EP1601454A1

EP1601454A1 - Coating meltable substances and substance mixtures

Info

Publication number: EP1601454A1
Application number: EP04716560A
Authority: EP
Inventors: Sandra Hoffmann; Peter Victor
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2003-03-12
Filing date: 2004-03-03
Publication date: 2005-12-07
Also published as: DE10310679B3; US20060073206A1; WO2004080585A1

Abstract

The invention relates to a method for coating meltable substances or substance mixtures. A melt of the substance (mixture) drips into a melt of the coating agent(s) where it solidifies at least on the surface thereof and the solidified melt, which is coated on at least the surface thereof, is subsequently separated from the melt of the coating agent(s).

Description

"Coating fusible substances and substance mixtures"

The present invention relates to a method for coating substances, in particular fusible substances. It relates in particular to the coating of substances that can be used in detergents or cleaning agents.

The coating of substances for technical and / or aesthetic reasons is widely known in the prior art. For example, Pharmaceuticals are often provided with coatings to make them easier to apply and / or only to be released at certain times. Coating with colored coating materials for aesthetic reasons or for reasons of distinctness is also widely used here. In technical products, coatings are often used to protect the coated materials from environmental influences. For example, enzymes are often coated to protect them from atmospheric oxygen or aggressive substances. Similar cases exist in almost all branches of industry, for example the food, animal feed, building materials, adhesives, cosmetics or washing or cleaning agent industries.

The widespread use of coated substances has resulted in a large number of processes for applying corresponding coatings to substrates. A widely used method is the application of a melt, solution, dispersion, suspension or emulsion of the coating material to the substrates and subsequent solidification or evaporation of solvent.

By means of a melt, relatively thick coatings are obtained, which naturally consume a lot of coating material. Thinner coatings can be achieved by using solutions (or dispersions, etc.), but in some cases a considerable amount of solvent has to be evaporated and possibly recovered, which on the one hand lowers the throughputs during production and on the other hand increases the costs. In general, coating processes are difficult to carry out continuously because the size of the batch to be coated increases the problems such as non-uniform coatings and / or bonding of the individual substrate particles. The object of the present invention was to provide a simple, inexpensive and continuously executable coating process.

It has now been found that meltable substances can be coated particularly well if they are melted and introduced into a melt of the coating material.

In a first embodiment, the invention relates to a method for coating meltable substances or substance mixtures, in which a melt of the substance (mixture) drips into a melt of the coating agent (s), at least allowed to solidify there on its surface and at least the coated one melt solidified on its surface is subsequently separated from the melt of the coating agent (s).

According to the invention, a substance to be coated or a mixture of substances to be coated is first melted. This melt is dropped into a melt made from one or more coating materials and at least partially solidified there. Due to the temperature gradient between the melt of the material to be encased and the melt of the encapsulant, the former initially solidifies on its surface, a drop forming which has a liquid core and an envelope which on the inside is made of solidified material to be encased and on the outside of encapsulation material is formed. This structure already has sufficient stability to be removed from the melt of the wrapping material. The complete solidification of the liquid interior can take place during and / or after the removal process. In the context of the present invention, however, it is preferred not to carry out the subsequent method steps until the interior of the structure described above has completely solidified. The solidification time required for this can be varied by choosing the melting points of the coating material and the material to be coated, as well as by the respective temperatures of these materials and the size of the particles introduced. In the context of the present invention, the term “wrapping material” is used for a single coating material as well as for a mixture of different coating materials. “Wrapping material” therefore denotes the substance (s) that form the subsequent coating. Completely analogously, the term “substance to be coated” is not limited to a single substance. It can also be a mixture of substances. These can be melted together, provided that no phase separations occur. However, it is also possible to melt different substances separately without any problems and to be introduced separately into a melt. In the former case, a coated structure containing several substances is obtained, in the second case, each coated structure contains only one substance.

The term “dripped into the melt” encompasses the introduction of the substance to be encased in a molten form. Technical processes which involve a similar step are, for example, prilling, pastilling, pelleting, etc. The size of the coated particles can be varied, see below.

The method according to the invention can be carried out better and faster the more different the melting points of the wrapping material and the substance to be wrapped are. The higher the melting temperature of the material to be wrapped and the lower the melting temperature of the wrapping material, the faster the material to be wrapped solidifies in the melt of the wrapping material at least on its surface. The heat capacities of the substances also play a role, of course.

Particularly preferred processes according to the invention are characterized in that the melting point or melting range of the substance to be coated or the substance mixture is at least 5 ° C., preferably at least 10 ° C., particularly preferably at least 20 ° C., further preferably by at least 25 ° C. and in particular is at least 30 ° C above the melting point or melting range of the coating agent. There are limits to the melting point or the melting point difference insofar as the wrapping material is to form a stable wrapping on the material to be wrapped. Envelopes that already soften at room temperature are not technically usable, which is why - depending on the application of the process and the products produced with it - the melting point of the encapsulation material should not fall below 20 to 25 ° C. Due to the increasing process costs, the melting point of the material to be coated should not exceed 500 to 600 ° C, although much higher temperatures can also be achieved without problems.

