JP2005534728A - Automatic dishwashing detergent with improved anti-glass corrosion - Google Patents

Abstract

The present invention relates to an automatic dishwashing detergent or an automatic dishwashing aid. The agent comprises at least one zinc salt and at least one general formula (I) a A ₂ O · b BO · c C ₂ O ₃ · d D ₂ O ₅ · x SiO ₂ · f H ₂ O (I) Wherein A is an alkali metal and / or hydrogen, B is an alkaline earth metal and / or subgroup element, preferably an element from the group consisting of zinc, iron and manganese, C is an element of the periodic table The third main group element and / or subgroup element, preferably iron, and D are the fifth main group element and / or subgroup element of the periodic table of elements, and the following applies:
0 ≦ a ≦ 1; 0 ≦ b ≦ 0.5; 0 ≦ c / x ≦ 0.05; 0 ≦ d / x ≦ 0.25; 1.9 ≦ x ≦ 22; 0 ≦ f ≦ 40]
A crystalline sheet-like silicate represented by: The agent is characterized by significantly improved anti-glass corrosion properties.

Description

  The present invention belongs to the field of dishwasher detergents. In particular, the present invention relates to a dishwasher detergent comprising a zinc salt and a specific silicate.

With the continued automation of a wide variety of cleaning and cleaning processes in the home and industry, the importance of mechanical cleaning and cleaning compositions for fabrics and tableware has increased in the past decades.
So-called low alkaline detergents required for mechanical dishwashing often contain, as an alkaline carrier, a mixture of sodium disilicate and soda, a builder such as citric acid, for example in combination with a polycarboxylate, and is suitable Contains a low foaming nonionic surfactant. In addition, bleaching agents, bleach activators, silver and corrosion protection agents, and enzymes to improve detergency may be present. In a typical dishwasher cycle, the dishes placed in the basket are cleaned as a result of strong contact with an aqueous detergent solution at a pH of about 65 ° C. and a pH between 9 and 11, and then rinsed clean.
An important measure for evaluating dishwasher detergents and their detergency is the visual appearance of the dried dishes after washing. Any calcium carbonate deposit that occurs in the tableware or inside the machine has a causative influence on the economic success of such detergents, for example, as it can adversely affect customer satisfaction. A further long-standing problem with mechanical dishwashing is the corrosion of glassware. It can usually show itself in the appearance of cloudiness, streaking or scuffing, or iridescent glitter on the glass surface. This observed result shows that alkali metal ions and alkaline earth metal ions combined with hydrolysis of the silicate network escape from the glass and secondary deposition of silicate compounds on the glass surface. Essentially based on these two processes. In order to avoid such corrosion processes, the prior art gives a series of proposals regarding the use of zinc salts, for example.

  According to the teachings of US Pat. No. 3,677,820 (Whirlpool Corporation), a piece of zinc installed inside a dishwasher prevents corrosion of the glass surface during the cleaning operation.

  Finally, European patent application EP 0 383 482 (Procter & Gamble Company) describes a dishwasher detergent comprising an insoluble zinc salt, characterized by improved glass corrosion protection. In order to achieve such an effect, the insoluble zinc salt needs to have a particle size of less than 1.7 millimeters.

  However, the use of silicates to prevent glass corrosion during mechanical dishwashing has also been described.

  For example, international patent application WO 96/12783 (Henkel KGaA) does not contain phosphates with improved decorative and glass protection based on citrate-containing formulations containing crystalline layered silicates. Disclosed are dishwasher detergents, which contain a small amount of phosphate.

International patent application WO 99/57237 (Clariant GmbH, Henkel KGaA) has, as an essential component, a general formula NaMSi _x O _{2x + 1} · yH ₂ O [wherein M is sodium or hydrogen, x is 1.9-22. The numerical value and y are numerical values of 0 to 33), including a powdery or granular additive having a crystalline layered silicate and a polycarboxylic acid (co) polymer, and a glass protective effect and decoration Disclosed is a phosphate-containing dishwasher detergent that has a protective effect and also has excellent cleaning power.

  Accordingly, an object of the present invention is to provide a dishwasher detergent that does not corrosively change the surface of a glass product even during repeated use, and in particular, does not cause fogging, dirt or scratches on the glass surface, or iridescent glitter. Is to provide. This goal does not limit them in terms of formulation, but preferably any dosage form suitable as a composition for a dishwasher detergent, such as a powder formulation, a tablet formulation or a liquid formulation, a detergent It was to provide additives for dishwasher detergents as a constituent of mousse or donor products.

  It has been found that the above object is achieved by a dishwasher detergent or dishwasher detergent aid comprising at least one zinc salt as well as at least one crystalline sheet-like silicate. Accordingly, the present application provides at least one zinc salt and at least one general formula (I)

[Wherein A is an alkali metal and / or hydrogen,
B is an alkaline earth metal and / or subgroup element, preferably an element from the group consisting of zinc, iron and manganese,
C is the third main group element and / or subgroup element of the periodic table, preferably iron, and
D is a fifth main group element and / or subgroup element of the periodic table,
The following also applies:
0 ≦ a ≦ 1; 0 ≦ b ≦ 0.5; 0 ≦ c / x ≦ 0.05; 0 ≦ d / x ≦ 0.25; 1.9 ≦ x ≦ 22; 0 ≦ f ≦ 40]
A dishwasher detergent or a dishwasher detergent aid comprising a crystalline sheet-like silicate of formula

  In a preferred embodiment of the invention, the dishwasher detergent or dishwasher detergent aid comprises at least one zinc salt and at least one general formula (I)

[Wherein A is an alkali metal and / or hydrogen,
B is an alkaline earth metal and / or zinc,
C is the third main group element of the periodic table, and
D is the fifth main group element of the periodic table,
The following also applies:
0 ≦ a ≦ 1; 0 ≦ b ≦ 0.5; 0 ≦ c / x ≦ 0.05; 0 ≦ d / x ≦ 0.25; 1.9 ≦ x ≦ 22; 0 ≦ f ≦ 40]
A crystalline sheet-like silicate represented by:

  Finally, at least one zinc salt and at least one general formula (I)

[Wherein A is an alkali metal and / or hydrogen,
B is an alkaline earth metal,
C is the third main group element of the periodic table, and
D is the fifth main group element of the periodic table,
The following also applies:
0 ≦ a ≦ 1; 0 ≦ b ≦ 0.5; 0 ≦ c / x ≦ 0.05; 0 ≦ d / x ≦ 0.25; 1.9 ≦ x ≦ 22; 0 ≦ f ≦ 40]
Dishwasher detergents or dishwasher detergent aids comprising a crystalline sheet-like silicate of the formula are particularly suitable.

  In particularly preferred compositions of the invention, the crystalline sheet-like silicate is based on its weight up to 10 mol% of boron, preferably between 0.01 mol% and 10 mol%, preferably 0.01 mol%. % And 8 mol%, especially between 0.01 mol% and 5 mol%.

  In a further preferred embodiment of the composition according to the invention, the crystalline sheet-like silicate is up to 50 mol% of phosphorus, preferably between 0.01 mol% and 50 mol%, preferably 0.01 mol%. Between 40 mol%, especially between 0.01 mol% and 20 mol%.

  In a further preferred embodiment of the composition according to the invention, the following applies for general formula (I): a = 1 and b = c = d = 0; A is sodium or sodium or hydrogen. Accordingly, preferred subject matter of the present application is at least one zinc salt and at least one general formula (Ia)

[Wherein M is sodium or hydrogen,
x is a number from 1.9 to 22, preferably 1.9 to 4, and
y is a number from 0 to 33)
A dishwasher detergent or a dishwasher detergent aid comprising a crystalline sheet-like silicate represented by

  Regarding the corrosion inhibitory effect of the composition of the present invention, a zinc salt and a crystalline sheet-like silicate represented by the general formula (I) or the general formula (Ia) are contained in these compositions at a ratio of 10: 1 to 1. It has been found to be particularly advantageous when present in a ratio of: 50, preferably 5: 1 to 1:30, in particular 3: 1 to 1:10.

The crystalline sheet-like silicate represented by the formula (Ia) is, for example, Na-SKS, such as Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ · xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ xH ₂ O, macatite ) And Clariant GmbH (Germany).

Particularly suitable compositions for the purposes of the present invention are those comprising a crystalline sheet-like silicate of formula (Ia) wherein x is 2. Among them, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , Natrosilite), Na-SKS-9 (NaHSi ₂ O ₅・ H _{2 O), Na-SKS-} 10 (NaHSi 2 O 5 · 3H 2 O, kanemite), Na-SKS-11 ( t-Na 2 Si 2 O 5) and Na-SKS-13 is (NaHSi ₂ O ₅₎ Particularly suitable, in particular Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). An overview of crystalline sheet-like silicates is given, for example, in a paper published in Seifen-Oele-Fette-Wachse, Vol. 116, No. 20/1990, pages 805-808.

  Within the scope of the present application, suitable dishwasher detergents or dishwasher detergent auxiliaries are in each case 0.1-20% by weight, preferably based on the total weight of these compositions It has a weight fraction of crystalline sheet-like silicate of general formula (I) or general formula (Ia) of 0.2 to 15% by weight and in particular 0.4 to 10% by weight.

  In addition to the identified crystalline sheet-like silicate, the composition of the present invention comprises a zinc salt (preferably both inorganic and organic salts are used). A non-exhaustive list of some suitable zinc salts is shown in the table below.

  In addition to insoluble inorganic zinc salts, ie salts having a solubility of less than 100 mg / l (20 ° C), preferably less than 10 mg / l (20 ° C), in particular insoluble (20 ° C) (eg zinc oxide) Within the scope of the present application, soluble inorganic zinc salts, i.e. greater than 100 mg / l, preferably greater than 500 mg / l, particularly preferably greater than 1 g / l, in particular 5 g / l Salts having a water solubility greater than are suitable components of the compositions of the present invention. Suitable soluble inorganic salts include zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. Thus, the application is more preferably selected from the group of inorganic zinc salts, preferably the group of soluble inorganic zinc salts, in particular the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. A dishwasher detergent or dishwasher detergent aid comprising at least one zinc salt.

  The spectrum of a preferred organic acid zinc salt according to the invention (preferably a zinc salt of an organic carboxylic acid) is a salt that is insoluble in water, ie less than 100 mg / l, preferably less than 10 mg / l And in particular from salts with insoluble solubility for water above 100 mg / l, preferably above 500 mg / l, particularly preferably above 1 g / l and especially above 5 g / l Covers a range of salts with solubility (all at a water temperature of 20 ° C.). The first group of zinc salts includes, for example, zinc citrate, zinc laurate, zinc oleate, zinc oxalate, zinc tartrate and zinc stearate, and the group of soluble organic zinc salts includes, for example, Zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate and zinc gluconate, zinc valerate and the zinc salt of p-toluenesulfonic acid.

  Thus, in a further preferred embodiment, the dishwasher detergent or dishwasher detergent aid of the present invention comprises an organic zinc salt group, preferably a soluble organic zinc salt group, particularly preferably an organic acid. A group of soluble zinc salts of monomers or organic acid polymers, in particular zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietic acid, zinc valerate and p- At least one zinc salt selected from the group consisting of zinc toluenesulfonate.

  Of course, preferred compositions of the present invention include a mixture of organic and inorganic zinc salts, particularly a mixture of soluble and insoluble inorganic zinc salts, or a mixture of soluble and soluble inorganic zinc salts, or insoluble. A mixture of an organic zinc salt and an insoluble inorganic zinc salt or a mixture of an insoluble organic zinc salt and a soluble inorganic zinc salt can also be included.

  Within the scope of this application, the weight of zinc salt, preferably based on the total weight of the composition, is independent of which zinc salt is used and is therefore particularly organic or inorganic zinc salt, soluble Regardless of whether zinc salts or insoluble zinc salts, or mixtures thereof are used, dishwasher detergents that are 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0.4 to 4% by weight or Examples include detergents for dishwashers.

  The compositions of the present invention are not subject to any restrictions with regard to their formulation and dosage form. Accordingly, dishwasher detergents or dishwasher detergent aids within the scope of the present invention may be provided in either solid or liquid form.

  Depending on the field of use of the process of the invention, it is necessary to release different or identical active substances and / or active substance preparations present in the composition of the invention in a time-controlled manner Or may be desired. This time-controlled release can occur on a variety of mechanisms, in other words, different “switch” principles. Based on the zinc salt and sheet-like silicate present in the composition of the invention, this means that these active substances are preferably released together, but one or more further active substances and / or activities To be released with a time lag against substance preparations, e.g. builder substances (builders, co-builders), surfactants, bleaches, bleach activators, enzymes, dyes, perfumes, corrosion protectants or polymers, etc. means. Here, the zinc salts and / or sheet-like silicates can be released into the aqueous liquid either before or after these active substances are released.

“Switches” that can affect the release behavior of an active substance or active substance preparation are, for example,
-The aggregate state and formulation form of the composition; the liquid composition often dissolves more quickly than the solid composition; the solid composition with a large surface area (eg powder, granule) has a solid composition with a relatively small surface area Dissolves faster than food (eg, tablets);
-Mechanical stability that may be a determinant of decay (depending on time, temperature or other parameters);
The realization of a specific temperature value in the course of the temperature, ie the temperature profile of the washing, cleaning or rinsing operation; the control via temperature is notably due to the temperature increasing with all stages of the rinsing operation In the case of washing machine detergents, it represents a reliable and therefore preferred embodiment;
-The pH, i.e. the establishment of a specific pH by the components of the cleaning active preparation, cleaning active preparation or rinsing active preparation, or components that determine or influence the pH during the course of the cleaning, cleaning or rinsing operation Disappearance of a specific pH following the decay of
-Ionic strength;
-The presence of enzymes-preferably the use of water-soluble packaging materials and their permeability to certain (mainly gas or liquid) components;
Etc.

  The above parameters are exemplary only and are not intended to limit the invention.

  For example, when preparing the composition of the invention in various formulations / aggregates as a combination product from two or more substances or substance mixtures, the composition of the invention comprising a zinc salt and a sheet-like silicate comprises: Preferably it is present in only one of these compositions. The various formulations / aggregates in this application are, for example, liquids, powders, granules, compacts, extrudates, moldings, gels, dispersions. Various such compositions may be formulated, for example, using packages having one, two, three, four or more receiving chambers, which are common, preferably water-soluble. A combination product can be obtained. The manufacturing method of such a package is well-known to those skilled in the art. Examples of such a method include a deep drawing method, an extrusion method, and a molding method. In the following, with reference to single chamber packages and twin chamber packages, many combinations of separately formulated compositions suitable for the present invention will be described:

  Water-soluble or water-dispersible packaging with one receiving chamber:

  Water-soluble or water-dispersible packaging with two receiving chambers:

  For the production of water-soluble and / or water-dispersible films, in principle all substances or substance mixtures that can be formulated in the form of films are suitable. However, it is particularly preferred that the water-soluble and / or water-dispersible film is (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and / or these. (This list should be considered illustrative and not limiting of the invention).

  In further similarly preferred embodiments, if the film comprises one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers, and mixtures thereof, It is advantageous for the invention.

  One or more particularly advantageous materials may be identified from the following examples (non-limiting list):

A mixture of polyvinyl alcohol or poly (vinyl alcohol-co-vinyl acetate) having a molecular weight in the range of 10000 to 200,000 g / mol and an acetate content of 0 to 30 mol%; Sorbitol, water, PEG, etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called slip agents (eg “Aerosil”), organic and inorganic pigment salts, blow molding agents (citric acid / citric acid / Processing additives such as sodium bicarbonate mixture);
An acrylic acid-containing polymer (for example, a copolymer, terpolymer or tetrapolymer) having at least 20% acrylic acid and a molecular weight of 5000 to 500,000 g / mol; particularly preferred as a comonomer is an acrylate ester (ethyl acrylate) , Methyl acrylate, hydroxyethyl acrylate, ethyl hexyl acrylate, butyl acrylate, and the like, and salts of acrylic acid (such as sodium acrylate), methacrylic acid and its salts and esters thereof (methyl methacrylate, ethyl methacrylate, And trimethylammonium methyl methacrylate chloride (TMAEMC) and methacrylate amidopropyltrimethylammonium chloride (MAPTAC)). Further monomers (acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone, etc.) can likewise be used advantageously;
Polyethylene oxide, preferably polyethylene oxide having a molecular weight of 600 to 100,000 g / mol, and vinyl acetate, acrylic acid and its salts and esters thereof, methacrylic acid and its salts and esters thereof, acrylamide, styrene, styrene sulfonate and Derivatives thereof modified by graft copolymerization using monomers such as vinylpyrrolidone (eg: polyethylene glycol-graft-vinyl acetate). The polyglycol fraction should be 5-100% by weight and the grafted fraction should be 0-95% by weight; the latter can consist of one or more monomers. Particular preference is given to graft fractions of 5 to 70% by weight; here the solubility in water decreases with the graft fraction;
-Polyvinylpyrrolidone (PVP) having a molecular weight of 2500-750,000 g / mol;
-Polyacrylamide having a molecular weight of 5000-5000000 g / mol;
-Polyethyloxazoline and polymethyloxazoline having a molecular weight of 5000 to 100,000 g / mol;
-Polystyrene sulfonate and salts of ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and (meth) acrylic acid ( Example, sodium (meth) acrylate), copolymers of polystyrene sulfonates with comonomers such as acrylamide, styrene, vinyl acetate, maleic anhydride, vinylpyrrolidone; comonomer content should be 0-80 mol%, molecular weight is Should be in the range of 5000 to 500000 g / mol;
-Polyurethanes, in particular diisocyanates (eg TMXDI) and polyalkylene glycols (especially polyethylene glycols with a molecular weight of 200-35000) or other bifunctional alcohols which give products with a molecular weight of 2000-1000 g / mol; Reaction products of
-Dicarboxylic acids (e.g. terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid etc.) and diols (e.g. polyethylene glycol, e.g. 200-35000) a polyester having a molecular weight of 4000 to 100,000 g / mol, based on those having a molecular weight of g / mol);
-Cellulose ether / ester (eg, cellulose acetate, cellulose butyrate, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, methylhydroxypropylcellulose, etc.);
-Polyvinyl methyl ether having a molecular weight of 5000-50000 g / mol.

  Also, embodiments of the water-soluble film that are particularly suitable for the present invention provide that the active substance and / or active substance preparation present in the receiving recess is particularly advantageously (although not necessarily) cleaned, cleaned, and cleaned. At certain points during the operation or rinsing operation, for example, upon reaching a specific temperature, or upon reaching a specific pH or specific ionic strength of the cleaning solution, or due to other controllable events or conditions, Consider the fact that it can be fed into an aqueous liquid through solubility in water (preferably controllable).

  The quality of the material and its quantity / thickness also directly affect these dissolution characteristics. Thus, within the scope of the present invention, it is particularly preferred that the water-soluble film has a thickness between 1 μm and 1000 μm, preferably between 5 μm and 500 μm and in particular between 10 μm and 200 μm. The process is characterized by this. The various film thicknesses intended to delay the release of the active substance and / or active substance preparation can be, for example and advantageously, one or more receiving chambers using one or more identical or different water-soluble films. Can be realized through multiple seals. Thus, the thickness of the water-soluble film for the purposes of the present invention is given as the sum of the thicknesses of the water-soluble individual films of the multilayer structure that seal the receiving recess.

  Particularly preferably for water-soluble films that dissolve in an aqueous liquid (based on a specific thickness that mutually determines stability) at a specific temperature, pH value, ionic strength or after a specific residence time. Materials. In this regard, such a melting operation will dissolve the entire film or when portions of the film are established when a particular parameter combination is established, while other portions still do not dissolve (if at all) ( However, it can be grasped only as a film portion, meaning that it only dissolves thereafter. The latter can be achieved by changing the quality of the material and by changing the amount (thickness) of the material or the geometry of the water-insoluble container. For example, the external shape of the water-insoluble container can prevent water from entering and delay the dissolution operation. In another preferred embodiment, films of various thicknesses (although made from the same material) can be formed to allow faster dissolution in thin areas. When such various thicknesses of water-soluble films are used to cover different receiving recesses, the active substances located in these receiving recesses are released at different times. In further similarly preferred embodiments, the films can be made from materials of varying solubility in water, such as polyvinyl alcohol (PVAL) having varying residual acetate contents.

