DE19948667A1 - Detergent component with double-controlled fragrance release - Google Patents

Abstract

Cleaning agent components which contain between 0.1 and 20 % by weight of one or more esters, ethers, acetals or ketals of fragrant agents, between 20 and 99.9 % by weight of a fusible substance or substances with a melting point above 30 DEG C and between 0 and 60 % by weight of additional active ingredients and/or auxiliary agents. Said cleaning agents only release the fragrant agents contained in them at a stage where they cannot be disintegrated and can be detected by the consumer.

Description

The present invention is in the field of automatic dishwashing detergents household dishwashers. It concerns detergent components for use in machine dishwashing detergents (MGSM) and cleaning agents together Solutions and detergent tablets containing such components.

The mechanical cleaning of dishes in household dishwashers includes übli a pre-rinse, a main rinse and a rinse cycle, which are from Zwi rinse cycles are interrupted. Most machines have the pre-rinse cycle can be switched on for heavily soiled dishes, but is only used in exceptional cases by the Ver user selected, so that in most machines a main wash, an intermediate rinse clean water and a rinse cycle. The temperature of the The main wash cycle varies depending on the machine type and program level selection 40 and 65 ° C. In the rinse cycle, a dosing tank in the machine turns into rinse aid agents added, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely used in the prior art wrote. Your job is primarily to keep limescale and deposits on the ge to prevent cleaned dishes. In addition to water and low-foaming non-ionic surfactants these rinse aids often also contain hydrotopes, pH adjusting agents such as citric acid or be lag-inhibiting polymers and often perfume.  

Machine dishwashing detergents themselves are also often perfumed. But both in the case of detergents and rinse aids, some of them are sensitive Fragrances under the drastic conditions in the rinse aid. As a result of this the "unpleasant smell" of lye perceived by the consumer when opening the Dishwasher insufficiently covered. In addition, only a small proportion gets of the cost-intensive fragrances to where it should have its effect.

International patent application WO 98/07812 proposes a solution to this problem (Procter & Gamble) before, fragrance release systems in automatic dishwashing detergents to incorporate which contain β-keto esters of fragrance alcohols. These esters are long sam split and should create a long-lasting fragrance impression. Here too become the esters due to the chemical and thermal load in the main and rinse aid already partially split, so that the sensitive fragrances decompose or with the Rinse water should be pumped out before the rinse cycle. The percentage of fragrance is still there substances that get to the desired place of action, low.

The task, therefore, was still to provide funds which contained this in them Release the perfume at a higher percentage or ideally completely there where on the one hand it no longer decomposes and on the other hand it is perceived by the consumer can be. The object of the present invention was to solve this problem.

It has now been found that the double-controlled release of fragrances, i.e. H. the targeted release of fragrance precursors at a later point in time in the clear rinse cycle the scent impression when opening the machine at the same concentration significantly improved in fragrances.

The present invention relates to a detergent component which

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

contains.

By incorporating the fragrance precursors into meltable substances, the free setting of these sensitive substances can be controlled specifically, so that the load through the alkaline cleaning liquor and the ambient temperatures are avoided until the meltable substances that release fragrance precursors. Because of the only now Splitting the fragrance precursors makes the released perfume significantly shorter overall thermally or chemically contaminated, so that less perfume due to environmental influences is disturbed. Overall, this leads to improved fragrance impressions.

Suitable fragrances for the detergent components according to the invention Fragrance alcohols, fragrance aldehydes and / or fragrance ketones, which are caused by reaction with acids, alcohol get aldehydes, ketones or fragrance alcohols, fragrance aldehydes and / or fragrance ketones in the esters, ethers, acetals or ketals are converted. The ingredients a) of the fiction modern detergent components are described below.

Preferred detergent components according to the invention contain as ingredient a) 0.25 to 17.5% by weight, preferably 0.5 to 15% by weight and in particular 1 to 10% by weight one or more esters of fragrance alcohols. The percentages by weight relate each on the entire detergent component. As acids with which Duftal carols can be esterified to form esters which can be used according to the invention acids, amino acids, phosphoric acids, silicas etc. Important and preferred Representatives from the groups mentioned are described below.

In the context of the present invention, particularly preferred detergent components contain as ingredient a) one or more β-keto esters of the formula R ¹ R ² R ³ C-C (O) -R, in which each radical R ¹ to R ^{3 is} selected independently of one another from the group -H, -CH ₃ , -CH ₂ (CH ₂ ) _n CH ₃ with n = 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 30, or the branch ten C _3-30 alkyl radicals and in which R stands for a fragrant alcohol residue.

Preferred fragrance alcohols from which the radical R can be derived are, for example, 2,4-dimethyl-3-cyclohexene-1-methanol (floralol), 2,4-dimethyl-cyclohexane-methanol (dihydrofloralol), 5,6-dimethyl-1- methyleneethylbicyclo [2.2.1] hept-5-en-2-methanol (Ar bozol), α, α-4-trimethyl-3-cyclohexene-1-methanol (α-terpineol), 2,4,6-trimethyl-3 - cyclohexene-1-methanol (isocyclogeraniol), 4- (1-methylethyl) cyclohexane-methanol (majol), α-3,3-trimethyl-2-norborane-methanol, 11-dimethyl-1- (4-methylcyclohex-3-enyl) methanol , 2-phenylethanol, 2-cyclohexylethanol, 2- (ortho-methylphenyl) ethanol, 2- (meta-methylphenyl) ethanol, 2- (para-methylphenyl) ethanol, 66-dimethylbicyclo [3.1.1] hept-2- en-2 -ethanol (Nopol), -2- (4-methylphenoxy) ethanol, 3,3-dimethyl-Δ ² -β- norbaornanethanol (Patchomint), 2-methyl-2-cyclohexylethanol, 1- (4-isopropylcyclotihexyl) ethanol, 1 -Phenylethanol, 1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-2- (4-methylphenyl) ethanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol, 2- (cyclodode cyl) propan-1-ol (hydroxy-ambrane), 2,2-dimethyl-3- (3-methylphenyl) -propan-1-ol (majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2- propen-1-ol (cinnamon alcohol), 2-methyl-3-phenyl-2-propen-1-ol (methyl cinnamon alcohol), α-n-pentyl-3-phenyl-2-propen-1-ol (α-amyl cinnamon alcohol) , Ethyl 3-hydroxy-3-phenylpropionate, 2, - (4-methylphenyl) -2-propanol, 3- (4-methylcyclohex-3-ene) butanol, 2-methyl-4- (2,2,3- trimethyl-3-cyclopenten-1-yl) butanol, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopent-3-enyl) -2-buten-1-ol, 3-methyl-2- buten-1-ol (prenol), 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, ethyl 3-hydroxybutyrate, 4-phenyl -3-buten-2-ol, 2-methyl-4-phenylbutan- 2-ol, 4- (4-hydroxyphenyl) butan-2-one, 4- (4-hydroxy-3-methoxyphenyl) butan-2-one , 3-methylpentanol, 3-methylpentene-1-ol, 1- (2-propenyl) cyclopentan-1-ol (plinol), 2-methyl-4-phenylpentanol (Pemplefleur), 3-methyl-5-phenylpentanol (phenoxanol) , 2-methyl-5-phenylethanol, 2-methyl-5- (2,3-dimethyltricyclo [2.2.1.0 ^(2,6) ] hept-3-yl) -2-penten-1-ol (San talol), 4-methyl-1-phenyl-2-pentanol, 5- (2,2,3-trimethyl-3-cyclopentenyl) -3-methylpentan-2-ol (Sandalor), (1-methyl-bicyclo [2 , 1,1] hepten-2-yl) -2-methylpent-1-en-3-ol, 3-methyl-1-phenylpentan-3-ol, 1,2-dimethyl-3- (1-methylethenyl) cyclopentane -1-ol, 2-isopropyl-5-methyl-2-hexenol, cis-3-hexen-1-ol, trans-2-hexen-1-ol, 2-isoprenoyl-4-methyl-4-hexen-1 -ol (Lavendurol), 2-ethyl-2-phenyl-3-hexenol, 1-hydroxymethyl-4-isopropenyl-1-cyclohexene (dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-ol (Carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol (dihydrocarvenol), 1-methyl-4-isopropenylcyclohexan-3-ol, 4-isopropyl-1-methylcyclohexanol (rootanol), 4-isopropyl-cyclohexanol, 4- Methyl-1- (1-methylethyl) -3-cyclohexen-1-ol, 2- (5,6,6-trimethyl-2-norbornyl) cyclohexanol, isobornylhexanol, 3,3,5-trimethylcyclohexanol, 1-methyl-4 -isopropylcyclohexan-3-ol, 1-methyl-4-isopropylcyclohexan-8-ol (dihydroterpineol), 1,2-dimethyl-3- (1-methylethyl) cyclohexan-1-ol, heptanol, 2,4-dimethylheptane -1-ol, 6-heptyl-5-hepten-2-ol (isolinalool), 2,4-dimethyl-2,6-heptanediol, 6,6-dimethyl-2-oxymethyl-bicyclo [3.1] hept- 2-ene (myrtenol), 4-methyl-2,4-heptadien-1-ol, 3,4,5,6,6-pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5-heptene -2-ol, 6,6-dimethyl-3-hydroxy-2-methylenebicyclo [3.1.1] heptane, 1.7.7-trimethylbicyclo [2, 2.1] heptan-2-ol, 2.6 - dimethylheptan-2-ol (dimetol), 2,6,6-trimethylbicyclo [1,3,3] heptan-2-ol, octanol, 2-octenol, 2-methyloctan-2-ol, 2-methyl-6- methylene-7-octen-2-ol (myrcenol), 7-methyloctan-1-ol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-6-octene - 1-ol (citronellol), 3,7-dimethyl-2,6-octadien-1-ol (geraniol), 3,7-dimethyl-2,6-octen-1-ol (nerol), 3.7- Dimethyl-7-methoxyoctan-2-ol (osyrol), 3,7-dimethyl-1,6-octadien-3-ol (Li nalool), 3,7-dimethyloctan-1-ol (pelargol), 3.7- Dimethyloctan-3-ol (tetrahydrolinalool), 2,4-octadien-1-ol, 3,7-dimethyl-6-octen-3-ol (dihydrolinalool), 2,6-dimethyl-7-octen-2-ol ( Dihydromyrcenol), 2,6-dimethyl-5,7-octadien-2-ol, 4, 7-dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol, 2,6-dimethyloctan-3-ol, 3,6-dimethyloctane 3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-3,5-octadien-2-ol (muguol), 3-methyl-1-octen-3-ol, 7 -Hydroxy-3,7-dimethyloctanal, 3-nonanol, 2,6-nonadien-1-ol, cis-6-non-1-ol, 6,8-dimethylnonan-2-ol, 3- (hydroxymethyl) -2 -nonanone, 2-non-1-ol, 2,4-nonadien-1-ol, 3,7-diimethyl-1,6-nonadien-3-ol, decanol, 9-decenol, 2-benzyl-M-dioxa - 5-ol, 2-decen-1-ol, 2,4-decadien-1-ol, 4-methyl-3-cdecen-5-ol, 3,7,9-trimethyl-1,6-decadien-3 -ol (isobutyl-linalool), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-dodecen-1-ol, 2,4, dodecadien-1-ol, 3,7,11- Trimethyl-1,6,10-dodecatrien-1-ol (farnesol), 2,7,11-trimethyl-2,6, 10-dodecatrien-3-ol (nerolidol), 3,7,11,15-tetramethylhexadec- 2-en-1-01 (phytol), 3,7,11,15-tetramethylhexadec-1-en-3-ol (isophytol), benzyl alcohol, para-methoxybenzyl alcohol (anisyl alcohol), para-cymen-7-ol, 4 -Methylbenzyl alcohol, 3,4- Methylenedioxybenzyl alcohol, meth ylsalicylate, benzylsalicylate, cis-3-hexenylsalicylate, n-pentylsalicylate, 2-phenylethylsalicylate, n-hexylsalicylate, 2-methyl-5-isopropylphenol, 4-ethyl-2-methoxylphenol, 4-allyl-2-methoxyphenol (E -Methoxy-4- (1-propenyl) phenol (isoeugenol), 4-allyl-2,6-dimethoxyphenol, 4-tert-butylphenol, 2-ethoxy-4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl -5-methylphenol (thymol), pentyl ortho-hydroxybenzoate, ethyl 2-hydroxybenzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-5-methoxy-1-methylbenzene, 2-tert- Butyl-4-methyl-1-hydroxybenzene, 1-ethoxy-2-hydroxy-4-propenylbenzene, 4-hydroxytoluene, 4-hydroxy-3-methoxybenzaldehd, 2-ethoxy-4-hydroxybenzaldehy, decahydro-2-naphthol, 2, 5,5-trimethyl-octahydro-2-naphthol, 1,3,3-trimethyl-2-norbornanol (fenchol), 3a, 4,5,6,7,7, a-hexahydro-2,4-dimethyl-4 , 7-methano-1H-inden-5-ol, 3a, 4,5,6,7,7, a-hexahydro-3,4-dimethyl-4,7-methano-1H-inden-5-ol, 2 -Methyl-2-vinyl-5- (1-hydroxy-1-methylethyl) tetrahydrofuran, β-carophyllene, vaniline and their mixtures.