In particularly preferred processes according to the invention, the melting point of the substance to be coated is in the range from 30 to 300 ° C., preferably from 40 to 250 ° C., particularly preferably from 50 to 200 ° C. and in particular from 60 to 170 ° C.

Suitable substances to be coated in the process according to the invention are substances or substance mixtures from a wide variety of substance classes. With regard to a preferred area of use of the end products of the process according to the invention, meltable detergent or cleaning agent ingredients are particularly preferred substances to be coated. Accordingly, preferred methods according to the invention are characterized in that one or more ingredients of washing or cleaning agents are used as the substance to be coated.

Preferred substances to be coated originate, for example, from the group of the monomeric and / or polymeric organic acids, preferably from the group of the mono- and / or dicarboxylic acids, particularly preferably the surfactant acids and / or from the group of the acids named below.

A class of substances that is outstandingly suitable as a substance to be coated are aliphatic and aromatic dicarboxylic acids, which can be melted individually, in a mixture with one another or also in a mixture with other substances and processed according to the invention. Particularly preferred dicarboxylic acids are summarized in the table below:

Instead of the dicarboxylic acids mentioned or in a mixture with them, the corresponding anhydrides can also be used, which is particularly advantageous in the case of citric acid, glutaric acid, maleic acid and phthalic acid.

In addition to the dicarboxylic acids, carboxylic acids and their salts are also suitable as materials to be coated. From this class of substances, citric acid and trisodium citrate as well as salicylic acid and glycolic acid have proven to be particularly suitable. It is also particularly advantageous to use fatty acids, preferably those with more than 10 carbon atoms, and their salts as the material to be coated. Carboxylic acids which can be used in the context of the present invention are, for example, hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. The use of fatty acids such as Dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotinic acid) and meltsiacetic acid (9) Hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (Petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t-octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatreic acid (linolenic acid) it is preferred not to use the pure species, but technical mixtures of the individual acids, as they are accessible from the fat hydrolysis. such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C _10, 48 % By weight C ₁₂ , 18% by weight C ₁₄ , 10% by weight C ₁₆ , 2% by weight C ₁₈ , 8% by weight C ₁₈ -, 1% by weight C ₁₈ -) _> Palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt .-% _C12, 15 wt .-% C _i4, 7 wt .-% C _16, 2 wt .-% C ₁₈ , 15 wt% C ₁₈ -, 1 wt% C ₁₈ -, tallow fatty acid (approx. 3 wt% C ₁₄ , 26 wt% C ₁₆ , 2 wt% C ₁₆ - , 2% by weight C ₁₇ , 17% by weight C ₁₈ , 44% by weight Cι ₈ -, 3% by weight Cιβ-, 1% by weight C ₁₈ - • ^■ ), hardened tallow fatty acid (approx 2 wt% C ₁₄ , 28 wt% Ci ₆ , 2 wt% C ι ₇ , 63 wt .-% C ₁₈ , 1 wt .-% C ₁₈ -), technical oleic acid (approx. 1 wt .-% C _12, 3 wt .-% C _14, 5 wt .-% C _1β, 6 wt .-% C ₁₆ - 1 wt .-% C _17, 2 wt .-% C _18, 70 % By weight C ₁₈ -, 10% by weight C ₈ -, 0.5% by weight C ₁₈ -), technical palmitin / stearic acid (approx. 1% by weight C ₁₂ , 2% by weight C _14, 45 wt .-% C _16, 2 wt .-% C ₁₇ 47 wt .-% C _1βl 1 wt .-% C ₁₈ -), and soybean oil fatty acid (about 2 wt .-% C _14, 15 wt. - _16% C, 5 wt .-% C _18, 25 wt .-% C ₁₈ - 45 wt .-% C ₁₈ - 7 wt .-% C ₁₈ -).

The above-mentioned carboxylic acids are largely obtained industrially from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. The alkali metal salts of the abovementioned carboxylic acids or carboxylic acid mixtures can also be used for the process according to the invention, if appropriate in a mixture with other materials. In addition to these soaps, other anionic surfactant acids are also suitable for the process according to the invention. Particularly important representatives of this class of substances are described below.

Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the process according to the invention. Their alkali metal, especially sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are mixed with sulfuric acid, chlorosulfonic acid, Amidosulfonic acid or sulfur trioxide to the relevant alkyl sulfuric acids and subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. In terms of quantity, the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids which can be used in the process according to the invention are the alkyl ether sulfuric acids, the salts of which, the alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates. Like the alkyl sulfuric acids, alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the alkyl ether sulfuric acids concerned.

Alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention. Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons. In Reed sulfochlorination, n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which, when hydrolysed with alkalis, provide the alkanesulfonates directly, and when reacted with water, the alkanesulfonic acids. Since di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.

Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins react with sulfur dioxide and oxygen under irradiation with UV light become. This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals. The reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical. The reaction of the two radicals with unreacted paraffin gives the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to give sulfuric acid. In order to keep the yield of the two end products alkylsulfonic acid and sulfuric acid as high as possible and to suppress side reactions, this reaction is usually carried out only up to degrees of conversion of 1% and then stopped.

Olefin sulfonates are produced industrially by the reaction of α-olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize to form so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids.