  In a particularly preferred embodiment, in addition to the specified components, the water-soluble and / or water-dispersible film may also contain one or more cleaning or cleaning active substances or these substances (eg films) Material and polyvinyl alcohol as a builder). In the first-mentioned case, since it is present in the preparation only in small amounts, its homogeneous mixing does not matter. The cleaning active ingredient, the cleaning active ingredient and the rinsing active ingredient are, for example, films or parts of films, eg active The ingredients can be accurately dissolved in the required washing, cleaning, and rinsing cycle stages so that the active ingredient can be incorporated into the liquid as a film lysate at a precise time. One example of this is not only the perfume desired in the final aspect of the washing or cleaning operation or rinsing operation, but also optical brighteners, UV protection agents, dyes and other cleaning active preparations, cleaning active preparations or rinses. It can also be an active preparation.

Further equally preferred embodiments of the compositions of the present invention within the scope of this application are one or more activities present in these compositions through the incorporation of matrix or coating materials of varying solubility or melting temperature. Time-controlled release of the substance and / or active substance preparation.
According to the above, the difference in the release rate of the active substance and / or active substance mixture can be achieved through the use of matrix materials or coatings having different melting temperatures. Particular preference is given here to using fusible or softening substances as matrix material or coating material for the active substance or active substance preparation. (Within the scope of the present invention, the term “coating” includes a complete coating, i.e. this particulate form, in addition to the coating of individual or multiple sides or surfaces of an object (such as a solid particulate composition, etc.). Encapsulation of the object is also included Sealing the receiving recess with a meltable material by pouring such a meltable material onto a particulate or gel-like active material / active material preparation is also referred to as a coating. "Active substance" or "active substance preparation" includes both the zinc salt / sheet-like silicate characterizing the composition of the invention and any other ingredients that may be present). The meltable material suitable for the present invention has a melting point exceeding 30 ° C. If the active agent preparation is released at different times (eg, during different wash cycles of the cleaning process), this can occur, for example, through the use of different meltable matrices or coatings. If two or more different meltable matrices are used, their melting points are preferably the difference in melting point that satisfies the temperature process of this cleaning process, ensuring separate dissolution of the individual matrix or coating. Is adapted to. In this connection, it is preferred that such materials for different matrices and / or coatings differ in at least 5 ° C., preferably 10 ° C., particularly preferably 15 ° C., in particular at least 20 ° C., with respect to their melting points. Can be mentioned. It is also preferred that at least one melting point of the fusible material forming the matrix or coating is less than 30 ° C., while at least one melting point of the other material forming the further matrix or coating is above 30 ° C. .

  If the use of a softening substance is intended as a matrix for the active substance or active substance preparation, this compounding material, which can soften under the influence of temperature, mixes this fusible or softening substance with the desired further ingredients, It can be formulated by heating the mixture to temperatures in the range where the material softens and then molding it at these temperatures. Such a coating can be effected, for example, by dipping, spraying, or circulating in a drum coater or coating pan when the softening material is used as follows. Particular preference is given to using waxes, paraffins, polyalkylene glycols, etc. as meltable or softening substances for the matrix or coating.

  It is advantageous if the fusible or softening material does not have a well-defined melting point as is customary for pure crystalline materials, but has a melting range that can include several degrees Celsius It was proved. The meltable or softening material preferably has a melting range that is between about 35 ° C and about 75 ° C. In this case, this means that the melting range appears within a predetermined 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 from about 2 ° C to about 3 ° C.

  The above properties are generally also satisfied by so-called waxes, with the exception of paraffin and polyethylene glycol. A more accurate description of these substance groups is given herein below. Reference is made to these descriptions at this point to avoid repetition.

  Further preferred options for time-delayed release of active substances or active substance preparations are for the purpose of time-lag release, preferably in the receiving chamber of water-soluble packaging or in moldings or press bodies (onion model) This is a zigzag spatial arrangement of these materials. Such a spatially zigzag arrangement is, for example, a layer-like or phase-like arrangement of active substances or active substance preparations. For this purpose, for example, lamellar tableting or lamellar molding of liquid active substances or active substance mixtures and their subsequent curing by solidification and / or crystallization are suitable. In the case of compacts or shaped bodies, the ingress of solvent can only take place through their surfaces, so this layer-like arrangement is based on those active substances or active substance mixtures located on the surface of such multiphase mixtures. Leading the release of. As a result, the phases erode in a time-shifted manner and the components are released in a time-shifted manner.

  The above method for time-controlled release of active substances and / or active substance mixtures is of course not intended per se, but serves for targeted control of the cleaning process. For example, mechanical dishwashing programs typically include various washing cycles, and the type and number of these washing cycles can be determined by the consumer through program selection. Examples of such cleaning cycles are pre-cleaning cycles, intermediate cleaning cycles and main cleaning cycles or rinsing cycles. For optimal results, all these various washing cycles require the intended administration of the corresponding active substance or active substance mixture. In particular, in order to optimize the combination of zinc salt and sheet-like silicate active ingredient used in the present invention, controlled premature control of zinc salt and / or sheet-like silicate and / or further active substances. Depending on the nature of the further active substance used, this or delayed release may be required here.

  The solid dosage form of the dishwasher detergent or dishwasher detergent aid of the present invention can be compacted, for example, from fine to coarse granular powder, roll compaction, for example obtained by spray drying or granulation It is not only a substance mixture, but also a solidified melt or molding obtained by extrusion or tableting. Within the scope of the present invention, such moldings are, for example, slab shapes, rod or bar configurations, cubes, cuboids and corresponding spatial elements having equal sides, and in particular cylindrical shapes having a circular or oval cross section. It has virtually all configurations that can be handled normally, such as configurations. This last configuration includes a configuration that presents an actual tablet or compact cylindrical cross section having a height to diameter ratio of greater than one. Suitable tableting or extrusion compositions within the scope of the present invention may differ, for example, due to their composition, their fraction of the total volume of the molding and / or their visual appearance. It has the following phase.

  Such multiphase molding phases can be further characterized by different dissolution behavior in the aqueous phase. Such molding is suitable, for example, for time-controlled release (controlled release) of specific components during a specific wash cycle of a dishwasher program. In a preferred embodiment, one of the molding phases has as a main component a fusible or softening material from the group of waxes, paraffins and / or polyalkylene glycols. Furthermore, it has proven advantageous if the moldings or molding components comprising these fusible or softening substances are at least predominantly insoluble in water. The solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C., and should preferably be less than 5 mg / l. However, in such cases, the fusible or softening material is least likely to be water (including elevated temperature water) in order to avoid as much as possible the temperature-dependent release of the active substance. Should have a certain solubility. Release of the active substance occurs in this way when the melting point or softening point is reached. A further suitable means for obtaining controlled release of the components from the multiphase tablet (especially the combination of zinc salt and sheet-like silicate of the present invention) is the compaction of two or more individual phases with different pressures. is there. As known, the disintegration and dissolution properties of the tablet or tablet phase depend inter alia on the compaction pressure directed to the tablet phase during tableting, so simply through the use of different compaction pressures, It is possible to produce a tablet phase with dissolution properties. In this regard, it may be suitable for the present invention that the inventive combination of zinc salt and sheet-like silicate are located together in a phase subjected to a relatively high tableting pressure and therefore disintegrate more slowly. . However, depending on the composition of the cleaning composition, it is also advantageous to formulate the zinc salt and the sheet-like silicate together in a tableted tablet phase using a relatively low pressure. Finally, it is also suitable to formulate the zinc salt and the sheet-like silicate in different tablet phases. Here, the zinc salt is present in a relatively strong and compacted tablet phase in one advantageous embodiment, whereas in another preferred embodiment it is located in a relatively weak and compacted tablet phase. The

  Within the scope of this application, dishwasher detergent auxiliaries are the terms used for agents that are further added to standard commercial detergents, for example in the form of special glass protection agents. Such metering can be done before the start of each wash program or in the form of a depot product that results in a continuous release of the composition of the invention.

  Preferred solid compositions of the present invention are in the form of dosage units sufficient for one wash cycle. An example of such a prescription form is a dishwashing aid tablet.

  If the compositions of the present invention are in solid particulate form, but not in divided dosage units, the problem arises for these compositions that the individual components separate. In particular, it is necessary to avoid the separation of zinc salts and silicates present in the composition of the invention. Examples of such particulate dosage forms are powders or granules. In a preferred embodiment of the present invention, the zinc salt and / or crystalline sheet-like silicate present in the dishwasher detergent or dishwasher detergent aid is one or more additional active substances and / or builders. Formulated in particulate form with the substance and present as a blend.

  Since zinc salts and crystalline sheet-like silicates constitute only a small weight fraction of suitable dishwasher detergents, their formulation based on “dilution effect” is suitable for the dishwasher detergents of the present invention. Simplifies the metering of these salts in production. However, even if the composition of the present invention in the form of a special product for glass corrosion protection is only added by consumers to standard commercial detergents, administration is facilitated as a result of the formulation. Formulation advantages arise completely independently from whether the dishwasher detergent to which the corresponding formulation is added is in the form of a solid, liquid or gel.

  Suitable solid dosage forms of the dishwasher detergent according to the invention include, for example, fine to coarse granular powders such as obtained by spray drying or granulation. This type of powder can be marketed commercially or used as a premix for compaction (eg, tableting) and generally has a particle size in the range of 0.1-10 mm. In order to prevent the powder from separating from the added silicate and / or zinc salt formulation, it is preferred that these formulations have a particle size comparable to that of the powder.

Thus, the present application preferably provides a particle size of zinc salt and / or crystalline sheet-like silicate formulated with one or more active and / or builder materials to avoid separation processes such that the particle size is 0.1 mm. Between 10 and 10 mm, preferably between 0.2 and 8 mm and especially between 0.5 and 5 mm, preferably between 0.1 and 2.0 g / cm ³ , preferably between 0.2 and 1.6 g / cm ³ And in particular a dishwasher detergent, characterized by a particulate formulation further having a density of 0.4 to 1.2 g / cm ³ .

  Preferred dishwasher detergents according to the present invention comprise in particular in each case particles of zinc salt and / or crystalline sheet-like silicate formulated with one or more active substances and / or builder substances. 0.1 to 80% by weight, particularly preferably 0.2 to 70% by weight and particularly preferably 0.5 to 60% by weight of zinc salt or crystalline sheet-like silicate, based on the total weight of It is characterized by.

  Said particulate formulation is preferably according to the invention by spray drying and / or granulation and / or extrusion and / or roll compaction and / or tableting and / or solidification and / or crystallization, However, it is obtained in particular by spray drying and / or granulation.

  During spray drying, in the first step of the process, the aqueous slurry may contain, in addition to the zinc salt of the present invention, additional heat stable active and / or filter materials that do not volatilize or decompose under spray drying conditions. The slurry is then transported to the spray tower using a pump and sprayed through a nozzle located at the top of the tower. The slurry is dried with the rising warm air, and the attached water is evaporated. This means that the detergent component is obtained as a fine powder at the tower outlet. Additional temperature labile components such as bleach or fragrance can be added to these as required.

  Besides the spray drying, the formulation of the composition according to the invention can be carried out by a granulation process, particularly preferably by a fluidized bed process. Here, in addition to the zinc salt of the invention, the particulate floor material, which may contain further active substances and / or builder substances, lies on a horizontal perforated base through which gas (eg hot air) passes from below. . Under certain flow conditions, a state similar to that of the boiling liquid is established; the layer bounces bubbles, and the particles of floor material are located around the layer, swirling around in a constant manner, and therefore It stays in a specific range in a floating form. The large surface area of the swirl material is then in solid form at room temperature, for example, as well as additional substances such as solvents, solutions of active substances and / or builder substances, liquid active substances, but by increasing the temperature And / or reaction with further components that at least the surface softens and / or becomes sticky and adhesive under the influence of temperature by adding a very limited amount of liquid additive Enable. Typical examples of such substances are water and aqueous solutions, for example, aqueous solutions of the zinc salts of the present invention, surfactant compounds that are liquid or solid at room temperature (especially nonionic surfactants), or synthetic origins and / or It is also possible to use naturally occurring polymer compounds (eg carboxylate (co) polymers).

  A suitable procedure for further granulation is the use of a mixer / compactor as provided by Loedige as well as other suppliers for this purpose. As a result of changing different process parameters (such as the rotational speed of the mixer, the residence time of the individual components, the metering time of the individual components during the mixing operation, the geometry of the mixing elements used or the energy input, etc.) It is suitable for producing particles formulated according to the present invention in a particular manner, as it offers the consumer the possibility of targeted control over the product properties of the granules obtained. The particle size and / or density of the granules can thus be influenced in the intended manner. Accordingly, the formulation of the inventive zinc salt and one or more further active and / or builder substances in the mixer / compactor is particularly suitable within the scope of the present invention.

  Finally, there is the possibility of mixing the inventive zinc salts and / or silicates described above with further individual components (in terms of their bulk density only slightly different from the bulk density of the salts). Such mixtures have the same tendency to separate components on storage, transport and processing, and thus similarly the desired safe and silicate and / or zinc salts of the present invention in a particular manner. Suitable for reliable weighing. Thus, preferably within the scope of the invention, the bulk density of the individual components mixed together is a maximum of 200 g / l, preferably a maximum of 150 g / l, preferably a maximum of 100 g / l and Mention may be made in particular of mixtures of silicates and / or zinc salts with further active substances and / or builder substances, characterized by a maximum of 50 g / l.

  Builders and / or actives used in the above-described formulations of suitable dishwasher detergents of the present invention include, for example, builders (including co-builders), surfactants, in addition to other customary components of detergents Agents, bleaches, bleach activators, enzymes, dyes, fragrances, corrosion protectants or polymers.

  All the substances are generally suitable as active substances and / or builder substances for the zinc salt formulations of the invention, but particularly preferably within the scope of the invention one or more active substances and / or builder substances A zinc salt formulation formulated with an active and / or builder substance from the group of phosphates, carbonates, bicarbonates, sulfates, silicates, citrates, citric acid and acetates, Dishwashing, preferably in any case in an amount of 20 to 99% by weight, particularly preferably 30 to 98% by weight and particularly preferably 40 to 95% by weight, based on the total weight of the particles Machine detergent or dishwasher detergent aid.

  Further particularly preferred active substances and / or builder substances for the preparation of zinc salts within the scope of the invention are surfactants (preferably nonionic surfactants) and / or carboxylate polymers (especially Polysulfocarboxylate).

  For further description of particularly suitable surfactants or carboxylate polymers and polysulfocarboxylates, reference may be made again to the following description to avoid repetition.

  The silicates present in the dishwasher detergent or dishwasher detergent aid of the present invention are also present in these compositions, preferably formulated with other active or builder substances. . Here, in particular active substances or builder substances from the group of organic mono- or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids are used.

  Accordingly, the present application more preferably provides that the crystalline sheet-like silicate of general formula (I) or general formula (Ia) is one or more additional active and / or builder substances, preferably Dishwashing characterized by being formulated in particulate form with one or more additional active and / or builder substances from the group of organic mono- or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids and present as a formulation Provide detergents for machine cleaners or dishwashers.

  Zinc salts and / or crystalline sheet-like silicates formulated with one or more active and / or builder substances and present in the form of particles can be protected against environmental influences and therefore their storage stability Coatings may be provided to improve properties or affect dissolution behavior. Coating materials and processes for coating particulate compositions are widely described in the literature. Only the particularly preferred embodiments are described below.

  Particular preference is given to using a fusible or softening substance as the coating material. (Within the scope of the present invention, the term “coating” refers to a complete coating, ie a particulate object, as well as a coating of individual or more than one side or surface of a particulate composition formulated according to the present invention. The meltable material suitable for the present invention has a melting point of about 30 ° C. If the formulated zinc salt and / or crystalline sheet-like silicate is released at different times, e.g. during different cleaning cycles of the cleaning process, this may be different, e.g. Can happen through the use of. The melting points of these substances are preferably adapted to the temperature difference of the cleaning process, the melting point difference satisfying ensuring independent dissolution of the individual matrix or coating. If it is intended to release zinc salts and crystalline sheet-like silicates at different times, it is preferably at least 5 ° C., preferably 10 ° C., particularly preferably 15 ° C. and in particular with respect to their melting points. And different coating materials with a difference of at least 20 ° C. It is also preferred that the melting point of at least one fusible substance forming the coating is less than 30 ° C., while the melting point of at least one other substance forming the further matrix or coating exceeds 30 ° C.

  Such a coating can be applied, for example, by dipping, spraying or circulating in a drum coater or coating pan. With regard to the coating, it is particularly preferable to use wax, paraffin, polyalkylene glycol and the like as the melting or softening substance.

  A meltable or softening material does not exhibit a well-defined melting point, as it normally appears in pure crystalline materials, but instead has a melting range that includes several degrees Celsius under certain circumstances In some cases proved to be advantageous. The meltable or softening material preferably has a melting range that is between about 45 ° C and about 75 ° C. In this case, this means that the melting range appears within a predetermined temperature interval and does not define the width of the melting range. The width of the melting range is preferably at least 1 ° C, preferably from about 2 ° C to about 3 ° C.

  The above characteristics are usually satisfied by so-called wax. A “wax” generally is a series of natural or artificially melts that do not decompose at temperatures above 40 ° C., have a relatively low viscosity, and do not exhibit spinnability just above the melting point. It is understood as meaning the substance obtained. They have a high temperature dependent consistency and solubility.

  Depending on their origin, waxes are divided into three groups: natural waxes, chemically modified waxes and synthetic waxes.

  Natural waxes include, for example, plant waxes (eg, candelilla wax, carnauba wax, beeswax, esparto wax, cork wax, Guaruma wax, rice germ oil wax, sugar cane wax, cucumber wax, or montan wax ), Animal waxes (eg beeswax, shellac wax, whale wax, lanolin (wool wax), or caudal grease), mineral waxes (eg ceresin or ozokerite (geowax)), or petrochemical waxes (eg petrolatum, paraffin) Wax or microcrystalline wax).

  Examples of the chemically modified wax include hard wax (for example, montan ester wax, Sassol wax, or hydrogenated jojoba wax).

  Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Also, the fusible or softening materials that can be used in compounded materials that are curable by cooling are compounds from other classes of materials that satisfy the requirements with respect to the softening point. Synthetic compounds that have proven suitable are, for example, higher esters of phthalic acid (particularly dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG)). Also suitable are waxes prepared synthetically from lower carboxylic acids and fatty alcohols (eg dimyristyl tartrate, which is marketed under the name Cosmacol® ETLP (Condea)). Conversely, synthetic or semi-synthetic esters of lower alcohols and fatty acids derived from natural sources can also be used. Examples of this substance class include Tegin (registered trademark) 90 (Goldschmidt) and glycerol monostearate palmitate. Shellac (eg, Schellack-KPS-Dreiring-SP (Kalkhoff GmbH)) can also be used as a meltable or softening material.

  The wax included within the scope of the present invention is, for example, so-called wax alcohol. Wax alcohol is a water-insoluble fatty alcohol of relatively high molecular weight, generally having about 22 to 40 carbon atoms. Wax alcohols occur as a major component of many natural waxes, for example, in the form of wax esters of relatively high molecular weight fatty acids (wax acids). Examples of wax alcohols are lignostearyl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melysyl alcohol. The formulated zinc salt or crystalline sheet-like silicate inclusions can also contain wool wax alcohol, if desired. This is understood to mean triterpenes and steroidal alcohols (eg lanolin, which is commercially available eg under the trade name Argowax® (Pamentier & Co)). Additional components of the fusible or softening material that can be used within the scope of the present invention are, at least in part, fatty acid glycerol esters or fatty acid alkanolamines, but if desired, water-insoluble or slightly water-soluble polyalkylenes. It is also a glycol compound.

