derivatives such as cyanopyridines, nitrile quats and / or cyanamide derivatives can also be used. the preferred bleach activators are sodium 4- (octanoyloxy) benzol sulfonate, undecenoyloxy benzene sulfonate (UDOBS), sodium dodecanoyloxy benzene sulfonate (DOBS) and / or decanoyloxy benzoic acid (DOBA, OBC 10 patent) Formanidinium salts can also be mentioned. A mixture of several bleach activators can also be used. Such bleach activators are in the usual range of 0.01 to 20% by weight, preferably 0.1 to 15% by weight, in particular 1% by weight. % to 10% by weight, based on the total composition

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes or transition metal complexes known from the European patents EP-A-0 446 982 and EP-A-0 453 003 can also be included as so-called bleaching catalysts Transition metal compounds in question include in particular the manganese-iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE-A-195 29905 and their N-analog compounds known from German patent application DE-A-196 20 267, the from the German patent application DE-A-195 36 082 known manganese, iron-cobalt, ruthenium or molybdenum-carbonyl complexes, the manganese, iron, cobalt, ruthenium described in German patent application DE-A-196 05 688 -, Molybdenum, titanium, vanadium and copper complexes with nitrogen-containing Tnpod ligands, which result from the German patent application DE-A-196 20 411 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt complexes described in the German patent application DE 44 16 438, which are described in the European patent application EP-A- 0 272 030 described cobalt complexes, the manganese complexes known from the European patent application EP-A-0 693 550, the manganese, iron, cobalt and copper complexes known from the European patent EP-A-0 392592 and / or those described in European patent EP-A-0 443 651 or European patent applications EP-A-0 458 397, EP-A-0 458 398, EP-A-0 549 271, EP-A-0 549 272, Manganese complexes described in EP-A-0 544 490 and EP-A-0 544 519 combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE-A-196 13 103 and international patent application WO-A-95/27775 known bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in customary amounts, preferably in an amount up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight. % to 0.1% by weight, in each case based on the total average.

As further constituents, the compositions according to the invention can contain surfactants selected from anionic, nonionic, cationic, amphoteric surfactants and mixtures thereof. The surfactants are preferably present in an amount of 0.1 to 80% by weight, preferably 0.1 to 50% by weight and in particular 0.1 to 25% by weight, based on the composition.

If the surfactants are in liquid form, they can also serve as the sole solvent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ . ₁₄ alcohols with 3 EO to 7 EO, C alcohol with 7 EO, C ₁₃ .ι ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ .i ₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ₂ -ι alcohol with 3 EO and Cι ₂ -ι ₈ alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but rather statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols. In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms, in particular in 2-division, and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or preferably according to that in the international patent application Patent application WO-A-90/13533 can be prepared.

Nonionic surfactants of the amine oxide type, for example N-coco-alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, the fatty acid alkanolamides and the fatty amine alkoxylates may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula I,

R1

I

R-CO-N- [Z] I

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula II

Ff-OR ⁴

IR ² -CO-N- [Z] II

in which R ^{2 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{3 is} a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms and R ^{4 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are preferably C _8- thereby ι ₃ - alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C ₁₂ _ι ₈ monoolefins with terminal or internal double bond by sulfonation obtained with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products suitable are alkanesulfonates, which are from Cι ₂ .ι ₈ alkanes, for example by Sulfochloπerung or sulfoxidation and subsequent hydrolysis or neutralization obtained. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of the d ₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myπstyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. The Cj ₂ -C ₆ alkyl sulfates and C ₁₂ -C ₅ alkyl sulfates and C ₁ - ds alkyl sulfates are preferred from a washing-technical point of view. In addition, 2,3-alkyl sulfates, which are produced for example according to U.S. Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The sulfuric acid monoesters of the straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂ ι-alcohols, such as 2-methyl-branched Cg.n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ -ι ₈ fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in surfactant compositions or cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ . ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yi chain or salts thereof. Other anionic surfactants that are particularly suitable are soaps that are used in particular at higher pH values. Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, for example coconut oil - Soap mixtures derived from palm kernel, olive oil or tallow fatty acids

Depending on the pH, the anionic surfactants, including the soaps, can be present in the form of the free acids or their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine

Zwitterionic surfactants are surface-active compounds that contain at least one quaternary ammonium group and at least one -COO ^(} or -SO ^ group in the molecule. Particularly suitable zwitterionic surfactants are so-called betaines such as N-alkyl-N, N-dimethylammonium. glycιnate, for example, the cocoalkyl-dimethylammonium glycinate, N-acylaminopropyl-N N-dimethylammonium glycinate, for example the cocoacylaminopropyl-dimethylammonium glycinate and 2-alkyl-3-carboxymethyl-3-hydroxyethyl-ιmιdazolιne each with 8 to 18 C-atoms in the - or acyl group and the cocoacylaminoethylhydroxyethylcarboxymethylgiycinat A preferred zwitterionic surfactant is the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine

Ampholytic surfactants are surface-active compounds which, in addition to a C _{8 18} -alkyl or -acyl group, contain at least one free ammo group and at least one -COOH or -S0 ₃ H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkylimmodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaunne, N-alkylsarcosine 2-alkylaminopropionic acid and alkylaminoacetic acid C with each 8 to 8 atoms in the alkyl group Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and Cj _{2 18} - acylsarcosine

Suitable examples of surfactants containing amino groups are the fatty amine alkoxylates Suitable examples are quaternary ammonium compounds of the formulas (III) and (IV)

R ⁶ CH ₃ l + l +

R ⁵ - N - R ⁷ X ^" OC-O-fCHz) ,, - N - (CH ₂ ) _n -0-COR ⁸ X ^"

I I

R ⁵ R ⁹ - (CH ₂ ) _n

(III) (IV)

where R ^{5 is} an acychic alkyl radical having 12 to 24 carbon atoms, R ^{6 is} a saturated C 1 -C 8 alkyl or hydroxyalkyl radical, R ^{7 is} either R ⁵ or R ⁶ and COR ^{8 is} an aliphatic acyl radical having 12 to 22 carbon atoms 0, 1, 2 or 3 double bonds and R ⁹ is H or OH, where n is 1, 2 or 3 and X is either a halide, methosulfate, methophosphate or phosphate ion, and mixtures of these compounds are particularly preferred Compounds containing alkyl radicals with 16 to 18 carbon atoms

Examples of cationic compounds of the formula (MI) are didecyldimethylammonium chloride, ditallow dimethylammonium chloride or dihexadecylammonium chloride. Examples of compounds of the formula (IV) are methyl-N- (2-hydroxyethyl) -N, N-dι (talgacyl-oxyethyl) ammonium methosulfate, Bιs- (palmιtoyl) -ethyl-hydroxyethyl-methyl-ammonium-methosulfate or methyl-N, N-bιs (acyloxyethyl) -N- (2-hydroxyethyl) ammonium-methosulfate If quaternized compounds of formula (II) are used, the unsaturated alkyl chains are preferred, the acyl groups are preferred whose corresponding fatty acids have an iodine number between 5 and 25, preferably between 10 and 25 and in particular between 15 and 20 and which have a cis / trans isomer ratio (in% by weight) of 30 70, preferably greater than 50 50 and in particular larger than 70 30

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazohnium compounds of the formula (V)

R "

(V)

wherein R ^{10 is} a saturated alkyl group having 12 to 18 carbon atoms, R ^{11 is} an alkyl group having 1 to 4 carbon atoms or H and Z is an NH group or oxygen and A is an anion.

Further suitable quaternary compounds are described by formula (VI)

(R ¹² ) ₃ N - (CH ₂ ) _n - CH - OOCR ¹³

CHs— OOCR ⁸

(VI) wherein R ¹² each independently represents a C _M alkyl, alkenyl or hydroxyalkyl group, R ¹³ each independently represents a C _8-28 alkyl group and n is a number between 0 and 5.

In addition to the compounds of the formulas (III) and (IV), short-chain, water-soluble, quaternary ammonium compounds can also be used, such as trihydroxyethyl methylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Protonated alkylamine compounds which have a plasticizing effect and the non-quaternized, protonated precursors of the cationic emulsifiers are also suitable

The quaternized protein hydrolyzates are further cationic compounds which can be used according to the invention

Also suitable according to the invention are cationic silicone cones, such as, for example, the commercially available products Q2-7224 (manufacturer Dow Corning, a stabilized methylmethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also referred to as amodimethicone) SM-2059 (Manufacturer General Electric), SLM-55067 (manufacturer Wacker) and Abιl ^® -Quat 3270 and 3272 (manufacturer Th Goldschmidt, diquatemare polydimethylsiloxane Quaternium- 80)