Alkylbenzenesulfonals as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950s, to produce alkylbenzenesulfonates, propylene was tetramerized to give branched α-dodecylene and the product was converted to tetrapropylenebenzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized. This economical possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced the soaps as the main surfactant in washing and cleaning agents.

Due to the lack of biodegradability of TPS, there was a need to prepare new alkylbenzenesulfonates that are characterized by improved ecological behavior. These requirements are met by linear alkylbenzenesulfonates, which today are almost exclusively alkylbenzenesulfonates and are given the abbreviation ABS. Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins. For this purpose, petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrated to the n-olefins, resulting in both α- and i-olefins. The resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: when using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, on the other hand, if hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be reduced to approx. 20% by weight , Finally, the sulfonation of linear alkylbenzenes is now possible on a large industrial scale with oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the most important. For the sulfonation, special film or tube bundle reactors are used, which deliver as a product a 97% by weight alkylbenzenesulfonic acid (ABSS) which can be used as anionic surfactant acid in the context of the present invention.

By choosing the neutralizing agent, a wide variety of salts, i.e. Alkylbenzenesulfonates. For reasons of economy, it is preferred to prepare and use the alkali metal salts and, among them, the sodium salts of the ABSS. These can be described by the general formula I:

in which the sum of x and y is usually between 5 and 13. Processes according to the invention in which C _8-16 -, preferably C _9- ι ₃ - alkylbenzenesulfonic acids are used as the anionic surfactant in acid form are preferred. It is under the the present invention further preferably, C _8- ι ₆ -, preferably C _9-13 - use alkylbenzenesulfonic acids derived from alkylbenzenes having a tetralin content below 5 wt .-%, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C _8-16 -, preferably C _9-13 - alkylbenzenesulfonic acids used have a 2-phenyl isomer content of less than 22% by weight. , based on the alkylbenzenesulfonic acid.

In summary, methods according to the invention are preferred in which oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, sorbic acid, phthalic acid, terephthalic acid, citric acid, dodecanedioic acid, trinic acidic acid, stium acidic acid, stearic acidic acid, stium acidic acid, stearic acid acid, stearic acid acid, stearic acid acid, Anhydrides of the abovementioned acids or mixtures of these substances can be used. Citric acid and / or citrates, in particular trisodium citrate, and / or citric acid anhydride are particularly preferably used in the process according to the invention as the substance to be coated.

Other suitable materials which can be enveloped by the state of the melt by the process according to the invention are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and / or sodium hydrogen sulfate. The eutectic mixture of potassium hydrogen sulfate and sodium hydrogen sulfate has also proven to be particularly suitable, which consists of 60% by weight of NaHSO ₄ and 40% by weight of KHSO ₄ . Accordingly, processes according to the invention are preferred which are characterized in that hydrogen carbonates, in particular alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate and / or hydrogen sulfates, in particular alkali metal hydrogen sulfates, are specifically used as the substance to be coated

Potassium bisulfate or sodium bisulfate and / or the eutectic mixture of potassium bisulfate and sodium bisulfate, which consists of 60% by weight of NaHSO ₄ and 40% by weight of KHSO ₄ . Another class of substance that can be melted and processed according to the invention are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9). Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP. HEDP is preferably used from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced

Heavy metal binding capacity. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned. Processes according to the invention in which phosphonates, preferably hydroxyalkane or aminoalkanephosphonates, particularly preferably 1-hydroxyethane-1, 1-diphosphonate (HEDP) as di- or tetrasodium salt and / or ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriamine-pentamethylene-phosphonophosphonate (phosphonate), are preferred as substances to be coated ) and their higher homologs, especially in the form of neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP, are therefore preferred.

Other suitable materials that can be enveloped according to the invention via the state of the melt are sugar. In the context of the present invention, the term “sugar” denotes single and multiple sugars, that is to say monosaccharides and oligosaccharides in which 2 to 6 monosaccharides are linked to one another in an acetai-like manner. , Penta and hexasaccharides.

Monosaccharides are linear polyhydroxy aldehydes (aldoses) or polyhydroxy ketones (ketoses). They usually have a chain length of five (pentoses) or six (hexoses) carbon atoms. Monosaccharides with more (heptoses, octoses, etc.) or fewer (tetrosen) carbon atoms are relatively rare. Some monosaccharides have over a large number of asymmetric carbon atoms. For a hexose with four asymmetric carbon atoms, this results in a number of 24 stereoisomers. The orientation of the OH group at the highest numbered asymmetric C atom in the Fischer projection divides the monosaccharides into D and L configured rows. In the naturally occurring monosaccharides, the D configuration is far more common. If possible, monosaccharides form intramolecular hemiacetals, so that ring-like structures of the pyran (pyranoses) and furan type (furanoses) result. Smaller rings are unstable, larger rings are only stable in aqueous solutions. The cyclization creates another asymmetric carbon atom (the so-called anomeric carbon atom), which doubles the number of possible stereoisomers. This is indicated by the prefixes α- u. ß- expressed. The formation of hemiacetals is a dynamic process, which depends on various factors such as temperature, solvent, pH value, etc. Mixtures of both anomeric forms are usually present, sometimes also as mixtures of the furanose and pyranose forms.