  Particularly suitable fusible or softening substances are from the group of polyethylene glycol (PEG) and / or polypropylene glycol (PPG), preferably polyethylene glycol having a molar mass between 1500 and 36000, particularly preferred Is polyethylene glycol having a molar mass of 2000 to 6000, and particularly preferably polyethylene glycol having a molar mass of 3000 to 5000. Corresponding processes are also suitable, characterized in that the plastically deformable compounding material comprises at least one substance from the group of polyethylene glycol (PEG) and / or polypropylene glycol (PPG).

  Here, preferably the only fusible or softening material includes a coating comprising propylene glycol (PPG) and / or polyethylene glycol (PEG). Polypropylene glycol (abbreviated PPG) that can be used according to the present invention is a propylene glycol polymer that satisfies the following general formula:

[Wherein n can be estimated as a value between 10 and 2000]. Preferred PPGs have a molar mass between 1000 and 10000, corresponding to n values between 17 and about 170.

  Polyethylene glycol (abbreviated PEG) that can be suitably used according to the present invention has the following general formula:

An ethylene glycol polymer that satisfies [where n can be estimated as a value between 20 and about 1000]. The preferred molecular weight range here is a preferred range of values n in formula IV, from about 30 to about 820 (exactly: 34 to 818), particularly preferably from about 40 to about 150 (exactly: 45 to 136) and especially about 70 to about 120 (exactly: 68 to 113).

  In a further preferred embodiment, the coating material comprises paraffin wax.

  Compared to other names of natural waxes, paraffin waxes do not contain hydrolyzable groups, so that no hydrolysis of the wax occurs in an alkaline detergent environment (eg as expected for wax esters). Within the scope of the present invention, paraffin wax has advantages.

  Paraffin wax consists mainly of alkanes and low fractions of isoalkanes and cycloalkanes. The paraffin used according to the invention is preferably essentially free of components having a melting point above 70 ° C. (particularly preferably above 60 ° C.). Below this melting temperature in the detergent solution, the high melting point alkane fraction in paraffin can leave an undesirable wax residue on the surface to be cleaned or on the product to be cleaned. Such wax residues should generally be avoided as they lead to an unattractive appearance of the cleaned surface.

  Suitably processed meltable or softening materials comprise at least one paraffin wax having a melting range of 50 ° C to 60 ° C. Suitable coating materials are characterized by including paraffin wax in the melting range of 50 ° C to 55 ° C.

  Preferably, the content of solid alkanes, isoalkanes and cycloalkanes that are solid at room temperature (generally about 10 ° C. to about 30 ° C.) in the paraffin wax used is as high as possible. As the amount of wax component that is solid at room temperature in the wax increases, it becomes a useful wax for the purposes of the present invention. As the proportion of solid wax components increases, the resistance to impact or friction with other surfaces of the process end product increases, resulting in relatively long lasting protection. A high proportion of oil or liquid wax components can lead to weakening of the coating as a result of pore opening and exposure of the active substance to ambient effects.

  In addition to paraffin as the main component, the meltable or softening material may also include one or more of the above waxes or wax-like materials. In a further preferred embodiment of the invention, the mixture forming the fusible or softening material should be such that the compounding material and the coating formed therefrom are at least largely water insoluble. At a temperature of about 30 ° C., the solubility in water should not exceed about 10 mg / l, preferably less than 5 mg / l.

  However, in such cases, the fusible or softening material has a minimal solubility in water, even to elevated temperature water, in order to avoid temperature-dependent release of the active substance as much as possible. Should.

  Suitable coating materials processed in accordance with the present invention include one or more substances having a melting range of 40 ° C. to 75 ° C. as meltable or softening materials, in each case based on the weight of the coating material, 6-30% by weight, preferably 75-25% by weight and especially 10-20% by weight.

  Apart from the choice of a suitable coating, the dissolution behavior of zinc salts or silicate compounds can also be influenced by the compacting process. In this regard, in addition to the pressure level used and the use of auxiliaries (eg binders, etc.), in particular, the selection of the co-formulated active substance and / or builder substance is extremely important. Any gelation of substances or substance mixtures based on, for example, compacted silicates (particularly disilicates) and / or polycarboxylates and / or delayed dissolution / dispersion and in aqueous liquids Based on the above, mixtures of different polycarboxylates are particularly suitable as “donor materials” for zinc salts or crystalline sheet-like silicates.

  A further type of formulation for the dishwasher detergent or dishwasher detergent aid of the present invention that is particularly suitable within the scope of this application is a polymer matrix. Such polymer matrices can be used universally in various program cycles, characterized by simple and cost-effective manufacturing methods, and can contain various amounts of active agent.

  Accordingly, the present application also provides a dishwasher detergent or dishwasher detergent aid, wherein a zinc salt and / or crystalline sheet-like silicate is preferably present in the polymer matrix. .

  The active ingredient-containing polymer matrix can be produced cost-effectively in a wide variety of shapes. Depending on the choice of water-soluble or water-insoluble polymer, the composition of the present invention can be formulated as a dishwasher detergent package or as a basket into which the composition is introduced. For example, both introduction types can be combined with each other by means of a carrier basket made of a water-insoluble active ingredient-containing polymer matrix containing a polymer body made of a water-soluble active ingredient-containing polymer matrix. Such products can release the active agent from various matrices to varying degrees at different times, leading to an optimal concentration of active substance at any time during the washing program.

  In a composition suitable for the present invention, if both zinc salt and silicate are formulated and present in a polymer matrix, the formulation is in a preferred embodiment of the present invention in the same polymer matrix, or Either in a different matrix (ie, the zinc salt is present, for example, formulated in polymer A, while the silicate is formulated in polymer B). Finally, the zinc salt and silicate can be formulated through the same polymer, but in separate matrices.

  Thus, the compositions of the present invention can be realized using both water-insoluble polymers and water-soluble polymers, or mixtures thereof. Suitable dishwasher detergents or dishwasher detergent aids are characterized in that the polymer matrix contains one or more water-soluble polymers.

  The polymer matrix of the present invention can be universally formulated. Therefore, according to the present invention, for example, a pre-soaking agent, a pre-detergent, a main cleaning cycle detergent or a rinsing aid can be provided. Furthermore, the composition of the present invention may be a combined product obtained by combining two or more of the above-mentioned agents. Also, for example, the composition of the present invention as an additive suspended in a dishwasher can be formulated without problems. The active ingredient-containing polymer matrix is, for example, a compact form that is either a core that fills the recesses of a detergent tablet or a shaped body that is introduced into the dishwasher as a co-additive, such as a Deodorand hanger. Can be incorporated into the composition of the present invention in a form. Also, baskets suitable for detergent receiving tablets can be made from the active ingredient-containing polymer matrix. One important thing to keep in mind is that the active ingredient-containing polymer matrix can also be used as a package for dishwasher detergents. This means that the consumer does not have to put out the contents of the product, avoiding direct contact with the product (which appears to be undesirable) and saving other packaging materials, it is completely water soluble. Are particularly attractive with respect to the active ingredient-containing polymer matrix.

Particularly preferred compositions of the present invention are those wherein the polymer matrix is
a) 5-99.5% by weight of one or more polymers,
b) at least one zinc salt and at least one general formula (Ia)

[Wherein M is sodium or hydrogen,
x is a number from 1.9 to 22, preferably 1.9 to 4, and
y is a number from 0 to 33)
A crystalline sheet-like silicate represented by (wherein the total weight of zinc salt and crystalline silicate is 0.5 to 95% by weight);
c) characterized in that it contains 0-30% by weight of active ingredients and / or adjuvants (where the given weight refers in each case to the total weight of the active ingredient-containing polymer matrix) .

  The polymer matrix of the composition suitable for the present invention comprises 5-99.5% by weight of one or more polymers. Within the scope of this specification, and in accordance with the IUPAC definition, the term “polymer” collectively has a chemically uniform structure, but is generally composed of macromolecules that differ with respect to degree of polymerization, molecular weight, and chain length. Represents a substance. According to this IUPAC definition, which does not take into account the path from which the term is derived, a polymer is described as `` one or more types of atoms or groups of atoms (so-called building blocks, basic building blocks or repeating units) are repeatedly arranged adjacent to each other. It is a substance composed of many molecules. Polymer macromolecules of various sizes are sufficiently identical or similar with respect to the physical properties of the material (especially viscoelasticity) so that they do not change when the number of building blocks is slightly increased or decreased. It is composed of molecular weight building blocks (monomers). The size of the macromolecule means that the end groups have a relatively small impact on the polymer properties, and in most cases they mean that they are not given explicitly in the structural formula given below.

  As used herein, the polymer of the composition of the present invention that forms the matrix can be of either natural or synthetic origin. Preferred compositions of the present invention have a polymer matrix of 7.5-95% by weight, preferably 10-90% by weight, particularly preferably 12.5-85% by weight, more preferably 15-82.5% by weight and especially Characterized by containing 20 to 80% by weight of one or more polymers (weight data refer to polymer matrix containing active ingredient).

  The average molar mass of the polymer present in the preferred compositions of the invention is preferably at least 5000 g / mol, particularly preferably at least 10000 g / mol and in particular at least 12000 g / mol.

  As already described, suitable compositions of the present invention can include either water insoluble or water soluble polymers, and mixtures of these polymers. Compositions suitable for the present invention based on a water-insoluble polymer matrix are those in which the polymer matrix consists of polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polyurethane, polyamide and mixtures thereof. Characterized by containing one or more water-insoluble polymers.

Instead of water-insoluble polymers or mixtures thereof, water-soluble polymers of natural or synthetic origin can form the polymer matrix. Further preferred compositions of the invention are characterized in that the polymer matrix comprises one or more water-insoluble polymers. Here, the water-soluble polymer is preferably selected from the following:
i) Polyacrylic acid and its salts
ii) Polymethacrylic acid and its salts
iii) polyvinylpyrrolidone,
iv) vinyl pyrrolidone / vinyl ester copolymer,
v) Cellulose ether
vi) Polyvinyl acetate, polyvinyl alcohol and their copolymers
vii) Graft copolymer of polyethylene glycol and vinyl acetate
viii) Alkylacrylamide / acrylic acid copolymers and their salts
ix) Alkylacrylamide / methacrylic acid copolymer and its salts
x) Alkylacrylamide / methylmethacrylic acid copolymer and its salts
xi) Acrylic acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and salts thereof
xii) Acrylic acrylamide / methacrylic acid / alkylamino (meth) acrylic acid copolymer and salts thereof
xiii) Alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and salts thereof
xiv) Alkylacrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymer and salts thereof
xv) a copolymer consisting of
xv-i) Unsaturated carboxylic acids and their salts
xv-ii) Cationic derivatized unsaturated carboxylic acids and their salts
xvi) alkylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts
xvii) alkylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers, and alkali metals and their ammonium salts
xviii) Methacryloylethylbetaine / methacrylate copolymer
xix) Vinyl acetate / crotonic acid copolymer
xx) Acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymer
xxi) a graft polymer of a vinyl ester, an acrylic ester or a methacrylic ester itself, or a mixture thereof, or a copolymer thereof with crotonic acid, acrylic acid or methacrylic acid, and polyethylene oxide and / or polyalkylene glycol,
xxii) Grafted copolymers from copolymerization of the following monomers
xxii-i) at least one nonionic type monomer,
xxii-ii) at least one ionic type monomer,
xxiii) Copolymers obtained by copolymerization of at least one monomer from each of the following three groups:
xxiii-i) an ester of an unsaturated alcohol and a short-chain saturated carboxylic acid and / or an ester of a short-chain saturated alcohol and an unsaturated carboxylic acid,
xxiii-i) unsaturated carboxylic acid,
xxiii-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of group d6ii) carboxylic acids and saturated or unsaturated, linear or branched C _8-18 alcohols.

  In addition to the polymer, the active ingredient-containing polymer matrix comprises at least one zinc salt that can be released from the matrix and / or at least one crystalline sheet-like silicate of general formula (I) or general formula (Ia). Has contents. Preferred inventive compositions are characterized in that they comprise at least one zinc salt and at least one crystalline sheet-like silicate of the general formula (I) or general formula (Ia). Here, the total weight of these components is in each case 1 to 90% by weight, preferably 1.5 to 80% by weight, particularly preferably based on the total weight of the active ingredient-containing polymer matrix. It is 2 to 70% by weight, more preferably 2.5 to 60% by weight and especially 3 to 50% by weight.

  The dishwasher detergent or dishwasher detergent aid of the present invention can contain various amounts of the active ingredient-containing polymer matrix. Whether the active ingredient-containing polymer matrix is present in the composition, for example, in the form of granules or granules, whether it is formed as part of a molded body, or whether it contains the composition as a package Depending on the weight of the active ingredient-containing polymer matrix in the entire composition can vary. Here, preferably an activity of 1 to 40% by weight, preferably 1.5 to 35% by weight, particularly preferably 2 to 30% by weight and in particular 2.5 to 20% by weight, based on the total weight of the composition Mention may be made of the compositions of the invention comprising a component-containing polymer matrix.

  Particularly preferred polymer matrices are in a weight fraction of 0.01 to 1% by weight, preferably 0.02 to 0.5% by weight and in particular 0.04 to 0.2% by weight, based on the total weight of the polymer matrix in any case. At least one zinc salt is included in such an amount as to include the oxidized form of zinc.

  As stated at the outset, the incorporation of active ingredient-containing polymer matrices suitable for the present invention into the compositions of the present invention does not lead to any limitation with regard to the dosage form or formulation of these compositions. Thus, in addition to conventional dishwasher detergents, presoak or prewash products, rinse aids, machine care compositions or additives may be provided in the form of the compositions of the present invention. One preferred embodiment of the composition of the present invention is provided as a molding wherein the polymer matrix is introduced separately into the dishwasher and releases the agent from the polymer matrix over several washing cycles. I envision. This molding may be a dosing basket for other products (eg, detergents) or may embody further uses of glass protection as a separate and independent molding. A possible shape is, for example, close to the known dishwasher deodorant. The configuration of the plastic part in a translucent, milky or completely transparent form (eg stylized diamond form) is visually attractive. Such product configuration can visualize to the consumer the gloss resulting from glass protection.

  Molding versatility is not subject to any limitations due to plastic processing options. The active ingredient-containing polymer matrix can be molded without problems using current methods.

  Molding is carried out by processes customary in the plastics processing industry, preferably in particular film production and further processing, blow molding and extrusion. A common feature for all of these processes is that the plastic granules are melted using an extruder and passed to a molding tool. Here, the plastic granules can already contain inhibitors of glass corrosion (though they can be added during melting in the extruder). This enables a particularly cost-effective production of an active ingredient-containing polymer matrix suitable for the present invention.

  In a further preferred embodiment, the dishwasher detergent or dishwasher detergent aid according to the present invention provides and administers the active substance present in these compositions in a targeted manner. Formulated in a manner that allows. Within the scope of this application, particularly suitable for this purpose are, like adhesive sticks, that do not change their spatial-geometric shape during storage and transport, but are also subject to pressure effects on the surface. And, when the dosage form moves into the contact area with the surface, it loses its shape due to the shear forces that occur in the field. As a result of the acting shear force, the composition will remain in place with its new spatial-geometric shape if the surface is damaged and the effect of the shear force ceases (thus again dimensional stability) Is). The use of such suitable formulations makes it possible to apply and administer the composition of the invention in a targeted manner.

  Such a dimensionally stable dishwasher detergent or tableware that can be spread on the surface under the action of shear forces due to the nature of the material, but maintains its three-dimensional shape without the action of shear forces Washer detergent aids can be advantageously characterized by their penetration. Within the scope of the present invention, the penetration is defined as a numerical value that appears when the hardness of the composition of the present invention is determined using a Texture Analyzer (TA-XT2-I type, manufactured by Stable Micro System). To make this measurement, set the following test parameters:

TA mode: Measuring force in the pressure direction
TA option: Simple test trigger value 0.2 g
PPS 200

  The penetration is determined by pressing a specific measuring tool (TA-15 45 ° cone, stainless steel) against the test material at the specified feed rate (0.5 mm / s) to the specified penetration (5.0 mm). It is determined by drawing again from the material at a predetermined speed (0.2 mm / s). The investigated test material had a temperature of 23 ° C. and the measurements were performed at room temperature of 20 ° C. Starting from the experimental setup, the measuring device confirmed the numerical value in grams [g]. For purposes of this application, this number is defined as the penetration. As determined by the above method, suitable dimensionally stable dishwasher detergents or dishwasher detergent auxiliaries are 200-1000 g, preferably 250-900 g, particularly preferably 300-800 g and In particular, it was found to have a penetration of 350 to 700 g.

  Thus, the present invention is more preferably dimensionally stable and has a penetration of 200-1000 g, preferably 250-900 g, particularly preferably 300-800 g and especially 350-700 g. A dishwasher detergent or a dishwasher detergent aid of the present invention having a degree is provided.

  Within the scope of the present invention, the term “dimensional stability” refers to a three-dimensional shape that does not collapse with crush stability under the usual conditions of manufacture, storage, transport and handling by the consumer (this has been proposed over time). Maintain the spatial-geometric shape obtained by manufacturing, i.e., for example, do not liquefy, under the usual conditions of manufacturing, storage, transportation and consumer handling ) Represents a dishwasher detergent or dishwasher detergent aid with inherent dimensional stability.

  The penetration of 200-1000 g typical for the preferred compositions of the invention cannot be achieved with pure forms of the active substance (such as zinc salts or sheet-like silicates). Therefore, it is necessary to provide a carrier material or matrix material for these active substances that corresponds to the physical demands on the composition of the invention. Furthermore, such a matrix should be compatible with the active agent present therein (ie not specifically reacting with them and stabilizing them). Furthermore, the carrier material should not compromise the desired cleaning operation and should therefore also be compatible with all other substances used during cleaning and / or care operations. Finally, the matrix material should preferably be water soluble or water dispersible to avoid residues appearing in subsequent uses of the composition of the present invention. Particularly preferred are carrier materials that have a cleaning or care function at the same time in addition to the function of the matrix for the active substance. From the large number of possible carrier materials, it has been found that many substance groups are particularly advantageous within the scope of the present invention. These materials are discussed in detail below.

  Accordingly, preferably dimensionally stable dishwasher detergents or dishwasher detergent auxiliaries of the present invention are within the scope of this application and they are polyvinylpyrrolidone and / or polyvinyl alcohol and / or polyvinyl acetate. And / or polyacrylates and / or polyalkylene glycols and / or fats and / or fatty acids and / or fatty acid esters and / or fatty acid amides and / or fatty alcohols and / or waxes and / or paraffins and / or wax alcohols and / or It is characterized by comprising a surfactant, preferably a nonionic surfactant and / or dextrin and / or starch ether. Here, the component / weight of these components in the total weight of the dimensionally stable dishwasher detergent and / or dishwasher aid is preferably 30% and 99% by weight. Particularly preferably between 40% and 95% by weight and in particular between 50% and 95% by weight.

  The dishwasher detergent or dishwasher detergent aid of the present invention may also be formulated in the form of a liquid or flowable composition in addition to the solid or dimensionally stable forms described above. Accordingly, in a further preferred embodiment of the invention, the dishwasher detergent or dishwasher detergent aid has a viscosity of 500 to 500,000 mPas, preferably 900 to 200,000 mPas and in particular 1300 to 100,000 mPas. Have. The viscosity of the composition of the invention is measured using customary standard methods (eg Brookfield viscometer LVT-II, 20 rpm and 20 ° C., spindle 3). The expression “liquid or flowable composition” is used below for a composition having a viscosity of 500 to 500,000 mPas, preferably 900 to 200,000 mPas and in particular 1300 to 100,000 mPas.

