JP2009504817A - Detergents and detergents containing 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexa-hydrotriazine as bleach activators - Google Patents

Abstract

Detergents and detergents containing 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexa-hydrotriazine as a bleach activator.
The present invention relates to detergents and detergents comprising persalts or hydrogen peroxide and 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexa-hydrotriazine as a bleach activator. .

Description

  The present invention provides 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexahydrotriazine, its granules and cogranulates in the bleaching of colored soils on textile materials and hard surfaces. The present invention relates to a method used for enhancing the bleaching action of oxygen compounds. The present invention further relates to detergents and detergents containing triacetyldioxohexahydrotriazine as a bleach activator.

  Inorganic peroxygen compounds, especially hydrogen peroxide, and solid peroxygen compounds that dissolve in water while releasing hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have traditionally been disinfected and used as oxidants. Used for bleaching purposes. The oxidizing action of these substances depends strongly on the temperature in the dilute solution, for example when using hydrogen peroxide or perborate in an alkaline bleaching solution, the fouling is only possible at temperatures above about 80 ° C. A sufficiently fast bleaching of the fiber material is achieved.

  The low temperature oxidation action of peroxide bleaches such as perborate, percarbonate, persilicate and perphosphate is the addition of a bleach peroxyacid precursor known as a bleach activator. It is known that Many materials are conventionally known as bleach activators. They are usually reactive organic compounds having an O-acyl group or an N-acyl group, which together with the hydrogen peroxide source form the corresponding peroxyacid in an alkaline solution.

  Representative examples of bleach activators include, for example, N, N, N ′, N′-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium-4-benzoyloxy Benzenesulfonate (SBOBS), sodium trimethylhexanoyloxy-benzenesulfonate (STHOBS), tetraacetylglycoluril (TAGU), sodium-nonanoyloxy-benzenesulfonate (NOBS), decanoyloxybenzoic acid and sodium-isononanoyloxy-benzene Sulfonate (ISONOBS).

  By adding these activators to aqueous peroxide solutions, perhydrolysis occurs while releasing organic peracids. This enhances the bleaching action of the solution to such an extent that even at temperatures of 40-60 ° C., the same effect is obtained as when the peroxide solution is used alone at 95 ° C.

  The main disadvantage of the aforementioned bleach activators is that they typically leave a large amount of leaving groups (eg, phenol sulfonates) that are of no value in the bleaching process after perhydrolysis. For example, only two acetyl groups in the form of peracetic acid are released from TAED, while the other two remain in the leaving group and go to wastewater without being used.

  Thus, from an ecological point of view, preferred bleach activators are bleach activators in which as many active groups as possible are present in the molecule, all of which are liberated in the perhydrolysis stage. An example of this is diacetyldioxohexahydrotriazine (DADHT), which converts two acetyl groups to peracetic acid in the presence of persalt or hydrogen peroxide. Synthesis and granulation of DADHT are described in, for example, Patent Document 1, Patent Document 2, and Patent Document 3.

In the literature, 2,4-dioxo-1,3,5-hexahydrotriazine (DHT) is converted to 1,3,5-triacetyl-2,4-dioxohexahydro-1,3,5 by using ketones. -It is described that it can be converted to triazine (TADHT) (Non-patent Document 1). With respect to this compound, neither physicochemical data nor performance data is known except for X-ray structural analysis (Non-Patent Document 2).
East German Patent Application Publication (DD) No. 219034 East German Patent Application Publication (DD) No. 229696 East German Patent Application Publication (DD) No. 253634 W. Beckmann et.al., Chem. Techn., 40 (10), 423, 1988 KO Klepp et al., Z. Kristallogr. NCS, 215 (1), 151, 2000

  It has now been surprisingly found that TADHT reacts with persalt or hydrogen peroxide and releases three molecules of peracetic acid. For similar peracetylated compounds such as TAGU or PAG, it is known that 30-50% acetyl groups remain in the molecule depending on the reaction conditions without releasing all acetyl groups during the perhydrolysis process This was unexpected.

  The subject of the present invention is a detergent comprising persalt or hydrogen peroxide and 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexahydrotriazine (TADHT) as bleach activator And a detergent.

  The phrase “detergent and detergent” also includes disinfectants and bleaches.

  In these detergents and detergents, the bleach activator TADHT according to the invention can be present together with the peroxy compound in a weight proportion of about 0.1-20%, preferably 0.5-10%, in particular 0.5-5.0%. . The weight percentage of this peroxy compound is usually 2-40%, preferably 4-30%, in particular 5-20%.