Monosaccharides which can be used as sugar in the context of the present invention are, for example, the tetroses D (-) - erythrose and D (-) - threose and D (-) - erythrulose, the pentoses D (-) - ribose, D (-) - ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose as well as D (-) - lyxose and the hexoses D (+) - allose, D (+) - old rose, D (+) - glucose , D (+) - Mannose, D (-) - Gulose, D (-) - ldose, D (+) - Galactose, D (+) - Talose, D (+) - Psicose, D (-) - Fructose, D (+) - sorbose and D (-) - tagatose. The most important and most widespread monosaccharides are: D-glucose, D-galactose, D-mannose, D-fructose, L-arabinose, D-xylose, D-ribose and the like. 2-deoxy-D-ribose.

Disaccharides are made up of two simple monosaccharide molecules linked by glycosidic bonds (D-glucose, D-fructose, etc.). If the glycosidic bond lies between the acetal carbon atoms (1 for aldoses and 2 for ketoses) of both monosaccharides, the ring shape is fixed in both; the sugars show no mutarotation, do not react with ketone reagents and no longer have a reducing effect (Fehling negative: trehalose or sucrose type). If, on the other hand, the glycosidic bond connects the acetal carbon atom of one monosaccharide with any of the second, this can still take the open-chain form, and the sugar has a reducing effect (Fehling positive: maltose type). The main disaccharides are sucrose (cane sugar, sucrose), trehalose, lactose (milk sugar), lactulose, maltose (malt sugar), cellobiose (cellulose breakdown product), gentobiose, melibiose, turanose and others.

Trisaccharides are carbohydrates, which are made up of 3 glycosidically linked monosaccharides and for which one sometimes comes across the incorrect term triosen. Trisaccharides are relatively rare in nature, examples are gentianose, kestose, maltotriose, melecitose, raffinose, and as an example of trisaccharides containing streptomycin and validamycin containing aminosugars.

Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of this class of compounds are stachyose, lychnose (galactose-glucose-fructose-galactose) and secalose (from 4-fructose units).

In the context of the present invention, saccharides from the group consisting of glucose, fructose, sucrose, cellubiosis, maltose, lactose, lactulose, ribose and mixtures thereof are preferably used as sugars.

According to the invention, preferred methods are characterized in that as a substance to be coated sugars, particularly monosaccharides, disaccharides, trisaccharides, tetra-, penta- and / or hexasaccharides, preferably sucrose, particularly preferably isomalt ^®, are used. As isomalt ^® in the context of the present application, a mixture of 6-O-α-D-glucopyranosyl-D-sorbitol (1, 6-GPS) and 1-O-α-D-glucopyranosyl-D-mannitol (1, 1 -GPM). In a preferred embodiment, the weight fraction of the 1,6-GPS in the total weight of the mixture is less than 57% by weight. Mixtures of this type can be prepared industrially, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the isomaltose obtained to form an odorless, colorless and crystalline solid.

Another particularly preferred material that can be coated according to the invention is urea, the diamide of carbonic acid, which is sometimes also referred to as carbamide and can be described by the formula H ₂ N-CO-NH ₂ . Urea forms colorless, odorless crystals with a density of 1.335, which melt at 133 ° C. Urea is soluble in water, methanol, ethanol and glycerin with a neutral reaction. In particular in a mixture with other substances, urea is outstandingly suitable as a material for the process according to the invention. For example, non-ionic surfactants, fragrances, dyes, etc. can be melted and coated together with the urea in large quantities. Mixtures of urea and nonionic surfactants which contain up to 50% by weight of nonionic surfactant, based on the mixture, are particularly preferred. Preferred methods according to the invention are characterized in that urea is used as the substance to be coated.

As already indicated, further active substances can be added to the substance to be coated as long as the additions survive the temperature conditions in the melt. This can be, for example, dyes and / or fragrances; nonionic surfactants or other ingredients of detergents or cleaning agents are also suitable.

A description of the preferred wrapping agents follows. Processes preferred according to the invention are characterized in that polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are used as coating agents, PEG and / or PPG having melting points of 3 to 150 ° C., preferably 30 to 120 ° C., more preferably of 40 to 100 ° C and in particular from 50 to 80 ° C, are preferred. Suitable coating agents are therefore both substances which are solid at room temperature and liquids which are liquid at room temperature. If coating agents are liquid at room temperature, the resulting coated substances are coated in a preferred embodiment with a second coating agent which is solid at temperature. In the context of the present application, however, coating agents which are solid at room temperature are preferably used. Accordingly, particularly preferred processes are characterized in that polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are used as coating agents, PEG and / or PPG having melting points of 30 to 150 ° C., preferably 30 to 120 ° C., being further preferred from 40 to 100 ° C and in particular from 50 to 80 ° C are preferred.

Polyethylene glycols are polymers of ethylene glycol that have the general formula II H- (O-CH ₂ -CH ₂ ) _n -OH (II)

are sufficient, where n can take values between 1 (ethylene glycol) and several thousand. There are various nomenclatures for polyethylene glycols that can lead to confusion. The specification of the average relative molecular weight following the specification "PEG" is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and directly after the hyphen is followed by a number which corresponds to the number n in the formula V mentioned above. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5 ^t Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997) are, for example, PEG-4, PEG-6, PEG-8, PEG-9 , PEG-10, PEG-12, PEG-14 and PEG-16 can be used. Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

Polypropylene glycols (PPG) are polymers of propylene glycol that have the general formula III

H- (O-CH-CH ₂ ) _n -OH (III)

I CH ₃

are sufficient, where n can take values between 1 (propylene glycol) and several thousand.

