EP1209221B1 - Use of cyclic sugar ketons as catalysts for peroxy compounds - Google Patents

Description

The present invention relates to the use of certain cyclic sugar ketones to enhance bleaching action of peroxygen compounds in the bleaching of stained soils on both textiles and hard surfaces, as well as detergents and cleaners containing such cyclic sugar ketones.

Inorganic peroxygen compounds, particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes. The oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H ₂ O ₂ or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.

At lower temperatures, the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators. For this purpose, numerous proposals have been worked out in the past, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, also Carboxylic anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate (NOBS), sodium isononanoyloxy-benzenesulfonate (ISONOBS) and acylated sugar derivatives, such as pentaacetylglucose. By adding these substances, the bleaching effect aqueous peroxide solutions are increased so that even at temperatures around 60 ° C substantially the same effects as with the peroxide solution alone at 95 ° C occur.

In the search for energy-saving washing and bleaching processes in recent years application temperatures well below 60 ° C, especially below 45 ° C down to the cold water temperature in importance. At these low temperatures, the effect of the previously known activator compounds usually decreases noticeably. There has therefore been no lack of efforts to develop more effective activators for this temperature range without a convincing success to date.

A starting point for this is the use of transition metal salts and their complexes, as described e.g. in EP 0 392 592, EP 0 443 651, EP 0 458 397, EP 0 544 490 or EP 0 549 271. Although certain manganese complexes are known from EP 0 630 964 which, although they have no pronounced effect on bleach reinforcement of peroxygen compounds, do not discolor dyed textile fibers, they can cause the bleaching of soil or dye removed from the fiber in wash liquors. From DE 44 16 438 manganese, copper and cobalt complexes are known, which can carry ligands from a variety of substance groups and are to be used as bleaching and oxidation catalysts. WO 97/07191 proposes complexes of manganese, iron, cobalt, ruthenium and malenbdenum with salen-type ligands as activators for peroxygen compounds in hard surface cleaning solutions. The use of metal-containing bleach activators, however, often has the disadvantage that, under unfavorable circumstances, damage to the textile fabric can occur.

Furthermore, metal-free bleach catalysts are described in the literature. For example, US Pat. No. 3,822,114 describes bleaching agents which, in addition to an organic or inorganic peroxygen compound, contain ketones or aldehydes as bleach boosters. US Pat. No. 3,822,114 teaches in Tables 2, 3, 4 and 5 Use of a variety of cyclic and open-chain ketones, which have good activity at temperatures above 80 ° F. However, there are no indications that sugar-based ketones can be used, nor are they effective at temperatures below 80 ° F. In WO 95/31527 bicyclic and tricyclic ketones are described as bleach activators. Examples include decalin-1,5-dione, methyldecalin-1,6-dione and tricycloundecanediones. Furthermore, US Pat. No. 5,785,887 describes open-chain or cyclic monoketals of diketones, such as cyclohexanedione, as bleach activators. Also in this document there is no evidence of ketones on sugar basis.

The aim of the present invention is to improve the oxidation and bleaching action of, in particular, inorganic peroxygen compounds at low temperatures below 80 ° C., in particular in the temperature range from about 5 ° C. to 45 ° C.

Surprisingly, it has now been found that certain keto-containing sugars in the presence of organic or inorganic peroxygen compounds significantly contribute to the cleaning performance against colored soils that are on textiles or on hard surfaces.

worin R¹ und R² Wasserstoff, C₁-C₂₂-Alkyl, C₂-C₂₂-Alkenyl oder Phenyl, R³ C₁-C_4-Alkoxy, Phenyl-CH₂-O- oder eine Gruppe der Formel

R⁴ Wasserstoff oder R³ und R⁴ zusammen eine Gruppe der Formel

und n die Zahlen Null oder 1 bedeuten, als Katalysatoren für Persauerstoffverbindungen.The invention relates to the use of cyclic sugar ketones of the general formula

wherein R ¹ and R ^{2 are} hydrogen, C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl or phenyl, R ^{3 is} C ₁ -C ₄ alkoxy, phenyl-CH ₂ -O- or a group of the formula

R ^{4 is} hydrogen or R ³ and R ⁴ together form a group of the formula

and n is zero or 1, as catalysts for peroxygen compounds.