In addition to the β-keto esters, betaine esters are also preferred ingredients a) within the scope of the present invention. Preference is also given to detergent components which contain one or more betaine esters of the formula R ¹ R ² N- [C (R ³ ) (R ⁴ )] _n3 -C (O) -OR, in which each radical R ¹ and R ^{2 is} independent is selected from one another from - [C (R ³ ) (R ⁴ ) _n3 - C (O) -OR, - (CH ₂ ) _n -N {[C (R ³ ) (R ⁴ ) _n3 -C (O) - OR} ₂ and - {(CH ₂ ) _n1 -N [C (R ³ ) (R ⁴ ) -C (O) -O- R] _n3 ) _n2 - (CH ₂ ) _n1 -N (R ³ ) - [ C (R ³ ) (R ⁴ )] _n3 -C (O) -OR, each radical R ³ and R ^{4 is} independently selected from the group -H, -CH ₃ , -CH ₂ (CH ₂ ) _n CH ₃ with n = 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 30, the branched C _3-30 alkyl radicals or the substituted and unsubstituted aryl radicals, in which R is a fragrance alcohol radical and n stands for numerical values from 1 to 20, n1 for numerical values from 1 to 20, n2 for the numerical values 1, 2, 3, 4, 5 or 6 and n3 for the numerical values 1, 2 or 3.

The succinic acid esters of the fragrance alcohols mentioned above can also be preferred Use as ingredient a) of the detergent components according to the invention. Before drawn detergent components therefore contain one or more fragrance alcohol Succinate and / or di-fragrance alcohol succinate. This is particularly preferred Substance class the digeranylsuccinate.

Silica is also an acid for the esterification of fragrance alcohols, so that preferred detergent components are characterized in that they have a or contain several silicic acid esters of fragrance alcohols.

From this class of substances, silicic acid esters of the formula below are particularly preferred

in which R ¹ and R ⁴ are selected independently of one another from the group of straight-chain or branched, saturated or unsaturated, substituted or unsubstituted C _1-6 -hydrocarbon radicals and the aromatic alcohol radicals, each R ² and R ³ is selected independently of one another from the Group of scented alcohol residues and n values between 2 and 20.

The compounds mentioned can be prepared by simple transesterification of oligosilicic acid esters of lower alcohols with fragrance alcohols, it being possible to use both individual fragrance alcohols and fragrance alcohol mixtures. Depending on the reaction time and conditions, the lower alcohols are split off and the scent alcohols are bound, the alcohols along the Si-O-Si chain being exchanged more easily than the terminal alcohols. In this way, oligomeric silicic acid esters can be produced in which the radicals R ² and R ^{3 are} scented alcohol residues, while the terminal radicals R ¹ and R ^{4 are} still unreacted, that is to say residues of lower alcohols.

Oligosilicic acid esters of lower alcohols are commercially available, with methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and tert-butanol usually being used for the esterification. The representation not completely with scented alcohols around esterified oligosilicic acid esters leads to silicic acid esters of the above formula in which R ¹ and R ⁴ are selected independently of one another from the group methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and tert-butyl. Such compounds are preferred in the context of the present invention.

Phosphoric acids can also be esterified with fragrance alcohols. So are more preferred Detergent components characterized in that they have one or more Phos contain phosphoric esters of fragrance alcohols.  

The acid function of amino acids can also be esterified with fragrance alcohols, whereby all commercially available amino acids as part of the fragrance precursors a) invented detergent components according to the invention can be used, for example glycine, Ala nin, valine, leucine, isoleucine, phenylalanine, cystine, cysteine, etc. Preferred reini Agent components are characterized in that they have one or more ami non-acid esters of fragrance alcohols, preferably cysteine, alanine, glutamic acid, glycine and / or phenylalanine esters.

In addition to the esters or in their place, ethers of fragrances can also be used as In Content a) may be contained in the detergent components according to the invention. Here are detergent components which contain, as ingredient a) 0.25 to 17.5% by weight, preferably 0.5 to 15% by weight and in particular 1 to 10% by weight of one or more Contain ether of fragrance alcohols, preferred.

Preferred ethers in the context of the present invention are the glycosides from Duftal alcohols and among these the glucosides, preferably the β-glucosides. Accordingly detergent components are preferred that contain one or more fragrance alcohol Glycosides, preferably fragrance alcohol glucosides, contain.

A large number in the context of the present invention in the form of their esters or ethers or in the form of acetals or ketals usable fragrance alcohols was ge called. Particularly preferred detergent components are characterized in that that as the fragrance alcohol residue R, the residues of one or more fragrance alcohols from the group 1-octanol, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2- Methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butycyclohexanol, 3,5,5- Trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenyl pentanol, 3-octanol, 3-pentanol, 3- Phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butycyclohexanol, 6.8- Dimethyl-2-nonanol, 6-non-1-ol, 9-decen-1-ol, alpha-methylbenzyl alcohol, alpha Terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, beta-terpineol, butyl salicylate, Citronellol, cyclohexyl salicylate, decanol, dihydromyrcenol, dimethylbenzylcarbinol, Dimethylheptanol, dimethyloctanol, ethyl salicylate, ethylvaniline, eugenol, geraniol, hep  tanol, hexyl salicylate, isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol, n- Hexanol, n-pentanol, nerol, nonanol, octanol, para-menthan-7-ol, phenylethyl alcohol, Phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-cis-6- Nonadicnol, trans-2-non-1-ol, trans-2-octenol, undecanol, vanillin, cinnamon alcohol ent hold.

In addition to the esters and ethers, acetals or ketals can also be used as ingredient a) Use detergent components according to the invention. These connections zen the special attraction that it consists of both a fragrance molecule (alcohol or Alde hyd or ketone) and a non-fragrant molecule as well as two fragrance molecules len can be built. Detergent components, the ingredient a) 0.25 to 17.5% by weight, preferably 0.5 to 15% by weight and in particular 1 to 10% by weight or several acetals from fragrance aldehydes with alcohols and / or from aldehydes with Containing fragrance alcohols and / or from fragrance aldehydes with fragrance alcohols are preferred Embodiments of the present invention.

The acetals of fragrance aldehydes with non-fragrant alcohols can be composed of fragrance aldehydes and monools, where lower alcohols such as methanol, ethanol, propanol, isopropanol and the butanols have proven successful, but also longer-chain alcohols, for example C _6-30 alcohols, can be used are. However, it is also possible to use diols, which leads to cyclic acetals. Among these, five and six-membered rings have been found to be particularly suitable, so that detergent components are preferred which contain one or more cyclic acetals with a dioxolane structure from scent aldehydes with open-chain or cyclic vicinal diols, but also detergent components which contain one or more cyclic acetals 1,3-dioxane structure from fragrance aldehydes and open-chain or cyclic (n, n + 2) diols ent, preferred embodiments of the present invention.

As with scented alcohols, scent aldehydes contain a large number of compounds applications. In preferred detergent components, the acetals were made from one or more of the fragrance aldehydes from the group hydratropaldehyde, p-t-bucinal,  Cyclamal, Triplal, Hlional, Hexylcinnamic Aldehyde, Vanillin, Citral, Citronellal, Dodeca nal, Hydroxycitronellal, Octanal, Floralozon® won.

Completely analogous performances can also be performed on the ingredients a) according to the invention make usable ketals. Here, detergent components are preferred, which as Ingredient a) 0.25 to 17.5% by weight, preferably 0.5 to 15% by weight and in particular 1 up to 10% by weight of one or more ketals from fragrance ketones with alcohols and / or from Contain ketones with fragrance alcohols and / or from fragrance ketones with fragrance alcohols.

Should fragrance alcohols with non-fragrant ketones be converted into usable ketals , cyclohexanedione and 2,4-pentanedione are particularly preferred. Particularly preferred Detergent components are therefore characterized in that they have one or more right ketals of 1,4-cyclohexanedione and / or 12,4-pentanedione with scented alcohols.

As with acetals, preference is given to ketals which are composed of scented and scented ketones the or non-fragrant alcohols. Here too are the cyclic ones Representative particularly preferred, so that particularly preferred detergent compo are characterized in that they contain one or more cyclic ketals with Di Oxolane structure from fragrance ketones with open-chain or cyclic vicinal diols hold.

This makes another group of particularly preferred detergent components characterized in that they consist of one or more cyclic ketals with 1,3-dioxane structure Contain fragrance ketones and open-chain or cyclic (n, n + 2) diols.

As with alcohols and aldehydes, all of this can also be done with ketones Convert fragrance ketones familiar to those skilled in the art to ketals which can be used according to the invention. In particularly preferred detergent components, the ketals were made from one or several of the fragrance ketones from the group benzylacetone, methyl dihydrojasmonate, methy lamyl ketone, methyl nonyl ketone, carvone, geranylacetone, α-ionone, β-ions, γ-methyl ionone, Dasmacenon, Methyl-β-Naphthylketon won.  

The detergent components according to the invention contain as a second ingredient one or more meltable substance (s) with a melting point above 30 ° C, preferred detergent components are characterized in that they are as Ingredient b) 25 to 90, preferably 30 to 80, particularly preferably 35 to 70 and in particular contain in particular 40 to 60 wt .-% meltable substance (s).

To the fusible substances contained in the detergent composition according to the invention different requirements are made, on the one hand the Melting or solidification behavior, but also the material egg properties of the melt in the solidified state, d. H. in the cleaning according to the invention relate to middle components. Because the detergent component during transportation or location tion is to be permanently protected against environmental influences, the fusible substance a high stability against, for example, occurring during packaging or transport Have shock loads. The meltable substance should either at least partially have elastic or at least plastic properties to indicate an occurring To react to shock loads through elastic or plastic deformation and not to shatter chen. The meltable substance should have a melting range (solidification range) in one have such a temperature range at which other ingredients of the invention Detergent components are not exposed to excessive thermal stress. On the other hand, the melting range must be sufficiently high to be at least light increased temperature to provide effective protection for the active ingredients. Invention According to the meltable substances have a melting point above 30 ° C, with Rei Detergent components are preferred that only meltable substances with enamel points above 40 ° C, preferably above 45 ° C and especially above Have 50 ° C. Particularly preferred detergent components contain as content substance b) one or more substances with a melting range between 30 and 100 ° C, before preferably between 40 and 80 ° C and in particular between 50 and 75 ° C.

It has proven to be advantageous if the meltable substance does not have a sharply defined one Melting point shows how it usually occurs with pure, crystalline substances, but may have a melting range spanning several degrees Celsius.  

The meltable substance preferably has a melting range that is between approximately 52.5 ° C and about 80 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the Melting range. The width of the melting range is preferably at least 1 ° C. preferably about 2 to about 3 ° C.

The properties mentioned above are usually fulfilled by so-called waxes. "Waxing" is understood to mean a number of natural or artificially obtained substances, which usually melt above 50 ° C without decomposition and a little above the Melting point are relatively low viscosity and not stringy. You assign one strongly temperature-dependent consistency and solubility.

According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and synthetic waxes.

Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, Rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or pretzel fat, Mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as Petrolatum, paraffin waxes or micro waxes.

The chemically modified waxes include hard waxes such as Montanester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes generally include polyalkylene waxes or Understand polyalkylene glycol waxes. Compounds can also be used as ingredient b) from other classes of substances that meet the stated softening point requirements fulfill. Suitable synthetic compounds have, for example, higher esters of Phthalic acid, especially dicyclohexyl phthalate, commercially available under the name Unimoll® 66 (Bayer AG) is available. Synthetic ones are also suitable  Waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, the is available under the name Cosmacol® ETLP (Condea).

Preferably contains the contained in the detergent components according to the invention Ingredient b) a share of paraffin wax. This means that at least 10% by weight of the total meltable substances contained, preferably more, from paraffin wax consist. Paraffin wax contents (based on the total amount of meltable substance) of about 12.5% by weight, about 15% by weight or about 20% by weight, even higher proportions of, for example, more than 30% by weight are particularly preferred can. In a particular embodiment of the invention, the total amount of used fusible substance exclusively from paraffin wax.