Nonionic surfactants, for example, are suitable as further covering materials. In view of what has been said above about the melting points of the coating material, surfactants are preferred which have a melting point above 20 ° C., preferably above of 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C.

Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / 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, the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon 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 resulted.

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 _16-2o 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 ranks ethoxylates" are particularly preferred.

Thus, in particularly preferred process according to the invention ethoxylated (s) nonionic surfactant (s), which / from C _6-20 monohydroxyalkanols or C _6-2 o-alkyl phenols 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 was obtained.

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants. Preferred processes according to the invention are characterized in that the coating material used is ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total Make up the molecular weight of the nonionic surfactant.

Other nonionic surfactants with melting points above room temperature which are particularly preferably used contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which comprises 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25 % By weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

Further preferred nonionic surfactants which can be used according to the invention satisfy the formula

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 with 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.

Further preferred nonionic surfactants are the end group-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, if x is 3, the radical R ³ 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 can be used

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 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. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 have} 9 to 14 carbon atoms, R ³ stands for H and x assumes values from 6 to 15. If the latter statements are summarized, methods according to the invention are preferred in which 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

are used 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, 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.

Substances which are insoluble or only sparingly water-soluble can also be used as covering materials. In detergents or cleaning agents, such coverings then serve for a temperature-controlled release of the ingredients, while the coverings described above also release the covered material due to their release kinetics. Due to the more pronounced temperature change during a program, machine dishwashing in the area of detergents or cleaning agents is more suitable as an area of application for substances with a non-water-soluble coating than textile washing.

In the case of non-water-soluble coating materials, it has proven to be advantageous if the coating substance does not have a sharply defined melting point, as is usually the case with pure, crystalline substances, but instead has a melting range which may include several degrees Celsius. The coating substance preferably has a melting range which is between approximately 45 ° C. and approximately 75 ° 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, as a rule, melt above 40 ° C. without decomposition and are relatively low-viscosity and not stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.

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

The 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, walnut, lanolin (wool wax), or Bürzelfetl, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.

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

Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material that meet the requirements regarding the softening point can also be used as coating materials. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or semi-synthetic esters from lower are also Alcohols with fatty acids from native sources can be used. Tegin ^® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances. Shellac, for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as a coating material.

The so-called wax alcohols are also included in the waxes in the context of the present invention, for example. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms. The wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. The coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but also, if appropriate, water-insoluble or only slightly water-soluble polyalkylene glycol compounds can likewise be used at least in part as part of the coating.

Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline cleaning agent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups.

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. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if this melting temperature is not reached in the detergent fleet. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided. Preferably, the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature (generally about 10 to about 30 ° C.) is as high as possible. The more solid wax components present in a wax at room temperature, the more useful it is within the scope of the present invention. With increasing proportion of solid wax components, the resilience of the coating to impacts or friction on other surfaces increases, which leads to a longer-lasting protection of the coated active substances. High proportions of oils or liquid wax components can weaken the coating, opening pores and exposing the coated active substances to the environmental influences mentioned at the beginning.

As already mentioned at the beginning, a melt which is to be coated according to the invention can be built up from several components. If the corresponding ingredients cannot be melted together, for example because they show signs of phase separation, they can also be melted separately and dripped separately into the melt of the wrapping material. Corresponding methods in which several melts of substances to be coated are simultaneously dripped into the coating agent are preferred.

It is preferred according to the invention if the densities of the dropped droplet and the density of the melt from the wrapping material differ. It is particularly preferred if the density of the melt to be dropped is at least 1.1 times, preferably at least 1.2 times and in particular at least 1.3 times the density of the melt of the coating material.

The encapsulated particles are preferably separated from the melt of the encapsulating material by straining the encased particles. This can be done by means of appropriate scooping devices, but the separation is preferably carried out continuously. The use of perforated conveyor belts has proven particularly useful. Processes according to the invention in which the separation of the coated solidified melt from the melt of the coating agent is carried out by straining the coated particles from the melt of the coating material, preferably continuously, particularly preferably via perforated conveyor belts from the Melting basins beyond a draining section are preferred embodiments of the present invention.

The thickness of the coating (the coating layer) can, as already stated, be influenced by the size of the melt drops, by the residence time in the melt of the coating material, by the choice of melting points and melt temperatures, etc. In methods preferred according to the invention, it is 0.1 to 2500 μm, preferably 5 to 500 μm and in particular 10 to 200 μm.

In addition, particularly preferred methods according to the invention are characterized in that the solidified coated substance has particle sizes of 0.5-50 mm, preferably of 1 to 10 mm and in particular of 1.5 to 5 mm.

The present invention furthermore relates to washing or cleaning agents which contain at least one end product of a process according to the invention.

Further ingredients of such washing or cleaning agents according to the invention are described below.