  As suitable components, such suitable liquid or flowable compositions of the present invention comprise one or more non-aqueous solvents. These are derived, for example, from the group of monoalcohols, diols, triols or polyols, ethers, esters and / or amides. Particularly preferred is a non-aqueous solvent that is water-soluble. Here, a “water-soluble” solvent for the purposes of this application is a solvent that is fully miscible with water (ie, has no miscibility gap) at room temperature.

  Suitable non-aqueous solvents are preferably derived from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in a given concentration range. The solvent is preferably ethanol, n-propanol or isopropanol, butanol, glycol, propanediol or butanediol, glycerol, diglycol, propyldiglycol or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol Ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl ether or propyl ether, dipropylene glycol methyl ether or dipropylene glycol ethyl ether, methoxytriglycol, Ethoxytriglycol or butoxytriglycol, 1- It is selected from butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

  Also, nonionic surfactants that are liquid at room temperature are suitable nonaqueous solvents within the scope of this application.

  Particularly suitable liquid or flowable dishwasher detergents or dishwasher detergent aids within the scope of the present invention are characterized by containing a non-aqueous solvent. Here, the solvent is preferably selected from the group of polyethylene glycol and polypropylene glycol, glycerol, glycerol carbonate, triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or isopropanol. .

  Preferably, the polyethylene glycol (abbreviated PEG) used according to the present invention is liquid at room temperature. PEG has the general formula (II)

[Wherein n can be estimated as a value between 1 (ethylene glycol, see below) and about 16]
It is a polymer of ethylene glycol that satisfies the following. There are various nomenclatures for polyethylene glycol, which can lead to confusion. In the art, it is common to describe the average relative molecular weight after the letter “PEG”, thus “PEG 200” characterizes polyethylene glycol having a relative molar mass of about 190 to about 210. According to this nomenclature, polyethylene glycol PEG 200, PEG 300, PEG 400 and PEG 600 can usually be used in the art within the scope of the present invention.

  For cosmetic ingredients, different nomenclature is used, the abbreviation PEG is given a hyphen, and the hyphen is directly followed by the numerical value corresponding to the numerical value n in the above formula. According to this nomenclature (so-called INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997), for example, PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14 and PEG-16 may be used according to the present invention.

  Polyethylene glycol is, for example, trade name Carbowax (registered trademark) PEG 200 (Union Carbide), Emkapol (registered trademark) 200 (ICI Americas), Lipoxol (registered trademark) 200 MED (HUELS America), Polyglycol (registered trademark) E- 200 (Dow Chemical), Alkapol (registered trademark) PEG 300 (Rhone-Poulenc), Lutrol (registered trademark) E300 (BASF), and under the corresponding trade names with higher numerical values Yes.

  Polypropylene glycol (PPG) that can be used in the present invention has the general formula (III)

[Wherein n can be estimated as a value between 1 (propylene glycol, see below) and about 12]
It is a polymer of propylene glycol satisfying the above. Here, industrially significant ones are especially di-, tri- and tetrapropylene glycols, ie those represented by n = 2, 3 and 4 in the above formula.

Glycerol is a colorless, clear, viscous, odorless, sweet, hygroscopic liquid that has a density of 1.261 and solidifies at 18.2 ° C. Glycerol was originally only a byproduct of fat saponification. However, today it is synthesized in large quantities industrially. Most industrial processes start with propene, which is processed into glycerol via an intermediate stage of allyl chloride and epichlorohydrin. A further industrial process is the hydroxylation of allyl alcohol with hydrogen peroxide over a WO ₃ catalyst via the glycid stage.

Glycerol carbonate is obtained by esterifying ethylene carbonate or dimethyl carbonate and glycerol. The by-products produced are ethylene glycol or methanol, respectively. A further synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is reacted with CO ₂ under pressure in the presence of a catalyst to give glycerol carbonate. Glycerol carbonate is a clear, free ^- flowing liquid having a density of 1.398 gcm ⁻³ and boiling at 125-130 ° C. (0.15 mbar).

  Ethylene glycol (1,2-ethanediol, “glycol”) is a colorless, viscous, sweet, highly hygroscopic liquid that is miscible with water, alcohol and acetone and has a density of 1.113. The freezing point of ethylene glycol is -11.5 ° C; this liquid boils at 198 ° C. Industrially, ethylene glycol is obtained from ethylene oxide by heating under pressure with water. A promising preparation process may be based on acetoxylation of ethylene followed by hydrolysis or synthesis gas reaction.

  Propylene glycol exists in two isomers, 1,3-propanediol and 1,2-propanediol. 1,3-propanediol (trimethylene glycol) is a neutral, colorless and odorless sweet liquid that has a density of 1.0597, solidifies at -32 ° C, and boils at 214 ° C. 1,3-propanediol is prepared from acrolein and water by subsequent catalytic hydrogenation.

  Much more industrially important is 1,2-propanediol (propylene glycol), an oily, colorless, virtually odorless liquid with a density of 1.0381, which solidifies at -60 ° C and boils at 188 ° C. ). 1,2-propanediol is prepared from propylene oxide by water addition.

Propylene carbonate is a colorless, transparent, free-flowing liquid with a density of 1.21 gcm ⁻³ , a melting point of −49 ° C. and a boiling point of 242 ° C. Propylene carbonate is also commercially available by reacting propylene oxide and CO ₂ at 200 ° C. and 80 bar.

  In the preferred liquid or flowable dishwasher detergent or dishwasher detergent aid of the present invention, the non-aqueous solvent is in each case 0.1-70% by weight, preferably based on the total composition Is present in an amount of 0.5 to 60% by weight, particularly preferably 1 to 50% by weight, very particularly preferably 2 to 40% by weight and in particular 2.5 to 30% by weight.

  Within the scope of the present invention, “non-aqueous” is understood to mean a state in which the content of free water in the composition is significantly less than 5% by weight. The composition of the dishwasher detergent or the dishwasher detergent aid of the present invention in any case with respect to the content of free water (ie water not in the form of hydration water and / or constituent water) On the basis, it is preferred that it is less than 10% by weight, preferably less than 8% by weight and especially even less than 6% by weight. Thus, water is introduced into the composition essentially only in chemically and / or physically bound form, or as a component of solid raw materials or compounds, but not as a liquid, solution or dispersion. obtain.

  As a further preferred component, preferred liquid or flowable dishwasher detergents or dishwasher detergent aids of the present invention comprise one or more nonionic surfactants. According to the invention, the amount of nonionic surfactant used is preferably between 5% and 30% by weight. Particularly preferred compositions of the invention comprise 1 to 25% by weight of nonionic surfactants, more preferably 2 to 22.5% by weight, particularly preferably 3 to 20% by weight and in particular 4 to 17.5% by weight. Is included.

  For a more detailed description of these nonionic surfactants, to avoid repetition, reference is now made to the following description of suitable cleaning and cleaning active ingredients of preferred compositions of the present invention. The

  In order to adjust the viscosity, the composition according to the invention may comprise further components. By using it, for example, sedimentation behavior or casting suitability or fluidity can be controlled in a targeted manner. In non-aqueous systems, it has been found that the combination of structure-imparting agent and thickener is particularly successful.

A dishwasher detergent suitable for the purposes of the present invention further comprises
a) 0.1-1.0% by weight of one or more structure-imparting agents from the group of bentonite and / or at least partially etherified sorbitol;
b) comprises 5.0-30% by weight of one or more thickeners from the group of carbonates, sulfates and amorphous or crystalline disilicates.

  The structure-imparting agent a) is derived from the group of bentonite and / or at least partially etherified sorbitol. These materials are used to ensure the physical stability of the composition and to adjust the viscosity. Conventional thickeners (such as polyacrylates or polyurethanes) do not work in non-aqueous media, but the viscosity can be adjusted by using the materials in non-aqueous systems.

  Bentonite is a contaminated clay formed as a result of the weathering of volcanic tuff. Due to the high content of montmorillonite, bentonite has valuable properties such as expansibility, ion exchange and thixotropy. Here, it is possible to modify the properties of bentonite according to the intended use. Bentonite is often a clay component in tropical soil and is recovered as sodium bentonite (eg, in Wyoming / USA). Sodium bentonite has the most favorable application properties (swellability). This means that it is preferred to use for the purposes of the present invention. Naturally produced calcium bentonite is derived, for example, from Mississippi / USA or Texas / USA or Landshut / Germany. Naturally obtained Ca bentonite is artificially converted to more expansive Na bentonite by exchanging Ca with Na.

  The main constituent of bentonite is formed by so-called montmorillonite. This can also be used in pure form for the purposes of the present invention. Montmorillonite is a clay mineral belonging to phyllosilicate and dioctahedral smectite, and produces monoclinic pseudo hexagonal crystals. Montmorillonite appears to be completely amorphous, easily crushed and forms mainly white, off-white to yellow masses. It swells in water but does not become plastic and has the general formula

It can be expressed as

A suitable dishwasher detergent or dishwasher detergent aid is characterized in that the structure-imparting agent used is montmorillonite. Montmorillonite has a three-layer structure consisting of two tetrahedral layers electrostatically cross-linked via an intermediate octahedral layer of cations. The layers are not tied together in a hard manner and are reversible in water (2-7 volumes) and other substances (eg alcohol, glycol, pyridine, -picoline, ammonium compounds, hydroxyaluminosilicate ions, etc.) It can swell as a result of insertion. The above formula only represents an approximate formula. This is because montmorillonite has a large ion exchange capacity. Thus, Al can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Cr, Cu and other ions. As a result of such substitution, the layer becomes negatively charged. This is balanced by other cations (particularly Na ⁺ and Ca ²⁺ ).

  In combination with bentonite or if their use is not desired, at least partially etherified sorbitol can be used as a structure-imparting agent instead.

  Sorbitol is a hexahydric alcohol (sugar alcohol) belonging to hexitol. This removes 1 mol or 2 mol of water in the molecule relatively easily and forms cyclic ethers (eg sorbitan and sorbide). The elimination of water is also possible between molecules and forms an acyclic ether from sorbitol and the alcohol in question. Here, the formation of monoethers and bisethers is also possible, and a high degree of etherification (such as 3 and 4) can also occur. The at least partially etherified sorbitol preferably used for the purposes of the present invention is dietherified sorbitol, of which dibenzylidene sorbitol is particularly preferred. Here, a dishwasher detergent containing dietherified sorbitol (particularly dibenzylidene sorbitol) as the structure-imparting agent is preferably used.

  Suitable liquid or flowable compositions of the present invention may comprise a structure-imparting agent in an amount of 0.1 to 1.0% by weight, based on the total composition and the active material of the structure-imparting agent. Suitable compositions in any case are based on the total composition in an amount of 0.2 to 0.9% by weight, preferably in an amount of 0.25 to 0.75% by weight and in particular in an amount of 0.3 to 0.5% by weight. Contains agents.

  As a thickener, suitable liquid or flowable compositions of the present invention may include inorganic salts from the group of carbonates, sulfates and amorphous or crystalline disilicates. In this connection it is possible in principle to use the salts of all metals, preferably alkali metal salts. For the purposes of the present invention, thickeners that are particularly preferably used are alkali metal carbonates, alkali metal sulfates and / or amorphous and / or crystalline alkali metal disilicates, preferably carbonates. Sodium, sodium sulfate and / or amorphous or crystalline sodium disilicate.

  Suitable liquid or flowable compositions of the present invention comprise a thickener in an amount of 5-30% by weight, based on the total composition. Particularly preferred compositions are in each case thickened in an amount of 7.5 to 28% by weight, preferably 10 to 26% by weight and in particular 12.5 to 25% by weight, based on the total composition. Agent or a plurality of thickeners.

  With regard to increased sedimentation stability, it is preferred that the solids present in the composition of the invention are used as finely as possible. This is particularly advantageous for inorganic thickeners and bleaches. Preferably, the tableware according to the invention, wherein the average particle size of the bleaches and thickeners, and optionally the builders used, is less than 75 μm, preferably less than 50 μm and in particular less than 25 μm. Examples include detergents for washing machines.

  The liquid dishwasher detergents of the present invention may also include other viscosity modifiers or thickeners that establish the desired high viscosity. In this connection, it is possible to use all known thickeners, ie thickeners based on natural or synthetic polymers.

Naturally occurring polymers used as thickeners are, for example, agar, carrageenan, tragacanth, gum arabic, alginate, pectin, polysaccharides, guar flour, locust bean flour, starch, dextrin, gelatin and casein .
Modified natural substances are mainly derived from the group of modified starches and celluloses. Examples that may be mentioned here are carboxymethylcellulose and other cellulose ethers, hydroxyethylcellulose and hydroxypropylcellulose, and locust bean flour ether.

  Liquid or flowable dishwasher detergents or dishwasher detergent auxiliaries suitable within the scope of the present invention comprise hydroxyethylcellulose and / or hydroxypropylcellulose as thickener, in each case the total composition Preferably in an amount of 0.01 to 4.0% by weight, particularly preferably in an amount of 0.01 to 3.0% by weight and in particular in an amount of 0.01 to 2.0% by weight.

  A vast number of thickeners widely used in a wide variety of applications are fully synthetic polymers (such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes). is there.

  Thickeners from the class of materials are, for example, Acusol®-820 (methacrylic acid (stearyl alcohol-20 EO) ester-acrylic acid copolymer, 30% strength in water, Rohm & Haas), Dapral® ) -GT-282-S (alkyl polyglycol ether, Akzo), Deuterol® polymer-11 (dicarboxylic acid copolymer, Schoener GmbH), Deuteron®-XG (β-D-glucose, D-mannose And D-glucuronic acid based anionic heteropolysaccharide, Schoener GmbH), Deuteron®-XN (non-ionogenic polysaccharide, Schoener GmbH), Dicrylan® thickener-O (ethylene oxide adduct, water / 50% strength in isopropanol, Pfersse Chemie), EMA®-81 and EMA®-91 (ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (polyurethane emulsion, water / 19-21% concentration in diglycol ether, Rohm & Haas), M irox®-AM (anionic acrylic acid-acrylic ester copolymer dispersion, 25% concentration in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Shellflo® -S (high molecular weight polysaccharide, immobilized with formaldehyde, Shell) and Shellflo (R) -XA (xanthan biopolymer, immobilized with formaldehyde, Shell), widely used and available commercially It is.

  Suitable polymer thickeners are produced by Xanthomonas campestris and some other species under aerobic conditions and have a molar mass of 2 million to 15 million daltons. Xanthan, an anionic heteropolysaccharide. Xanthan is formed from a chain having β-1,4-linked glucose (cellulose) and a side chain. The subgroup structure consists of glucose, mannose, glucuronic acid, acetate and pyruvate. Here, the number of pyruvate units determines the viscosity of the xanthan.

  Similarly, thickeners preferably used for the purposes of the present invention are polyurethanes or modified polyacrylates and can be used, for example, in amounts of 0.1 to 5% by weight, based on the total product.

  Polyurethane (PUR) is prepared by polyaddition from dihydric or polyhydric alcohols and isocyanates, and has the general formula IV

Wherein R ¹ is a low molecular weight or polymeric diol group, R ² is an aliphatic or aromatic group, and n is a natural number.
Can be represented by: Where R ¹ is preferably a linear or branched C _2-12 -alkyl (alkenyl) group, but based on the fact that an additional —O—CO—NH group is attached to the group R ^1. As a result of the formation of different crosslinked polyurethanes from the above formula VIII, they can also be polyhydric alcohol groups.

Industrially important PURs are polyester and / or polyether diols such as toluene 2,4- or 2,6-diisocyanate (TDI, R ² = C ₆ H ₃ —CH ₃ ), 4,4′-methylenedi (Phenyl isocyanate) (MDI, R ² = C ₆ H ₄ —CH ₂ —C ₆ H ₄ ) or hexamethylene diisocyanate [HMDI, R ² = (CH ₂ ) ₆ ] or the like.

  Standard commercial polyurethane-based thickeners include, for example, Acrysol® PM 12 V (a mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel® Trademark) L75-N (nonionogenic PUR dispersion, 50% concentration in water, Borchers), Coatex® BR-100-P (PUR dispersion, 50% concentration in water / butyl glycol, Dimed), Nopco ( DSX-1514 (PUR dispersion, 40% concentration in water / butyl triglycol, Henkel-Nopco), thickener QR 1001 (20% concentration PUR emulsion in water / diglycol ether, Rohm & Haas ) And Rilanit® VPW-3116 (PUR dispersion, 43% concentration in water, Henkel). For the purposes of the present invention, when using an aqueous dispersion, it should be ensured that the water content of the product of the present invention remains within the predetermined range. If aqueous dispersions cannot be used for these reasons, other solvents or dispersions in solids can be used.

  Modified polyacrylates that can be used for the purposes of the present invention are derived, for example, from acrylic acid or methacrylic acid and have the general formula V

[Wherein R ³ is H or a branched or unbranched C _1-4 -alkyl (alkenyl) group, X is NR ⁵ or O, and R ⁴ is a branched chain which may be alkoxylated. Or an unbranched, optionally substituted C _8-22 -alkyl (alkenyl) group, R ⁵ is H or R ⁴ , and n is a natural number.
Can be represented by: In general, such modified polyacrylates are esters or amides of acrylic acid or α-substituted acrylic acid. Among these polymers, those in which R ³ is H or a methyl group are preferable. In polyacrylamide (X = NR ⁵ ), either a mono- (R ⁵ = H) N-substituted amide structure or a di- (R ⁵ = R ⁴ ) N-substituted amide structure is possible. Here, the two hydrocarbon groups attached to the N atom can be selected independently of one another from branched or unbranched C _8-22 -alkyl (alkenyl) groups which may be alkoxylated. Of the polyacrylic esters (X = O), alcohols obtained from natural or synthetic fats or oils and further alkoxylated (preferably ethoxylated) are preferred. The preferred degree of alkoxylation is between 2 and 30, particularly preferably between 10 and 15.

Since the polymers that can be used are industrial compounds, the designation of the group attached to X represents a statistical average that can vary in individual cases with regard to chain length or degree of alkoxylation. Formula V only gives the formula for the ideal homopolymer. However, it is also possible for the purposes of the present invention to use copolymers in which the proportion of monomer units satisfying formula V is at least 30% by weight. Thus, for example, copolymers of modified polyacrylates and acrylic acid or salts thereof which also have acidic H atoms or basic —COO 2 ^— groups can be used.

  Modified polyacrylates preferably used for the purposes of the present invention are of formula Va

Wherein R ⁴ is preferably an unbranched, saturated or unsaturated C _8-22 -alkyl (alkenyl) group, R ⁶ and R ⁷ are independently of each other H or CH ₃ The polymerization degree n is a natural number, and the alkoxylation degree is a natural number between 2 and 30, preferably between 10 and 20.
Is a polyacrylate-polymethacrylate copolymer satisfying R ⁴ is preferably a fatty alcohol group obtained from natural or synthetic sources, as well as the fatty alcohol is preferably ethoxylated (R ⁶ = H).

The product of formula Va is marketed, for example, in the form of a 30% strength by weight dispersion in water under the trade name Acusol® 820 (Rohm & Haas). In the case of the commercially available product, R ⁴ is a stearyl group, R ⁶ is a hydrogen atom, R ⁷ is H or CH ₃ , and the degree of ethoxylation is 20. The above statements regarding the water content of the product also apply to this dispersion.

  Suitable liquid or flowable dishwasher detergents or dishwasher detergent aids for the purposes of the present invention are 0.01 to 5% by weight, preferably 0.02 to 4% by weight, particularly preferably 0.05 to 3% by weight. % And in particular 0.1 to 1.5% by weight of polymer thickeners, preferably from the group of polyurethanes or modified polyacrylates, particularly preferably of formula VI

[Wherein R ³ is H or a branched or unbranched C _1-4 -alkyl (alkenyl) group, X is NR ⁵ or O, and R ⁴ is a branched chain which may be alkoxylated. Or an unbranched, C _8-22 -alkyl (alkenyl) group that can be substituted, R ⁵ is H or R ⁴ , and n is a natural number.
It is characterized by further containing the thickener shown by these.