Corresponding sugar ketones are e.g. in Z.-X. Wang et al., J. Org. Chem., 1997, 62, 2328-2329, Z.-X. Wang et al., J. Amer. Chem. Soc., 1997, 119, 11224-11235, W.Adam et al., Tetrahedron Asymmetry, 1999, 10, 2749-2755 and 1998, 9, 4117-4122. The ketones can be obtained, as known to those skilled in the art, by acetylation or ketalization of the corresponding sugars and subsequent oxidation of an alcohol function. Oxidation reactions are e.g. described in R.F. Butterworth and S. Hanessian, Synthesis, 1971, 19 and P.H. Grisebach and H. Schmid, Angew. Chem., Int. Ed. Engl., 1972, 11, 159.

These sugar ketones can, as J. Amer. Chem. Soc., 1997, 119, 11224-11235, in aqueous solution in the presence of peroxy compounds form dioxirane structures according to the following reaction equation:

These dioxirane compounds are the actual bleaching agent.

• 1,2:4,5-Di-O-isopropyliden-D-erythro-2,3-hexodiuro-2,6-pyranose,
• 1,2:4,5-Di-O-isopropyliden-L-erythro-2,3-hexodiuro-2,6-pyranose,
• 1,2:5,6-Di-O-isopropyliden-α-D-glucofuranos-3-ulosehydrat,
• Methyl-3,4-O-isopropyliden-ß-L-erythro-pentopyranosid-2-ulose

Particularly preferred sugar ketones are:

• 1,2: 4,5-Di-O-isopropylidene-D-erythro-2,3-hexodiuro-2,6-pyranose,
• 1,2: 4,5-Di-O-isopropylidene-L-erythro-2,3-hexodiuro-2,6-pyranose,
• 1,2: 5,6-Di-O-isopropylidene-α-D-glucofuranos-3-ulosehydrat,
• Methyl-3,4-O-isopropylidene-.beta.-L-erythro-pentopyranoside-2-ulose

Particular preference is furthermore given to the pyranose derivatives of the following formulas 1 to 3 and their lower homologues with C ₂ -, C ₃ -, C ₄ -, C ₅ -, C ₆ - or C ₇ - instead of the C ₈ radical:

The cyclic sugar ketones are used in the detergents and cleaners according to the invention which additionally also contain organic or inorganic peroxygen compounds in concentrations of 0.01-10%, preferably 0.1-8% and in particular 0.5-5%.

Suitable peroxygen compounds are, first and foremost, all alkali metal or ammonium peroxosulfates, for example potassium peroxomonosulfate (technical name: Caroat® or Oxone®). In addition, however, it is also possible to use alkali metal perborate mono- or tetrahydrate and / or alkali metal percarbonate, with sodium being the preferred alkali metal. In a particularly preferred embodiment, mixtures of peroxosulphates with perborates or Percarbonates in a mixing ratio of 1:10 to 10: 1, preferably 1: 5 to 5: 1 used. The concentration of the inorganic oxidizing agents on the total formulation of the cleaning agents is 5 - 90%, preferably 10 - 70%.

Additionally or alternatively, the cleaning agents according to the invention may contain organic-based oxidizing agents in the concentration range of 1 to 20%. These include all known peroxycarboxylic acids, e.g. Monoperoxyphthalic acid, dodecanediperoxyacid or phthalimidoperoxycarboxylic acids such as PAP.

The term bleaching is understood here to mean both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface. The same applies mutatis mutandis to the bleaching of stains on hard surfaces. Other potential applications are in personal care, e.g. in the bleaching of hair and to improve the effectiveness of denture cleaners. Furthermore, the complexes according to the invention find use in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.

Furthermore, the invention relates to a washing and cleaning agent such as detergents and bleaches for textile material, cleaning agents for hard surfaces such as dishwashing or denture cleaners containing the sugar ketones as defined above and peroxygen compounds.