Alkylamidoamines, especially fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amιd ^® S 18, are characterized not only by a good conditioning effect but also by their good biodegradability

Also readily biodegradable quaternary Esterverbindungen, so-called "esterquats", such as the Methylhy- marketed under the trade Stepantex® ^® are droxyalkyldialkoyloxyalkylammoniummethosulfate

An example of a quaternary sugar derivative that can be used as a cationic surfactant is the commercial product Glucquat ^® 100, according to the CTFA nomenclature a "lauryl methyl gluceth-10 hydroxypropyl dimonium chloride"

The agent according to the invention shows a shear thinning behavior, which means that the agents are still partially flowable under strong shear and can therefore be easily dosed from a tube or a suitable dispenser and can be distributed well on the substrate to be treated the original viscosity returns and the composition remains on the substrate without running. However, the shear thinning behavior also shows great advantages in the production and filling of the products. The viscosity of the agents according to the invention is preferably above 5,000 mPa * s, particularly preferably above 6,000 mPa ^* s and ins- especially over 10,000 mPa ^* s and can be adjusted with suitable theological additives. The viscosity can be measured using standard methods, such as the Brookfield RVD-VII viscometer at 20 rpm and 20 ° C., spindle 4).

Suitable theological additives are inorganic or polymeric organic compounds. Mixtures of several additives can also be used.

Inorganic theological additives include, for example, polysilicic acids, clay minerals such as montmorilionites, zeolites, silicas and bentonites.

The organic theological additives come from the groups of natural polymers, modified natural polymers and fully synthetic polymers.

Polymers originating from nature and used as theological additives are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.

Modified natural products mainly come from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and corn flour ether.

A large group of theological additives that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

The theological additives can be contained in an amount of up to 10% by weight, preferably from 0.05 to 5% by weight, and particularly preferably from 0.1 to 3% by weight, based on the finished composition.

Rheological additives from the substance classes mentioned are commercially available and are sold, for example, under the trade names Acusol ^® -820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® - GT-282-S (alkyl polyglycol ether, Akzo), Deuteroι ^® polymer 11 (Dicarboxylic acid copolymer, Schoener GmbH), Deuteron ^® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schoener GmbH), Deuteron ^® -XN (non-ionic polysaccharide, Schoener GmbH), Dicrylaπ ^® thickener-0 (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion , 19-21% in water / diglycol ether, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylic ester copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo ^® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell), Shellflo ^® -XA (xanthan biopolymer, stabilized with formaldehyde, Shell), Kelzan and Keltrol (Kelco).

Another preferred polymeric theological additive is xanthan, a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million daltons. Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.

Xanthan can be described by the following formula:

Basic unit of xanthan

Examples of other preferred synthetic theological additives are polyurethanes and modified (meth) acrylates.

Polyurethanes (PUR) are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula VII

[-0-R ¹⁴ -0-C-NH-R ¹⁵ -NH-C-] _n (VII),

I

O

in which R ^{14 stands} for a low molecular weight or polymeric diol residue, R ¹⁵ for an aliphatic or aromatic group and n for a natural number. R ¹⁴ is preferably a linear or branched C _2- ι ₂ -alk (en) yi group, but can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the above formula I in that the radical R ¹⁴ further -O-CO-NH groups are bound. Technically important PUR are made from polyester and / or polyether diols and, for example, from 2,4- or 2,6-toluenediisocyanate (TDI, R ¹⁵ = C ₆ H ₃ -CH ₃ ), 4,4'-methylene di (phenyl isocyanate) (MDI, R ¹⁵ = C ₆ H ₄ -CH ₂ -C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ⁵ = (CH) β].

Commercial theological additives based on polyurethane are, for example, under the names Acrysol ^® PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel ^® L75-N (non-ionic PUR dispersion , 50% in water, Borchers), Coatex ^® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco ^® DSX-1514 (PUR dispersion, 40% in water / Butyltrigylcol, Henkel-Nopco), thickener QR 1001 (20% PUR emulsion in water / Digylcolether, Rohm & Haas) and Rilanit ^® VPW-31 16 (PUR dispersion, 43% in water, Henkel) available.

Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula VIII

R ¹⁶

I

[-CHrC-l _n (VIII),

C-X-R 17

in which R ^{16 represents} H or a branched or unbranched C _1-4 alk (en) yl radical, X represents N- R ¹⁸ or O, R ^{19 represents} an optionally alkoxylated branched or unbranched, possibly substituted C ₈ . ₂₂ -alk (en) yl radical, R ^{18 is} H or R ¹⁷ and n is a natural number. Such modified polyacrylates are generally esters or amides of acrylic acid or an α-substituted acrylic acid. Preferred among these polymers are those in which R ^{16 represents} H or a methyl group. In the case of the polyacrylamides (X = NR ¹⁸ ), both single (R ¹⁸ = H) and double (R ⁸ = R ¹⁷ ) N-substituted amide structures are possible, the two hydrocarbon radicals attached to the N atom being independently of one another from optionally alkoxylated branched or non-branched branches C ₈ . ₂₂ -Alk (en) yl residues can be selected. Among the polyacrylic esters (X = O), preference is given to those in which the alcohol has been obtained from natural or synthetic fats or oils and is additionally alkoxylated, preferably ethoxylated. Preferred degrees of alkoxylation are between 2 and 30, with degrees of alkoxylation between 10 and 15 being particularly preferred.

Since the polymers that can be used are technical compounds, the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of aoxylation. Formula VIII only provides formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight can also be used in the context of the present invention. For example, copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic -COO groups can also be used.

Modified polyacrylates to be preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula Villa

R 20

[-CH ₂ -C-] "Villa,

C- (0-CH-CH ₂ ) _a OR 17

> 19

in which R ^{7 is} a preferably unbranched, saturated or unsaturated C _8-22 alk (en) yl radical, R ¹⁹ and R ²⁰ independently of one another are H or CH ₃ , the degree of polymerization n is a natural number and the degree of aikoxylation a is a natural number is between 2 and 30, preferably between 10 and 20. R ¹⁷ is preferably a fatty alcohol residue obtained from natural or synthetic sources, the fatty alcohol in turn preferably being ethoxylated (R ¹⁹ = H). Products of the formula IIa are commercially available for example under the name Acusol ^® 820 (Rohm & Haas) in the form of 30 wt -% ιger dispersions available In the commercial product mentioned ¹⁷ stands in water R is a stearyl radical, R ¹⁹ is a hydrogen atom, R ²⁰ is H or CH ₃ and the degree of ethoxy a is 20

In combination with the theological additives mentioned above, additional complexing agents can be used to stabilize the viscosity. Examples of complexing agents are described below

A further increase in viscosity can also be achieved by adding electrolytes (neutral salts). Examples of such salts are the alkali halides, in particular chlorides, alkali metal bicarbonates, alkane sulfates and alkali metal phosphates, sodium chloride and sodium sulfate being particularly preferred

Solvents that can be used in the liquid to gel-like compositions come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the stated concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, 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, ethyl or propyl ether, dipropylene glycol monomethyl or isopropyl ether, or ethyl ether - ethyl ether, methoxy, ethoxy or butoxy glycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Solvents can be used in the compositions according to the invention in amounts between 0.1 and 20% by weight, but preferably below 15% by weight and in particular below above 10% by weight

The compositions according to the invention can contain further ingredients which further improve the application technology and / or aesthetic properties of the composition. In the context of the present invention, preferred compositions can additionally contain one or more substances from the group of builders, cobuilders, enzymes, pH regulators, fragrances , Perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, soil release compounds, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer agents inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, swelling and anti-slip agents, abrasives, complexing agents and UV absorbers.

The individual ingredients can be present as solids. These solids are preferably in particle sizes as are customary in the detergent and cleaning agent sector, and nanoscale particles can also be present. The solids present particularly preferably have, at least in part, a particle size between 1 and 1000 nm.

The builders that can be contained in the compositions according to the invention include, in particular, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{2x +} ι H ₂ 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ß- and δ-

Sodium disilicates Na ₂ Si ₂ θ ₅ -yH ₂ 0 preferred.