  The solid or dimensionally stable and liquid or flowable dishwasher detergents or dishwasher detergent aids of the present invention provide consumers with conventional containers (eg, bottles, screw glassware, canisters). , Balloons, beakers or spray vessels) (consumers weigh to use the detergent or detergent aid from the container). Also, relatively high viscosity compositions can be supplied in tubes or metered dispensers, as is known for toothpaste or sealing compositions. Such containers are now usually prepared from water-insoluble polymers and can consist, for example, of all customary water-insoluble packaging materials well known to those skilled in the art. Suitable polymers that can be mentioned here are in particular hydrocarbon-based plastics. Particularly suitable polymers include polyethylene, polypropylene (more preferably oriented polypropylene) and polymer mixtures (eg, a mixture of the polymer and polyethylene terephthalate). Also suitable are one or more polymers from the group consisting of polyvinyl chloride, polysulfone, polyacetal, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate, cellulose acetobutyrate and mixtures of the polymers or copolymers containing the polymers. .

  However, a particularly preferred embodiment of the present invention is such that the consumer can take advantage of the administration benefits from the “tablet” dosage forms known to the consumer and that they rapidly dissolve the compositions of the present invention and It is intended to assist the consumer in the form of a pre-dispensed composition of the invention so that it can be combined with release rate and performance advantages. Similarly, such pre-distributed compositions of the present invention may be in the form of a water insoluble package. As a result, consumers must open them in a proper manner before use. However, it is also possible to package the dispensed compositions of the present invention so that consumers can place them directly in the dishwasher (ie with the packaging without further handling steps) It is. Examples of such a package include a water-soluble or water-disintegratable package (for example, a water-soluble film pouch), a water-soluble or water-disintegratable non-woven pouch or other package, or water-soluble Examples include polymer flexible bodies or rigid bodies (preferably in the form of filled hollow bodies that can be produced, for example, by deep drawing, injection molding, blow molding, calendering, etc.).

  Accordingly, the present invention preferably provides the dishwasher detergent or dishwasher detergent aid of the present invention packaged in a water-soluble inclusion.

  The dishwasher detergent or dishwasher detergent aid of the present invention preferably comprises an inclusion that is completely or partially water soluble. The shape of the inclusion body is not limited to a specific shape. In principle, all Archimedean and Platonic bodies (ie three-dimensional bodies) are suitable as inclusion body shapes. Examples of the shape of the inclusion body are a capsule, a cube, a sphere, an oval, a rectangular parallelepiped, a cone, a rod or a pouch. A hollow body having one or more compartments is also suitable as an enclosure for a dishwasher detergent. In a preferred embodiment of the invention, the inclusion bodies have the form of capsules, spheres or pouches, as are also used, for example, in the administration of drugs in pharmacy. The latter is preferably sealed or glued on at least one side. Here, the adhesive used in a particularly preferred embodiment of the invention is an adhesive that is water-soluble.

  According to a preferred embodiment of the invention, the water-soluble polymeric material that partially or completely surrounds the dishwasher detergent or dishwasher detergent aid is a water-soluble package. This is understood to mean a flat component that partially or completely surrounds the dishwasher detergent. The exact shape of such a package is not critical and can be widely adapted to the conditions of use. For example, processed plastic films or sheets, capsules and other imaginable shapes that are processed into different shapes (eg tubes, sashes, cylinders, bottles, disks, etc.) are suitable. According to the invention, it is particularly preferred that after being filled with a part of the detergent of the invention or with the detergent itself, it is glued and / or sealed, for example for packaging (eg tubes, sashes etc.) The film which can be given is mentioned.

  Also suitable for the present invention is a plastic film package made of a water-soluble polymer material due to the properties that can be tailored in an excellent manner to the desired physical conditions. Such films are mainly known from the prior art.

  In summary, hollow bodies of any shape that can be produced by injection molding, bottle blow molding, deep drawing, etc., and film hollow bodies (especially pouches) are also used for the distributed compositions of the present invention. It is suitable as a package. Therefore, a suitable dishwasher detergent or detergent for a dishwasher of the present invention comprises a water-soluble inclusion body, a water-soluble film pouch and / or an injection molded part and / or a blow molded part and / or It is characterized by including a deep drawing part.

  According to the invention, it is preferred that one or more enclosures are sealed. This offers the advantage that the dishwasher detergent is optimally protected against environmental influences, in particular against moisture. Furthermore, based on these sealed enclosures, the invention can be further developed to detergents containing at least one gas for protecting the contents of the enclosure against moisture (see below). about).

  Suitable materials for fully or partially water-soluble inclusion bodies are in principle in the aqueous phase under the prescribed conditions (temperature, pH, concentration of cleaning active ingredient) of the washing, rinsing or cleaning operation. All materials that are completely or partially soluble to it. The polymer material is particularly preferably polyvinyl alcohol (which may be partially acetalized), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starch, and said It belongs to the group consisting of a mixture of materials (polymer blend, composite, co-extruded, etc.). Particularly suitable are gelatin and polyvinyl alcohol and a composite of the two materials (in either case) with starch or modified starch. Inorganic salts and mixtures thereof are also suitable materials for at least partially water-soluble inclusion bodies.

  Preferred dishwasher detergents or dishwasher detergent auxiliaries of the present invention are those in which the inclusions are acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers, and mixtures thereof Characterized by comprising one or more materials from the group consisting of:

  Particularly preferred dishwasher detergents or dishwasher detergent auxiliaries according to the invention are those in which the inclusion body is one or more water-soluble polymers, preferably polyvinyl alcohol (which may be acetalised) (PVAL ), Polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof, more preferably characterized by comprising (optionally acetalized) polyvinyl alcohol (PVAL). Attached.

  Here, “polyvinyl alcohol” (abbreviated as PVAL, sometimes abbreviated as PVOH) is a general structural formula

Indicated by

Is a name for a polymer containing a small amount (about 2%) of structural units of the type

  Standard commercial polyvinyl alcohol is supplied as a white yellow powder or granules having a degree of polymerization in the range of about 100-2500 (molar mass about 4000-100,000 g / mol), 98-99 mol% or 87-89 mol % Degree of hydrolysis and therefore also contains the remaining content of acetyl groups. Polyvinyl alcohol is characterized on the manufacturer side by showing the degree of polymerization, degree of hydrolysis, number of hydrolysis and dissolution viscosity of the starting polymer.

  Depending on the degree of hydrolysis, polyvinyl alcohol is soluble in water and polar organic solvents that are not stronger than water (formamide, dimethylformamide, dimethyl sulfoxide); they are (chlorinated) hydrocarbons, esters, lipids and oils Not attacked by. Polyvinyl alcohol is classified as toxicologically acceptable and is at least partially biodegradable. Solubility in water can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts, or by treatment with dichromate, boric acid or borax. The coating made of polyvinyl alcohol does not mainly pass gas (oxygen, nitrogen, helium, hydrogen, carbon dioxide, etc.) but allows water vapor to pass.

  For the purposes of the present invention, polyvinyl alcohol having a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and particularly 82 to 88 mol% is used. Inclusion bodies containing are preferred.

As the material for the inclusion body, it is preferable to use polyvinyl alcohol having a specific molecular weight range. According to the present invention, the inclusion body has a molecular weight of 10,000 to 10,000 gmol ⁻¹ , preferably 11,000 to 90,000 gmol ^{− 1,} particularly preferably in the range of from 13,000 to 70000 gmol ^-1 to from 12000 to 80000 gmol ^-1 and in particular, it is preferable to include a polyvinyl alcohol.

  The degree of polymerization of such suitable polyvinyl alcohols is between about 200 and about 2100, preferably between about 220 and about 1890, particularly preferably between about 240 and about 1680 and especially between about 260 and about 1500. Between.

  The polyvinyl alcohol is widely commercially available, for example, under the trade name Mowiol (registered trademark) (Clariant). Polyvinyl alcohols that are particularly suitable within the scope of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8- 88.

  Additional polyvinyl alcohols that are particularly suitable as materials for hollow bodies are shown in the table below:

  Further polyvinyl alcohols suitable as materials for hollow shapes are ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 ( Du Pont product name), ALCOTEX® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trade name of Harlow Chemical Co.), Gohsenol (registered) Trademark) NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trade names of Nippon Gohsei KK).

  The solubility of PVAL in water can be altered by aldehyde post-treatment (acetalization) or ketone post-treatment (ketalization). Polyvinyl alcohols found to be particularly suitable and particularly advantageous due to their markedly good solubility in cold water are acetalized or ketals, depending on the aldehyde group or keto group of the saccharide or polysaccharide or mixtures thereof, respectively. It has been It has proven particularly advantageous to use a reaction product of PVAL and starch.

  Furthermore, the solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromate, boric acid, borax, so it is adjusted to the desired value in the intended manner. be able to. PVAL films do not mainly pass gas (oxygen, nitrogen, helium, hydrogen, carbon dioxide, etc.) but pass water vapor.

  An example of a suitable water-soluble PVAL film is the PVAL film available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON®”. Their solubility in water can be adjusted to an exact degree. Films of this product series are also available that are soluble in the aqueous phase over the entire temperature range relevant to this application.

  Polyvinylpyrrolidone is abbreviated as PVP and has the following general formula:

Can be represented by: PVP is prepared by free radical polymerization of 1-vinylpyrrolidone. Standard commercial PVP has a molar mass in the range of about 2500-750,000 g / mol and is supplied as a white hygroscopic powder or as an aqueous solution.

  Polyethylene oxide is abbreviated as PEOX and has the general formula

Mostly prepared industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in a system containing a small amount of water and ethylene glycol as the starting molecule. They have a molar mass ranging from about 200 to 5000000 g / mol, corresponding to a degree of polymerization n of about 5 to> 100,000. Polyethylene oxide has a very low concentration of active hydroxy end groups and only exhibits weak glycol properties.

  Gelatin is mainly a polypeptide (molar mass: about 15000 to> 250,000 g / mol) obtained by hydrolysis of collagen present in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin mainly corresponds to the amino acid composition of the collagen from which it is obtained and varies depending on its origin. The use of gelatin as a water-soluble shell material is quite widespread, particularly in the form of hard or soft gelatin capsules in pharmacy. Gelatin is not widely used in film form due to its high cost compared to the polymers specified above.

  Within the scope of the present invention, preferably the packaging is at least partly from a water-soluble film of at least one polymer from the group consisting of starch and starch derivatives, cellulose and cellulose derivatives (especially methylcellulose) and mixtures thereof. And dishwasher detergents.

  Starch is a homoglycan in which glucose units are linked α-glycosidically. Starch is composed of two components of different molecular weights: about 20-30% linear amylose (MW about 50,000-150000) and 70-80% branched amylopectin (MW about 300,000-2000000). In addition, there are small amounts of lipids, phosphates and cations. Amylose forms a long, helical, closely linked chain with about 300-1200 glucose molecules as a result of binding at positions 1, 4 whereas the chain in the case of amylopectin averages After 25 glucose structure blocks, 1,6 bonds branch into a branch-like structure with about 1500-12000 glucose molecules. Like pure starch, starch derivatives obtained from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble inclusion bodies for cleaning composition parts, rinsing composition parts and cleaning composition parts within the scope of the present invention. It is. Such chemically modified starches include, for example, compositions from esterification or etherification in which the hydrogen atom of the hydroxyl group is replaced. However, starch in which the hydroxyl group is substituted with a functional group that is not bonded via an oxygen atom can also be used as a starch derivative. The group of starch derivatives includes, for example, alkali metal starch, carboxymethyl starch (CMS), starch esters and starch ethers, and amino starch.

Pure cellulose has a formal overall composition (C ₆ H ₁₀ O ₅ ) _n and, considering formally, cellobiose (for which part is composed of two molecules of glucose) β- 1,4-polyacetal. Suitable cellulose consists of about 500 to 5000 glucose units and thus has an average molar mass of 50000 to 500000. Also, cellulose-based disintegrants that can be used within the scope of the present invention are cellulose derivatives obtained from cellulose by a polymer-like reaction. Such chemically modified cellulose includes, for example, a composition from esterification or etherification in which the hydrogen atom of the hydroxyl group is replaced. However, cellulose in which a hydroxyl group is substituted with a functional group that is not bonded via an oxygen atom can also be used as a cellulose derivative. Examples of the cellulose derivative group include alkali metal cellulose, carboxymethyl cellulose (CMC), cellulose ester and cellulose ether, and aminocellulose.

  Suitable inclusion bodies for at least partly water-soluble films are between 5000 g / mol and 500000 g / mol, preferably between 7500 g / mol and 250,000 g / mol and in particular 10000 g / mol and 100000 g. at least one polymer having a molar mass between g / mol. The inclusions have different material thicknesses depending on the manufacturing process. Preferably, the dishwasher detergent according to the invention, wherein the wall thickness of the enclosure is 10 to 5000 μm, preferably 20 to 3000 μm, particularly preferably 25 to 2000 μm and in particular 100 to 1500 μm. Or the detergent adjuvant for dishwashers is mentioned.

  When a film pouch is selected as the package, the water-soluble film forming the inclusion body is preferably 1 to 300 μm, preferably 2 to 200 μm, particularly preferably 5 to 150 μm and especially 10 It has a thickness of ˜100 μm.

  These water-soluble films can be manufactured by various manufacturing processes. In principle, blow molding processes, calendering processes and casting processes should be mentioned. In a preferred process, the film is blown using air with a blowing mandrel starting from the melt to obtain a hose. In a calendering process, which is also a suitable manufacturing process type, raw materials plasticized with suitable additives are subdivided to form a film. Here, a drying step following fragmentation may be particularly necessary. In a casting process, which is also a suitable type of manufacturing process, the aqueous polymer preparation is placed on a heatable drying roll and allowed to cool after evaporation of the water and the film is removed in sheet form. It is. If necessary, the sheet is further pulverized before or during removal.

  In accordance with the present invention, when used in accordance with instructions during mechanical cleaning, the inclusion body becomes totally water soluble (ie, completely dissolves) when the conditions under which dissolution is expected are achieved. Embodiments are preferred. Particularly suitable fully water-soluble inclusion bodies are, for example, capsules made of gelatin (preferably made of soft gelatin), or pouches made of PVAL (which may be partially acetalized), or gelatin or (partially PVAL or one or more organic and / or inorganic salt spheres (preferably soft gelatin spheres). The essential advantage of this embodiment is that the inclusion body is in practically relevant short time under precisely defined conditions in the cleaning liquid (as a non-limiting example, a few seconds to 5 minutes can be specified) In other words, it must be at least partially dissolved and, therefore, the enclosed contents (ie, the cleaning active material or two or more materials) must be introduced into the liquid as required.

  In another embodiment of the invention, which is also suitable on the basis of advantageous properties, the water-soluble inclusion bodies are inferior in water solubility, or even water insoluble, or in elevated temperature water. It includes a portion that is soluble only with respect to a portion that is readily water-soluble or water-soluble at low temperatures. In other words, the inclusion body is not only made of one homogeneous material having the same water solubility in all regions, but also made of materials having different water solubility. In this regard, only one region of good solubility and a region with poorer or poorer solubility in water, or even insoluble, or at elevated temperatures, only at different pH or changes. A distinction should be made only between the electrolyte concentration and the region where the solubility in water achieves the desired value. This leads to certain regions of inclusion bodies being dissolved while other regions remain intact when the product is used according to the instructions under regulatable conditions. Thus, inclusion bodies provided with holes or holes are those through which water and / or liquid can pass, dissolve the cleaning active ingredient, the rinsing active ingredient or the cleaning active ingredient and allow them to flow out of the inclusion body. Form. Similarly, inclusion body systems in the form of multiple chamber pouches or hollow bodies (eg, spheres: “onion system”) disposed within each other may be provided. In this way, systems with controlled release of cleaning actives, rinsing actives or cleaning actives can be prepared.

  The present invention is not limited to prescribing such systems. For example, an inclusion body can be provided in which a homogeneous polymeric material includes a small region of an incorporated formulation (eg, a salt formulation) that dissolves more rapidly in water than the polymeric material. On the other hand, two or more polymeric materials with different water solubilities can also be mixed (polymer blends) so that faster dissolving polymeric materials are slower than materials that dissolve slower with water or liquid under certain conditions. Even quickly collapse.

  Regions of inclusions that are inferior in water solubility, or regions that are completely water insoluble, or regions that are only water soluble at elevated temperatures are essential to materials in areas that are readily water soluble or water soluble at low temperatures. Region of a chemically corresponding material but having a higher layer thickness and / or having a different degree of polymerization of the same polymer and / or having a high degree of cross-linking of the same polymer structure And / or having a high degree of acetalization (in the case of PVAL, for example due to sugars, polysaccharides (such as starch)) and / or the content of water-insoluble salt components and / or the content of water-insoluble polymers Having an object corresponds to a particularly preferred embodiment of the invention. Even in view of the fact that the inclusion bodies do not dissolve completely, the cleaning composition part of the present invention can be prepared to have advantageous properties upon release of the dishwasher detergent into a particular liquid.

  The water soluble shell material is preferably transparent. For the purposes of the present invention, transparency is more than 20%, preferably more than 30%, most preferably more than 40% and in particular more than 20% transmission in the visible spectral range of light (410-800 nm). Is understood to mean more than 50%. Thus, as soon as the visible spectrum wavelength of light has a transmission of more than 20%, it can be considered transparent within the scope of the present invention.

  The dishwasher detergent of the present invention packaged in a transparent enclosure or container may contain a stabilizer as an essential ingredient. For the purposes of the present invention, stabilizers are materials that protect the detergent components in their water-soluble transparent inclusions from degradation or inactivation as a result of light irradiation. Antioxidants, UV absorbers and fluorescent dyes have been found to be particularly suitable.

For the purposes of the present invention, particularly suitable stabilizers are antioxidants. In order to prevent undesired changes in the formulation and hence free radical degradation due to light irradiation, the formulation may contain an antioxidant. Antioxidants that can be used here are, for example, phenol, bisphenol and thiobisphenol, which are substituted by sterically hindered groups. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and long chain (C ₈ -C ₂₂ ) esters of gallic acid (such as dodecyl gallate) ). Other classes of substances include aromatic amines (preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus (such as phosphines, phosphites and phosphonites), citric acid and citric acid derivatives. (Such as isopropyl citrate), compounds containing enediol groups, so-called reductones (such as ascorbic acid and its derivatives (such as ascorbyl palmitate)), organic sulfur compounds (3,3'-thiodipropionic acid and C _1-18 -Alkanols (especially esters of C _10-18 -alkanols), metal ion deactivators (such as nitrilotriacetic acid) capable of complexing auto-oxidation catalytic metal ions (eg copper) and their Modifications and blends Antioxidants in amounts up to 35% by weight, preferably in amounts up to 25% by weight, particularly preferably 0.0%. It can be present in the formulation from 1 to 20% by weight and in particular from 0.03 to 20% by weight.