  In certain embodiments, the triacetyldioxohexahydrotriazines of the present invention are used in detergents and detergents in the form of granules. Such granules can comprise 5 to 95% by weight, but preferably 20 to 90% by weight, of the triacetyldioxohexahydrotriazine of the present invention. As another component, the granules can further comprise a bleach activator. Preference is given here to decanoyloxybenzoic acid, nonanoyloxybenzenesulfonate-sodium, tetraacetylethylenediamine or nitrilquat, for example trimethylammonium acetonitrile tosylate or diethylmethylammonium acetonitrile-tosylate. For the production of granules, granulation aids (Granulierhilfsmittel) and / or coating substances can additionally be used.

  As used herein, the phrase “bleaching” means both bleaching of soil present on the surface of the fiber material and bleaching of soil present in the cleaning liquid separated from the surface of the fiber material. The same applies to bleaching of dirt on hard surfaces. Furthermore, in the personal care field, it may be used, for example, for bleaching hair and for improving the effect of denture cleaning. Furthermore, the complex compounds of the present invention can also be used in commercial cleaning, wood and paper bleaching, cotton bleaching, and disinfectants.

  Furthermore, the present invention uses the cationic nitriles described above to clean textile materials and hard surfaces, especially tableware, in an aqueous solution optionally containing another detergent component or detergent component, particularly a peroxygen-based oxidizing agent. The invention relates to detergents and detergents for hard surfaces, in particular for dishware, preferably for use in automatic dishwashers.

  The method of use of the present invention aims to obtain a secondary product having a stronger oxidizing action in the presence of a hard surface contaminated with colored soils or a soiled fiber material corresponding thereto. As follows: creating a condition in which the peroxide oxidizing agent and TADHT can react with each other. Such conditions exist especially when the reaction partners meet each other in an aqueous solution. This can occur by separately adding the peroxygen compound and TADHT to a solution optionally containing a detergent or detergent. However, it is particularly advantageous for the process of the invention to use hard surface detergents or detergents according to the invention comprising TADHT and optionally a peroxygen-containing oxidizing agent. When using a detergent or detergent that does not contain peroxygen, the peroxygen compound can be added separately to the solution as it is, or preferably as an aqueous solution or suspension.

  The detergents and detergents according to the invention can exist as solid substances in the form of granules, powders or tablets, as other shaped bodies, homogeneous solutions or suspensions, and in principle, apart from TADHT and peroxygen compounds May contain all known ingredients customary in such compositions. The composition according to the present invention comprises in particular builder substances, surfactants, peroxygen compounds, additional peroxygen activators or organic peracids, water-miscible organic solvents, sequestering agents, thickeners, preservatives. Pearlescent agents, emulsifiers, and enzymes, and special additives with color or fiber protection. Other adjuvants such as electrolytes, pH modifiers, silver corrosion inhibitors, foam modifiers, and colorants and fragrances are also possible.

  Suitable peroxygen compounds include hydrogen peroxide and compounds that release hydrogen peroxide under cleaning and cleaning conditions, such as alkali metal peroxides, organic peroxides such as urea-hydrogen peroxide adducts, and Inorganic persalts such as alkali metal perborates, alkali metal percarbonates, alkali metal perphosphates, alkali metal persilicates, alkali metal persulfates and alkali metal peroxynitriles. Mixtures of two or more of these compounds are suitable as well. Sodium perborate tetrahydrate is preferred, sodium perborate monohydrate and sodium percarbonate being particularly preferred. Sodium perborate monohydrate is preferred because of its good storage stability and good water solubility. For environmental reasons, sodium percarbonate is preferred.

  A further suitable group of peroxide compounds are alkali metal hydroperoxides. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide. Aliphatic or aromatic monopercarboxylic acids or dipercarboxylic acids and the corresponding salts are also suitable as peroxy compounds. Examples include peroxynaphthoic acid, peroxylauric acid, peroxystearic acid, N, N-phthaloylaminoperoxycaproic acid, 1,12-diperoxidedecanedioic acid, 1,9-diperoxy Azelaic acid, diperoxy sebacic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-dioic acid and 4,4′-sulfonyl-bisperoxybenzoic acid.

  In addition to TADHT in the present invention, the detergent and detergent may further contain a suitable bleach activator in a usual amount (about 1 to 10% by weight) based on the form of granules.

  Bleach activators include organic compounds with O-acyl or N-acyl groups, especially activated carboxylic esters, especially sodium-nonanoyloxy-benzenesulfonate, sodium-isononanoyloxy-benzenesulfonate, sodium -4-benzoyloxy-benzenesulfonate, sodium-trimethylhexanoyloxy-benzenesulfonate, carboxylic anhydride, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5- Diacetoxy-2,5-dihydrofuran, lactone, Acylale, carboxylic acid amide, acyl lactam, acylated urea and oxamide, N-acylated hydantoins such as 1-phenyl-3-acetylhydantoin, hydrazide, Triazole, Hydrotriazine, urazole, diketopiperazide, sulfurylamide, polyacylated alkylenediamines such as N, N, N ', N'-tetraacetylethylenediamine, acylated triazine derivatives, especially 1,5-diacetyl-2,4 -Dioxohexahydro-1,3,5-triazine, acylated glycolurils, especially tetraacetylglycoluril, N-acylimides, especially N-nonanoylsuccinimide, and acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetyl xylose and octaacetyl lactose, and acetylated, optionally N-alkylated glucamine and gluconolactone and / or N-acylated lactams, such as N-benzoylcaprolactam, 4th grade Nitori Compounds, such as quaternary trialkylammonium nitrile salts, in particular, are preferred those selected from the group cyanomethyl trimethylammonium salts, heterocyclic quaternary nitrile compounds substituted.