Paraffin waxes have a frame compared to the other natural waxes mentioned The present invention has the advantage that in an alkaline Detergent environment no hydrolysis of the waxes takes place (as for example is to be expected in the wax esters), since paraffin wax has no hydrolyzable groups contains.

Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and Cycloalkanes. The paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent fleet undesirable wax residues on the surfaces to be cleaned or the goods to be cleaned. Such Wax residues usually lead to an unsightly appearance of the cleaned Surface and should therefore be avoided.

Preferred detergent components contain at least one par as ingredient b) Affine wax with a melting range from 30 ° C to 65 ° C.

The content of the paraffin wax used is preferably at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes if possible  high. The more solid wax components in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing proportion Solid wax components increase the resilience of the detergent component against bumps or friction on other surfaces, resulting in a longer lasting Protection of the active ingredients leads. High levels of oils or liquid wax components can lead to a weakening, which opens pores and the active ingredients Be exposed to the environmental influences mentioned above.

In addition to paraffin, the meltable substance can also contain one or more of the abovementioned Contain waxes or wax-like substances. It should preferably be the fusible one Substance-forming mixture should be such that the detergent component are at least largely water-insoluble. The solubility in water should be at a Temperature of about 30 ° C do not exceed about 10 mg / l and preferably below 5 mg / l lie.

In any case, the material should preferably have the lowest possible water Solubility, even in water at elevated temperature, to have a temperature-independent release of the active substances as far as possible ver avoid.

The principle described above serves to delay the release of ingredients a certain time in the cleaning cycle and can be particularly advantageous use if in the main wash cycle at a lower temperature (e.g. 55 ° C) is rinsed so that the active substance from the rinse aid particles only in the rinse aid higher temperatures (approx. 70 ° C) is released.

However, the principle mentioned can also be reversed in that the active ingredient (s) released from the material, not released, but accelerated. This can be seen in easily achieved by the fact that, as fusible substances, but releasing accelerators are used so that the solidified melt is not slowly solves, but quickly. In contrast to the bad described above water-soluble dissolution retarders, preferred dissolution accelerators are readily water-soluble. The  The solubility of the dissolving accelerator can be made even clear by certain additives be increased, for example by incorporating easily soluble salts or Shower systems. Such accelerated meltable substances (with or without additives of other solubility improvers) lead to a rapid release of the enclosed active substances at the beginning of the cleaning cycle.

As a release accelerator, i.e. fusible substances for the accelerated release of the Active substances from the detergent components are particularly suitable The synthetic waxes mentioned from the group of polyethylene glycols and Polypro pylene glycols, so that preferred detergent components as ingredient b) at least a substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) included.

Polyethylene glycols (abbreviation PEG) which can be used according to the invention are polymers of ethylene glycol which have the general formula I

H- (O-CH ₂ -CH ₂ ) _n -OH (I)

are sufficient, where n can have values between 1 (ethylene glycol) and over 100,000. Decisive in evaluating whether a polyethylene glycol can be used according to the invention is the physical state of the PEG at, d. H. the melting point of the PEG must be above of 50 ° C, so that the monomer (ethylene glycol) and the lower oligomers with n = 2 to approx. 16 cannot be used because they have a melting point below 50 ° C point. The higher molecular weight polyethylene glycols are polymolecular, i.e. H. they be consist of collectives of macromolecules with different molecular weights. For Po There are various nomenclatures in polyethylene glycols that lead to confusion can. The specification of the average relative molecular weight in the Connection to the indication "PEG", so that "PEG 200" is a polyethylene glycol with a relati Characterized ven molecular weight from about 190 to about 210. According to this nomenclature Within the scope of the present invention, the technically customary polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 are preferred.  

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the above formula III. According to this nomenclature (known as INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) according to the invention, for example, PEG-32, PEG-40, PEG-55, PEG 60, PEG-75, PEG-100, PEG-150 and PEG-180 can preferably be used according to the invention.

Polyethylene glycols are commercially available, for example, under the trade names Carbowax® PEG 540 (Union Carbide), Emkapol® 6000 (ICI Americas), Lipoxol® 3000 MED (HÜLS America), Polyglycol® E-3350 (Dow Chemical), Lutrol® E4000 (BASF) and the corresponding trade name with higher numbers.

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula II

are sufficient, where n values can be between 1 (propylene glycol) and approx. 1000. Similar Lich, as with the PEG described above, it comes to the assessment whether a poly propylene glycol can be used according to the invention on the physical state of the PPG, d. H. the melting point of the PPG must be above 50 ° C so that the monomer (propy lenglycol) and the lower oligomers with n = 2 to approx. 15 cannot be used since they have a melting point below 30 ° C.

In addition to the PEG and which can preferably be used as solution-accelerated meltable substances Of course, PPGs can also be used with other substances, provided that they are sufficiently high Have water solubility and have a melting point above 30 ° C.  

So-called fatty substances can also be used as ingredient b) or as a proportion thereof. Under fatty substances b) in the context of this application at normal temperature (20 ° C) liquid to solid substances from the group of fatty alcohols, fatty acids and fatty acids derivatives, especially the fatty acid esters, understood. Implementation products from Fettalko fetching with alkylene oxides as well as the salts of fatty acids count within the scope of the present the application to the surfactants and are not fatty substances in the sense of the invention. As According to the invention, fatty substances can preferably be fatty alcohols and fatty alcohol mixtures, Fatty acids and fatty acid mixtures, fatty acid esters with alkanols or diols or polyo oils, fatty acid amides, fatty amines etc. Preferred detergent components are therefore characterized in that the ingredient b) comprises fatty substances).

The total amount of the detergent components according to the invention can contained ingredient b) consist of fatty substances. But it is also possible and be preferred to use as ingredient b) mixtures which both described the above contained waxes as well as fatty substances. Mixtures have proven particularly useful gene from fatty substances and paraffins or from fatty substances and polyethylene glycols, which be based on the weight of the mixture contain more than 20 wt .-% fat (s).

Regardless of whether the ingredient b) consists entirely or partially of fatty substances, detergent components according to the invention are preferred which contain as ingredient b) or proportion thereof 12.5 to 85 wt .-%, preferably 15 to 80 wt .-%, especially before add 17.5 to 75 wt .-% and in particular 20 to 70 wt .-% fat (s), each based on the total weight of the component included.

Preferred detergent components contain one or more as ingredient b) Substances from the groups of fatty alcohols, fatty acids and fatty acid esters.

Examples of fatty alcohols are the alcohols 1-hexanol (capro alcohol), 1-heptanol (enant alcohol), 1-octanol (capryl alcohol), 1-nonanol (pelargon alcohol), 1-decanol (capric alcohol), 1, which are accessible from native fats and oils -Undecanol, 10- undecen-1-ol, 1-dodecanol (lauryl alcohol), 1-tridecanol, 1-tetradecanol (myristyl alcohol), 1-pentadecanol, 1-hexadecanol (cetyl alcohol), 1-heptadecanol, 1-octadecanol (Ste aryl alcohol), 9-cis-octadecen-1-ol (oleyl alcohol), 9-trans-octadecen-1-ol (erucyl alcohol), 9-cis-octadecen-1,12-diol (ricinol alcohol), all-cis-9, 12-octadecadien-1-ol (linoleyl alcohol), all-cis-9,12,15-octadecatrien-1-ol (linolenyl alcohol), 1-nonadecanol, 1-eicosanol (arachidyl alcohol), 9-cis-eicosen-1- ol (gadoleyl alcohol), 5,8,11,14-eicosatetraen-1-ol, 1-heneicosanol, 1-docosanol (behenyl alcohol); 1-3-cis-docosen-1-ol (erucyl alcohol), 1-3-trans-docosen-1-ol (brassidyl alcohol) and mixtures of these alcohols. According to the invention, Guerbet alcohols and oxo alcohols, for example C _13-15 oxo alcohols or mixtures of C _12-18 alcohols with C _12-14 alcohols, can also be used without difficulty as fatty substances. However, alcohol mixtures can of course also be used, for example those such as the C _16-18 alcohols prepared by Ziegler ethylene polymerization. Specific examples of alcohols which can be used as component b) are the above-mentioned alcohols and lauryl alcohol, pal mityl and stearyl alcohol and mixtures thereof.

Particularly preferred detergent components according to the invention contain as ingredient b) one or more C _10-30 fatty alcohols, preferably C _12-24 fatty alcohols, with particular preference given to 1-hexadecanol, 1-octadecanol, 9-cis-octadecen-1-ol, all-cis-9,12-octadecadien-1-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof.

Fatty acids can also be used as ingredient b) or parts thereof. Technically, most of these are obtained from native fats and oils by hydrolysis. While the alkaline saponification which was carried out in the past century led directly to the alkali salts (soaps), only water is used on an industrial scale to split the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as fatty substances in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. In the context of the present compound, preference is given to Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (pal mitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triscoic acid (melissinic acid), triacoic acid as well as the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidinic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-linadecenoic acid , 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolens ure). Of course, tridecanoic acid, pentadecanoic acid, margaric acid, nonadecanoic acid, erucic acid, elaeostearic acid and arachidonic acid can also be used. For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids, as are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18'), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% C _12, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _18'), tallow fatty acid (ca. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C _{16 '} , 2 wt% C ₁₇ , 17 wt% C ₁₈ , 44 wt% C _18' , 3% by weight C _{18 '} , 1% by weight C _18''' , hardened tallow fatty acid (approx. 2% by weight C ₁₄ , 28% by weight C ₁₆ , 2% by weight C ₁₇ , 63 wt .-% C _18: 1 wt .-% C _{18 '),} technical grade oleic acid (about 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _16, 6 wt. % C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 '} , 0.5% by weight C _18''' ), technical palmitin / stearic acid (approx. 1 wt% C ₁₂ , 2 wt% C ₁₄ , 45 wt% C ₁₆ , 2 wt% C ₁₇ , 47 wt% C _18: 1 wt .-% C _{18 ')} and soybean oil fatty acid (about 2 wt .-% C _14, 15 Wt .-% C _16, 5 wt .-% C _18, 25 wt .-% C _{18 ',} 45 wt .-% C _18', 7 wt .-% C _{18 ''').}

The esters of fatty acids with alkanols, diols or polyo can be used as fatty acid esters Use len, with fatty acid polyol esters being preferred. Com. As fatty acid polyol ester Men mono- or diesters of fatty acids with certain polyols into consideration. The fatty acid Ren, which are esterified with the polyols are preferably saturated or unsaturated Fatty acids with 12 to 18 carbon atoms, for example lauric acid, myristic acid, palmitin acid or stearic acid, preferably the technically obtained mixtures of the fatty acid ren are used, for example those derived from coconut, palm kernel or tallow fat acid mixtures. In particular acids or mixtures of acids with 16 to 18 C Atoms such as tallow fatty acid are for esterification with the polyvalent Al suitable for alcohol. As polyols, who are esterified with the above-mentioned fatty acids  in the context of the present invention, sorbitol, trimethylolpropane, Neopentyl glycol, ethylene glycol, polyethylene glycols, glycerin and polyglycerols in Be dress.

Preferred embodiments of the present invention provide that as the polyol, the is esterified with fatty acid (s), glycerin is used. Accordingly, fiction Moderate detergent components are preferred that contain one or more as ingredient b) Contain fatty substances from the group of fatty alcohols and fatty acid glycerides. Especially preferred detergent components contain as component b) a fatty substance the group of fatty alcohols and fatty acid monoglycerides. Examples of such preferred Fat substances used are glycerol monostearic acid esters or glycerol monopalmitic acid esters.

The detergent components according to the invention can only be found in the content substances a) and b) exist and then serve the targeted release of fragrances. she However, they can also contain other active substances and / or auxiliary substances which advantageous either in the manufacture or storage of the detergent components cause adverse effects, or the product has an additional added benefit lend it to your application. Ingredients are therefore particularly active ingredients of detergents or cleaning agents as ingredient c) of the compo according to the invention suitable. For example, the use of surfactants in the invention Detergent components lead to a significant performance advantage.

Preferred detergent components contain as ingredient c) 5 to 60, preferably as 10 to 55, particularly preferably 15 to 52.5 and in particular 20 to 50 wt .-% Ten sid (e). All surfactants from the groups of anionic, nonionic, cationic or amphoteric surfactants are used, with preferred cleaning agent components are characterized in that as ingredient c) anionic (s) and / or nonionic surfactant (s), preferably nonionic surfactant (s).