  A further class of suitably used stabilizers are UV absorbers. UV absorbers can improve the light resistance of the formulation components. They are understood as meaning organic substances (photoprotective filters) that can absorb ultraviolet light and re-release the absorbed energy in the form of long wavelength radiation (eg heat). Compounds having these desired properties are, for example, benzophenone compounds and benzophenone derivatives having substituents at the 2-position and / or 4-position that become effective as a result of inactivation without radiation. Also suitable are substituted benzotriazoles (eg, water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast® (Trademark) H), etc.), 2-position may be substituted with cyano group, 3-position phenyl-substituted acrylate (cinnamic acid derivative), salicylate, organic Ni complex and natural substances (umbelliferone and endogenous urocanin) Acid). Biphenyl and especially stilbene derivatives are of particular importance; these are marketed as Tinosorb® FD or Tinosorb® FR ex Ciba. Examples of UV-B-absorbers include 3-benzylidene camphor or 3-benzylidene norcamphor and their derivatives (eg, 3- (4-methylbenzylidene) camphor); 4-aminobenzoic acid derivatives (preferably 2 -Ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate); cinnamic acid esters (preferably 2-ethylhexyl 4-methoxycinna Mart, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene)); salicylic acid ester (preferably 2-ethylhexyl salicylate) Sulfonate, 4-isopropylbenzyl salicylate, homomenthyl salicylate); benzophenone derivatives (preferably 2-hydro Xy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4′-methylbenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone); benzalmalonic acid ester (preferably di-2-ethylhexyl, 4- Methoxybenzmalonate); triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyltriazone or dioctylbutamide Triazone (such as Uvasorb® HEB); propane-1,3-dione (eg 1- (4-tert-butylphenyl) -3- (4′-methoxyphenyl) propane-1,3-dione Etc.); a ketotricyclo (5.2.1.0) decane derivative. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; sulfonic acid derivatives of benzophenone (Preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts); sulfonic acid derivatives of 3-benzylidene camphor (eg 4- (2-oxo-3-bornyldenmethyl) benzenesulfone Acid and 2-methyl-5- (2-oxo-3-bornyldene) sulfonic acid and the like) and salts thereof.

  Suitable typical UV-A filters are in particular benzoylmethane derivatives (eg 1- (4′-tert-butylphenyl) -3- (4′-methoxyphenyl) propane-1,3-dione, 4- tert-butyl-4′-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4′-isopropylphenyl) propane-1,3-dione, and the like), and enamine compounds. Of course, UV-A filters and UV-B filters can also be used in a mixture. As with the soluble material, insoluble photoprotective pigments (ie, finely dispersed (preferably nanonized) metal oxides or salts) are suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide, and also iron oxide, zirconium oxide, silicon oxide, manganese oxide, aluminum oxide and cerium oxide, and mixtures thereof. Salts that can be used are silicate (talc), barium sulfate or zinc stearate. Oxides and salts are already used in the form of skin care and skin protection emulsions and decorative cosmetic pigments. Here, the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. Although particles having a shape that is elliptical or deviates from a sphere in some other manner may be used, they may have a sphere. In addition, the pigment may be subjected to surface treatment (that is, hydrophilicity or hydrophobicity). A typical example is coated titanium dioxide, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents here are mainly silicon, and particularly preferably trialkoxyoctylsilane or simethicone. It is preferred to use micronized zinc oxide.

  The UV absorber may be present in the dishwasher detergent in an amount of up to 5% by weight, preferably in an amount of up to 3% by weight, particularly preferably 0.01-2.0% by weight and in particular 0.03-1% by weight. .

  A further class of stabilizers that can be suitably used are fluorescent dyes. These include 4,4'-diamino-2,2'-stilbene disulfonic acid (flavonic acid), 4,4'-distyrylbiphenyl, methylumbelliferone, coumarin, dihydroquinolinone, 1,3-diaryl. Examples include pyrazoline, naphthalimide, benzoxazole, benzisoxazole and benzimidazole systems, and pyrene derivatives substituted with a heterocycle. Of particular importance in this regard are sulfonates of diaminostilbene derivatives, and polymeric fluorescent materials disclosed in US 5,082,578.

  The fluorescent material may be present in the formulation in an amount of up to 5% by weight, preferably in an amount of up to 1% by weight, particularly preferably 0.01-0.5% by weight and in particular 0.03-0.1% by weight.

  In a preferred embodiment, the stabilizer is used in any desired mixture. The stabilizer is used in an amount of up to 40% by weight, preferably in an amount of up to 30% by weight, particularly preferably 0.01-20% by weight, in particular 0.02-5% by weight.

  Suitable dishwasher detergents or dishwasher detergent auxiliaries are independent of the way they are formulated, bleach, bleach activator, polymer, builder, surfactant, enzyme, electrolyte, pH control Contains at least one cleaning or cleaning active substance from the group of agents, fragrances, fragrance carriers, dyes, hydrotropic agents, foam inhibitors, antibacterial active ingredients, fungicides, fungicides, corrosion inhibitors, non-aqueous solvents . These materials are described in more detail below.

[builder]
According to the present invention, all builders (especially silicates, carbonates, organic cobuilders and phosphates) commonly used in dishwasher detergents or dishwasher detergent aids are Can be incorporated into washing and cleaning detergents and cleaners.

A suitable crystalline layered sodium silicate has the general formula NaMSi _x O _{2x + 1} · H ₂ O (wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is from 0 to 20). And a suitable value for x is 2, 3 or 4. Preferred crystalline phyllosilicates of the given formula are those in which M is sodium and x is assumed to be a value of 2 or 3. In particular, both β- and δ- sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are suitable.

Having delayed dissolution and secondary detergent properties, 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and especially 1: 2 to 1: 2.6 Na ₂ O: a SiO ₂ coefficients It is also possible to use amorphous sodium silicate. The dissolution delay compared to conventional amorphous sodium silicate can be introduced in various ways, for example by surface treatment, compounding, compaction / compression, or by overdrying. Within the scope of the present invention, the term “amorphous” is also understood as meaning “X-ray amorphous”. This means that in X-ray diffraction experiments, the silicate does not give the sensitive X-ray reflections typical of crystalline materials and, at best, scattered radiation having a width of several diffraction angle units. Means to give one or more maximum values of X-rays. However, it is very possible that particularly good builder properties can result in electron diffraction experiments, even when the silicate particles give poorly defined diffraction maxima or sharp diffraction maxima. This should be interpreted as the effect that the product has a fine crystalline region with dimensions of 10 nm to several hundred nm (values up to 50 nm and in particular values up to 20 nm are preferred). Compressed / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly suitable.

  Carbonates that may be present in the composition are either monoalkali metal carbonates or dialkali metal carbonates or sesquicarbonates. Suitable alkali metal ions are sodium ions and / or potassium ions. In one embodiment, it is preferred to mix at least partially, separately or subsequently, as further components in the carbonate and / or bicarbonate. Also, for example, blends of carbonates, silicates and optionally further adjuvants (such as anionic surfactants or other (especially organic) builder substances) may be separated into the finished composition. May be present as a component of

  Of course, if such use should not be avoided for reasons of environmental protection, generally known phosphates can be used as builder substances. Among the many commercially available phosphates, alkali metal phosphates, particularly preferably pentasodium triphosphate or pentapotassium triphosphate (sodium tripolyphosphate or potassium tripolyphosphate) are very popular in the detergent and cleaner industry. Is important to.

Alkali metal phosphate is a general term for alkali metal (especially sodium and potassium) salts of various phosphoric acids. Of these, metaphosphoric acid (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ can be distinguished in addition to high molecular weight typical phosphoric acid. Phosphate has many advantages: they act as an alkaline carrier, prevent limescale film on machine components or limescale deposits on the product, and further contribute to cleaning performance.

Suitable phosphates are sodium dihydrogen phosphate (NaH ₂ PO ₄ ), disodium hydrogen phosphate (dibasic sodium phosphate, Na ₂ HPO ₄ ), trisodium phosphate (trisodium phosphate, Na ₃ PO ₄ ), tetrasodium diphosphate (sodium pyrophosphate, Na ₄ P ₂ O ₇ ), high molecular weight sodium phosphate and potassium phosphate formed by condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ . Among them, between cyclic typical phosphate, sodium metaphosphate or potassium metaphosphate and chain-like type phosphate, sodium polyphosphate or potassium polyphosphate, and pentasodium triphosphate (Na ₅ P ₃ A distinction can also be made between O ₁₀ (sodium tripolyphosphate)).

  In addition to the identified sodium phosphate, the corresponding potassium salt or a mixture of both can also be used; and according to the invention, a mixture of sodium tripolyphosphate and sodium potassium tripolyphosphate, or potassium tripolyphosphate and tripolyline A mixture of potassium sodium phosphate or sodium tripolyphosphate, potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used.

  Dishwasher detergents or dishwasher detergent auxiliaries suitable for the purposes of the present invention do not contain sodium hydroxide and / or potassium hydroxide.

  Suitable water-soluble builders are, for example, tripotassium citrate and potassium water glass.

  Suitable dishwasher detergents or dishwasher detergent aids are 20-60% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali phosphates Metal salts, particularly preferably pentasodium triphosphate and pentapotassium triphosphate (sodium tripolyphosphate and potassium tripolyphosphate).

  In a preferred embodiment of the invention, the content of water-soluble builder in the composition is within a relatively narrow range. In this connection, preferably a water-soluble builder is included in each case in an amount of 22.5 to 55% by weight, preferably 25 to 50% by weight and in particular 27.5 to 45% by weight, based on the total composition. , Dishwasher detergents or dishwasher detergent aids.

The composition according to the invention can particularly advantageously comprise a condensed phosphate as a water softening substance. These materials can be derived by condensation from acidic salts of orthophosphoric acid (phosphoric acid) and form a group of phosphates, also called molten or hot phosphates, due to their preparation. Condensed phosphates are divided into metaphosphates [M ^I n (PO ₃ ) _n ] and polyphosphates (M ^I _{n + 2} P _n O _{3n + 1} or M ^I _n H ₂ P _n O _{3n + 1} ) Can be.

The term “metaphosphate” is a generic name for condensed phosphates that originally have a composition of M _n [P _n O _3n ] (M = monovalent metal), but today, most often cyclic cyclo ( Limited to salts with poly) phosphate anions. In the case of n = 3, 4, 5, 6, etc., the names are tri-, tetra-, penta-, hexametaphosphate and the like. According to the systematic nomenclature of isopolyanions, anions where n = 3 are referred to as cyclotriphosphates, for example.

Metaphosphate is obtained by melting NaH ₂ PO ₄ at temperatures above 620 ° C. (where the so-called Madrell salt is also formed as an intermediate) and Graham salt (inaccurately referred to as sodium hexametaphosphate). It is obtained as a substance associated with These salts and chlorates are now linear polyphosphates that are usually not included in metaphosphates, but can likewise be advantageously used as water softeners for the purposes of the present invention.

A crystalline water-insoluble mudrel salt, (NaPO ₃ ) _x (where x is> 1000), which can be obtained from NaH ₂ PO ₄ at 200-300 ° C., is cyclic metaphosphate [ Convert to Na ₃ (PO ₃ ) ₃ ] (which melts at 620 ° C.). Quenched glass-like melt is a glass-like condensed phosphate with a composition of water-soluble Graham salt (NaPO ₃ ) _40-50 or (NaPO ₃ ) _15-20 , depending on the reaction conditions Is known). The wrong name hexametaphosphate is still used for both compositions. The so-called chlorate salt (NaPO ₃ ) _n (where n is >> 5000) is similarly generated from a 600 ° C. hot melt of the Madrell salt when left at about 500 ° C. for a short time. It forms high polymer water soluble fibers.

  “Hexametaphosphates” Budit® H6 and H8 (Budenheim) have been found to be particularly suitable water softeners from the condensed phosphate class identified above.

  Particularly suitable within the scope of this application are dishwasher detergents or dishwasher detergent auxiliaries further comprising one or more substances from the group of acidifying agents, chelate complexing agents or film-inhibiting polymers. is there.

  Possible acidifying agents are either inorganic acids or organic acids if they are compatible with the other ingredients. For reasons of consumer protection and handling safety, solid mono-, oligo- and polycarboxylic acids can be used in particular. From this group there are likewise preferably citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. These acid anhydrides can also be used as acidifying agents. Maleic anhydride and succinic anhydride are particularly commercially available. Similarly, organic sulfonic acids (such as amidosulfonic acid) can be used. Compositions that are commercially available and can also be suitably used as acidifying agents for the purposes of the present invention include Sokalan® DCS (trademark of BASF), succinic acid (up to 31% by weight) and glutaric acid (Up to 50% by weight) and adipic acid (up to 33% by weight).

  A further possible component group is chelate complexing agents. A chelate complexing agent is a substance that forms a cyclic compound with metal ions. Here, the single ligand occupies more than one coordination site on the central atom. That is, it is at least “bidentate”. Thus, in this case, the stretched compound usually provides a ring in close proximity by ion-mediated complex formation. The number of ligands to be bonded depends on the coordination number of the central ion.

  Conventional and suitable chelate complexing agents for the purposes of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers that can act as ligands and usually react with appropriate metal atoms to form chelate complexes (ie either in the main chain itself or in a chain lateral to it) Polymers having functional groups at the same time can also be used according to the invention. The resulting polymer-bound ligand of the metal complex can be derived from just one polymer or from a different polymer chain. The latter leads to cross-linking of the material if the complexing polymer is not previously cross-linked via a covalent bond.

  The complexing group (ligand) of the usual complex-forming polymer is iminodiacetic acid group, hydroxyquinoline group, thiourea group, guanidine group, dithiocarbamate group, hydroxamic acid group, amidoxime group, aminophosphoric acid, (cyclo) polyamino Groups, mercapto groups, 1,3-dicarbonyl groups and crown ether groups, some of which have very particular activity against ions of different metals. The base polymers of many complexing polymers that are also commercially important are polystyrene, polyacrylates, polyacrylonitrile, polyvinyl alcohol, polyvinyl pyridine and polyethyleneimine. Natural polymers (such as cellulose, starch or chitin) are also complexing polymers. Furthermore, they can be given additional ligand functionality as a result of polymer-like modifications.

For the purposes of the present invention, the following groups are particularly preferred:
(i) a polycarboxylic acid having a total of at least 5 carboxyl groups and optionally present hydroxyl groups,
(ii) nitrogen-containing mono- or polycarboxylic acids,
(iii) geminal diphosphonic acid,
(iv) aminophosphonic acid,
(v) phosphonopolycarboxylic acid,
(vi) one or more chelate complexing agents from cyclodextrins, in each case based on the weight of the dishwasher composition, in an amount of more than 0.1% by weight, preferably more than 0.5% by weight, in particular Dishwasher detergents or dishwasher detergent auxiliaries are preferably included, preferably in an amount of more than 1% by weight and in particular more than 2.5% by weight.

For the purposes of the present invention, all complexing agents of the prior art can be used. They can belong to different chemical groups. It is preferred to use the following individually or in mixtures with each other:
a) a polycarboxylic acid (such as gluconic acid) having a total of at least 5 carboxyl groups and optionally present hydroxyl groups,
b) Nitrogen-containing mono- or polycarboxylic acids (ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nitridodiacetic acid-3-propionic acid, isoserine diacetic acid, N, N-di (β-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)), their higher homologs having up to 8 carbon atoms, and their hydroxy or amino group-containing derivatives, and 1-aminoethane-1,1-diphosphonic acid, its higher homologs having up to 8 carbon atoms, and their hydroxy or amino group-containing derivatives,
d) aminophosphonic acid (such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) or nitrilotri (methylenephosphonic acid)),
e) phosphonopolycarboxylic acids (such as 2-phosphonobutane-1,2,4-tricarboxylic acid), and
f) Cyclodextrin.

  For the purposes of this patent application, polycarboxylic acid a) is understood as meaning carboxylic acids (including monocarboxylic acids) in which the sum of the carboxyl groups and hydroxyl groups present in the molecule is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids (especially EDTA) are preferred. At the alkaline pH value of the treatment solution required according to the invention, these complexing agents are at least partly in the form of anions. It is immaterial whether they are introduced in the acid form or in the salt form. When salts are used, alkali metal salts, ammonium salts or alkylammonium salts (especially sodium salts) are preferred.

  Similarly, film inhibiting polymers can be present in the compositions of the present invention. These materials, which can have chemically different structures, originate, for example, from the group of low molecular weight polyacrylates having a molar mass between 1000 and 20000 daltons. Preferred are polymers having a molar mass of less than 15000 daltons.

  Film inhibiting polymers may also have cobuilder properties. Organic cobuilders that can be used in the dishwasher detergents according to the invention are in particular polycarboxylate / polycarboxylic acids, polycarboxylate polymers, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. It is. These substance classes are described below.

  Organic builder substances that can be used are, for example, polycarboxylic acids which can be used in the form of sodium salts. The term polycarboxylic acid means a carboxylic acid having more than one acid functional group. Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA). If not for reasons), and mixtures thereof. Suitable salts are those of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures thereof.

  The acid itself can also be used. In addition to their builder action, acids typically also have the properties of acidifying components and thus help to establish the lower and milder pH of the detergent or cleaner. In this connection, special mention is made of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

  Also suitable as builders or film inhibitors are polycarboxylate polymers; these include, for example, alkali metal salts of polyacrylic acid or alkali metal salts of polymethacrylic acid (eg, 500-70000 g / mol). Having a relative molecular weight).

For purposes of this specification, the molar mass imparted to the polycarboxylate polymer is essentially determined using gel permeation chromatography (GPC) using a UV detector, the weight average of each acid form. it is the molar mass M _W. Measurements are made against an external standard polyacrylic acid that gives realistic molecular weight values for structural similarity to the polymer under investigation. These numbers differ considerably from the molecular weight values obtained using polystyrene sulfonic acid as a standard. The molar mass measured with respect to polystyrene sulfonic acid is usually considerably higher than the molar mass given herein.

  Organic cobuilders that can be used in detergents within the scope of the present invention are in particular polycarboxylate / polycarboxylic acid, polycarboxylate polymer, aspartic acid, polyacetal, dextrin, further organic cobuilders (see below), and phosphonates. It is. These substance classes are described below.

  Organic builder substances that can be used are, for example, polycarboxylic acids which can be used in the form of sodium salts. The term polycarboxylic acid means a carboxylic acid having more than one acid functional group. Examples of these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid, aminocarboxylic acid, nitrilotriacetic acid (NTA). If not for reasons), and mixtures thereof. Suitable salts are those of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycine diacetic acid, sugar acids and mixtures thereof.

  The acid itself can also be used. In addition to their builder action, acids typically also have the properties of acidifying components and thus help to establish the lower and milder pH of the detergent or cleaner. In this connection, special mention is made of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof.

  Also suitable as builders are polycarboxylate polymers; these are, for example, polyacrylic acid or alkali metal salts of polymethacrylic acid (for example having a relative molecular weight of 500-70000 g / mol). is there.

Within the scope of this specification, the molar mass imparted to the carboxylate polymer is essentially determined using gel permeation chromatography (GPC) using a UV detector, the weight average molar mass M of each acid. _W. Measurements are made against an external standard polyacrylic acid that gives realistic molecular weight values for structural similarity to the polymer under investigation. These numbers differ considerably from the molecular weight values obtained using polystyrene sulfonic acid as a standard. The molar mass measured with respect to polystyrene sulfonic acid is usually considerably higher than the molar mass given herein.

  Suitable polymers are in particular polyacrylates. This preferably has a molecular weight of 1000-20000 g / mol. Due to their excellent solubility, preferably in this group, short-chain polyacrylates having a molar mass of 1000 to 10000 g / mol (particularly preferably 1200 to 4000 g / mol) can likewise be mentioned. .

  In the composition of the invention, it is particularly preferred to use either a polyacrylate or a copolymer of an unsaturated carboxylic acid, a sulfonic acid group-containing monomer and optionally further ionic or non-ionogenic monomers. Use. The sulfonic acid group-containing copolymer is described in detail below.

However, it is also possible to provide the product of the invention which is a so-called “trinity” product combining conventional detergents, rinsing aids and salt displacement functions. In this regard, preferably 0.1 to 70% by weight
i) an unsaturated carboxylic acid;
ii) a sulfonic acid group-containing monomer;
iii) Dishwasher detergents according to the present invention further comprising copolymers with further ionic or non-ionogenic monomers as required.

  These copolymers lead to a portion of the tableware treated with such a composition that is significantly cleaner in later cleaning operations than to a portion of the tableware rinsed with a conventional composition.

  A further positive effect is a reduction in the drying time of the part of the dishes treated with the detergent. That is, the consumer can remove the dishes from the machine sooner and reuse them after the cleaning program is complete.