Essentially, the use of the sugar ketone as a bleach catalyst is to create conditions under which a peroxidic oxidizing agent and the cyclic sugar ketone can react with one another in the presence of a hard surface contaminated with colored soils, with the aim of producing more strongly oxidizing secondary products with dioxirane structure. Such conditions are especially present when the reactants meet in aqueous solution. This can be done by separately adding the peroxygen compound and the sugar ketone to an optional wash Detergent-containing solution done. Particularly advantageously, the detergent or cleaning agent already contains from the outset the cyclic sugar ketone and optionally a peroxygen-containing oxidizing agent. The peroxygen compound may also be added to the solution separately, in bulk or as a preferably aqueous solution or suspension, when a non-oxygen detergent or cleaner is used.

The detergents and cleaners according to the invention, which may be in the form of granules, powdered or tablet-form solids, other shaped articles, homogeneous solutions or suspensions, may contain, in principle, all known and conventional ingredients in addition to the stated cyclic sugar ketone. The detergents and cleaners according to the invention may in particular contain builder substances, surface-active surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestering agents, enzymes, and special additives with a color or fiber-sparing action. Other auxiliaries such as electrolytes, pH regulators, silver corrosion inhibitors, foam regulators, as well as dyes and fragrances are possible.

In addition, a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof. Abrasives are preferably not more than 20 wt .-%, in particular from 5 to 15 wt .-%, contained in the cleaning agents according to the invention.

The detergents and cleaners may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants. Such surfactants are present in detergent compositions according to the invention in proportions of preferably from 1 to 50% by weight, in particular from 3 to 30% by weight, whereas in hard-surface cleaners normally lower proportions, that is to say amounts of up to 20% by weight. . in particular up to 10 wt .-% and preferably in the range of 0.5 to 5 wt .-% are included. Dishwashing detergents typically use low-foam compounds.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of alpha-sulfo fatty acids (ester sulfonates), for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.

Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof. Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₈ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. 2,3-Alkyl sulfates, which are prepared, for example, according to US Pat. Nos. 3,234,158 and 5,075,041, are suitable anionic surfactants. Also suitable are the sulfuric monoesters of the straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols containing on average 3.5 moles of ethylene oxide (EO) or C ₁₂ -C ₁₈ -fatty alcohols containing 1 to 4 EO.

The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ -C ₁₈ fatty alcohol residues or mixtures of these. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate). As further anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.

The anionic surfactants, including soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position , or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, are alcohol ethoxylates having linear radicals of alcohols of natural origin 12 to 18 C atoms, z. From coconut, palm, tallow fat or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ -alcohols with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

in der Rest R¹-CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff; einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 1 0 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht.The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (I)

in the radical R ¹ -CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen; is an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.

in der R³ einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 21 Kohlenstoffatomen, R⁴ einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 6 bis 8 Kohlenstoffatomen und R⁵ einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen bedeutet, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Alyloxy-substituierten Verbindungen können dann beispielsweise gemäß WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 21 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 6 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or an aryl radical or a Oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives this rest stands. [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-allyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to WO 95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.

Also, nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylaminoxid. and the fatty acid alkanolamide may be suitable.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953, WO 95/19954 and WO 95/19955. Other surfactant types may have dendrimeric structures.

A detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polymeric alkali metal phosphates which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. The water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali aluminosilicates, in amounts of up to 50% by weight. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X. Their calcium binding capacity, which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram. Suitable builders are still crystalline alkali silicates which may be present alone or in admixture with amorphous silicates. The alkali metal silicates useful as builders 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 silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio of Na ₂ O: SiO, of 1: 2 to 1: 2.8. Those with a molar ratio of Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the process of European Patent Application EP 0 425 427. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si are used _x O _{2x + 1} · yH ₂ O, in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 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 are .beta.- and SS-sodium (Na ₂ Si ₂ O ₅ · y H ₂ O are preferred, with beta-sodium disilicate, for example, obtained by the method described in International Patent Application WO 91/08171. .Beta. Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Also prepared from amorphous silicates are virtually anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a Number from 1.9 to 2.1 can be prepared as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 425 428. In a further preferred embodiment of such agents, a crystalline layer of sodium layer silicate is used Module from 2 to 3, as can be made from sand and soda by the method of European Patent Application EP 0 436 835. Crystalline N Atriumsilikate with a modulus in the range of 1.9 to 3.5, as they are obtainable by the methods of European patents EP 0 164 552 and / or EP 0 294 753 are used in a further preferred embodiment of the invention means. In a preferred embodiment of compositions according to the invention, a granular compound is precipitated Alkali silicate and alkali carbonate, as described, for example, in international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion®. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In compositions containing both amorphous and crystalline alkali silicates, the weight ratio is from amorphous alkali metal silicate to crystalline alkali metal silicate, preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
Such builder substances are preferably contained in agents according to the invention in amounts of up to 60% by weight, in particular from 5 to 40% by weight.