Amorphous sodium silicates with a module Na ₂ 0: Si0 ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is so inter- pretend that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Fine-crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ 0 ^■ (1-n) K ₂ 0 ^■ Al ₂ 0 ₃ ^■ (2 - 2.5) Si0 ₂ ^■ (3.5 - 5.5) H ₂ 0

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups, C ₁₂ -C ₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, it is also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the aicali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HP0 ₃ ) _n and orthophosphoric acid H ₃ P0 _{4 in} addition to higher molecular weight distinctive representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in tissues and also contribute to cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ P0 ₄ , exists as a dihydrate (density 1, 91 like ^"3 , melting point 60 °) and as a monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ 0 ₇ ) at 200 ° C, and at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ 0 ₉ ) and Maddrell's salt (see below). NaH ₂ P0 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ P0 ₄ , is a white salt with a density of 2.33 ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HP0 ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 moles (density 1, 68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ 0) and 12 moles of water (density 1, 52 like ^"3 , melting point 35 ° with loss of 5 H ₂ 0), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ 0 when heated. Disodium hydrogen phosphate is obtained by neutralizing phosphoric acid with soda solution using Phenolphthalein produced as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HP0, is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ P0, are colorless crystals which, as dodecahydrate, have a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ 0 ₅ ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ 0 ₅₎ having a density of 2.536 like. ³ trisodium phosphate is readily soluble in water with an alkaline reaction and is disodium phosphate by evaporating a solution of exactly 1 mole and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ P0, is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction , It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry

Tetranate diphosphate (sodium pyrophosphate), Na P ₂ 0 ₇ , exists in anhydrous form (density 2.534, preferably ³ , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836, preferably ³ , melting point 94 ° with loss of water ) Both substances are colorless crystals which are soluble in water with an alkaline reaction. Na ₄ P ₂ 0 ₇ is formed when dinate phosphate is heated to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hard formers and therefore reduces the hardness of the water potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 ^"3 , which is soluble in water , the pH of the 1% solution at 25 ° being 10.4

The condensation of NaH ₂ P0 or KH ₂ P0 ₄ results in higher molar sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates, in particular for the latter there are a large number of terms in use Melting or glowing phosphates, Graham's salt, Kurrol's and Maddrell's salt All higher sodium and potassium phosphates are collectively referred to as condensed phosphates

The technically important Pentanatπumtπphosphat, Na ₅ P ₃ O ₁₀ (Natπumtπpolyphosphat), is an anhydrous or with 6 H ₂ 0 crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (0) (ONa) -0] _n -Na with n = 3 In 100 g of water about 17 g at room temperature, at 20 ° approx. 20 g, at 100 ° about 32 g of salt free from water of crystallization. After heating the solution to 100 ° for two hours, about 8% orthophosphate is formed by hydrolysis and 15% diphosphate. In the production of pentasodium phosphate, phosphoric acid is reacted with sodium hydroxide solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying, similar to Graham's salt and sodium diphosphate, pentanatium phosphate, and many insoluble metal compounds, as well as many insoluble metal compounds - phosphate, K ₅ P ₃ Oι ₀ (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P ₂ 0 ₅ , 25% K ₂ 0) on the market. The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimethosphate with KOH:

(NaP0 ₃ ) ₃ + 2 KOH - »Na ₃ K ₂ P ₃ O ₁₀ + H ₂ 0

According to the invention, these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid and derivatives thereof, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.

Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives, as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH value of Detergents or cleaning agents In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned

Polymeric polycarboxyates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol

For the purposes of this document, the molar masses specified for polymeric polycarboxyates are weight-average molar masses M _{w of} the particular acid form, which were generally determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers.This information differs significantly from the molecular weight data for which polystyrene sulfonic acids are used as standard.The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights specified in this document

Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates can in turn have a molecular weight of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol. mol, are preferred

Also suitable are copolymeric polycarboxyates, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable Molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol

The (co) polymeric polycarboxyates can be used either as a powder or as an aqueous solution. The amount of (co) polymeric polycarboxylates in the compositions is preferably 0 5 to 20% by weight, in particular 3 to 10% by weight. To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,

Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. An oxidized oligosaccharide is also suitable, a product oxidized on the C _{6 of} the saccharide ring being particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylenediamine-N, N ^'- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context.