  For the purposes of the present invention, formula VII

Wherein R ^{1 to} R ³ are, independently of each other, —H, —CH ₃ , a linear or branched saturated alkyl group having 2 to 12 carbon atoms, 2 to 12 carbon atoms A straight-chain or branched mono- or polyunsaturated alkenyl group having the above, an alkyl or alkenyl group as defined above substituted with —NH ₂ , —OH or —COOH, or —COOH or —COOR ^{4 wherein} R ⁴ is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 12 carbon atoms)
The unsaturated carboxylic acid represented by is suitable as a monomer.

Among the unsaturated carboxylic acids which can be represented by the formula VII, particularly preferred are acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H; R ³ = CH ₃ ) And / or maleic acid (R ¹ = COOH; R ² = R ³ = H).

  In the case of sulfonic acid group-containing monomers, preferably the formula VIII

Wherein R ^{5 to} R ⁷ are, independently of each other, —H, —CH ₃ , a linear or branched saturated alkyl group having 2 to 12 carbon atoms, 2 to 12 carbon atoms A straight-chain or branched mono- or polyunsaturated alkenyl group having the above, an alkyl or alkenyl group as defined above substituted with —NH ₂ , —OH or —COOH, or —COOH or —COOR ^{4 wherein} R ⁴ is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 12 carbon atoms), and X is optionally present, — (CH ₂ ) _n — (Where n = 0 to 4), -COO- (CH ₂ ) _k- (where k = 1 to 6), -C (O) -NH-C (CH ₃ ) ₂ -and -C ( O) -NH-CH (CH ₂ CH ₃ )-is a spacer group.
The thing shown by is mentioned.

  Among these monomers, preferably the formula VIIIa, VIIIb and / or VIIIc

Wherein R ⁶ and R ⁷ are independently of each other selected from —H, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) ₂ and X Are present as needed,-(CH ₂ ) _n- (where n = 0 to 4), -COO- (CH ₂ ) _k- (where k = 1 to 6), -C ( It is a spacer group selected from O) -NH-C (CH ₃ ) ₂ -and -C (O) -NH-CH (CH ₂ CH ₃ )-
The thing shown by is mentioned.

Here, particularly suitable sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid (in formula IIa, X = —C (O) NH—CH (CH ₂ CH ₃ )), 2-acrylamide-2 -Propanesulfonic acid (in formula VIIIa, X = -C (O) NH-C (CH ₃ ) ₂ ), 2-acrylamido-2-methyl-1-propanesulfonic acid (in formula VIIIa, X = -C (O _{) NH-CH (CH 3)} CH 2 -), in 2-methacrylamide-2-methyl-1-propanesulfonic acid (formula VIIIb, X = -C (O) NH-CH (CH 3) CH 2 -) (wherein VIIIb, X = -C (O) NH-CH 2 CH (OH) CH 2 -) 3- methacrylamide-2-hydroxypropane sulfonic acid, allyl sulfonic acid (wherein VIIIa, X = CH ₂₎ , methallyl sulfonic acid (wherein IIb, X = CH _2), allyl oxybenzene sulfonic acid (wherein _{VIIIa, X = -CH 2 -OC 6} H 4 -), in methallyl oxybenzene sulfonate (formula VIIIb, _{X = -CH 2 -OC 6 H 4} -), 2- hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen-1-sulfonyl Acid (wherein VIIIb, X = CH _2), styrenesulfonic acid (wherein _{VIIIa, X = C 6 H 4} ), vinylsulfonic acid (wherein VIIIa, X is absent), 3-sulfopropyl acrylate (formula VIIIa In which X = -C (O) NH-CH ₂ CH ₂ CH _2- ), 3-sulfopropyl methacrylate (in formula VIIIb, X = -C (O) NH-CH ₂ CH ₂ CH _2- ), sulfomethacryl Amides (in formula VIIIb, X = —C (O) NH—), sulfomethylmethacrylamide (in formula VIIIb, X = —C (O) NH—CH ₂ —) and water-soluble salts of the acids.

  Suitable further ionic or non-ionogenic monomers are in particular ethylenically unsaturated compounds. A suitable content of group iii) monomers in the polymers used according to the invention is less than 20% by weight, based on the polymer. Particularly preferably used polymers consist only of monomers of groups i) and ii).

In summary,
i) Formula VII

Wherein R ^{1 to} R ³ are, independently of each other, —H, —CH ₃ , a linear or branched saturated alkyl group having 2 to 12 carbon atoms, 2 to 12 carbon atoms A straight-chain or branched mono- or polyunsaturated alkenyl group having the above, an alkyl or alkenyl group as defined above substituted with —NH ₂ , —OH or —COOH, or —COOH or —COOR ^{4 wherein} R ⁴ is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 12 carbon atoms)
An unsaturated carboxylic acid represented by

ii) Formula VIII

Wherein R ^{5 to} R ⁷ are, independently of each other, —H, —CH ₃ , a linear or branched saturated alkyl group having 2 to 12 carbon atoms, 2 to 12 carbon atoms A straight-chain or branched mono- or polyunsaturated alkenyl group having the above, an alkyl or alkenyl group as defined above substituted with —NH ₂ , —OH or —COOH, or —COOH or —COOR ^{4 wherein} R ⁴ is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 12 carbon atoms), and X is optionally present, — (CH ₂ ) _n — (Where n = 0 to 4), -COO- (CH ₂ ) _k- (where k = 1 to 6), -C (O) -NH-C (CH ₃ ) ₂ -and -C ( O) -NH-CH (CH ₂ CH ₃ )-is a spacer group.
A sulfonic acid group-containing monomer represented by

iii) Copolymers with further ionic or non-ionogenic monomers as required are particularly suitable.

Particularly suitable copolymers are
i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid;
ii) Formula VIIIa, VIIIb and / or VIIIc:

Wherein R ⁶ and R ⁷ are independently of each other selected from —H, —CH ₃ , —CH ₂ CH ₃ , —CH ₂ CH ₂ CH ₃ , —CH (CH ₃ ) ₂ and X Are present as needed,-(CH ₂ ) _n- (where n = 0 to 4), -COO- (CH ₂ ) _k- (where k = 1 to 6), -C ( It is a spacer group selected from O) -NH-C (CH ₃ ) ₂ -and -C (O) -NH-CH (CH ₂ CH ₃ )-
One or more sulfonic acid group-containing monomers represented by:
iii) It further comprises ionic or non-ionogenic monomers as required.

  The copolymer present in the product may contain various amounts of monomers from groups i) and ii), and optionally iii). Here, representative monomers from all groups i) may be combined with representative monomers from all groups ii) and representative monomers from all groups iii). Particularly preferred polymers have the specific structural units described below.

  Thus, for example, preferably the formula IX

Wherein m and p are in each case an integer natural number between 1 and 2000, and Y is a substituted or unsubstituted aliphatic, aromatic or arylaliphatic 1 to A spacer group selected from hydrocarbon groups having 24 carbon atoms, wherein Y is —O— (CH ₂ ) _n — (where n = 0 to 4), —O— (C ₆ H ₄ )-, -NH-C (CH ₃ ) ₂ -or -NH-CH (CH ₂ CH ₃ )-are preferred spacer groups]
And the products of the present invention characterized by comprising one or more copolymers containing the structural unit represented by

  These polymers are prepared by copolymerization of acrylic acid and sulfonic acid group-containing acrylic acid derivatives. The copolymerization of sulfonic acid group-containing acrylic acid derivatives and methacrylic acid likewise leads to another polymer which is preferably used in the products of the invention. This is because the product has the formula X

Wherein m and p are in each case an integer natural number between 1 and 2000, and Y is a substituted or unsubstituted aliphatic, aromatic or arylaliphatic 1 to A spacer group selected from hydrocarbon groups having 24 carbon atoms, wherein Y is —O— (CH ₂ ) _n — (where n = 0 to 4), —O— (C ₆ H ₄ )-, -NH-C (CH ₃ ) ₂ -or -NH-CH (CH ₂ CH ₃ )-are preferred spacer groups]
Characterized in that it comprises one or more copolymers containing structural units represented by

  In a completely similar manner, acrylic acid and / or methacrylic acid can also be copolymerized with sulfonic acid group-containing methacrylic acid derivatives. As a result, the structural unit in the molecule changes. For example, the formula XI

Wherein m and p are in each case an integer natural number between 1 and 2000, and Y is a substituted or unsubstituted aliphatic, aromatic or arylaliphatic 1-24 A spacer group selected from hydrocarbon groups having a carbon atom, wherein Y is —O— (CH ₂ ) _n — (wherein n = 0 to 4), —O— (C ₆ H ₄ ) — A spacer group which is -NH-C (CH ₃ ) ₂ -or -NH-CH (CH ₂ CH ₃ )-is preferred]
Products of the present invention comprising one or more copolymers containing structural units of the formula are likewise preferred embodiments of the present invention and are also preferably suitable for formula XII

Wherein m and p are in each case an integer natural number between 1 and 2000, and Y is a substituted or unsubstituted aliphatic, aromatic or arylaliphatic 1 to A spacer group selected from hydrocarbon groups having 24 carbon atoms, wherein Y is —O— (CH ₂ ) _n — (where n = 0 to 4), —O— (C ₆ H ₄ )-, -NH-C (CH ₃ ) ₂ -or -NH-CH (CH ₂ CH ₃ )-are preferred spacer groups]
And products characterized by containing one or more copolymers containing structural units represented by

  Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly suitable monomer from group i). This means that the formula XIII

Wherein m and p are in each case an integer natural number between 1 and 2000, and Y is a substituted or unsubstituted aliphatic, aromatic or arylaliphatic 1 to A spacer group selected from hydrocarbon groups having 24 carbon atoms, wherein Y is —O— (CH ₂ ) _n — (where n = 0 to 4), —O— (C ₆ H ₄ )-, -NH-C (CH ₃ ) ₂ -or -NH-CH (CH ₂ CH ₃ )-are preferred spacer groups]
Provides a product suitable for the present invention characterized by comprising one or more copolymers containing structural units of formula XIV and the formula XIV

Wherein m and p are in each case an integer natural number between 1 and 2000, and Y is a substituted or unsubstituted aliphatic, aromatic or arylaliphatic 1 to A spacer group selected from hydrocarbon groups having 24 carbon atoms, wherein Y is —O— (CH ₂ ) _n — (where n = 0 to 4), —O— (C ₆ H ₄ )-, -NH-C (CH ₃ ) ₂ -or -NH-CH (CH ₂ CH ₃ )-are preferred spacer groups]
To give a product characterized by comprising one or more copolymers containing structural units of formula

  In summary, the dishwasher detergent or dishwasher detergent aid according to the invention comprises, as component b), the formula IX and / or X and / or XI and / or XII and / or XIII and / or XIV

Wherein m and p are in each case an integer natural number between 1 and 2000, and Y is a substituted or unsubstituted aliphatic, aromatic or arylaliphatic 1 to A spacer group selected from hydrocarbon groups having 24 carbon atoms, wherein Y is —O— (CH ₂ ) _n — (where n = 0 to 4), —O— (C ₆ H ₄ )-, -NH-C (CH ₃ ) ₂ -or -NH-CH (CH ₂ CH ₃ )-are preferred spacer groups]
It is preferred to include one or more copolymers containing structural units represented by

  In the polymer, all or some of the sulfonic acid groups can be present in neutralized form. That is, the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced with a metal ion (preferably an alkali metal ion and particularly a sodium ion). Corresponding products characterized by the sulfonic acid groups in the copolymer being in a partially or fully neutralized form are suitable according to the invention.

  The monomer distribution of the copolymers used in the products of the invention is based on the polymer in each case, preferably in any case i) in the case of copolymers comprising only monomers from groups i) and ii). Or ii) is from 5 to 95% by weight, particularly preferably from 50 to 90% by weight of monomers from group i) and from 10 to 50% by weight of monomers from group ii).

  In the case of terpolymers, particularly preferably 20 to 85% by weight of monomers from group i), 10 to 60% by weight of monomers from group ii) and 5 to 30% by weight of monomers from group iii) The thing containing is mentioned.

The molar mass of the polymer used in the products of the present invention can be varied to adapt the polymer properties to the desired intended use. Suitable dishwasher detergents are characterized in that the copolymer has a molar mass of 2000-200000 gmol ⁻¹ , preferably 4000-25000 gmol ⁻¹ and especially 5000-15000 gmol ⁻¹ .

  The content of one or more copolymers in the products of the invention can be varied depending on the intended use and desired product performance. Preferred dishwasher detergents according to the invention are 0.25 to 50%, preferably 0.5 to 35%, particularly preferably 0.75 to 20% and especially 1 to 15% by weight of copolymer or copolymers. Is characterized by the presence of.

  As already mentioned above, in the composition according to the invention, it is particularly preferred that the polyacrylate, the unsaturated carboxylic acid copolymer, the sulphonic acid group-containing monomer, optionally further ionic or non-ionogenic monomers. Use. Polyacrylates are described in detail above. Particularly suitable are combinations of the above sulfonic acid group-containing copolymers and low molar mass polyacrylates (for example in the range between 1000 and 4000 daltons). Such polyacrylates are commercially available under the trade names Sokalan® PA15 and Sokalan® PA25 (BASF).

  Also suitable are polycarboxylate copolymers, in particular copolymers of acrylic acid and methacrylic acid and copolymers of acrylic acid or methacrylic acid and maleic acid. Copolymers that have been found to be particularly suitable are copolymers of acrylic acid and maleic acid containing 50-90% by weight acrylic acid and 50-10% by weight maleic acid. Their relative molecular weights based on free acids are generally 2000 to 100000 g / mol, preferably 20000 to 90000 g / mol and in particular 30000 to 80000 g / mol.

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

  In order to improve the solubility in water, the polymer may contain allyl sulfonic acid (such as allyloxybenzene sulfonic acid and methallyl sulfonic acid) as monomers.

  Also, biodegradable polymers containing more than two different monomer units, eg polymers containing acrylic acid and maleic acid salts and vinyl alcohol or vinyl alcohol derivatives as monomers, or acrylic acid as monomers Particularly preferred are polymers of these and salts of 2-alkylallylsulfonic acids and sugar derivatives.

  Further suitable copolymers have, as monomers, preferably acrolein and acrylic acid / acrylate or acrolein and vinyl acetate.

  Further suitable builder substances which can likewise be mentioned are aminodicarboxylic acid polymers, their salts or their precursors. Particularly preferred are polyaspartic acid and salts thereof and derivatives thereof.

  A further suitable builder material is polyacetal. This can be obtained by reacting a dialdehyde with a polyol carboxylic acid having 5 to 7 carbon atoms and at least three hydroxyl groups. Suitable 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).

  Further suitable organic builder substances are carbohydrate oligomers or polymers which can be obtained by partial hydrolysis of dextrins, for example starch. Hydrolysis can be performed according to customary processes, such as acid- or enzyme-catalyzed processes. The hydrolyzate preferably has an average molar mass in the range of 400-500000 g / mol. Here, polysaccharides having a dextrose equivalent (DE) in the range of 0.5 to 40 (particularly 2 to 30) are preferred. DE is a customary measure of the reducing effect of polysaccharides compared to dextrose (DE = 100). Either maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37, and so-called yellow dextrins and whites with a high molar mass in the range 2000-30000 g / mol Dextrins can also be used.

Such oxidized derivatives of dextrin are reaction products with oxidizing agents that can oxidize at least one alcohol function of their sugar ring to a carboxylic acid function. Products in which C _{6 of the} sugar ring is oxidized may be particularly advantageous.

  Also, oxydisuccinate and other derivatives of disuccinate (preferably ethylenediamine disuccinate) are other suitable cobuilders. Ethylenediamine-N, N′-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salt. Furthermore, in this connection glycerol disuccinate and then glycerol triscinate are also suitable. A suitable usage in formulations containing zeolite and / or silicate is 3 to 15% by weight.

  Further organic cobuilders that can be used are, for example, acetylated hydroxycarboxylic acids and salts thereof. It can also exist in the lactone form and contains at least 4 carbon atoms, at least 1 hydroxyl group and no more than 2 acid groups.

  A further class of substances having cobuilder properties are phosphonates. These are in particular hydroxyalkane phosphonates and aminoalkane phosphonates. Of the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a cobuilder. It is preferably used as sodium salt, neutral disodium salt and tetrasodium salt which gives an alkaline (pH 9) reaction. Suitable aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriamine pentamethylene phosphonate (DTPMP), and their higher homologues. They are preferably used in the form of neutrally reacting sodium salts (eg as the hexasodium salt of EDTMP or as the heptasodium and octasodium salts of DTPMP). The builders used in this case are from the class of phosphonates (preferably HEDP). Furthermore, aminoalkane phosphonates have a significant heavy metal binding capacity. Thus, it may be preferred to use aminoalkane phosphonates (especially DTPMP), or mixtures of the phosphonates, especially when the composition also includes a bleach.

  In addition, all compounds that can form complexes with alkaline earth metal ions can be used as cobuilders.

  Within the scope of the present application, the composition according to the invention comprises, in each case, a builder, preferably a builder from the group of silicates, carbonates, organic cobuilders and / or phosphates. On the basis of 0.1 to 99.5% by weight, preferably 1 to 95% by weight, particularly preferably 5 to 90% by weight and in particular 10 to 80% by weight.

[Surfactant]
Within the scope of the present application, suitable detergents comprise one or more surfactants from the group of anionic, nonionic, cationic and / or amphoteric surfactants.

The anionic surfactants used are, for example, sulfonate type and sulfate type surfactants. Suitable sulfonate type surfactants are preferably C _9-13 -alkylbenzene sulfonates, olefin sulfonates (ie, mixtures of alkene sulfonates and hydroxyalkane sulfonates) and, for example, C ₁₂ having terminal or internal double bonds. _{Disulfonates,} such as those obtained from _-18 -monoolefins by sulfonation with sulfur trioxide gas followed by alkali or acid hydrolysis of the sulfonated product. Also suitable are alkanesulfonates obtained from C _12-18 -alkanes, for example by sulfochlorination or sulfooxidation with subsequent hydrolysis or neutralization. Similarly, esters of α-sulfo fatty acids (ester sulfonates) such as hydrogenated coconut fatty acids, palm kernel fatty acids or tallow fatty acid α-sulfonated methyl esters are suitable.

  Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are monoesters, diesters and triesters, as obtained in the preparation by esterification of monoglycerol with 1-3 mol fatty acids or in the transesterification of triglycerides with 0.3-2 mol glycerol, and Is understood to mean a mixture of Here, suitable sulfated fatty acid glycerol esters are saturated fatty acids having 6 to 22 carbon atoms (eg caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid). It is a sulfated product.

Suitable alkyl (alkenyl) sulfates are C ₁₂ -C ₁₈ -fatty alcohols (eg from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol or C ₁₀ -C ₂₀ -oxo alcohol Fatty acid) sulfuric acid half esters and alkali metal salts (especially sodium salts) of secondary chain sulfuric acid half esters of these chain lengths. Preference is given to alkyl sulphate (alkenyl) of this chain length which contains synthetic linear alkyl groups prepared on the basis of petrochemistry and which has a degradation behavior similar to that of equivalent compounds based on lipochemical raw materials. From the standpoint of washing, C ₁₂ -C ₁₆ -alkyl sulfate and C ₁₂ -C ₁₅ -alkyl sulfate and C ₁₄ -C ₁₅ -alkyl sulfate are preferred. Also suitable anionic surfactants are 2,3-alkyl sulfates which can be obtained as commercial products of the Shell Oil Company under the name DAN®.

Alternatively, linear or branched C _7-21 -alcohol ethoxylated with 1-6 mol ethylene oxide (2-methyl-branched C ₉ with 3.5 mol ethylene oxide (EO) on average) Also suitable are sulfuric acid monoesters such as _-11 -alcohol or C _{12-18 -fatty} alcohols with 1 to 4 EO. Due to their high foaming behavior, they are only used in detergents in relatively small amounts (eg in amounts of 1-5% by weight).