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C _12-16 monoolefins having a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids is suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca. pric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which is biodegradable analogously to the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 -Fatty alcohols with 1 to 4 EO, are suitable. Because of their high viewing behavior, they are used in 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 in particular 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 are non-ionic surfactants (see description below). Again, sulfosuccinates, the fatty alcohol residues of which 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) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable 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 from natural Fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can 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 in the form of their Sodium or potassium salts, especially in the form of the sodium salts.

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 residue is linear or preferably in the 2-position May be methyl branched or may contain linear and methyl branched radicals in the mixture, as are usually present in oxoalko radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms 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 preferred nonionic surfactants, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 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-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alka nolamides may be suitable. The amount of these nonionic surfactants is before preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.  

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (III),

in the 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 (IV)

in the R for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or is 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 propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can be reacted with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

Low-foaming nonionic surfactants are used as preferred surfactants. The detergent components according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols, preferably having 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 residue branches linearly or preferably in the 2-position methyl may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, Alko holethoxylate with linear residues from alcohols of native origin with 12 to 18 C-Ato men, z. B. from coconut, palm, tallow or oleyl alcohol; and an average of 2 to 8 EO per mole of alcohol is preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particularly preferred are detergent components according to the invention, the one contain nonionic surfactant, which has a melting point above room temperature has. Accordingly, preferred detergent components are characterized by it net that as ingredient c) nonionic (s) surfactant (s) with a melting point above  of 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C, contain.

Suitable nonionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic ten side, which can be solid or highly viscous at room temperature. Will be at room temperature used highly viscous nonionic surfactants, it is preferred that these have a viscosity above half of 20 Pa.s, preferably above 35 Pa.s and in particular above 40 Pa.s exhibit. Also non-ionic surfactants, which have a waxy consistency at room temperature, are preferred.

Preferred nonionic surfactants to be used as solid at room temperature originate from the group pen of the alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and Mixtures of these surfactants with structurally more complex surfactants such as Po lyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, this is nonionic Surfactant with a melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 C- Atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has gone.

A particularly preferred nonionic surfactant which is solid at room temperature is made from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide won. Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred detergent components according to the invention contain as ingredient c) ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, in particular more preferably up to 20% by weight and in particular up to 15% by weight of the total moles mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene Have polyoxypropylene block copolymer units. The alcohol or alkylphenol part such nonionic surfactant molecules preferably make up more than 30% by weight, especially be preferably more than 50% by weight and in particular more than 70% by weight of the total molma such nonionic surfactants. Preferred detergent components are thereby indicates that it contains as ingredient c) ethoxylated and propoxylated nonionic surfactants ten, in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonioni make up surfactant.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of a polyoxypropy len / polyoxyethylene / polyoxypropylene block polymer blends, the 75 wt .-% of a vice returned block copolymers of polyoxyethylene and polyoxypropylene with 17 moles of ethyl lenoxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Po lyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles Ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

Nonionic surfactants, which can be used with particular preference, are from for example under the name Poly Tergent® SLF-18 from Olin Chemicals true.

A further preferred detergent components according to the invention contain non-ionic surfactants of the formula as ingredient c)

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1.5 and y is at least 15.

Further preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 represents} H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ≧ 2, each R ³ in the above formula can be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different if x ≧ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which can be joined together in any order, for example (EO ) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO ) (PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa.

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula applies

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 C atoms, R ³ stands for H and x assumes values from 6 to 15.

If the latter statements are summarized, cleaning agent components according to the invention are preferred which contain end-capped poly (oxyalkylated) nonionic surfactants of the formula as ingredient c)

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

contain, in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, isopropyl , n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18 stands, are particularly preferred.  

Above were surfactants, especially nonionic surfactants, as optional content Substance c) described the detergent components according to the invention. Next to the The use of surfactants can also have beneficial effects by using other In Contains detergents or cleaning agents in the cleaning agents according to the invention achieve tel components. For example, it may be preferred to use ingredients Bleaching system, d. H. Bleaching agents and / or bleach activators and / or bleaching catalysts to be incorporated into the detergent components according to the invention. The use too of enzymes or dirt-dissolving or dispersing polymers, so-called soil release polymers or corrosion inhibitors, especially so-called silver protectives, as ingredient c) of the detergent components according to the invention possible and preferred. Preferred detergent components are thereby characterized in that it contains as ingredient c) one or more substances from the groups of Bleaching agents, bleach activators, bleaching catalysts, enzymes, polymers, corrosion inhibitors contain bitters, silver preservatives and mixtures thereof.

The detergent components according to the invention can be used as ingredient c) or Proportion thereof further active substances and / or auxiliary substances from the groups of dyes, fragrance fe, anti-settling agents, floating agents, anti-floating agents, thixotropic agents and dispersants yeast aids in amounts of 0 to 10% by weight, preferably 0.25 to 7.5% by weight, particularly preferably from 0.5 to 5% by weight and in particular from 0.75 to 2.5% by weight, contain. While colors and fragrances are the usual ingredients of washing or cleaning agents agents described below, the ingredients for the inventions detergent components according to the invention are specific, described below.

At exceptionally low temperatures, for example at temperatures below 0 ° C, can the detergent component according to the invention with shock or friction break. To improve the stability at such low temperatures, the meltable substances, if necessary, additives are added. Suitable additives must be able to be mixed completely with the molten wax The melting range of the meltable substances does not change significantly, the elasticity the detergent component at low temperatures, the Permeability of the detergent component to water or moisture in the  generally do not increase and must not increase the viscosity of the melt to such an extent that processing becomes difficult or even impossible. Suitable additives that the Brittleness of a material consisting essentially of paraffin at low temperatures low temperatures, for example EVA copolymers, hydrogenated resin acid methyl esters, Polyethylene or copolymers of ethyl acrylate and 2-ethylhexyl acrylate.

It may also be advantageous to add further additives to the meltable substance, to prevent premature separation of the mixture, for example. The for this Anti-settling agents that can also be used, which are also referred to as floating agents, are made of the prior art, for example from paint and printing ink production, be knows. To sedimentati at the transition from the plastic solidification area to the solid There are ways to avoid ons manifestations and concentration differences of the substances for example surface-active substances, waxes dispersed in solvents, Montmorillonites, organically modified bentonites, (hydrogenated) castor oil derivatives, soybeans cithin, ethyl cellulose, low molecular weight polyamides, metal stearates, calcium soaps or hydrophobicized silicas. Other substances that cause the effects mentioned come from the groups of anti-floating agents and thixotropic agents and can chemically as silicone oils (dimethylpolysiloxanes, methylphenylpolysiloxanes, polyether modified methyl alkyl polysiloxanes), oligomeric titanates and silanes, polyamines, salts made of long-chain polyamines and polycarboxylic acids, amine / amide-functional polyester or amine / amide-functional polyacrylates.

Additives from the classes of substances mentioned are commercially extremely diverse available. Commercial products that are advantageous in the context of the method according to the invention Aerosil® 200 (pyrogenic pebbles acid, Degussa), Bentone® SD-1, SD-2, 34, 52 and 57 (Bentonite, Rheox), Bentone® SD-3, 27 and 38 (hectorite, Rheox), Tixogel® EZ 100 or VP-A (organically modified Smec tit, Südchemie), Tixogel® VG, VP and VZ (montmorillonite loaded with QAV, Südche mie), Disperbyk® 161 (block copolymer, Byk-Chemie), Borchigen® ND (sulfo-free er ion exchanger, Borchers), Ser-Ad® FA 601 (servo), Solsperse® (aromatic Ethoxylate, ICI), Surfynol® types (Air Products), Tamol® and Triton® types (Rohm & Haas), Texaphor®963, 3241 and 3250 (polymers, Henkel), Rilanit® types (Hen  kel), Thixcin® E and R (castor oil derivatives, Rheox), Thixatrol® ST and GST (castor oil Derivatives, Rheox), Thixatroh SR, SR 100, TSR and TSR 100 (polyamide polymers, Rheox), Thixatrol® 289 (polyester polymer, Rheox) and the various M-P-A® Types X, 60-X, 1078-X, 2000-X and 60-MS (organic compounds, Rheox).

The auxiliaries mentioned can be used in the detergent components according to the invention depending on the material and active substance used in varying amounts become: Usual use concentrations for the anti-settling, anti floating, thioxotropic and dispersing agents are in the range from 0.5 to 8.0% by weight, preferably between 1.0 and 5.0% by weight, and particularly preferably between 1.5 and 3.0 wt .-%, each based on the total amount of meltable substance and Active substances.

Particularly preferred emulsifiers in the context of the present invention are polyglycerol esters, in particular esters of fatty acids with polyglycerols. These preferred polyglycerol esters can be described by the general formula V.

in which R ¹ in each glycerol unit is independently H or a fatty acyl radical having 8 to 22 carbon atoms, preferably having 12 to 18 carbon atoms, and n is a number between 2 and 15, preferably between 3 and 10.

These polyglycerol esters are known in particular with degrees of polymerization n = 2, 3, 4, 6 and 10 and are commercially available. As materials of the type mentioned can also be found in cosmetic formulations widespread, some of these substances are classified in the INCI nomenclature (CTFA International Cosmetic Ingredient Dictionary and Handbook, ^5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997). This standard cosmetic work contains, for example, information on the keywords POLYGLYCERYL-3-BEESWAX, POLYGLYCERYL-3-CETYL ETHER, POLYGLYCERYL-4-COCOATE, POLYGLYCERYL-10-DECALINOLEATE, POLY- GLYCERYL-10-DECAOLETELARY POLYGLYTE GLYCERYL-2-DIISOSTEARATE, POLYGLYCERYL-3-DIISOSTEARATE, POLY- GLYCERYL-10-DIISOSTEARATE, POLYGLYCERYL-2-DIOLEATE, POLY- GLYCERYL-3-DIOLEATE, POLYGLYCERYL-6-DIOLYATELY POLYGLY DISTEARATE, POLYGLYCERYL-6- DISTEARATE, POLYGLYCERYL-10-DISTEARATE, POLYGLYCERYL-10- HEPTAOLEATE, POLY-GLYCERYL-12-HYDROXYSTEARATE, POLYGLYCERYL- 10-HEPTASTEARATE, POLYGLYXERYLYARATE-6-HEALTH 4-ISOSTEARATE, POLY-GLYCERYL-6- ISOSTEARATE, POLY-GLYCERYL-10-LAURATE, POLY- GLYCERYLMETHACRYLATE, POLYGLYCERYL-10-MYRISTATE, POLYGLYCERYL-2-OLEATE, POLYGLYCERYL-3-OLEATE 6-OLEATE, POLYGLYCERYL-8-OLEATE, POLYGLYCERYL-10-OLEATE, POLYGLYCERYL-6-PENTAOLEATE, POLYGLYCERYL-10-PENTAOLEATE, POLYGLYCERYL-6-PENTASTEARATE, POLYGLYCERYL-10-PENTASTEARATE, POLYGLYCERYL-2-SESQUI- IOSOSTEARATE, POLYGLYCERYL-2-SESQUIOLEATE, POLYGLYLARATE-POLYGLYCARATE POLYGLYCERYL-8-STEARATE, POLYGLYCERYL-10-STEARATE, POLY- GLYCERYL-2-TETRAISOSTEARATE, POLYGLYCERYL-10-TETRAOLEATE, POLYGLYCERYL-2-TETRASTEARATE, POLYGLYCERYL-2-TRIISOLYTE-TRYISOLATE The commercially available products from different manufacturers, which are classified under the abovementioned keywords in the work mentioned, can advantageously be used as emulsifiers in process step b) according to the invention.

Another group of emulsifiers which can be used in the rinse aid particles according to the invention are substituted silicones which carry side chains reacted with ethylene or propylene oxide. Such polyoxyalkylene siloxanes can be described by the general formula VI

in which each radical R ¹ independently of one another for -CH ₃ or a polyoxyethylene or propylene group - [CH (R ² ) -CH ₂ -O] _x H group, R ² for -H or -CH ₃ , x for a number between 1 and 100, preferably between 2 and 20 and in particular less than 10, and n indicates the degree of polymerization of the silicone.

Optionally, the polyoxyalkylenesiloxanes mentioned can also be attached to the free OH groups of the Polyoxyethylene or polyoxypropylene side chains are etherified or esterified. The Unetherified and unesterified polymer from dimethylsiloxane with polyoxyethylene and / or In the INCI nomenclature, polyoxypropylene is called DIMETHICONE COPOLYOL designated and is under the trade names Abil® B (Goldschmidt), Alkasil® (Rhône- Poulenc), Silwet® (Union Carbide) or Belsil® DMC 6031 commercially available.

The DIMETHICONE COPOLYOL ACETATE esterified with acetic acid (for example Belsil® DMC 6032, -33 and -35, Wacker) and the DIMETHICONE COPOLYOL BUTYL ETHERS (e.g. KF352A, Shin Etsu) are also considered within the scope of the present invention Emulsifiers can be used.