Further useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders. As enzymes, hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned are suitable. All these hydrolases are useful in washing for removing stains such as stains containing protein, fat or starch and Graying in cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit color transfer. Bacterial strains or fungi such as Bacillus are particularly suitable Subtihs, Bacillus licheniformis Streptomyceus griseus and Humicola insolens Enzymatic active substances obtained Preferably, proteases of the subtihsin type and in particular proteases obtained from Bacillus lentus are used nd amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, in particular however protease and / or Lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Examples of such lipolytically active enzymes are the known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. The suitable amylases include, in particular, α-amylases, iso-amylases, pullulanases and pectinases The cellulases used are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ in their CMCase and avicelase activities, targeted mixing can be used the desired activities are set in the cellulases

In order to bring the pH of the compositions according to the invention into the desired range, the use of pH adjusting agents may be indicated. All known acids or alkalis can be used here, provided their use is not normally prohibited for application-related or ecological reasons or for reasons of consumer protection The amount of these adjusting agents does not exceed 2% by weight of the total formulation In order to improve the aesthetic impression of the compositions according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers in order not to stain them

Foam inhibitors that can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils

Suitable soil release compounds are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and those from the Polymers of phthalic acid and / or terephthalic acid or their derivatives known in the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid. Poiymere

Optical brighteners (so-called "white toners") can be added to the compositions according to the invention in order to eliminate graying and yellowing of the treated textiles.These substances absorb on the fiber and bring about a brightening and a pretreated bleaching effect by converting invisible ultraviolet radiation into visible long-wave light, whereby the white from the sunlight aosorbierte ultraviolet light as a pale bluish fluorescence is emitted and pure for the yellow shade of the grayed or yellowed washing results Suitable compounds originate for example from the substance classes of the 4,4 ^{'-Dιamιno-2,2'} - stilbendisulfonsauren (Flavonsauren) 4,4 ^{'-Dιstyryl-bιphenylen,} Methylumbelhferone, Cumanne, dihydroquino none, 1, 3-Dιarylpyrazol'ne, Naphthalsaureimide, benzoxazole, benzisoxazole and benzimidazole systems, and the Pyrendenvate substituted by heterocycles are the optical brighteners commonly used in amounts of between 0 , 0 1 and 0.5% by weight, based on the finished composition Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and other starch products than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, preference is given to cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 10% by weight, based on the Means used.

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction, the compositions according to the invention can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To control microorganisms, the compositions according to the invention can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, organic cationic compounds such as cationic surfactants, eg. B. benzalkonium chlorides, alkylarlylsulfonates, halophenols and phenol mercuric acetate, it being possible to dispense entirely with these compounds in the compositions according to the invention.

An increased wearing comfort can result from the additional use of antistatic agents which are additionally added to the compositions according to the invention. Antistatic agents increase the surface conductivity and thus enable the better flow of charges formed.As a rule, external antistatic agents are substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces.These mostly surface-active antistatic agents can be broken down into nitrogen-containing (nurse, amide, quaternary ammonium compounds ), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkylsulfonates, alkylsulfates) antistatic agents. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect

In order to improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the treatment of the treated textiles, for example, silicone condensates can be used in the compositions according to the invention. These additionally improve the rinsing behavior of the compositions according to the invention due to their foam-inhibiting properties the alkyl groups have one to five carbon atoms and are partially or completely fluorinated. Preferred silicones are polydimethylsiloxanes, which may or may not have been deπvated and then amino-functional! or are quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones range from 100 to 100,000 mPas at 25 ° C., the silicones in amounts between 0 2 and 5% by weight, based on the total composition, can be used

In particular, agents for cleaning hard surfaces can contain so-called abrasives, such as quartz flours, micro glass balls, plastic flours and wood flours

In order to avoid the decomposition of certain detergent ingredients catalyzed by heavy metals, substances can be used which complex heavy metals. Suitable heavy metal complexing agents are, for example, ethylenediaminetetraacetic acid (EDTA) or nitinotinyl acetic acid (NTA) in the form of the free acids or as alkali metal salts of the foregoing and derivatives as well as alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates

A preferred class of complexing agents are the phosphonates, which in preferred compositions are present in amounts of 0.01 to 2.0% by weight, preferably 0.05 to 1.5 % By weight and in particular from 0.1 to 1.0% by weight are included. These preferred compounds include, in particular, organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotronic (methylenephosphonic acid) (ATMP), dimethyltriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts. Other suitable complexing agents are low molecular weight hydroxycarboxylic acids, which also have builder properties , such as citric acid, tartaric acid, malic acid, or gluconic acid or salts thereof, citric acid or sodium citrate being particularly preferred. The complexing agents can be used in an amount of 1 to 25% by weight, preferably 3.0 to 10.0% by weight and in particular 4 , 0 to 5.0% by weight, based on the finished composition