  In addition to or instead of the conventional bleach activators described above, sulfonimines, open chain or cyclic quaternary iminium compounds such as dihydroisoquinolinium betaine and / or further bleach-accelerating agents Transition metal salts or monocyclic or polycyclic transition metal complexes with acyclic or macrocyclic ligands may also be included.

  Said detergents and detergents can comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, and cationic , Zwitterionic and amphoteric surfactants. Such surfactants are preferably included in the detergents of the present invention in a proportion of 1% to 50% by weight, in particular 3% to 30% by weight, whereas hard surface detergents are usually , In smaller proportions, ie up to 20% by weight, in particular up to 10% by weight and preferably in an amount ranging from 0.5% to 5% by weight. A low foaming compound is typically used as a detergent for use in an automatic dishwashing process.

Suitable anionic surfactants are in particular soaps containing soaps and sulfate or sulfonate groups. As sulfonate type surfactants, preferably C ₉ -C ₁₃ alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene sulfonates and hydroxyalkane sulfonates, and monoolefins having terminal or internal double bonds, for example, Examples include disulfonates such as those obtained by sulfonation using sulfur trioxide gas and subsequent alkali or acid hydrolysis of the sulfonation product. Also suitable are alkane sulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation followed by hydrolysis or neutralization. Also suitable are alpha-sulfo fatty acids (ester sulfonates), such as alpha sulfonated methyl esters of hydrogenated coconut fatty acids, palm kernel fatty acids or animal fatty acids, which contain 8-20 carbons in the fatty acid molecule. Produced by sulfonation of methyl esters of fatty acids derived from plants and / or animals with atoms, followed by neutralization to obtain water-soluble mono-salts.

In addition, sulfated fatty acid glycerol esters, which are monoesters, diesters and triesters and mixtures thereof, are also suitable anionic surfactants. Alkyl (alkenyl) sulfates include, for example, alkali metal salts of sulfuric monoesters of C _{12 to} C ₁₈ fatty alcohols selected from coconut fatty alcohol, animal fat alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, Preference is given to sodium salts or the alkali metal salts of sulfuric acid monoesters of C ₈ -C ₂₀ oxoalcohols and monoesters of secondary alcohols of this chain length, in particular sodium salts. Also preferred are alkyl (alkenyl) sulfates of the above-mentioned chain length, which contain synthetic linear alkyl groups produced on the basis of petrochemistry. 2,3-alkyl sulfates are also suitable anionic surfactants. Sulfuric monoesters of linear or branched alcohols ethoxylated with 1-6 mol ethylene oxide, for example 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol ethylene oxide (EO), or 1- C ₁₂ -C ₁₈ fatty alcohols with 4 EO are also suitable.

Preferred anionic surfactants, referred to as sulfosuccinates or as sulfosuccinates, are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, in particular ethoxylated fatty alcohols. Also included are salts of alkylsulfosuccinic acid which is Preferred sulfosuccinates contain C _{8 to} C ₁₈ fatty alcohol groups or mixtures thereof. Furthermore, the anionic surfactant includes a fatty acid derivative of an amino acid, for example, a fatty acid derivative of N-methyltaurine (tauride) and / or a fatty acid derivative of N-methylglycine (sarcosinate). Furthermore, examples of the anionic surfactant include soap in an amount of 0.2 to 5% by weight, for example. Saturated fatty acid soaps such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid salts, and especially natural fatty acids such as coconut fatty acid, palm kernel fatty acid or animal fatty acid A soap mixture is suitable.

  Anionic surfactants including soaps can be present in the form of their sodium, potassium or ammonium salts or as soluble salts of organic bases such as monoethanolamine, diethanolamine or triethanolamine. The anionic surfactant is preferably present in the form of these sodium or potassium salts, in particular in the form of the sodium salt. Anionic surfactants are preferably included in the detergents according to the invention in amounts of 0.5 to 10% by weight, in particular in amounts of 5 to 25% by weight.

Nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, particularly preferably 8 to 18 carbon atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mole of alcohol. ), Wherein the alcohol group may be linear or preferably methyl-branched at the 2-position, or as typically present in oxoalcohol groups A straight-chain group and a methyl-branched group may be mixed. However, naturally occurring alcohols having 12 to 18 carbon atoms, e.g. linear groups from palm, palm, tallow or oleyl alcohol, and alcohol ethoxylates with an average of 2 to 8 EO per mol of alcohol Is particularly preferred. Preferred ethoxylated alcohols include, for example, C _{12 to} C ₁₄ alcohols with 3 EO or 4 EO, C _{9 to} C ₁₁ alcohols with 7 EO, C ₁₃ to C with 3 EO, 5 EO, 7 EO or 8 EO C ₁₅ alcohol, 3 EO, 5 EO or C ₁₂ -C ₁₈ alcohol with 7 EO, and mixtures thereof, for example, the C ₁₂ -C ₁₈ alcohols with C ₁₂ -C ₁₄ alcohols and 7 EO having 3 EO A mixture is included. The degree of ethoxylation described above is a statistical average, which may be an integer or a fraction for a particular product. The alcohol ethoxylate preferably has a narrow homolog distribution (narrow range ethoxylate: NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (beast) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

Nonionic surfactants include alkyl glycosides of the general formula RO (G) _x where R is primary linear or methyl branched, in particular methyl branched at the 2-position 8-22 Also included are the alkyl glycosides described above, which are aliphatic groups having individual, preferably 12-18 carbon atoms, and G is a glycoside unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x representing the distribution of monoglycosides and oligoglycosides is an arbitrary number between 1 and 10 and may be a fractional value because it is an analytically determined quantity; x is preferably 1.2 to 1.4 . Similarly, a polyhydroxy fatty acid amide of formula (I), wherein the R ¹ CO group is an aliphatic acyl group having 6 to 22 carbon atoms, R ² is hydrogen; An alkyl or hydroxyalkyl group having carbon atoms, and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Hydroxy fatty acid amides are also suitable.

The polyhydroxy fatty acid amide is preferably derived from a reducing sugar having 5 or 6 carbon atoms, in particular glucose. The group of polyhydroxy fatty acid amides is a compound of formula (II), wherein R ³ is a linear or branched alkyl or alkenyl group having 7 to 12 carbon atoms and R ⁴ is 2 to 8 A straight-chain, branched or cyclic alkylene group or arylene group having ⁵ carbon atoms, and R ⁵ is a straight-chain, branched or cyclic alkyl group or aryl group or oxyalkyl group having 1 to 8 carbon atoms, preferably C _{A 1 to} C ₄ alkyl group or a phenyl group, and [Z] is a linear polyhydroxyalkyl group, the alkyl chain being substituted by at least two hydroxyl groups, or an alkoxy of this group Also included are compounds of the above formula (II) which are derivatized, preferably ethoxylated or propoxylated derivatives. Here, [Z] is preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compound can then be converted to the desired polyhydroxy fatty acid amide by reacting with a fatty acid methyl ester in the presence of an alkoxide as a catalyst.

  Can be used as a single nonionic surfactant or in combination with other nonionic surfactants, in particular with alkoxylated fatty alcohols and / or alkyl glycosides, preferably used nonionic Another group of surfactants includes alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated, preferably fatty acid alkyl esters having 1 to 4 carbon atoms in the alkyl chain, especially Examples include fatty acid methyl esters. Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N, N-dimethylaminoxid and N-tallow alkyl-N, N-dihydroxyethylamine oxide ( N-Talgalkyl-N, N-dihydroxyethylaminoxid) and fatty acid alkanolamides are also suitable.

  Furthermore, examples of the surfactant include so-called gemini surfactants. Such compounds are generally known to have two hydrophilic groups per molecule. These groups are usually separated from each other by so-called “spacers”. This spacer should usually be a carbon chain long enough so that the hydrophilic groups have sufficient spacing and they act independently of each other. Such surfactants generally exhibit very low critical micelle concentrations and exhibit the ability to significantly reduce the surface tension of water. Gemini-type polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides can also be used. Still another type of surfactant may be one having a dendrimere strukturen.

Suitable organic or inorganic builders are neutral or particularly alkaline reactive salts capable of precipitating or complexing calcium ions. Suitable builder substances which are not particularly environmentally problematic are those of the general formula NaMSi _{(x) 2} O _{(2x + 1)} (wherein M is sodium or hydrogen, x is 1.9-22, preferably 1.9-4 And y represents a number from 0 to 33), for example, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS- 7 (β-Na ₂ Si ₂ O ₅ , Natrosilit), Na-SKS-9 (NaHSi ₂ O ₅ * H ₂ O), Na-SKS-10 (NaHSi ₂ O ₃ * 3H ₂ O, Kanemit), Na- SKS-11 (t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ), and fine crystalline 100 It is a synthetic hydrous zeolite, especially of the NaA type, having a calcium binding capacity CaO / g in the range of ~ 200 mg.