The same applies to emulsifiers as to meltable substances and the rest Ingredients that can be used over a wide range. Usually, emulsifiers of the type mentioned make up 1 to 25% by weight, preferably 2 to 20% by weight and in particular 5 to 10% by weight of the weight of the Detergent component.

As already mentioned above 87196 00070 552 001000280000000200012000285918708500040 0002019948667 00004 87077n, a suitable choice of the ingredients a) to c) the physical and chemical properties of the cleaning according to the invention vary medium components in a targeted manner. For example, only ingredients are used  sets that are liquid at the melting temperature of the mixture can be easily produce phase mixtures, which are also ge due to special storage stability mark molten state. The addition of solids, such as paint pigments or substances with higher melting points automatically lead to two-phase Mixtures that are also excellent in storage stability and extremely low have a tendency to separate.

Regardless of the composition of the detergent composition according to the invention Those detergent components are preferred which are characterized by a melt point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and in particular are marked between 55 and 65 ° C.

At room temperature, the detergent components according to the invention stared at mixtures of the ingredients mentioned, any external shape can take. It is also possible to apply the mixtures as a melt to carriers and thus to provide carrier material-based detergent components, those at room temperature from the carrier material (s) and one on these carrier materials solidified melt exist. All solids are suitable as carrier materials do not soften at the temperature of the melt and that is sufficient have large absorption capacity for the melt. Particularly preferred vehicles Materials are builders, which are described in detail below.

Another object of the present invention is a method for producing particulate detergent components, which is characterized in that a melt from

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

applied to one or more carrier materials and the mixture is shaped tet.  

In this process variant, a melt is first produced, the further active and may contain auxiliary substances. This is placed on a carrier material and in Mi processing with this carrier material.

In the production process mentioned for the rinse aid particles according to the invention Process variants are preferred in which the meltable substance, 25 to 85% by weight, preferably 30 to 70% by weight and in particular 40 to 50% by weight of the melt matters.

The melt can be applied to the carrier material in all customary mixtures devices are carried out. The shaping processing step for the Ge Mix of melt and carrier material is also not subject to any process engineering Restrictions, so that the person skilled in the art can also make use of the processes familiar to him can choose. In the applicant's attempts, methods have proven to be preferred where the shaping processing by granulating, compacting, peeling animals, extruding or tableting.

The method according to the invention comprises the application of melts from the contents substances a) to d) on carrier materials. In principle, melt and carrier (s) can be in varying amounts may be contained in the resulting rinse aid particles. Preferred Processes are characterized in that a mixture of 5 to 50 wt .-%, before preferably 10 to 45% by weight, particularly preferably 15 to 40% by weight and in particular 20 up to 35% by weight of a melt from the ingredients a) to d) and 50 to 95% by weight preferably 55 to 90% by weight, particularly preferably 60 to 85% by weight and in particular 65 up to 80 wt .-% carrier material (ien) is processed shaping.

Regarding the ingredients used in the method according to the invention and the processed carrier material-based detergent components according to the invention the same applies as stated above.

The detergent components according to the invention can also be free of carrier material be formulated so that they consist only of the ingredients a) to d). To Her  have particulate detergent components according to the invention in particular the prilling, the pastilling and the scaling by means of a cooling roller zen proven.

Another object of the present invention is therefore, in a first embodiment, a method for producing prilled detergent components, in which a melt is made

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

injected into a cold gas stream.

The method according to the invention, which is briefly referred to as prilling, comprises the her position granular body made of meltable substances, the melt from the contents substances a) to d) sprayed onto the top of a tower in a defined droplet size is solidified in free fall and the prills at the bottom of the tower accumulate as granules.

In general, all gases can be used as the cold gas stream, the Temperature of the gas is below the melting temperature of the melt. Long time To avoid falling stretches, cooled gases are often used, for example with frozen air or even with liquid nitrogen that is injected into the spray towers.

The grain size of the resulting prills can be varied by the choice of droplet size particle sizes in the range from 0.5 to 2 mm, preferably around 1 mm.

An alternative method of twisting is pastilling. A further embodiment of the present invention therefore provides a method for producing pastilized detergent components, in which a melt is made

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

dosed on chilled pastilles.

Pastilling, sometimes referred to as pelleting, includes the dose tion of the melt from the ingredients a) to d) on rotating, inclined plates, one Have temperature below the melting temperature of the melt and preferably be cooled below room temperature. Process variants can also be used here in which the pastilles are frozen. Here, however Measures against the condensation of air humidity are taken.

The pastillation provides larger particles, the sizes between technically common processes rule 2 and 10 mm, preferably between 3 and 6 mm.

As an even more cost-effective variant for the production of particulate detergent components of the above-mentioned composition from melts, the use of cooling rollers is appropriate. Another object of the present invention is therefore a process for the production of particulate detergent components, in which a melt is made

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

applied or sprayed onto a chill roll, scraped off the solidified melt and if it did crushed required.  

The use of cooling rollers enables the desired setting to be made easily Particle size range that in this method according to the invention also below 1 mm, for example at 200 to 700 microns.

Another object of the present invention is therefore the use of partially Chen-shaped detergent components

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

in detergents for automatic dishwashing.

These machine dishwashing detergents (MGSM) can be liquid or solid, with the fixed form of supply is of paramount importance. Fixed machine Dishwashing detergents can be supplied to the consumer as a "powder" or as a tablet Hand be given, the detergent components of the present inven can be incorporated into both types of offers.

Another object of the present invention is also a particulate machine dishwashing detergent, containing builders and optionally further cleaning agent ingredients, which contains particulate detergent components, based on their weight,

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

contain.  

The ingredients of automatic dishwashing detergents are described below. Some of these can also be used as ingredient d) or carrier materials in the invention according to detergent components.

The most important ingredients in automatic dishwashing detergents are builders. In the cleaning agents according to the invention for machine dishwashing all builders commonly used in detergents and cleaning agents hold, especially so zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - including the phosphates. The builders mentioned below are all used as carrier materials for the inventors suitable detergent components according to the invention, as already explained above has been.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, 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. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. 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 β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in the international patent application WO-A-91/08171 .

Amorphous sodium silicates with a modulus Na ₂ O: SiO 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 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, compaction / 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 provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline ranges of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a release delay compared to the conventional water glass glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used 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 (approx. 80% by weight zeolite X), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

n Na ₂ O. (1-n) K ₂ O. Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of we less than 10 µm (volume distribution; measurement method: Coulter Counter) on and included preferably 18 to 22% by weight, in particular 20 to 22% by weight of bound water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. Among the large number of commercially available phosphates, the Alka limetal phosphates with particular preference for pentasodium or pentapotassium tri phosphate (sodium or potassium tripolyphosphate) in detergents and cleaning agents Industry the most important.  

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C, in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to pH 4.5 with caustic soda and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 .

Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when He's heating Thomas slag 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.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate 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 hardness 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 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. 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. A large number of terms are used in particular for the latter: melt or glow 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 pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 WO. Na with n = 3. In 100 g of water, about 17 g of the water of crystallization-free salt dissolves at room temperature, about 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). 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 trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O.

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphos phate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tri Polyphosphate and sodium potassium tripolyphosphate can be used according to the invention.

As organic cobuilders in the dishwasher according to the invention agents in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, As Paraginic acid, polyacetals, dextrins, other organic cobuilders (see below) and Phosphonates are used. These classes of substances are described below.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, with such carboxylic acids under polycarboxylic acids can be understood that carry more than one acid function. For example, these are Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures  from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adi Pinic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of the sen.

The acids themselves can also be used. The acids have besides their buil the effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. 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 information 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 given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, the This group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to  Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 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 polycarboxylates can be either as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the agent is before preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer ten.

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

Further preferred copolymers are those which are described in German patent applications DE- A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred Paraginic acids or their salts and derivatives, which in addition to cobuilder properties have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl have groups that can be obtained. Preferred polyacetals are from Dialde hyden such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from Obtained 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 obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is a poly saccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glu can be used cosesirupe 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 30,000 g / mol.

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. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and Gly are also preferred in this context cerintrisuccinate. Suitable amounts are in zeolite and / or silicate salts gene formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is in particular hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt  the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Ho mologist in question. 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, used. HEDP is preferred as a builder from the phosphonate class turns. The aminoalkanephosphonates also have a pronounced heavy metal bin de assets. Accordingly, it can, especially if the agent also ent bleach hold, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth train ions as cobuilders.

Contain preferred particulate machine dishwashing detergents according to the invention Builders in amounts from 20 to 80 wt .-%, preferably from 25 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the weight of the agent.

In addition to the builders, there are in particular substances from the groups of surfactants Bleach, bleach activators, enzymes, polymers, as well as color and fragrance important ingredients of detergents. Important representatives from the above Substance classes are described below, with respect to the description of the Surfactants is referred to the explanations above.

Preferred particulate machine dishwashing detergents further contain one or several substances from the groups of bleaching agents, bleach activators, bleach catalysts, Surfactants, corrosion inhibitors, polymers, dyes and fragrances, pH adjusting agents, complex formers and the enzymes. As mentioned above, some of these can Be part of the detergent components according to the invention.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Other bleaching agents that can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyro phosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as per benzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

"Sodium percarbonate" is a non-specific term for sodium carbonate peroxohydrates which, strictly speaking, are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as peroxy viewed carbonate. It was not until 1909 that the compound was Addition compound recognized, nevertheless the historical designation "sodium per carbonate "prevailed in practice.

The industrial production of sodium percarbonate is mainly produced by precipitation from an aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12% by weight of mother liquor, is then centrifuged off and dried in fluidized bed dryers at 90.degree. The bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process. As a rule, the percarbonate is stabilized by an additional coating. Coating processes and substances used for coating are widely described in the patent literature. Basically, all commercially available percarbonate types can be used according to the invention, such as those offered by the companies Solvay Interox, Degussa, Kemara or Akzo.

Cleaning agents according to the invention can also include bleaches from the group of organi bleach. Typical organic bleaching agents are the diacyl peroxides, such as B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acid ren, the examples being especially the alkyl peroxy acids and the aryl peroxy acids be called. Preferred representatives are (a) peroxybenzoic acid and its ring substituent ated derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and Magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimido-peroxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N- nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9- Diperoxyazelaic acid, diperocysebacic acid, diperoxybrassylic acid, the diperoxy phthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6- aminopercapronic acid) can be used.

As a bleach in the cleaning agents according to the invention for the machine Dishwashing can also use chlorine or bromine-releasing substances. Suitable chlorine or bromine releasing materials include, for example heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, Tribromo isocyanuric acid, dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

The bleaches mentioned can also be partially used to achieve "post-bleaching" the detergent components according to the invention, where they represent ingredient d) len, are introduced into the automatic dishwashing detergents according to the invention.

Bleach activators that support the action of the bleaching agents are, for example, Ver bonds containing one or more N or O acyl groups, such as substances the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylene diamine TAED, tetraacetyl methylene diamine TAMD and  Tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2- dioxohexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

Compounds which are aliphatic under perhydrolysis conditions can be used as bleach activators cal peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms Atoms, and / or optionally substituted perbenzoic acid can be used. Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated tria Zinderivate, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acy gelled Glycolurile, in particular tetraacetylglycoluril (TAGU), N-acylimide, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol koldiacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters as well as acetylated sorbitol and mannitol as their mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acety gelled, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated Lactams, for example N-benzoylcaprolactam. Hydrophilically substituted acylacetals and Acyl lactams are also preferred. Combinations of conventional ones Bleach activators can be used.

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts in the detergents for machine dishwashing len are incorporated. These fabrics are bleach-boosting over transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru Amine complexes can be used as bleaching catalysts.  

Bleach activators from the group of multi-acylated alkylene are preferred diamines, especially tetraacetylethylenediamine (TAED), N-acylimides, especially N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight up to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight on the entire medium.

Bleach-enhancing transition metal complexes, especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate in usual amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and be particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total Means used. But in special cases, more bleach activator can be used the.

Enzymes in particular come from the cleaning agents according to the invention from the classes of hydrolases such as proteases, esterases, lipases or lipolytic acting enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases help to remove stains such as protein, greasy or starchy stains. Oxidoreductases can also be used for bleaching be used. Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and en derived from their genetically modified variants active enzymatic agents. Proteases of the subtilisin type and esp special proteases obtained from Bacillus lentus. Here are En enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes, in particular  special however protease- and / or lipase-containing mixtures or mixtures with lipo enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Also have peroxidases or oxidases proved to be suitable in some cases. Suitable amylases include in particular special alpha-amylases, iso-amylases, pullulanases and pectinases.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can for example 0.1 to 5 wt .-%, preferably 0.5 to 4.5 wt .-% be.