Finally, the compositions according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the lightfastness of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in 2- and / / which are effective through radiation-free deactivation. or 4-position Also substituted benzotazoles, in the 3-position phenyl-substituted acrylates (cinnamon acid redevines), optionally with cyano groups in the 2-position, stilbene derivatives, biphenyls, sahcylates, organic Ni complexes and natural substances such as umbelhferone and the body's own urocanoic acid are also suitable

In a preferred embodiment, the composition according to the invention contains 1 to 10% by weight of bleach, up to 15% by weight of nonionic surfactant, up to 15% by weight of anionic surfactant, up to 15% by weight of further surfactants, 0.01 to 5% by weight. % rheological additives, 0.01 to 3% by weight of complexing agent, 0.1 to 10% by weight of citrate and water and, if appropriate, further conventional detergent ingredients

The agents according to the invention can be produced continuously or in batches in a manner known per se. The finished agents can be packaged in any desired forms using which the substrate can be treated, for example in bottles, tubes or as pens For textile pretreatment of the fiber, the composition according to the invention is usually applied to the fiber over a period of up to 24 hours, in particular from one minute to one hour and particularly preferably from five minutes to 30 minutes. The textiles are usually contaminated with dried-on stains or dirt, which are usually very difficult to remove. The compositions can simply be applied to the textiles and left there, the dirt removal can also be done by mechanical support, e.g. B. be supported by rubbing or by treatment with a sponge or a brush.

As a rule, the compositions according to the invention are applied in undiluted form to the textiles or to the substrate to be treated or used as an additive with a commercially available detergent.

Also for the treatment of non-textile surfaces, in particular hard surfaces, the agents according to the invention can be applied to the soiling and left there for a longer period of time. The non-textile substrates are also usually contaminated with dried-on stains or dirt, which can be easily removed if it is treated over a longer period of time, the agent according to the invention optionally being diluted with water.

Claims

claims

1. Agent for the treatment of substrates containing surfactants and / or bleaches and optionally solvents, characterized in that the agent has a shear thinning behavior.

2. Composition according to claim 1, characterized in that as bleaching agent hydrogen peroxide and / or in water H ₂ 0 ₂ supplying compounds, such as Natπumperbo- ratte tetrahydrate, sodium perborate monohydrate, sodium percarbonate or corresponding percarbonate salts, persilicate, peroxypyrophosphates, persulfates such as monopersulfate, urea -Peroxyhydrate, citrate perhydrates, organic peroxides and peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaliminoperacids or diperdodecanedioic acid, particularly preferably H ₂ 0 ₂ , are used.

3. Composition according to one of claims 1 or 2, characterized in that bleaching agent is contained in an amount of 0.1 to 35 wt .-%, based on the entire composition.

4. Composition according to one of claims 1 to 3, characterized in that it contains bending activator.

5. Composition according to one of claims 1 to 4, characterized in that surfactants are contained in an amount of 0.1 to 80 wt .-%, based on the composition.

6. Composition according to one of claims 1 to 5, characterized in that it has a viscosity above 6000 mPa ^* s, preferably above 10,000 mPa ^* s.

7. Composition according to one of claims 1 to 6, characterized in that it contains at least one rheological additive.

8 Agent according to claim 7, characterized in that the theological additive is contained in an amount of up to 10% by weight, preferably from 0.05 to 7% by weight, based on the finished composition

9 Agent according to one of claims 7 or 8, characterized in that the theological additive is selected from agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum flour, starch, dextrins, gelatin and casem, modified starches and celluloses, in particular xanthan, and fully synthetic polymers

10 agent according to one of claims 1 to 9, containing one or more substances from the group of builders, cobuilder enzymes, electrolytes, solvents, pH adjusters, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, soil release compounds, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, swelling and anti-slip agents, abrasives, complexing agents and UV absorbers

11 Agent according to one of claims 1 to 10, characterized in that containing solids at least partially have a particle size between 1 and 1000 nm

12 Use of the agent according to one of claims 1 to 11 for the pretreatment of soiled textiles

13. Use of the agent according to one of claims 1 to 12 for the pretreatment of hard surfaces