The detergents, cleaning agents or auxiliary washing agents according to the invention can contain all the usual ingredients of detergents or cleaning agents. These are described below.

The washing or cleaning agents according to the invention preferably contain surfactant (s), it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants in textile detergents, the proportion of anionic surfactants being greater than the proportion of nonionic surfactants. The total surfactant content of the washing or cleaning agents according to the invention is preferably below 30% by weight, based on the total agent.

Anionic surfactants or surfactant acids as a component of the melt to be coated and nonionic surfactants as (component of) the coating or as an ingredient in the the melt to be coated has already been described above. In addition, the nonionic surfactants used can preferably be alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably in the 2-position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO 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 _2-18 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, C 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 preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester. Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

I

R-CO-N- [Z]

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ^ 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 following formula,

R ¹ -OR ²

I

R-CO-N- [Z]

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

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

The nonionic surfactant content of preferred washing or cleaning agents according to the invention which are suitable for textile washing is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the total agent.

Low-foaming nonionic surfactants are preferably used in automatic dishwashing detergents.

Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent. In contrast, these surfactants are of significantly greater importance in detergents. The washing or cleaning agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.

The agents according to the invention can contain, for example, cationic compounds of the formulas IV, V or VI as cationic active substances: R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (IV)

(CH ₂ ) _n -TR ²

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (V)

I I I

R ¹ TT

I I

R ² R ²

R ¹

I

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (VI)

R ⁴

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n - TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In particular, agents according to the invention which are formulated as fabric softeners contain cationic surfactant (s) of the formulas (IV), (V) and / or (VI). Preferred fabric softeners contain 0.5 to 50% by weight, preferably 1 to 45% by weight and in particular 2.5 to 40% by weight of at least one cationic surfactant, cationic surfactants of the formula (IV) being preferred. The anionic surfactants have been described in detail above in their acid form. The anionic surfactant content of preferred textile detergents according to the invention is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total composition. Cleaning agents according to the invention for machine dishwashing are preferably free from anionic surfactants.

In the context of the present invention, preferred agents additionally contain one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and sliding agents and UV absorbers.

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

The use of the generally known phosphates as builder substances is possible according to the invention, provided that such use in detergents should not be avoided for ecological reasons. Detergents for automatic dishwashing are usually phosphate-based and preferably contain 30 to 70% by weight, particularly preferably 35 to 65% by weight and in particular 45 to 60% by weight of phosphate (s), in each case based on the total agent. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

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 in themselves: They act as alkali carriers, prevent limescale deposits on machine parts or lime incrustations in fabrics and also contribute to cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ , trisodium phosphate, tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , tertiary sodium phosphate, Na ₃ PO ₄ , sodium trimetaphosphate (Na ₃ P ₃ O ₉₎ and Maddrell's salt (see below), potassium dihydrogen phosphate (KH ₂ PO _4), dipotassium hydrogen phosphate (secondary or, dibasic potassium phosphate), K ₂ HPO _4, tripotassium phosphate (tertiary or tribasic potassium phosphate), K_iPO _4, potassium polyphosphate (KPO ₃₎ _x , Potassium diphosphate (potassium pyrophosphate), K ^ O ^

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate 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, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water 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% strength 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 are also in the Can be used within the scope 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 can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x +} ι Η 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. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ß- and δ-

Sodium disilicates Na ₂ Si ₂ O ₅ -yH ₂ O preferred.

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

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 (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O '(1-n) K ₂ O ^■ AI ₂ O ₃ ^■ (2 - 2.5) SiO ₂ ^■ (3.5 - 5.5) H ₂ O

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Other important builders are in particular the carbonates, citrates and silicates. Trisodium citrate and / or pentasodium tripoyl phosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicate and / or metasilicate are preferably used.

Alkali carriers can be present as further constituents. Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates,

Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the The abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used for the purposes of this invention.

A builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.

A builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.

In addition, other ingredients may be present, washing, rinsing or cleaning agents according to the invention being preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.

Another possible group of ingredients are the chelating agents. Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.

Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, that is to say polymers which carry functional groups either in the main chain themselves or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, Hydroxamic acid, amidoxime, aminophosphoric acid, (cycl.) Polyamino, mercapto, 1, 3-dicarbonyl and crown ether residues with, for. T. very specific Activities against ions of different metals. The base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.

In the context of the present invention, particular preference is given to detergents or cleaning agents which contain one or more chelate complexing agents from the groups of

(i) polycarboxylic acids, in which the sum of the carboxyl and optionally

Hydroxyl groups is at least 5,

(ii) nitrogen-containing mono- or polycarboxylic acids,

(iii) geminal diphosphonic acids,

(iv) aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) cyclodextrins

in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the By means of, included.