In addition to those contained in the detergent components according to the invention Perfume precursors can be used in the dishwasher detergents according to the invention Dyes and fragrances are added to the aesthetic impression of the resulting Improve products and give consumers a visual and senso in addition to performance to provide a "typical and distinctive" product. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type become. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethy lisobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclo hexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example as benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lili al and bourgeonal, to the ketones z. B. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethylal alcohol and terpineol, the hydrocarbons mainly include terpenes such as Lime and pinene. However, mixtures of different fragrances are preferred used, which together create an appealing fragrance. Such perfume oils can NEN also contain natural fragrance mixtures, such as those from plant sources are common, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Exactly if appropriate, muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon  leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and rennet danum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention , but it can also be advantageous to apply the fragrances to carriers. As such carrier materials have proven themselves, for example, cyclodextrins, the Cy clodextrin-perfume complexes can also be coated with other auxiliaries can. Incorporation of the fragrances as ingredient d) into the invention ß detergent components is possible and leads to a scent impression when opening machine.

To improve the aesthetic impression of the agents according to the invention, it can (or Parts of it) can be colored with suitable dyes. Preferred dyes whose Selection presents no difficulty for the expert, has a high storage stability and insensitivity to the other ingredients of the agent and to Light as well as no pronounced substantivity towards those treated with the means the substrates such as glass, ceramics or plastic dishes so as not to stain them.

The cleaning agents according to the invention can protect the items to be washed or the Ma schine corrosion inhibitors contain, especially silver protection in the area of automatic dishwashing have a special meaning. The be knew substances of the prior art. In general, silver protection in particular medium selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes be used. Benzotriazole and / or alky are particularly preferably to be used laminotriazole. Active chlorine is also often found in cleaner formulations agents that can significantly reduce the corrosion of the silver surface. In chlorine Free cleaners are especially oxygen and nitrogenous organic redoxakti ve compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, Hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of this compound classes. Also salt-like and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Are preferred here  the transition metal salts which are selected from the group of the manganese and / or Cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Manganese and manganese sulfate. Zinc compounds can also be used for prevention corrosion on the wash ware.

The particulate machine dishwashing detergents according to the invention can contain detergent components according to the invention in varying amounts, wherein the content depending on the composition of the detergent components and depending on the ge desired application success is higher or lower. Preferred particulate automatic dishwashing detergents contain the particulate detergent component in amounts of 0.5 to 30% by weight, preferably 1 to 25% by weight and in particular from 3 to 15% by weight, in each case based on the total average.

The detergent components according to the invention can be of their composition be designed so that they are in the main wash cycle (and also in optional Vor rinse cycles) or only to a minor extent. This ensures that the surfactants are only released in the rinse cycle and develop their effect here. In addition to this chemical assembly, there is one depending on the type of dishwasher physical packaging required so that the rinse aid particles in the water changes in the machine are not pumped out and therefore the rinse cycle is no longer possible be available. Domestic dishwashers contain before the lye pump, which the water or the cleaning solution after each cleaning course pump out of the machine, a strainer that clogs the pump Prevent dirt residues. Is heavily contaminated dishes by the consumer rinses, this strainer must be cleaned regularly, which is due to the light Accessibility and removability is easily possible. The invention Detergent components are now preferred in terms of size and shape designed so that you can insert the dishwasher even after cleaning gang, d. H. after exposure to movement in the machine and the cleaning solution, not happen. This ensures that Reini Detergent components are in the dishwasher, which under the Einwir  the warmer water release the active substance (s) and the desired clarity bring rinsing effect. Preferred particulate in the context of the present invention automatic dishwashing detergents are characterized in that the particulate rice detergent component particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and in particular between 2 and 20 mm.

The detergent components can be used in the dishwashing detergents according to the invention with the aforementioned sizes from the matrix of the other particulate In protruding substances, but the other particles can also have sizes that are in the range mentioned, so that overall a cleaning agent is formulated consists of large detergent and detergent component particles. In particular especially if the detergent components according to the invention are colored, For example, if it has a red, blue, green or yellow color, it is for the Er appearance of the product, d. H. of the entire cleaning agent is advantageous if the Detergent components are visibly larger than the matrix of the particles of the other ingredients of the detergent. Here are particulate according to the invention machine dishwashing detergent preferred, which (without considering the particulate gene detergent component) particle sizes between 100 and 3000 microns, preferred as between 300 and 2500 microns and in particular between 400 and 2000 microns sen.

If the cleaning agents according to the invention are formulated as a powder mixture, it can - Especially in the case of very different sizes of detergent component and Detergent matrix - a partial ent on the one hand when the package is shaken mixture occur, on the other hand, the dosage in two successive Reini different courses, because the consumer does not always necessarily have the same amount Detergent and detergent component dosed. Should be desired tech nically an equal amount per cleaning cycle, this can be done via the Packaging of the agents according to the invention in sachets made of water-soluble, which is familiar to a person skilled in the art licher film can be realized. Also a particulate machine dishwashing detergent, which is characterized in that a dosing unit in a bag made of water-soluble The present invention relates to a film which is welded in.  

As a result, the consumer has only one bag, for example a cleaning medium powder and several optically prominent detergent component particles contains, in the dosing compartment of his dishwasher. This execution form of the present invention is therefore a visually attractive alternative to conventional detergent tablets.

Since the consumer is not just a particulate detergent for the machine Ge dishwashing uses, but also would like to use moldings, these are one further object of the present invention. For this purpose, the melt from the Formulate ingredients a) to c) as a phase of a shaped body, for example the Form of a layer, a core-shaped insert, etc.

Another object of the present invention is thus a multi-phase detergent tablets for machine dishwashing, containing builders and optionally other detergent ingredients, in which at least one phase

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

consists.

The individual phases of the shaped body can be within the scope of the present invention have different spatial shapes. The simplest possible implementation is in two or multi-layer tablets, each layer of the shaped body one Represents phase. However, it is also possible according to the invention to produce multiphase moldings Deliver in which individual phases take the form of inclusions in another phase (s) exhibit. In addition to so-called "ring-core tablets" there are, for example, casings abletten or combinations of the embodiments mentioned possible. examples for multi-phase moldings can be found in the illustrations of EP-A-0 055 100 (Jeyes), the Toilet cleaning blocks describes. The most technically widespread spatial form at the moment phase shaped body is the two- or multi-layer tablet. As part of the present  According to the invention, it is therefore preferred that the phases of the shaped body take the form of layers have and the molded body is 2-, 3- or 4-phase.

The moldings according to the invention can take on any geometric shape where with in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthor hombic, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, seven- and octagonal- prismatic and rhombohedral shapes are preferred. Completely irregular too Base areas such as arrow or animal shapes, trees, clouds, etc. can be realized. If the molded bodies according to the invention have corners and edges, these are preferred wisely rounded. As an additional optical differentiation, an embodiment with rounded corners and chamfered ("chamfered") edges preferred.

Instead of the layer structure, it is also possible to produce moldings which are the part of the invention moderate detergent component in the form of other phases. Here it is proven to produce base moldings which have one or more cavity (s) and the melt from the ingredients a) to d) of the cleaning agent according to the invention Fill the tel component into the cavity and allow it to solidify there. By this man Positioning process, preferred multiphase detergent tablets result from a base molding which has a cavity and an at least partially part contained in the cavity.

The cavity in the pressed part of such shaped bodies according to the invention can in any case have de shape. You can cut through the molded body, d. H. an opening at various which have sides, for example on the top and bottom of the molded body, it can but also a cavity that does not go through the entire molded body, the opening thereof is only visible on one side of the molding. The shape of the cavity can also vary widely zen can be chosen freely. For reasons of procedural economy, there have been continuous Holes, the openings of which lie on opposite surfaces of the shaped bodies, and wells with an opening on one side of the molded body have proven successful. In preferred washing and detergent tablets, the cavity has the shape of a through hole on, the openings of which are located on two opposite shaped body surfaces. The  The shape of such a through hole can be chosen freely, with molded body are preferred in which the through hole is circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal Hori has zonal sections. Also completely irregular hole shapes like arrow or animal shapes, Trees, clouds, etc. can be realized. As with the moldings are in In the case of angular holes, those with rounded corners and edges or with rounded preferred corners and chamfered edges.

The geometric implementation forms mentioned above can be combined as desired combine other. Shaped bodies with a rectangular or square base can round holes as well as round shaped bodies with achtec holes, with no limit to the variety of possible combinations are. For reasons of process economy and aesthetic consumer perception Shaped articles with a hole are particularly preferred in which the shaped body base area and the hole cross section have the same geometric shape, for example shaped bodies with square base and centrally integrated square hole. Especially ring shaped bodies are preferred, i. H. circular shaped body with a circular hole.

If the above Principle of the hole open on two opposite sides of the molded body is reduced to an opening, mold bodies are obtained. According to the invention Detergent tablets in which the cavity is in the form of a trough has are also preferred. As with the "perforated bodies", they can be invented molded article according to the invention also in this embodiment, any geometric shape assume, in particular concave, convex, biconcave, biconvex, cubic, tetra gonal, orthorhombic, cylindrical, spherical, segment-like, disc-shaped ge, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five-, you ben- and octagonal-prismatic and rhombohedral shapes are preferred. Also completely irregular base areas such as arrow or animal shapes, trees, clouds, etc. will be realized. If the molded body has corners and edges, these are preferred rounded. As an additional optical differentiation is an embodiment with abge rounded corners and chamfered ("chamfered") edges preferred.  

The shape of the trough can also be chosen freely, with molded bodies being preferred which at least one trough has a concave, convex, cubic, tetragonal, orthorhombi cal, cylindrical, spherical, segment-like, disc-shaped, tetrahedral, dode cathedral, octahedral, conical, pyramidal, ellipsoid, pentagonal, octagonal and octagonal prismatic and rhombohedral shape can take. Completely irregular Mul too shapes such as arrow or animal shapes, trees, clouds, etc. can be realized. As with the molded bodies, troughs are with rounded corners and edges or with rounded corners and chamfered edges preferred.

In the case described above, the part at least partially contained in the cavity consists solely of the ingredients a) to d) of the detergent components. However, it is also possible to introduce detergent components based on carrier material into the cavity (s). For reasons of process economy, however, multiphase detergent tablets are preferred in which the part contained in the cavity is made of

• a) 0.1 to 20 wt .-% of one or more esters, ethers, acetals or ketals of fragrance fabrics,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above from 30 ° C,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

consists.

The size of the trough or through hole compared to the overall shape body depends on the intended use of the molded body. Depending on with how much more active substance the remaining hollow volume is filled should and whether contain a smaller or larger amount of detergent component the size of the cavity may vary. Regardless of the intended use Detergent tablets are preferred in which the volume ratio of pressed part ("base molding") to detergent component 2: 1 to 100: 1, before preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1, is.  

In addition to the volume ratio mentioned, a mass ratio of the two can also be used Parts are given, the two values on the densities of the base molding or correlate the detergent component with each other. Independent of Density of the individual parts are detergent tablets according to the invention per preferred, in which the weight ratio of the base molding to cleaning agent tel component 1: 1 to 100: 1, preferably 2: 1 to 80: 1, particularly preferably 3: 1 to 50: 1 and in particular 4: 1 to 30: 1.

Analogous information can also be given for the surfaces, each from the base molded body or from the detergent component are visible. Here are laundry or detergent tablets are preferred, in which the externally visible surface surface of the detergent component 1 to 25%, preferably 2 to 20%, particularly be preferably 3 to 15% and in particular 4 to 10% of the total surface of the shaped body matters.

The detergent component and the base molding are preferably optically un colored differently. In addition to the optical differentiation, application technology cal advantages through different solubilities of the different shaped body areas be achieved. Detergent tablets, in which the cleaning middle component dissolves faster than the base molding, are preferred according to the invention. By incorporating certain components, the solubility of the Reini Component can be accelerated in a targeted manner, on the other hand, the release certain ingredients from the detergent component for advantages in washing or cleaning process.

Of course, detergent tablets according to the invention are also molded preferred, in which the detergent component dissolves later in the washing program than the base molding. Performance benefits from this delayed release can be seen achieve, for example, that with the help of a more slowly soluble cleaning agent tel component active substance (s) are only released in later rinses. So can for example in automatic dishwashing due to slow-dissolving cleaning medium components are achieved that in the rinse aid further active substance (s)  Is available. Through additional substances such as non-ionic surfactants, acidification detergents, soil release polymers etc. can be used to improve rinse aid results. Incorporation of perfume is also possible without any problems; by its delayed In dishwashers, release can cause the "lye smell" that often occurs in Opening the machine can be eliminated. The ingredients acidifying agent, should- Release polymers etc. are on the detergent components of the invention then related ingredients d).