  Zeolites and layered silicates can be included in the composition in amounts up to 20% by weight.

  Furthermore, unneutralized or partially neutralized polymeric (copolymeric) polycarboxylic acids are also suitable. These include acrylic acid or methacrylic acid homopolymers, or other ethylenically unsaturated monomers such as acrolein, dimethylacrylic acid, ethylacrylic acid, vinylacetic acid, allylacetic acid, maleic acid, fumaric acid, Itaconic acid, methallylsulfonic acid (allylsulfonic acid), vinylsulfonic acid, styrenesulfonic acid, acrylamidomethylpropanesulfonic acid, and phosphorus group-containing monomers such as vinylphosphoric acid, allylphosphoric acid and acrylamidomethylpropane phosphoric acid and their salts And copolymers with hydroxyethyl acrylate sulfate (hydroxyethyl methacrylate sulfate), allyl alcohol sulfate and allyl alcohol phosphate).

  Preferred polymers (copolymers) have an average molar mass of 1000 to 100000 g / mol, preferably 2000 to 75000 g / mol, and in particular 2000 to 35000 g / mol.

  The degree of neutralization of the acidic groups is advantageously 0 to 90%, preferably 10 to 80%, in particular 30 to 70%.

  Suitable polymers include in particular homopolymers of acrylic acid and copolymers of acrylic acid (methacrylic acid) with maleic acid or maleic anhydride.

  Further, monoethylenically unsaturated dicarboxylic acid having 4 to 8 carbon atoms or a salt thereof 10 to 70% by weight, monoethylenically unsaturated monocarboxylic acid having 3 to 10 carbon atoms or a salt thereof 20 to 85 Derived from a terpolymer obtained by polymerizing 1% to 50% by weight, monounsaturated monomer that liberates hydroxyl groups on the polymer chain after hydrolysis, and 0 to 10% by weight monomer capable of radical copolymerization. Also suitable are copolymers.

  Similarly, monosaccharides, oligosaccharides, polysaccharides and modified polysaccharides, and graft polymers of animal or vegetable proteins are also suitable.

Preferably a copolymer consisting of sugar and other polyhydroxy compounds and a monomer mixture, the monomer mixture, monoethylenically unsaturated C ₃ -C ₁₀ monocarboxylic acid or a C ₃ -C ₁₀ monocarboxylic acids and / or mono-, 45 to 96% by weight of a mixture of its cation-bearing salt, monoethylenically unsaturated monosulfonic acid group-containing monomer, monoethylenically unsaturated sulfate, vinyl phosphate, and / or monovalent cation of these acids 4 to 55% by weight of salts with ions, and 0 to 30% by weight of water-soluble unsaturated compounds modified with 2 to 50 mol of alkylene oxide per 1 mol of monoethylenically unsaturated compounds.

  Further suitable polymers are polyaspartic acid or derivatives thereof in a form that is not neutralized or only partially neutralized. Also particularly suitable are graft polymers in which acrylic acid, methacrylic acid, maleic acid, and further ethylenically unsaturated monomers are grafted onto a salt of polyaspartic acid, usually obtained by hydrolysis of the polysuccinimide described above. In this case, it is possible to omit the addition of the acid which is usually necessary for the production of the polyaspartic acid in a partially neutralized form. The amount of polyalpartate is typically selected such that the degree of neutralization of all carboxyl groups introduced into the polymer does not exceed 80%, preferably 60%.

  Further usable builders are, for example, carboxylic acids such as citric acid, preferably used in the form of sodium salts, in particular trisodium citrate and trisodium citrate dihydrate, nitrilotriacetic acid and its water solubility Carboxymethyloxysuccinic acid, ethylenediaminetetraacetic acid, monohydroxysuccinic acid, dihydroxysuccinic acid, α-hydroxypropionic acid, gluconic acid, meritic acid, and alkali metal salts of benzopolycarboxylic acid. Also suitable are phosphate-containing builders, such as alkali metal phosphates present in the form of alkaline, neutral or acidic sodium or potassium salts.

  Examples of these include trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, a degree of oligomerization in the range of 5 to 1000, especially 5 to 50. And oligomeric trisodium phosphate having a mixture of sodium and potassium salts. These builder substances are contained at 5 to 80% by weight, preferably 10 to 60% by weight.

  The desired viscosity of the liquid composition can be obtained by adding water and / or an organic solvent, or by adding a combination of an organic solvent and a thickener.

  In principle, all mono- or polyhydric alcohols are useful as organic solvents. Preferably, alcohols having 1 to 4 carbon atoms are used, such as methanol, ethanol, propanol, isopropanol, linear and branched butanol, glycerin and mixtures of these alcohols. Preferred alcohols further include polyethylene glycol having a relative molecular weight of 2000 or less. In particular, it is preferred to use polyethylene glycol having a relative molecular weight of 200 to 600 in an amount of up to 45% by weight and polyethylene glycol having a relative molecular weight of 400 to 600 in an amount of up to 5 to 25% by weight. Preference is given to mixtures in which the ratio of monomeric alcohol, for example ethanol-containing solvent and polyethylene glycol, is from 0.5: 1 to 1.2: 1.