The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid.

Polyphosphonic acids, especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used. Also preferred are polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins of international patent application WO 93/161 10 or international patent application WO 92/18542 or European patent EP 0 232 202, polymeric acrylic acids, methacrylic acids, Maleic acids and copolymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Commercially available products are, for example, Sokafan® CP 5, CP 10 and PA 30 from BASF. Suitable are still Copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid.
The second acidic monomer or its salt may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers can be prepared in particular by processes which are described in German patents DE 42 21 381 and DE 43 00 772, and generally have a molecular weight between 1000 and 200,000. Further preferred copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.

The organic builder substances can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% aqueous solutions are used. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.

Suitable water-soluble builder components in hard surface cleaners according to the invention are in principle all builders customarily used in detergents for dishwashing, for example the above-mentioned alkali metal phosphates. Their amounts may be in the range of up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total mean. Other possible water-soluble builder components, in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the above-mentioned type of polycarboxylates, which act as co-builders in hard water regions, and naturally occurring hydroxycarboxylic acids, such as mono-, dihydroxysuccinic acid, alpha- Hydroxypropionic acid and gluconic acid. Preferred organic builder components include the salts of citric acid, especially sodium citrate. As sodium citrate, anhydrous tri-sodium citrate and preferably trisodium citrate dihydrate are suitable. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the pH value ultimately set in the cleaning agents according to the invention, the acids corresponding to the said co-builder salts may also be present.

In addition to the sugar ketones used according to the invention, conventional bleach activators, that is to say compounds which release peroxycarboxylic acids under perhydrolysis conditions, can be used. Suitable are the usual bleach activators containing O- and / or N-acyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyl- or isononanoyloxybenzenesulfonate (NOBS or ISONOBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose , Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used.

The enzymes optionally contained in the agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamyl®, amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or those disclosed in International Patent Applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®. The enzymes used can be adsorbed on carriers and / or embedded in encapsulants, as described, for example, in International Patent Applications WO 92/131347 or WO 94/23005, in order to protect them against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, particularly preferably enzymes which are stabilized against oxidative degradation, as described, for example, in International Patent Applications WO 94/02597, WO 94/02618, WO 94/18314, WO 94/23053 or WO 95/07350.

Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio of SiO ₂ / M ₂ O (M = alkali metal) of from 1: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 40% by weight. in particular 3 to 30 wt .-%, based on the total agent, be contained. The alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.

A further subject of the invention is a machine for cleaning dishes containing 15 to 65% by weight, in particular 20 to 60% by weight of water-soluble builder component, 5 to 25% by weight, in particular 8 to 17% by weight. Oxygen-based bleaching agents, respectively; based on the total agent, and 0.1 to 5 wt .-% of one or more of the cyclic sugar ketones defined above. Such an agent is preferably low alkaline, that is its weight percent solution has a pH of 8 to 11.5, especially 9 to 11.

In a further embodiment of inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.

To effect silver corrosion protection, silver corrosion inhibitors can be used in dishwashing detergents according to the invention. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, molybdenum, vanadium or cerium salts and / or complexes, as well as Salts and / or complexes of the metals present in the complexes suitable according to the invention with other than in formula (I) predetermined ligands.

If the agents foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4% by weight, of a foam-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettsäureamide and mixtures thereof and other other known commercially available foam inhibitors are added. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred. Further optional ingredients in the compositions according to the invention are, for example, perfume oils.

Among the organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers. Such water-miscible solvents are preferably present in the detergents according to the invention not more than 20% by weight, in particular from 1 to 15% by weight.