In preferred embodiments of the present invention, the base molding has a high specific weight. Detergent tablets, which are characterized in that the base tablet has a density above 1000 gdm ^-3 , preferably above 1025 gdm ^-3 , particularly preferably above 1050 gdm ^-3 and in particular above 1100 gdm ^-3 preferred according to the invention.

In order to facilitate the disintegration of highly compressed moldings, it is possible to disintegrate on aids, so-called tablet disintegrants, to incorporate them into the disintegration to shorten times. Under tablet disintegrants or disintegrators according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical Technologie "(6th edition, 1987, pp. 182-184) understood auxiliary substances that are necessary for the rapid Disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in provide resorbable form.

These substances, which are also referred to as "explosives" due to their effect, ver increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known disintegration aid medium are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used. Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or mo differentiated natural substances such as cellulose and starch and their derivatives, alginates or casein Derivatives.  

Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids tel, each based on the weight of the molded body. Contains only the basic molding Desinte tion aids, the information given relates only to the weight of the ba molded body. In the incorporation of disintegration aids in the Invention modern detergent components count as ingredients d).

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets form such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6 % By weight. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally considered, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the disintegrating agent based on cellulose. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not finely divided form, but before mixing into the premixes to be pressed  converted into a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally cogranu Contained form, are in the German patent applications DE 197 09 991 (Ste fan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel). These writings are also more detailed information on the Her position of granulated, compacted or cogranulated cellulose disintegrants men. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular to at least 90% by weight between 400 and 1200 µm. The above and in the writings cited described coarser disintegration aids on cellulose In the context of the present invention, bases are preferred as disintegration aids used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

As a further disintegrant based on cellulose or as part of this compo microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine cellulo produced by the hydrolysis sen supplies the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm sen and, for example, to granules with an average particle size of 200 microns are pactable.

Contain preferred detergent tablets within the scope of the present invention additionally a disintegration aid, preferably a disintegration aid Cellulose base, preferably in granular, cogranulated or compacted form, in Amounts from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the weight of the molded body.

The detergent tablets according to the invention can moreover both in Basic molded body as well as a gas-developing brew in the detergent component  system included. The gas-developing shower system can consist of a single substance exist, which releases a gas on contact with water. Among these connections is ins special to call the magnesium peroxide, which releases oxygen on contact with water puts. Usually, however, the gas-releasing bubble system itself consists of min at least two components that react with one another to form gas. While here one Many systems are conceivable and executable, for example nitrogen, oxygen or release hydrogen, it will in the washing and cleaning according to the invention Fibrous system used bubble system based on both economic and let choose based on ecological considerations. Preferred shower systems best hen from alkali metal carbonate and / or hydrogen carbonate and an acidification medium, which is suitable to free carbon dioxide from the alkali metal salts in aqueous solution clog.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium are salts are clearly preferred over the other salts for cost reasons. Self ver the pure alkali metal carbonates or -hydrogen carbonates are used; rather, mixtures of different car bonates and hydrogen carbonates may be preferred for washing technology reasons.

In preferred shaped detergent bodies, 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal car bonates or bicarbonates and 31 to 15, preferably 2 to 12 and in particular 3 up to 10% by weight of an acidifying agent, in each case based on the total shaped body per, used.

As an acidifying agent that releases carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihy drug phosphates and other inorganic salts can be used. However, are preferred organic acidifiers are used, with citric acid being particularly preferred added acidifier. However, the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. Wine is preferred from this group acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid  like polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid are also a settable. Commercially available and as an acidifying agent in the context of the present Sokalan® DCS (trademark of BASF) is also preferably used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adi pinic acid (max. 33% by weight).

In the context of the present invention, preference is given to detergent tablets a substance from the group of organic as an acidifying agent in the shower system Di-, tri- and oligocarboxylic acids or mixtures of these can be used.

The particulate detergents and / or detergent tablets can, like the detergent components according to the invention, be packaged after production, the use of certain packaging systems having proven particularly useful. Another aspect of the present invention is a combination of (a) particulate cleaning agent (s) according to the invention and / or (a) washing or cleaning agent shaped body (s) according to the invention and a cleaning agent shaped body and the cleaning agent and / or the washing and cleaning agent (s) containing packaging system, the packaging system having a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of detergent component and / or detergent and / or detergent tablets (s) and packaging system according to the invention has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day, if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%. The specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permissible (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m- 45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of calcium chloride and the exposure time, the moisture vapor transmission rate can be determined

calculate, where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate within the scope of the present invention. The absorption capacity of air for water vapor increases with temperature up to a respective maximum content, the so-called saturation content, and is given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is already saturation with 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) .100 = 83%. If you cool this air, then the saturation (100% RH) is reached at the so-called dew point (in the example: 14 °), ie, if it cools further, a precipitate is formed in the form of mist (dew). Hygrometers and psy chrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in La Borehouses with humidity control to +/- 2% RH depending on the device type. adjust exactly.  

Even over saturated solutions of certain salts form in closed systems constant and well-defined relative humidity at a given temperature, that on the phase equilibrium between partial pressure of water, saturated solution and soil body are based.

The combinations according to the invention can of course in turn be secondary packaging, such as cardboard boxes or trays, are packaged, with the Se secondary packaging no further requirements have to be made. The secondary packaging is therefore possible, but not necessary.

Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m ² / day to less than 15 g / m ² / day.

The packaging system of the combination according to the invention encloses depending on the design Form of the invention a certain amount of cleaning agent according to the invention component, a certain amount of a particulate detergent setting or one or more detergent tablets. It is there preferred according to the invention, either to design a shaped body such that it has a Application unit of the detergent and cleaning agent includes, and this molded body to be packed individually, or to pack the number of moldings in one packaging unit ken, which comprises an application unit in total. At a target dosage of 80 g According to the invention, detergents and cleaning agents are possible, a 80 g weight To manufacture detergent tablets and to pack them individually, it is According to the invention, however, it is also possible to use two washing and cleaning agents weighing 40 g each Packing the shaped body in a packaging to form a Kombinati according to the invention to get on. This principle can of course be expanded, so that fiction three, four, five or even more detergents and cleaning agents according to combinations can contain molded articles in a packaging unit. Of course, two can or more moldings in one package have different compositions sen. In this way it is possible to spatially separate certain components separate, for example to avoid stability problems.  

The packaging system of the combination according to the invention can differ from the materials and take on any external shape. From economic For reasons of and for reasons of easier processability, however, there are packaging systems Steme preferred, in which the packaging material is light in weight, easily process and is inexpensive. In combinations preferred according to the invention the packaging system consists of a sack or pouch made of single-layer or laminated Paper and / or plastic film.

The detergent tablets can be unsorted, i. H. as loose bulk tion, be filled into a bag made of the materials mentioned. But it is from aesthetic table reasons and for sorting the combinations in secondary packaging moves, the detergent tablets individually or in several sorted in Fill sacks or bags. For individual application units for washing and cleaning molded article, which are in a sack or pouch, has in Tech nik the term "flow pack" naturalized. Such "flow packs" can then - again preferably sorted - optionally packed in outer packaging, what the compact Offer form of the molded body underlines.

The sacks or bags made of one layer, which are preferably to be used as a packaging system Mixed or laminated paper or plastic film can be used in many different ways and be designed, for example as an inflated bag without a central seam or as Bags with central seam, which are caused by heat (hot fusion), adhesives or adhesive tapes which are locked. Single-layer bag or sack materials are the known Papers, which may or may not be impregnated, as well as plastic films, which are opposed can also be co-extruded. Plastic films that are within the scope of the present Er can be used as a packaging system are, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI-Verlag, Düssel Dorf 1988, page 193. Figure 111 shown there indicates at the same time breakpoints on the water vapor permeability of the materials mentioned.

Combinations particularly preferred within the scope of the present invention as a packaging system, a sack or bag made of single-layer or laminated art  material film with a thickness of 10 to 200 microns, preferably from 20 to 100 microns and esp special from 25 to 50 µm.

Although it is possible, wax-coated in addition to the films or papers mentioned Papers in the form of cardboard boxes as a packaging system for washing and cleaning to use medium shaped bodies, it is preferred in the context of the present invention if the packaging system does not include boxes made of wax-coated paper. The The term “packaging system” in the context of the present invention always the primary packaging of the detergent component, detergent together composition or molded article, d. H. the packaging that is directly on the inside with the Detergent component, detergent composition or molded body surface is in contact. There is no requirement for an optional secondary packaging stations, so that all common materials and systems can be used here nen.

As already mentioned above, the detergent components contain Reini detergent compositions or detergent tablets of the inventions combination according to the invention, depending on its intended use Detergents and cleaning agents in varying amounts. Regardless of the use For the purpose of the agent or molded article, it is preferred according to the invention that the agent (s) or the detergent tablets have a relative equilibrium has / have moisture of less than 30% at 35 ° C.

The relative equilibrium moisture of the detergents or detergents Shaped bodies can be determined using standard methods following investigations the following procedure was chosen: A water permeable 1 liter container with a lid, which has a closable opening for the introduction of samples was carried out with a total of 300 g washing and cleaning medium shaped bodies filled and kept at a constant 23 ° C for 24 h to ensure a uniform Ensure the temperature of the vessel and substance. The water vapor pressure in the room A hygrometer (Hygrotest 6100, Testoterm Ltd., England) can be determined. The water vapor pressure is now measured every 10 minutes,  up to two successive values show no deviation (equilibrium moisture speed). The above Hygrometer allows direct display of the recorded values in% relative humidity.

Embodiments of the combination according to the invention are also preferred which the packaging system is designed to be resealable. Also combinations, where the packaging system has a microperforation, can be fiction according to implement with preference.

As mentioned above, detergent components, detergents can be added compositions or detergent tablets for automatic dishwashing produce the inventive method. A cleaning procedure is accordingly ren for cleaning dishes in a dishwasher, characterized in that one or more particulate cleaning agent (s) according to the invention and / or one or more detergent tablets according to the invention by inserting the dosing chamber of the dishwasher and running a washing program, in the course of which opens the dosing chamber and the cleaning agent and / or the or the shaped body are dissolved, another object of the present Er finding.

Also in the cleaning process according to the invention, one can check the metering chamber spruce and the detergent components or detergents according to the invention compositions or the molded article (s) according to the invention, for example in insert the cutlery basket. It goes without saying that a dosing aid is also used here fe, for example, a basket that is attached to the sink, easily possible Lich. Accordingly, a cleaning process for cleaning dishes in one Dishwasher characterized in that one or more inven tion moderate (s) detergent and / or one or more inventive moderate detergent tablets with or without dosing aid in the rinse insert the dishwasher and run a washing program, during which the or the cleaning agents and / or the or the shaped body are dissolved, a wide rer object of the present invention.

Claims (58)

1. Detergent component containing

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries.