  Suitable solvents further include, for example, triacetin (glycerin triacetate) and 1-methoxy-2-propanol.

  As the thickener, hydrogenated castor oil, salts of long chain fatty acids are preferable, and these are preferably used in an amount of 0 to 5% by weight, particularly 0.5 to 2% by weight, for example, sodium stearate, stearic acid Potassium, aluminum stearate, magnesium stearate and titanium stearate, or sodium and / or potassium salts of behenic acid, and polysaccharides, especially xanthan gum, Guar-Guar, Agar-Agar, alginate and tylose (Tylosen), carboxymethylcellulose and hydroxyethylcellulose, high molecular weight polyethylene glycol monoesters and polyethylene glycol diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone, and sodium chloride and Electrolytes such as ammonium chloride is used.

The thickening agent is preferably a water-soluble polyacrylate, which is cross-linked with, for example, about 1% sucrose polyallyl ether and has a relative molecular weight greater than 1 million. Examples of these are polymers available under the name Carbopol ^(R) 940 and 941. The crosslinked polyacrylate is used in an amount of 1% by weight or less, preferably in an amount of 0.2 to 0.7% by weight.

Enzymes optionally included in the compositions of the present invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases such as BLAP ^(R) , Optimase ^(R) , Opticlean ^(R) , Proteases such as Maxacal ^(R) , Maxapem ^(R) , Duraxym ^(R) , Purafect ^(R) OxP, Esperase ^(R) and / or Savinase ^(R) , Termamyl ^(R) , Amylase-LT ^(R) , Amylases such as Maxamyl ^(R) , Duramyl ^(R) , Purafectel OxAm, cellulases such as Celluzyme ^(R) , Carezyme ^(R) , K-AC (R) and / or WO 96/34108 and international known cellulase and / or lipase by Publication No. 96/34092 pamphlet, for ^{example, Lipolase (R), Lipomax (} R), include Lumafast ^(R) and / or Lipozym ^(R). The enzyme used is adsorbed to a carrier substance, for example as described in WO 92/111347 and WO 94/23005, in order to prevent it from being deactivated sooner than expected. And / or embedded in the coating material. These are preferably contained in detergents and detergents in amounts of up to 10% by weight, in particular 0.05-5% by weight, and particularly preferably enzymes stabilized against oxidative degradation are used.

The automatic dishwashing detergent of the present invention preferably comprises a conventional alkali metal carrier, such as an alkali metal silicate, alkali metal carbonate and / or alkali metal bicarbonate. The alkali metal carriers which are commonly used, carbonates, bicarbonates, and 1: 1 to 2.5: alkali metal silicate having a first _{SiO 2 / M 2 O (M} = alkali metal atom) molar ratio included. Alkali metal silicates are included in amounts of up to 40% by weight, in particular 3 to 30% by weight, based on the total composition. The alkali metal carrier system used in the detergents of the present invention is preferably a mixture comprising carbonate and bicarbonate, preferably sodium carbonate and sodium bicarbonate, which are up to 50% by weight, preferably 5%. Contained in an amount of ~ 40% by weight.

  Furthermore, the present invention relates to a bleaching agent based on 15 to 65% by weight, in particular 20 to 60% by weight of a water-soluble builder component, 5 to 25% by weight, in particular 8 to 17% by weight, based on the total amount of the composition. And a composition for an automatic dishwasher comprising 0.1-5 wt% TADHT. Such compositions are preferably weakly alkaline, i.e. solutions exhibiting this weight percent have a pH value of 8 to 11.5, in particular 9 to 11.

  In a further embodiment of the composition of the invention for an automatic dishwasher, 20-60% by weight of a water-soluble organic builder, in particular alkali metal citrate, 3-20% by weight alkali metal carbonate and 3-40% by weight Of alkali metal disilicates.

  For protection from silver corrosion, a silver corrosion inhibitor can be used in the dishwashing detergent of the present invention. Preferred silver corrosion inhibitors include 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.

  If the composition foams vigorously in use, up to 6% by weight, preferably about 0.5-4% by weight of a foam control compound, preferably a combination of silicon, paraffin, paraffin and alcohol, hydrophobic silicic acid ( It is also possible to add foam-modifying compounds selected from the group comprising hydrophobicized Kieselsaeuren, fatty acid bisamides (Bisfettsaeureamide), and mixtures thereof, and other known commercially available foam inhibitors. Foam inhibitors, particularly silicon and / or paraffin containing foam inhibitors, are preferably bound to a water-soluble or dispersible particulate carrier material. Particularly preferred is a mixture comprising paraffin and Bistearylethylendiamid. Another optional ingredient in the composition of the present invention is, for example, perfume oil.