To establish a desired, by the mixture of the other components not automatically resulting pH value, the compositions of the invention system and environmentally acceptable acids, especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10% by weight, in particular from 0.5 to 6% by weight, in the compositions according to the invention.

The compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roller compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared. Solutions according to the invention in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

For the production of particulate compositions having an increased bulk density, in particular in the range of 650 g / l to 950 g / l, is one known from European Patent EP 0 486 592, an extrusion step exhibiting Preferred method. Another preferred preparation by means of a granulation process is described in the European patent EP 0 642 576. The preparation of compositions according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1000 g / l can also be achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.

To prepare the inventive compositions in tablet form, the procedure is preferably such that mixing all ingredients together in a mixer and the mixture using conventional tablet presses, for example eccentric presses or rotary presses, under pressing pressures in the range of 200 10 ⁵ Pa to 1,500 · 10 ⁵ Pa , This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strengths of normally over 150 N. Preferably, a tablet thus produced has a weight of 1-5 g to 40 g, in particular from 20 g to 30 g, with a diameter from 3-5 mm to 40 mm.

Examples example 1

Synthesis of 1,2: 4,5-di-O-isopropylidene-D-erythro-2,3-hexodiuro-2,6-pyranose, 73.6 g of D-fructose were dissolved in a mixture of 1.5 l of acetone and 30 ml of dimethoxypropane suspended. At 0 ° C with stirring 15 ml of perchloric acid (70%) was added. After 6 hours at 0 ° C, the reaction mixture was adjusted to pH 7-8 with ammonium hydroxide and the solvent removed. The remaining residue was recrystallized from hexane. Melting point 116-118 ° C. 10.4 g of the alcohol thus obtained were dissolved in 200 ml of dichloromethane and mixed with 45 g of molecular sieve (3A). Subsequently, 23 g of PCC were added with stirring and stirred for 3 h. After filtration, the solution became concentrated and the residue recrystallized several times from dichloromethane / hexane. The product is obtained as a white solid, m.p .: 100-103 ° C.

Example 2

Synthesis of 1,2: 5,6-di-O-isopropylidene-α-D-glucofuranos-3-ulose hydrate The compound was prepared according to literature. The melting point is 102-104 ° C.

Example 3

Synthesis of methyl 3,4-O-isopropylidene-β-L-erythro-pentopyranoside-2-ulose The compound was prepared according to literature. The melting point is 90-95 ° C.

Example 4 Concentration dependence of bleaching

To determine the concentration dependence of the bleach, experiments were carried out in the Linitest apparatus at 40 ° C. Tissue on cotton (WFK-Krefeld) was used as the test fabric. 200 ml of a wash liquor (2 g / l P-free WMP detergent (WFK-Krefeld) in water hardness 15 ° dH) were mixed with Caroat® (350 mg / l, Degussa, Frankfurt). For the individual washing experiments, an increasing concentration of the sugar ketone according to Example 1 was added. Washing time: 30 min, washing temperature: 40 ° C. Before and after washing, the whiteness of the test soiling was determined by means of an Elrepho measuring instrument. As a result, the increase in whiteness (ΔΔE) was represented as a function of the ketone concentration: Concentration ketone 0 mg / l 25 mg / l 50 mg / l 100 mg / l ΔΔ E 0 13.1 17.5 18.5

The result shows that even with low concentrations of the sugar ketone according to Example 1, excellent bleaching results are obtained.

Example 5: pH dependence of the bleach

To determine the pH dependence of the bleaching of the sugar ketone according to Example 1, washing tests were carried out at 20 ° C. in a beaker at a constant pH. Concentration of sugar ketone: 40 mg / l, Caroate concentration: 350 mg / l. The evaluation was carried out according to Example 4. PH value 7 8th 9 10 11 12 Reflectance values ΔΔ E 0.5 10.1 15.3 15.4 7.5 1.5

The results show that the compound according to the invention has a bleaching optimum in the range of pH 8-11.