2. Detergent component according to claim 1, characterized in that it as Ingredient a) 0.25 to 17.5 wt .-%, preferably 0.5 to 15 wt .-% and in particular re contains 1 to 10% by weight of one or more esters of fragrance alcohols. 3. Detergent component according to claim 2, characterized in that it contains one or more β-keto esters of the formula R ¹ R ² R ³ CC (O) -R, in which each radical R ¹ to R ^{3 is} independently selected from the group -H, -CH ₃ , -CH ₂ (CH ₂ ) _n CH ₃ with n = 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 30, or the branched C _{3- 30} alkyl residues and in which R stands for a fragrance alcohol residue. 4. Cleaning agent component according to claim 2 or 3, characterized in that they th one or more betaine ester of the formula R ¹ R ² N- [C (R ³⁾ (R ⁴⁾ _n3 -C (O) -OR contained in each R ¹ and R ^{2 are} independently selected from - [C (R ³ ) (R ⁴ ) _n3 -C (O) -OR, - (CH ₂ ) _n -N {[C (R ³ ) (R ⁴ ) ] _n3 -C (O) -OR} ₂ and - {(CH ₂ ) _n1 - N [C (R ³ ) (R ⁴ ) -C (O) -OR] _n3 } _n2 - (CH ₂ ) _n1 -N (R ³ ) - [C (R ³ ) (R ⁴ )] _n3 -C (O) -OR, each radical R ³ and R ^{4 is} independently selected from the group -H, -CH ₃ , -CH ₂ ( CH ₂ ) _n CH ₃ with n = 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 to 30, the branched C _3-30 alkyl radicals or the substituted and unsubstituted aryl radicals in which R stands for a scented alcohol residue and n for numerical values from 1 to 20, n1 for numerical values from 1 to 20, n2 for the numerical values 1, 2, 3, 4, 5 or 6 and n3 for the numerical values 1, 2 or 3. 5. Detergent component according to one of claims 2 to 4, characterized records that it contains one or more fragrance alcohol succinates and / or di-fragrance alcohol Contains succinate. 6. Detergent component according to one of claims 2 to 5, characterized records that it contains one or more silicic acid esters of fragrant alcohols. 7. Detergent component according to one of claims 2 to 6, characterized records that it contains one or more phosphoric acid esters of fragrant alcohols. 8. Detergent component according to one of claims 2 to 7, characterized records that it contains one or more amino acid esters of fragrant alcohols, preferably two se contains cysteine, alanine, glutamic acid, glycine and / or phenylalanine esters. 9. detergent component according to claim 1, characterized in that it as Ingredient a) 0.25 to 17.5 wt .-%, preferably 0.5 to 15 wt .-% and in particular re contains 1 to 10% by weight of one or more ethers of fragrance alcohols. 10. Detergent component according to claim 9, characterized in that it has a or contains several fragrance alcohol glycosides, preferably fragrance alcohol glucosides. 11. Detergent component according to one of claims 2 to 10, characterized is characterized by the fact that it is the residue of one or more fragrance alcohols as the fragrance alcohol residue R. the group 1-octanol, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butylcyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 3- Pentanol, 3-phenylpropanol, 4-heptenol, 4-isopropyl-cyclohexanol, 4-tert- Butycyclohexanol, 6,8-dimethyl-2-nonanol, 6-nonen-1-ol, 9-decen-1-ol, alpha- Methylbenzyl alcohol, alpha-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, beta-terpineol, butyl salicylate, citronellol, cyclohexyl salicylate, decanol, dihy dromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethylsa licylate, ethylvaniline, eugenol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeuge  nol, isopulegol, linalool, menthol, myrtenol, n-hexanol, n-pentanol, nerol, nonanol, Octanol, para-menthan-7-ol, phenylethyl alcohol, phenol, phenyl salicylate, tetrahydro geraniol, tetrahydrolinalool, thymol, trans-2-cis-6-nonadienol, trans-2-nonen-1-ol, contains trans-2-octenol, undecanol, vanillin, cinnamon alcohol. 12. Detergent component according to claim 1, characterized in that it as Ingredient a) 0.25 to 17.5 wt .-%, preferably 0.5 to 15 wt .-% and in particular re 1 to 10% by weight of one or more acetals from fragrance aldehydes with alcohols and / or from aldehydes with fragrance alcohols and / or from fragrance aldehydes with fragrance contains alcohol. 13. Detergent component according to claim 12, characterized in that it is a or more cyclic acetals with dioxolane structure from fragrance aldehydes with open term or cyclic vicinal diols. 14. Detergent component according to claim 12 or 13, characterized in that they one or more cyclic acetals with 1,3-dioxane structure from fragrance aldehydes and contains open-chain or cyclic (n, n + 2) diols. 15. Detergent component according to one of claims 12 to 14, characterized records that the acetals from one or more of the fragrance aldehydes from the group Hydratropaldehyde, p-t-bucinal, cyclamal, triplal, halional, hexylcinnamic acid aldehyde, Vanillin, Citral, Citronellal, Dodecanal, Hydroxycitronellal, Octanal, Floralozon® ge were won. 16. Detergent component according to claim 1, characterized in that it as Ingredient a) 0.25 to 17.5 wt .-%, preferably 0.5 to 15 wt .-% and in particular re 1 to 10 wt .-% of one or more ketals from fragrance ketones with alcohols and / or from ketones with scented alcohols and / or from scented ketones with scented alcohols contains.   17. Detergent component according to claim 16, characterized in that it is a or several ketals of 1,4-cyclohexanedione and / or 12,4-pentanedione with scented alcohol fetch contains. 18. Detergent component according to one of claims 16 or 17, characterized records that it contains one or more cyclic ketals with dioxolane structure from fragrance keto contains with open chain or cyclic vicinal diols. 19. Detergent component according to one of claims 16 to 18, characterized records that it contains one or more cyclic ketals with 1,3-dioxane structure from fragrance contains ketones and open-chain or cyclic (n, n + 2) diols. 20. Detergent component according to one of claims 16 to 19, characterized records that the ketals from one or more of the fragrance ketones from the group Ben zylacetone, methyl dihydrojasmonate, methyl amyl ketone, methyl nonyl ketone, carvone, Geranylacetone, α-ionone, β-ions, γ-methylionone, dasmacenone, methyl-β- Naphthyl ketone were obtained. 21. Detergent component according to one of claims 1 to 20, characterized records that as ingredient b) 25 to 90, preferably 30 to 80, especially be preferably 35 to 70 and in particular 40 to 60% by weight of meltable substance (s) holds. 22. Detergent component according to one of claims 1 to 21, characterized records that as ingredient b) one or more substances with a melting pot range between 30 and 100 ° C, preferably between 40 and 80 ° C and in particular between 50 and 75 ° C, contains. 23. Detergent component according to one of claims 1 to 22, characterized records that as ingredient b) at least one paraffin wax with a melt range from 30 ° C to 65 ° C.   24. Detergent component according to one of claims 1 to 23, characterized records that as ingredient b) at least one substance from the group of polyes contains ethylene glycols (PEG) and / or polypropylene glycols (PPG). 25. Detergent component according to one of claims 1 to 24, characterized records that the ingredient b) comprises fatty substance (s). 26. Detergent component according to claim 25, characterized in that it as Ingredient b) or proportion thereof 12.5 to 85% by weight, preferably 15 to 80% by weight, particularly preferably 17.5 to 75% by weight and in particular 20 to 70% by weight Fat (s), each based on the total weight of the component contains. 27. Detergent component according to one of claims 25 or 26, characterized is characterized by the fact that it contains one or more substances as ingredient b) or part thereof the groups of fatty alcohols, fatty acids and fatty acid esters. 28. Detergent component according to one of claims 25 to 27, characterized in that it contains, as ingredient b) or part thereof, one or more C _10-30 fatty alcohols, preferably C _12-24 fatty alcohols, with particular preference for 1-hexadecanol, 1 Octadecanol, 9-cis-octadecen-1-ol, all-cis-9,12-octadecadien-1-ol, all-cis-9,12,15-octadecatrien-1-ol, 1-docosanol and mixtures thereof, contains. 29. Detergent component according to one of claims 1 to 28, characterized records that as ingredient c) 5 to 60, preferably 10 to 55, especially before contains 15 to 52.5 and in particular 20 to 50% by weight of surfactant (s). 30. Detergent component according to one of claims 1 to 29, characterized characterizes that as ingredient c) anionic (s) and / or nonionic (s) surfactant (s), preferably non-ionic surfactant (s). 31. Detergent component according to one of claims 1 to 30, characterized records that it contains as ingredient c) nonionic surfactant (s) with a melting point  above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C contains. 32. detergent component according to one of claims 1 to 31, characterized in that it contains as the ingredient c) ethoxylated (s) nonionic surfactant (s), the / which from C _6-20 - monohydroxyalkanols or C _6-20 alkylphenols or C _{16 -20} fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained. 33. Detergent component according to one of claims 1 to 32, characterized records that they contain as ingredient c) ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonioni make up tensides contains. 34. Detergent component according to one of claims 1 to 33, characterized in that it contains as the ingredient c) nonionic surfactants of the formula
R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ]
contains, in which R ^{1 represents} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1.5 and y stands for a value of at least 15. 35. detergent component according to one of claims 1 to 34, characterized in that it contains as the ingredient c) end-capped poly (oxyalkylated) nonionic surfactants of the formula
R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²
contains, in which R ¹ and R ² stand for linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R ^{3 stands} for H or a methyl, ethyl, n-propyl, iso- Propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
R ¹ O [CH ₂ CH (R ³ O] _x CH ₂ CH (OH) CH ₂ OR ²
in which x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred. 36. Detergent component according to one of claims 1 to 35, characterized records that as ingredient c) one or more substances from the groups of Bleaching agents, bleach activators, bleaching catalysts, enzymes, polymers, corrosion contains inhibitors, silver protection agents and mixtures thereof. 37. detergent component according to one of claims 1 to 36, characterized records that as ingredient c) or part thereof further active and / or auxiliary fe from the groups of dyes, fragrances, anti-settling agents, floating agents, anti floating agents, thixotropic agents and dispersing agents in amounts of 0 to 10% by weight, preferably from 0.25 to 7.5% by weight, particularly preferably from 0.5 to 5% by weight and in particular from 0.75 to 2.5% by weight. 38. Detergent component according to one of claims 1 to 37, characterized by a melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and especially between 55 and 65 ° C. 39. Process for the production of particulate detergent components, characterized in that a melt from

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

applied to one or more carrier materials and the mixture processed to give shape. 40. The method according to claim 39, characterized in that the shaping process processing by granulating, compacting, pelleting, extruding or tableting he follows. 41. Process for the production of prilled detergent components, characterized in that a melt is formed

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

injected into a cold gas stream. 42. Process for the preparation of detergent components, characterized in that a melt is formed

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

dosed on chilled pastilles. 43. A process for the production of particulate detergent components, characterized in that a melt is formed

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

applied or sprayed onto a chill roll, scraped off the solidified melt and, if necessary, shredded. 44. Use of particulate detergent components

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

in detergents for automatic dishwashing. 45. Particulate machine dishwashing detergent, containing builders and optionally other detergent ingredients, characterized in that it contains part-shaped detergent components, based on their weight,

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

contain. 46. Particulate dishwasher detergent according to claim 45, characterized records that it contains builders in amounts of 20 to 80 wt .-%, preferably 25 up to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the Ge importance of the remedy. 47. Particulate dishwasher detergent according to one of claims 45 or 46, characterized in that it also contains one or more substances from the group Pen of bleaching agents, bleach activators, bleach catalysts, surfactants, corrosion inhibitors  bitters, polymers, dyes and fragrances, pH adjusting agents, complexing agents and en contains zyme. 48. Particulate dishwasher detergent according to one of claims 45 to 47, characterized in that it is the particulate detergent component in amounts of 0.5 to 30% by weight, preferably 1 to 25% by weight and in particular contains from 3 to 15% by weight, based on the total average. 49. Particulate dishwasher detergent according to one of claims 45 to 48, characterized in that the particulate detergent component Particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and in particular between 2 and 20 mm. 50. Particulate dishwasher detergent according to one of claims 45 to 49, characterized in that it (without taking into account the particulate Rei detergent component) particle sizes between 100 and 3000 microns, preferably between 300 and 2500 microns and in particular between 400 and 2000 microns. 51. Particulate dishwasher detergent according to one of claims 45 to 50, characterized in that a dosing unit in a bag made of water-soluble The film is sealed. 52. Multi-phase detergent tablets for automatic dishwashing, containing builders and optionally further detergent ingredients, characterized in that at least one phase consists of

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

consists. 53. Multi-phase detergent tablet according to claim 52, characterized net that the phases have the form of layers and the molded body 2-, 3- or Is 4-phase. 54. Multi-phase detergent tablet according to claim 52, characterized net that he from a basic molded body, which has a cavity, and a min part of which is contained in the cavity. 55. Multi-phase detergent tablet according to claim 53, characterized in that the part contained in the cavity

• a) 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances,
• b) 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C.,
• c) 0 to 60% by weight of further active ingredients and / or auxiliaries

consists. 56. Combination of (a) particulate cleaning agent (s) according to one of claims 45 to 51 and / or (a) detergent or cleaning agent shaped body (s) according to one of claims 52 to 55 and one of the cleaning agent and / or the Packaging and detergent technology containing packaging system, characterized in that the packaging system has a moisture vapor permeability rate of 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system at 23 ° C and a relative equilibrium humidity of 85% is stored. 57. Cleaning process for cleaning dishes in a dishwasher, because characterized in that one or more particulate detergent (s) according to one of claims 45 to 51 and / or one or more washing or cleaning agents Gmittelformkörper according to any one of claims 52 to 55 in the metering chamber Insert dishwasher and run a washing program, in the course of which the  Dosing chamber opens and the cleaning agent (s) and / or the mold (s) body to be dissolved. 58. Cleaning method for cleaning dishes in a dishwasher, because characterized in that one or more particulate detergent (s) according to one of claims 45 to 51 and / or one or more washing or cleaning agents molded article according to one of claims 52 to 55 with or without metering aid in the dishwasher's washing compartment and run a washing program, in the course of the cleaning agent (s) and / or the molded article (s) be solved.