  Organic solvents that can be used in the composition of the invention include alcohols having 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and tert, especially when the composition is present in liquid or pasty form. -Butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof, and ethers derivable from the aforementioned compounds. Such water-miscible solvents are preferably present in the detergent according to the invention in an amount of up to 20% by weight, in particular 1 to 15% by weight.

  In order to adjust to the desired pH value that does not occur naturally by mixing the remaining ingredients, the composition of the present invention is compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycol Acids, succinic acid, glutaric acid and / or adipic acid, or mineral acids, in particular sulfuric acid or alkali metal hydrogensulfate, or bases, in particular ammonium hydroxide or alkali metal hydroxide, can be included. Such a pH adjusting agent is preferably included in the composition of the present invention in an amount of 10% by weight or less, particularly 0.5 to 6% by weight.

  Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, pentanediol or sorbic acid.

  Examples of the pearl brightener include glycol distearate such as ethylene glycol distearate and fatty acid monoglycol ester. Examples of the salt or extender include sodium sulfate, sodium carbonate, or sodium silicate (water glass).

  Representative individual examples of other additives include sodium borate, starch, saccharose, polydextrose, RAED, stilbene compounds, methylcellulose, toluene sulfonate, cumene sulfonate, soap and silicon.

  The composition according to the invention is preferably present as a formulation in powder form, granules or tablet form, which are mixed in a known manner, for example by mixing, granulating, roller compacting and / or spray drying heat-resistant ingredients. And can be prepared by mixing it with unstable components including enzymes, bleaches and bleach activators in particular. The compositions according to the invention in the form of aqueous solutions or solutions containing other customary solvents are particularly preferably prepared by simple mixing of the components which can be introduced into the automatic mixer as they are or as solutions.

  For the production of particulate compositions having a large bulk density (especially a bulk density in the range of 650 g / l to 950 g / l), a process comprising an extrusion step as disclosed in EP 0486592 is provided. preferable. Furthermore, a preferred method using a granulation process is described in EP 0642576. The present invention has a high bulk density in the range of 800 to 1000 g / l, is in the form of nicht staubenden, storage-stable and rieselfaehigen powders and / or granules The manufacture of the composition involves, in the first process step, mixing the builder component with at least a portion of the liquid mixture component to increase the bulk density of this premix (Vorgemisches) and then (intermediate if necessary) It can also be carried out after the drying step by mixing the remaining components of the composition comprising TADHT) with the premix obtained in this way.

  In order to produce the composition of the invention in tablet form, preferably all ingredients are mixed together in a mixer and the mixture is compressed by conventional tablet compression, such as eccentric compression or rotary compression. This method makes it possible to obtain tablets without any problems which are hard to break and yet have a sufficiently fast solubility under the conditions of use and usually have a bending strength of 150 N or more. The tablets thus produced preferably have a diameter of 3-5 mm to 40 mm and a weight of 1-5 g to 40 g, in particular 20 g to 30 g.

  In addition to the ingredients already mentioned, the detergents and detergents can include any conventional additive substances in amounts typically found in such compositions.

Example 1:
Synthesis of TADHT
1,3,5-triacetyl-2,4-dioxo-1,3,5-hexahydrotriazine (TADHT) was prepared as described in the literature (W. Beckmann et. Al., Chem. Techn., 40 ( 10), 423, 1988). The product is obtained as a white powder having a melting point of 166-169 ° C.
¹ H-NMR (DMSO): δ = 2.4 ppm (acetyl group in s, 6H, N1 and N3); 5.5 (acetyl group in s, 3H, N5); 5.5 (s, 2H, methylene group).

Example 2:
Manufacture of granules In a laboratory plow-shear mixer (Pflugscharmischer) (Loedige M5R with blade head), 875 g of TADHT powder is placed, temperature of T = 60 ° C at a mixer speed of n = 100 min ^-1 Heated. When the target temperature is reached, the mixer speed is increased to n = 250 min ^-1 and the blade head (Messerkopf) is activated and a quantity of 125 g of Genapol T-500 melt is measured into the mixer within 2 minutes. (Genapol T-500 = fatty alcohol glycol ether: commercial product from the company Clariant GmbH). This Genapol melt was heated to a temperature of T = 80 ° C. before metering in. After feeding the entire melt, the product mixture was further mixed for about 30 seconds and then removed from the mixer.