Example 6: Bleaching experiments on curry and red wine stain

The bleach activity of the inventive compounds of Examples 1 to 3 was tested on red wine and curry soiling on cotton (test fabric: WFK-Krefeld) at 20 ° C. Caroate concentration: 350 mg / l, ketone concentration: 20 mg / l. Washing time 30 min. test fabric Reflectance values ΔΔ E Curry / cotton Red / cotton Connection acc. Example 1 8.3 3.6 Connection acc. Ex. 2 nb 3.4 Connection acc. Example 3 nb 3,3

The results demonstrate a good effectiveness of the ketones according to the invention on both hydrophilic and hydrophobic stains.

Example 5

• 30 Gew.-% Natriumperboratmonohydrat
• 20 Gew.-% Kaliummonopersulfat
• 20 Gew.-% Natriumhydrogencarbonat
• 5 Gew.-% Natriumcarbonat
• 4 Gew.-% Natriumsulfat
• 7 Gew.-% Zitronensäure, Natriumsalz
• 1,5 Gew.-% cyclisches Zuckerketon gemäß Beispiel 1
• 1,5 Gew.-% organische Phosphonsäuren bzw. deren Salze
• 4 Gew.-% Polyethylenglykol 20 000
• 1,5 Gew.-% Polyvinylpyrrolidon
• 1,5 Gew.-% Aerosil 200/300
• 0,75 Gew.-% Natriumdodecylbenzolsulfonat
• 0,5 Gew.-% Gehärtete Triglyceride
• 1 Gew.-% Fettalkoholpolyglykoläther
• 1 Gew.-% Konservierungsmittel
• 0,5 Gew.-% Pfefferminzpulver, und
• 0,25 Gew.-% Indigotin L-Blue 2 und Chinolingelb L-Gelb 3

Example of a denture cleaner formulation

• 30% by weight of sodium perborate monohydrate
• 20 wt .-% potassium monopersulfate
• 20 wt .-% sodium bicarbonate
• 5% by weight of sodium carbonate
• 4% by weight of sodium sulfate
• 7% by weight of citric acid, sodium salt
• 1.5% by weight of cyclic sugar ketone according to Example 1
• 1.5% by weight of organic phosphonic acids or their salts
• 4% by weight of polyethylene glycol 20,000
• 1.5% by weight of polyvinylpyrrolidone
• 1.5% by weight Aerosil 200/300
• 0.75% by weight of sodium dodecylbenzenesulfonate
• 0.5% by weight Hardened triglycerides
• 1% by weight of fatty alcohol polyglycol ether
• 1% by weight preservative
• 0.5% by weight of peppermint powder, and
• 0.25% by weight Indigotin L-Blue 2 and quinoline yellow L-yellow 3

The ingredients mentioned are pressed by known techniques to a cleaning tablet. In the detergent test, the formulation shows excellent effectiveness.

Claims (5)

1. The use of cyclic sugar ketones of the formula

   

   in which R¹ and R² are hydrogen, C₁-C₂₂-alkyl, C₂-C₂₂-alkenyl or phenyl, R³ is C₁-C₄-alkoxy, phenyl-CH₂-O- or a group of the formula

   

   R⁴ is hydrogen or R³ and R⁴ together are a group of the formula

   

   and n is zero or 1, as catalysts for peroxygen compounds.
2. The use of cyclic sugar ketones as claimed in claim 1, wherein alkali metal or ammonium peroxosulfates or mixtures thereof with alkali metal perborate mono- or tetrahydrates and/or alkali metal percarbonates are used as peroxygen compounds.
3. The use of cyclic sugar ketones as claimed in claim 1, wherein the sugar ketones used are the compounds
   1,2:4,5-di-O-isopropylidene-D-erythro-2,3-hexodiuro-2,6-pyranose,
   1,2:4,5-di-O-isopropylidene-L-erythro-2,3-hexodiuro-2,6-pyranose,
   1,2:5,6-di-O-isopropylidene-α-D-glucofuranos-3-ulose hydrate,
   methyl-3,4-O-isopropylidene-ß-L-erythropentopyranosid-2-ulose.
4. The use of cyclic sugar ketones as claimed in claim 1, wherein a compound which eliminates peroxocarboxylic acid under perhydrolysis conditions is additionally used at the same time as the cyclic sugar ketone.
5. A laundry detergent, bleach or cleaner comprising a cyclic sugar ketone as set forth in claim 1 and a peroxygen compound.