All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:

a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediamine triacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, isopropynedioic acid, nitrosedioic diacetic acid, nitrosedioic diacetic acid, nitrosedioic diacetic acid, nitro-3-diacetic acid, nitro-dio-diacetic acid, and nitro-dio-diacetic acid, nitro-3-dio-diacetic acid, 3-nitro-dio-diacetic acid, and nitro-dio-diacetic acid, 3-nitro-dio-diacetic acid, and 3-nitro-dio-diacetic acid, and nitro-dio-diacetic acid, and 3-nitro-dio-diacetic acid, and 3-nitro-dio-diacetic acid, and 3-nitro-d-dio-diacetic acid, , N, N-Di- (ß-hydroxyethyl) glycine, N- (1, 2- Dicarboxy-2-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrilotriacetic acid (NTA), c) geminal diphosphonic acids such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), the higher of which Homologs with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups and 1-aminoethane-1, 1-diphosphonic acid, their higher homologues with up to 8 carbon atoms and derivatives thereof containing hydroxyl or amino groups, d) aminophosphonic acids such as ethylenediaminetetra ( methylenephosphonic acid), ethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1, 2,4-tricarboxylic acid and f) cyclodextrins.

In the context of this patent application, polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl and the hydroxyl groups contained in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.

Deposit-inhibiting polymers can also have cobuilder properties. Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic 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, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. These are preferably used coated according to the inventive method.

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

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. 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 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1000 to 4000 g / mol, can in turn be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention. The copolymers containing sulfonic acid groups are described in detail below.

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

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers , Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. In this case, ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably in the form of its sodium or magnesium salts. Also preferred in this context Glycerol disuccinates and glycerol trisuccinates. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

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

In addition to the substances from the classes of substances mentioned, the agents according to the invention can contain further usual ingredients of detergents, dishwashing detergents or cleaning agents, bleaching agents, bleach activators, enzymes, silver protection agents, colorants and fragrances being particularly important. These substances are described below.

Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, Peroxypyrophosphates, citrate perhydrates as well as H ₂ O ₂ providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the washing and cleaning agents according to the invention. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetyloxy and 2,5-diacetyloxy and 2,5-glycolacetyl, ethylene glycol 2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are preferred accordingly be used. Agents according to the invention preferably contain enzymes in total amounts of 1 × 10 ^"6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA process (bicinchoninic acid; 2,2'-bichinolyl-4,4 '-dicarboxylic acid) or the biuret method can be determined.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the enzyme, which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. The variants listed under the name BLAP ^{® are} derived from the protease from Bacillus lentus DSM 5483. Other proteases that can be used come from various Bacillus sp. and ß. gibsonii.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, which is sold under the trade name Protosol ^® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ^® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ^® and Protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from β. amyloliquefaciens or from ß. stearothermophilus and its further developments for use in detergents and cleaning agents. The enzyme from ß. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar ^® ST. Further development products of this α-amylase are from Novozymes among the Trade names Duramyl ^® and Termamyl ^® ultra, available from Genencor under the name Purastar ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^® . The α-amylase of B. amyloliquefaciens is sold by Novozymes under the name BAN ^®, and variants derived from the α- amylase ß. stearothermophilus under the names BSG ^® and Novamyl ^® , also from Novozymes.

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from ß. highlight agaradherens (DSM 9948); also those belonging to the sequence space of α-amylases. Fusion products of the molecules mentioned can also be used.

In addition, the Weiler developments of α-amylase from Aspergillus niger and A. oryzae available under the trade names Fungamyl ^® from Novozymes are suitable. Another commercial product is the Amylase-LT ^® .

Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtainable from Hurnicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^® , Lipolase ^® Ultra, LipoPrime ^® , Lipozyme ^® and Lipex ^® . Furthermore, the cutinases, which were originally isolated from Fusahum solani pisi and Hurnicola insolens, can also be used. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. Lipase ^® , Lipase AP ^® , Lipase M-AP ^® and Lipase AML ^® available. The Genencor company can use, for example, the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusahum solanii. Other important commercial products are the preparations M1 Lipase ^® and Lipomax ^®, originally sold by the Gist-Brocades company, and those by the Meito Sangyo KK, Japan, under the names Lipase MY-30 ^® , Lipase OF ^® and Lipase PL ^® mentioned enzymes to mention, also the product Lumafast ^® from Genencor.

Agents according to the invention, especially if they are intended for the treatment of textiles, can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects. These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a “stone washed” effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ^® . The products Endolase ^® and Carezyme ^® , also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800. Other possible commercial products from this company are Cellusoft ^® and Renozyme ^® . Cellulases can also be used; for example the 20 kD EG from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ^® and Biotouch ^® . Other commercial products from AB Enzymes are Econase ^® and Ecopulp ^® . Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93, the ones from Bacillus sp. CBS is available from Genencor under the trade name Puradax® ^® 670.93. Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ^® Neutra.

Agents according to the invention can contain further enzymes, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and ß-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , A ß-glucanase from a ß. alcalophilus is also suitable. The from ß. subtilis derived beta-glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, washing and cleaning agents according to the invention can contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain. Suitable commercial products are Denilite ^® 1 and 2 from Novozymes. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.

The enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Hurnicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.

Alternatively, the enzymes can be encapsulated both for the solid and for the liquid dosage form, for example by spray drying or Extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel or in those of the core-shell type in which an enzyme-containing core with a water, Air and / or chemical impermeable protective layer is coated. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.

Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

A protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage. When the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. Peptide aldehydes, ie oligopeptides with a reduced C-terminus, are also suitable. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors. Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can also stabilize an enzyme contained in them.