For granulation, a laboratory annular edge runner press (Labor-Ringkollerpresse: PP 85 from Schlueter) equipped with a 1 mm die was used. Prior to granulation, the substantial work area dies and edge runners were preheated to a temperature of T = 60 ° C. The resulting mixture from the plow shear type mixer was metered into an annular edge runner press operating at a rotation speed of n = 300 min ^{−1 at} a metering speed of about 80-100 g / min. The distance between the edge runner and the annular die was adjusted to about 0.4 mm, and the distance between the stripper blades (Abstreifermessers) was adjusted to about 4 mm. The resulting noodle shaped granules had a temperature of about 65-70 ° C. and were cooled to room temperature prior to subsequent processing. The product was finally fractionated in a laboratory sieve (Retsch AS 200 control) in order to remove less than 400 μm fines and coarser fractions greater than 1600 μm from the target product. The composition of the final noodle type granule is 87.5% TADHT and 12.5% Genapol T-500.

Example 3:
Production of co-granulates of TADHT and (cyanomethyl) -diethylmethylammonium tosylate
0.92 kg of TADHT powder, 0.92 kg of (cyanomethyl) -diethylmethylammonium tosylate powder and 0.16 kg of bentonite (for example Ikomont NA weiss, a commercial product from S & B Industrial Minerals GmbH), a laboratory mixer (Eirich R -02). The product was stirred vigorously for 2 minutes with a mixing tank speed of n = 32 min ⁻¹ (level 1) and a flow speed of n = 750 min ⁻¹ . The powder mixture thus produced was then compressed in a roll type compactor (Pharmaco Lactor L 200/30 P manufactured by Hosokawa Bepex). In order to fully compress the powder, the roll speed was varied in the range of about 4-8 min ^-1 and the screw speed was varied in the range of about 18-25 min ^-1 . The compressed pieces were then gently ground in a screening mill (Siebmuehle: (SKM / NR from Alexanderwerk)) operating with a sieve having an introduced mesh size of 1600 μm and a rotation speed of 33 min- ¹ . The ground product was finally fractionated in a laboratory sieve (Retsch AS 200 control) to remove fines below 400 μm, the composition of the final compact is 46% TAED, 46% (Cyanomethyl) diethylmethylammonium tosylate and 8% bentonite.

Example 4:
Bleaching ability of TADHT at 40 ° C compared to TAED
The bleaching ability of the TADHT powder was examined at 40 ° C. using a Linitest apparatus (Linitest-Geraet: manufactured by Heraus). Here, 5 g / l bleach-free basic detergent (WMP, WFK, Krefeld) and 0.5 g / l sodium perborate monohydrate (Degussa) were dissolved in water of hardness 3. Then 200 mg / l activator was added. The washing time was 30 minutes. As a bleach test cloth, cotton (CS-8 and BC-1, manufactured by WFK Testgewebe GmbH, Krefeld) soiled with grass and tea was used. The result of bleaching was evaluated as the difference in reflectivity measured after washing with an Elrepho-Geraet when compared to an unwashed fabric.

  It was confirmed that the bleach activator of the present invention (manufactured according to Example 1) exhibits a bleaching action superior to that of the conventional TAED.

  Substantially the same results were obtained when sodium perborate was replaced with sodium percarbonate monohydrate.

Example 5:
Bleaching ability of TADHT at 60 ° C compared to TAED
The bleaching ability of the TADHT powder was examined at 60 ° C. with a Linitest apparatus (Heraus). Here, 5 g / l bleach-free basic detergent (WMP, WFK, Krefeld) and 0.5 g / l sodium perborate monohydrate (Degussa) were dissolved in water of hardness 3. Then 200 mg / l activator was added. The washing time was 30 minutes. As a bleaching test cloth, cotton stained with red wine and tea (E114 test cloth (EMPA, CH,)) and BC-1 (manufactured by WFK Testgewebe GmbH, Krefeld) were used. The result of bleaching was evaluated as the difference in reflectivity measured with an Llefo apparatus after washing, compared to an unwashed cloth.

  It was confirmed that the bleach activator of the present invention (manufactured according to Example 1) exhibits a bleaching action superior to that of the conventional TAED.

  Substantially the same results were obtained when sodium perborate was replaced with sodium percarbonate monohydrate.

Example 6:
Peracid release
In a 2 L beaker, 8 g WMP basic detergent (WFK) and 1.5 g sodium perborate monohydrate are dissolved in 1 L water at about 20 ° C. Subsequently 0.5 g of activator is added, after which samples are taken at regular intervals and the content of peracetic acid is determined by iodometric titration.

  From TADHT, it can be confirmed that about 30% more peracetic acid is formed per weight unit than from TAED.

Claims (3)

  Detergents and detergents containing persalts or hydrogen peroxide and a bleach activator, wherein the bleach activator is 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexahydro Said detergent and detergent characterized by being a triazine.   2. Detergent and detergent according to claim 1, characterized in that it comprises 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexahydrotriazine in the form of granules.   2. Detergent and detergent according to claim 1, characterized in that it contains 0.1 to 20% by weight of 1,3,5-triacetyl-2,4-dioxo-1,3,5-hexahydrotriazine.