Lower aliphatic alcohols, but above all polyols, such as, for example, glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Di-glycerol phosphate also protects against denaturation due to physical influences. Calcium salts, such as calcium acetate or calcium formate, and magnesium salts are also used.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation against physical influences or pH fluctuations, among other things. Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of the enzymes against oxidative decay. Sulfur-containing reducing agents are also known. Other examples are sodium sulfite and reducing sugars.

Combinations of stabilizers are preferably used, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols further enhanced by the additional use of divalent cations, such as calcium ions.

Cleaning agents according to the invention for machine dishwashing may contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion on the wash ware.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not apparent for technical or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 5% by weight of the total formulation.

Foam inhibitors that can be used in the agents according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable anti-deposition agents, which are also made up according to the invention and are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention made up as textile detergents in order to eliminate graying and yellowing of the treated textiles. These substances absorb the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible light of longer wavelength converter, wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and produces the yellow shade of the grayed or yellowed laundry pure white. Suitable compounds originate for example from the substance classes of the 4,4 ^'diamino-2,2 ^' -Stylbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems as well as those substituted by heterocycles Table brighteners are usually used in amounts between 0.05 and 0.3% by weight, based on the finished agent. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition

The agents according to the invention can also be provided with additional benefits. For example, for agents made up according to the invention as textile detergents, there are color-transfer-inhibiting compositions, agents with an “anti-gray formula”, agents with ironing relief, agents with special fragrance release, agents with improved dirt release or prevention of re-soiling, antibacterial agents, UV protective agents, color-refreshing agents etc. Some examples are explained below:

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

In order to prevent undesirable changes in the agents and / or the treated textiles caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. To this connection class include, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antstatics, which are additionally added to the agents according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening effect.

To improve the water absorption capacity, the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 centistokes, the silicones being able to be used in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Furthermore, too Substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, saiicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid.

Claims

claims:

1. A method for coating meltable substances or substance mixtures, characterized in that a melt of the substance (mixture) dripped into a melt of the coating agent (s), there at least allowed to solidify on its surface and the coated melt solidified at least on its surface is subsequently separated from the melt of the coating agent (s).

2. The method according to claim 1, characterized in that the melting point or melting range of the substance or mixture of substances by at least 5 ° C, preferably by at least 10 ° C, particularly preferably by at least 20 ° C, more preferably by at least 25 ° C and in particular is at least 30 ° C above the melting point or melting range of the coating agent.

3. The method according to any one of claims 1 or 2, characterized in that the melting point of the substance to be coated in the range from 30 to 300 ° C, preferably from 40 to 250 ° C, particularly preferably from 50 to 200 ° C and in particular from 60 up to 170 ° C.

4. The method according to any one of claims 1 to 3, characterized in that polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are used as coating agents, PEG and / or PPG having melting points of 3 to 150 ° C, preferably from 30 to 120 ° C, more preferably from 40 to 100 ° C and in particular from 50 to 80 ° C, are preferred.

5. The method according to any one of claims 1 to 4, characterized in that as the substance to be coated oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, sorbic acid, phthalic acid, terephthalic acid, citric acid, stearic acid, dodecanoic acid , Trisodium citrate, salicylic acid and glycolic acid, anhydrides of the above acids or mixtures of these substances can be used.

6. The method according to any one of claims 1 to 5, characterized in that as the substance to be coated hydrogen carbonates, especially alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate and / or hydrogen sulfates, especially alkali metal hydrogen sulfates, especially potassium hydrogen sulfate or sodium hydrogen sulfate and / or the eutectic mixture of potassium hydrogen sulfate Sodium hydrogen sulfate, which consists of 60% by weight of NaHSO ₄ and 40% by weight of KHSO ₄ , can be used.

7. The method according to any one of claims 1 to 6, characterized in that as the substance to be coated phosphonates, preferably hydroxyalkane or aminoalkanephosphonates, particularly preferably 1-hydroxyethane-1, 1-diphosphonate (HEDP) as di- or tetrasodium salt and / or Ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs, in particular in the form of the neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt of DTPMP.

8. The method according to any one of claims 1 to 7, characterized in that as the substance to be coated sugar, in particular monosaccharides, disaccharides,

Trisaccharides, tetra-, penta- and / or hexasaccharides, preferably sucrose, particularly preferably isomalt ^®, are used.

9. The method according to any one of claims 1 to 8, characterized in that urea is used as the substance to be coated.

10. The method according to any one of claims 1 to 9, characterized in that several melts to be coated substances are simultaneously dripped into the coating agent.

11. The method according to any one of claims 1 to 10, characterized in that the separation of the coated solidified melt from the melt of the coating agent by straining the coated particles from the melt of the coating material, preferably continuously, particularly preferably over perforated conveyor belts from the melt pool beyond a drip line.

12. The method according to any one of claims 1 to 11, characterized in that the thickness of the covering is 0.1 to 2500 microns, preferably 5 to 500 microns and in particular 10 to 200 microns.

13. The method according to any one of claims 1 to 12, characterized in that the solidified coated substance has particle sizes of 0.5 -50 mm, preferably from 1 to 10 mm and in particular from 1.5 to 5 mm.

14. washing or cleaning agent containing at least one end product of a process according to one of claims 1 to 13.