Further suitable anionic surfactants are alkylsulfosuccinic acid salts. This is also referred to as sulfosuccinate or sulfosuccinate and corresponds to monoesters and / or diesters of sulfosuccinic acid and alcohols (preferably fatty alcohols and in particular ethoxylated fatty alcohols). Suitable sulfosuccinates contain C _{8-18 -fatty} alcohol groups or mixtures thereof. Particularly suitable sulfosuccinates contain fatty alcohol groups derived from ethoxylated fatty alcohols (which themselves correspond to nonionic surfactants (see description below)). In this regard, particular preference is likewise given to sulfosuccinates derived from ethoxylated fatty alcohols whose fatty alcohol groups likewise have a narrow homolog distribution. Similarly, alkyl (alkenyl) succinic acids or salts thereof preferably having 8 to 18 carbon atoms in the alkyl (alkenyl) chain may also be used.

  Suitable further anionic surfactants are in particular soaps. Saturated fatty acid soaps (such as lauric acid salt, myristic acid salt, palmitic acid salt, stearic acid salt, hydrogenated erucic acid salt and behenic acid salt), and especially natural fatty acids (eg, coconut fatty acid, palm Soap mixtures derived from (nuclear fatty acids or tallow fatty acids) are suitable.

  Anionic surfactants, including soaps, can exist in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases (such as mono-, di- or triethanolamine). The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular the sodium salt.

A further group of cleaning actives are nonionic surfactants. The nonionic surfactants used are preferably alkoxylated (preferably ethoxylated), in particular preferably 8 to 18 carbon atoms and an average of 1 per mol of alcohol. It is a primary alcohol with ~ 12 mol ethylene oxide (EO). Here, the alcohol group can be linear or preferably methyl-branched at the 2-position, or a straight-chain group and a methyl-branched group in the mixture, as normally present in oxoalcohol groups. May be contained. However, in particular, linear groups derived from naturally occurring alcohols having 12 to 18 carbon atoms (eg, coconut alcohol, palm alcohol, tallow fatty alcohol or oleyl alcohol) and an average of 2 to 2 per mole of alcohol Alcohol ethoxylates having an EO of 8 are preferred. Suitable ethoxylated alcohols include, for example, C _12-14 -alcohol with 3 EO or 4 EO, C _9-11 -alcohol with 7 EO, 3 EO, 5 EO, 7 EO or C _{13-15 -Alcohol} with 8 EO, 3 EO, 5 EO or C _{12-18 -Alcohol} with 7 EO and mixtures of these (C _12-14 with 3 EO _-Alcohol and 5 C _12-18 -alcohol mixtures with EO). A given degree of ethoxylation represents a statistical average. This can be an integer or a fraction for a particular product. Suitable 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 are tallow fatty alcohols with 14 EO, 25 EO, 30 EO or 40 EO.

  A further class of suitably used nonionic surfactants (which are used as a single nonionic surfactant or in combination with other nonionic surfactants) are preferably An alkoxylated (preferably ethoxylated) fatty acid alkyl ester, or an ethoxylated and propoxylated fatty acid alkyl ester, in particular a fatty acid methyl ester, having 1 to 4 carbon atoms in the alkyl chain.

A further class of nonionic surfactants that can be advantageously used are alkyl polyglycosides (APG). Alkyl polyglycosides that can be used are those of the general formula RO (G) _z , where R is linear or branched, in particular the methyl branched in the 2-position, saturated or unsaturated, 8-22. , Preferably an aliphatic group having 12 to 18 carbon atoms, and G is a monosaccharide unit having 5 or 6 carbon atoms, preferably a symbol representing glucose. Here, the degree of glycosylation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. ] Is satisfied. Preferable examples include use of linear alkyl polyglucoside (eg, alkyl polyglycoside consisting of a glucose group and an n-alkyl chain).

  A further class of suitably used nonionic surfactants (which are used as a single nonionic surfactant or in combination with other nonionic surfactants) are preferably , Alkoxylated (preferably ethoxylated) fatty acid alkyl esters, or ethoxylated and propoxylated fatty acid alkyl esters having 1 to 4 carbon atoms in the alkyl chain.

  Nonionic surfactants of amine oxide type (eg N-cocoalkyl-N, N-dimethylamine oxide and N-tallow-alkyl-N, N-dihydroxyethylamine oxide) and fatty acid alkanolamide type nonionic interfaces Activators may also be appropriate. The amount of these nonionic surfactants is preferably below the amount of ethoxylated fatty alcohols, in particular below half.

  Further suitable surfactants are those of formula (XV)

[Wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ¹ is hydrogen, an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, and [Z] is Linear or branched polyhydroxyalkyl groups having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups)
Is a polyhydroxy fatty acid amide. Polyhydroxy fatty acid amides are known substances and can usually be obtained by reductive amination of reducing sugars using ammonia, alkylamines or alkanolamines followed by acylation using fatty acids, fatty acid alkyl esters or fatty acid chlorides.

  The group of polyhydroxy fatty acid amides includes the formula (XVI)

Wherein R is a linear or branched, alkyl or alkenyl group having 7 to 12 carbon atoms, R ¹ is a linear, branched or cyclic, 2 to 8 An alkyl group or an aryl group having 2 carbon atoms, and R ² is a linear, branched or cyclic, 1-8 carbon atom, alkyl group, aryl group or oxyalkyl group, Here, a C _1-4 -alkyl group or a phenyl group is preferred, and [Z] is a linear polyhydroxyalkyl group in which the alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated (preferably Is an ethoxylated or propoxylated derivative of this group]
The compound shown by these is also mentioned.

[Z] is preferably obtained by reductive amination of a reducing sugar (eg glucose, fructose, maltose, lactose, galactose, mannose or xylose). The N-alkoxy- or N-aryloxy-substituted compound can then be converted to the desired polyhydroxy fatty acid amide by reacting with a fatty acid methyl ester in the presence of an alkoxide as a catalyst.
In the case of cleaning and cleaning compositions for mechanical dishwashing, suitable surfactants are generally all surfactants. However, for this intended use, preferred are the nonionic surfactants mentioned here (mainly low foaming nonionic surfactants). Particular preference is given to alkoxylated alcohols (especially ethoxylated and / or propoxylated alcohols). In this regard, those skilled in the art generally use alkoxylated alcohols as alkylene oxides (preferably ethylene oxide) and alcohols (preferably for the purposes of the present invention, preferably long chain alcohols ( _{C10- C18} , preferably Between C ₁₂ and C ₁₆ , eg C _11- , C _12- , C _13- , C _14- , C _15- , C _16- , C ₁₇ -and C ₁₈ -alcohol)) Understand as meaning. In general, n moles of ethylene oxide and 1 mole of alcohol yield a complex mixture of addition products of varying degrees of ethoxylation, depending on the reaction conditions. A further embodiment consists in the use of a mixture of alkylene oxides, preferably a mixture of ethylene oxide and propylene oxide. If desired, subsequent etherification with a short chain alkyl group (preferably a butyl group, etc.) leads to a class of “capped” alcohol ethoxylate materials that can be used as well within the scope of the present invention. obtain. Very particularly preferred within the scope of the invention here are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.

  Within the scope of the present invention, it has been found that low foaming nonionic surfactants having alternating ethylene oxide units and alkylene oxide units are particularly suitable as nonionic surfactants. Among these, a surfactant having an EO-AO-EO-AO block is also preferable. Here, in any case, 1 to 10 EO or AO groups are bonded to each other before a block from each other group follows. In this regard, it is preferred that the general formula XVII be used as the nonionic surfactant.

Wherein R ¹ is a linear or branched, saturated or mono- or polyunsaturated C _6-24 -alkyl group or C _6-24 -alkenyl group; each group R ² or R ³ Is independently selected from the other groups —CH ₃ ; —CH ₂ CH ₃ , —CH ₂ CH ₂ —CH ₃ , —CH (CH ₃ ) ₂ , and the indices w, x, y, z are Independently of one another, are integers from 1 to 6)
The detergent for dishwashers of this invention containing the surfactant shown by these is mentioned.

Suitable nonionic surfactants of formula XVII can be prepared from the corresponding alcohol R ¹ —OH and ethylene oxide or alkylene oxide by known methods. The group R ^{1 in} formula XVII above can vary depending on the origin of the alcohol. When natural origin is used, the group R ¹ has an even number of carbon atoms and is usually unbranched. Suitable examples include linear groups derived from naturally occurring alcohols having 12 to 18 carbon atoms (eg, coconut alcohol, palm alcohol, tallow fatty alcohol or oleyl alcohol). Alcohols that are available from synthetic sources are, for example, Gerve alcohol or groups that are methyl-branched at the 2-position, or linear and methyl-branched groups in a mixture, as is customarily present in oxoalcohol groups. Regardless of the type of alcohol used to prepare the nonionic surfactant present in the composition according to the present invention, preferably R ^{1 in} formula XVII is 6-24, preferably Mention is made of the dishwasher detergent according to the invention which is an alkyl radical having 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

In addition to propylene oxide, suitable alkylene oxide units which are present alternately with ethylene oxide units in suitable nonionic surfactants are in particular butylene oxide. However, further alkylene oxides are also suitable in which R ² and R ³ are, independently of one another, selected from —CH ₂ CH ₂ —CH ₃ and —CH (CH ₃ ) ₂ . Suitable dishwasher detergents are those wherein R ² and R ³ are the group —CH ₃ , w and x are independently of each other, a value of 3 or 4, and y and z are independently of each other 1 or Characterized by a value of 2.

In summary, for use in the compositions of the present invention, particularly preferred is 1-4 ethylene oxide units, followed by 1-4 propylene oxide units, followed by 1-4 ethylene oxide units. , Followed by nonionic surfactants having C _9-15 -alkyl groups with 1 to 4 propylene oxide units.

  Suitable additional surfactants to be used are low foaming nonionic surfactants. Particularly preferably, the dishwasher detergent of the present invention comprises a nonionic surfactant having a melting point above room temperature. As a result, suitable compositions have a melting point of 20 ° C., preferably above 25 ° C., particularly preferably between 25 ° C. and 60 ° C. and in particular between 26.6 ° C. and 43.3 ° C. It is characterized by including a nonionic surfactant.

  In addition to the nonionic surfactant present in the composition according to the present invention, suitable nonionic surfactants having a melting point or softening point within the above temperature range are, for example, solid or high viscosity at room temperature. Is a low foaming nonionic surfactant. When using nonionic surfactants that are highly viscous at room temperature, it is preferred for them to have a viscosity of more than 20 Pas, preferably more than 35 Pas and in particular more than 40 Pas. Also suitable are nonionic surfactants having a wax-like consistency at room temperature.

  The nonionic surfactants used that are solid at room temperature are preferably alkoxylated nonionic surfactants (especially ethoxylated primary alcohols) and structurally more complex with these surfactants. Originates from a group of mixtures of various surfactants (such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants). Furthermore, such (PO / EO / PO) nonionic surfactants are characterized by good foam control.

  In a preferred embodiment of the invention, the nonionic surfactant having a melting point above room temperature is a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms and preferably at least 12 per mole of alcohol or alkylphenol. An ethoxylated nonionic surfactant resulting from a reaction with mol, particularly preferably at least 15 mol, in particular at least 20 mol of ethylene oxide.

Particularly preferred nonionic surfactants used that are solid at room temperature are straight chain fatty alcohols having from 16 to 20 carbon atoms (C _16-20 -alcohols), preferably C ₁₈ -alcohols. From at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide. Among these, so-called “narrow range ethoxylates” (see above) are particularly preferred.

Thus, a particularly preferred composition of the invention comprises C _6-20 -monohydroxyalkanol or C _6-20 -alkylphenol or C _{16-20 -fatty} alcohol and more than 12 mol per mol of alcohol, preferably 15 Contains ethoxylated nonionic surfactants obtained from greater than mol and in particular greater than 20 mol of ethylene oxide.

  Further suitable nonionic surfactants have propylene oxide units in the molecule. Preferably, such PO units constitute 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 suitable nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols further comprising polyoxyethylene-polyoxypropylene block copolymer units. Here, the alcohol or alkylphenol part of such nonionic surfactant molecules is preferably more than 30% by weight, particularly preferably 50% by weight, of the total molar mass of such nonionic surfactants. More and especially make up more than 70% by weight. Suitable dishwasher detergents comprise up to 25%, preferably up to 20% and especially up to 15% by weight of propylene oxide units in the molecule of the total molar mass of the nonionic surfactant. Characterized by including ethoxylated and propoxylated nonionic surfactants.

  The further nonionic surfactant having a melting point above room temperature used particularly preferably comprises a 40-70% polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend. This consists of 75% polyoxyethylene and polyoxypropylene reverse block copolymer having 17 mol ethylene oxide and 44 mol propylene oxide, and 24 mol per mol trimethylolpropane, starting from trimethylolpropane. Contains 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, including ethylene oxide and 99 mol of propylene oxide.

  A nonionic surfactant that can be used particularly suitably is available, for example, from Olin Chemicals under the name Poly Tergent® SLF-18.

  A further preferred dishwasher detergent of the present invention is of the formula

Wherein R ¹ is a linear or branched, aliphatic, hydrocarbon group having 4 to 18 carbon atoms or a mixture thereof, R ² is a linear or branched 2 Hydrocarbon groups having ~ 26 carbon atoms or mixtures thereof, and x is a value between 0.5 and 1.5, and y is a value of at least 15)
The nonionic surfactant shown by these is included.

  Additional nonionic surfactants that can be suitably used are of the formula

Wherein R ¹ and R ² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups having 1 to 30 carbon atoms, R ³ is , H or methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x is a value between 1 and 30, k and j are 1 and 12 (Preferably between 1 and 5)]
Is an end-capped poly (oxyalkylated) nonionic surfactant represented by When the value x is ≧ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably straight-chain or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, particularly preferably A group having 8 to 18 carbon atoms. For the group R ³ , H, —CH ₃ or —CH ₂ CH ₃ is particularly preferred. Particularly preferred values for x are in the range of 1-20 (especially 6-15).

As noted above, each R ³ in the above formula can be different when x is ≧ 2. As a result of this, the alkylene oxide units in square brackets can vary. For example, when x is 3, the group R ³ may be chosen to form ethylene oxide (R ³ = H) units or propylene oxide (R ³ = CH ₃ ) units. This can be in any order (e.g. (EO) (PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO PO) (PO) (EO) and (PO) (PO) (PO)). Here, the value 3 for x is chosen for illustrative purposes and can be quite large. The range of variation increases as the value of x increases and includes, for example, too many (EO) groups combined with few (PO) groups, or vice versa.

  Particularly preferred end-capped poly (oxyalkylated) alcohols represented by the above formula have values of k = 1 and j = 1, so that the above formula is simplified as follows: :

In the last-mentioned formula, R ¹ , R ² and R ³ are as defined above, and x represents a numerical value of 1-30, preferably 1-20 and especially 6-18. Particularly preferred are surfactants in which the radicals R ¹ and R ² have 9 to 14 carbon atoms, R ³ is H and x is assumed to be a value of 6 to 15 .

  To summarize the last mentioned statement, preferably the formula

Wherein R ¹ and R ² are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon groups having 1 to 30 carbon atoms, R ³ is Methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl group, x is a value between 1 and 30, k and j are between 1 and 12, (Preferably a value between 1 and 5)
The end-capped poly (oxyalkylated) nonionic surfactant represented by

(Wherein x is a number from 1 to 30, preferably from 1 to 20 and especially from 6 to 18)
The detergent for dishwashers of this invention containing surfactant of the type shown by these is mentioned.

  In combination with the surfactant, an anionic surfactant, a cationic surfactant and / or an amphoteric surfactant can also be used. The latter are only less important due to their foaming behavior in dishwasher detergents, and in most cases, in any case, in amounts less than 10% by weight, usually based on the composition Can be used only in amounts that are even less than 5% by weight (eg 0.01-2.5% by weight). Accordingly, the composition of the present invention may also contain an anionic surfactant, a cationic surfactant and / or an amphoteric surfactant as a surfactant component.

  Within the scope of the present invention, a dishwasher detergent or dishwasher detergent aid is based on a surfactant (preferably a nonionic surfactant), in each case based on the total composition. In an amount of 0.5 to 10% by weight, preferably 0.75 to 7.5% by weight and in particular 1.0 to 5% by weight.

[bleach]
Bleaching agents and bleach activators are important components of detergents and cleaners. Suitable dishwasher detergents or dishwasher detergent aids may contain, within the scope of the present invention, one or more substances from a given group. Of the compounds used as bleaching agents that produce H ₂ O _{2 in} water, sodium percarbonate is particularly important. Further bleaching agents that can be used are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphate, citrate perhydrate, and H ₂ O ₂ yielding persalts or peracids (Such as perbenzoate, peroxophthalate, diperazeleic acid, phthalominoperacid or diperdodecanedioic acid).

“Sodium percarbonate” is a non-specific term for sodium carbonate peroxohydrate. Strictly speaking, this is not a “percarbonate” (ie a percarbonate salt) but a hydrogen peroxide adduct of sodium carbonate. The commercial product has an average composition of 2Na ₂ CO ₃ .3H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate is a white water-soluble powder having a density of 2.14 gcm ⁻³ and easily decomposes into sodium carbonate and oxygen having a bleaching effect and / or an oxidizing effect.

  The dishwasher detergent may also include a bleach from the group of organic bleaches. Within the scope of the present invention, a typical organic bleach that can be used as a component is a diacyl peroxide (eg, dibenzoyl peroxide, etc.). A further typical organic bleach is a peroxyacid (specific examples are alkylperoxyacids and arylperoxyacids). Suitable representative examples are (a) peroxybenzoic acid and its ring-substituted derivatives (such as alkylperoxybenzoic acid), and peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy Acids (peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthalominoperoxyhexanoic acid (PAP)], o-carboxybenzamide peroxycaproic acid, N-nonenylamide peradipic acid and N-nonenylamide pers Cinnato), and (c) aliphatic and arylaliphatic peroxydicarboxylic acids (1,2-diperoxycarboxylic acid, 1,9-diperoxyazelineic acid, diperoxysebacic acid, diperoxybrassic acid, Diperoxyphthalic acid, 2-decyldiperoxybutane-1,4-dio Kkuashido, N, N-Terefutaroiruji (6-aminopercaproic acid), etc.) may also be used.

  Also according to the invention, bleaching agents that can be used for mechanical dishwashing are substances that release chlorine or bromine. Among suitable chlorine releasing materials or bromine releasing materials, examples include heterocyclic N-bromoamides and N-chloroamides. Examples are trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations (such as potassium and sodium). Hydantoin compounds (such as 1,3-dichloro-5,5-dimethylhydantoin) are suitable as well.

  Within the scope of the present invention, advantageous compositions are preferably oxygen bleaches or groups of halogen bleaches, in particular chlorine bleaches, particularly preferably sodium percarbonate and / or sodium perborate monohydrate. One or more bleaches from the product, in each case based on the total composition, 0.5-40% by weight, preferably 1-30% by weight, particularly preferably 2.5-25% by weight and in particular 5 Contains in an amount of ~ 20% by weight.

[Bleaching activator]
To achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, within the scope of the present invention, the detergent may comprise a bleach activator. Bleach activators that may be used may be aliphatic peroxocarboxylic acids and / or substituted, preferably having 1 to 10 carbon atoms (especially 2 to 4 carbon atoms) under perhydrolysis conditions. It is a compound that produces perbenzoic acid. A substance having an O-acyl group and an N-acyl group having the number of carbon atoms and / or a benzoyl group which may be substituted is suitable. Preferably, polyacylated alkylenediamine (especially tetraacetylethylenediamine (TAED)), acylated triazine derivative (especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine) (DADHT)), acylated glycolurils (particularly tetraacetylglycoluril (TAGU)), N-acylimides (particularly N-nonanoylsuccinimide (NOSI)), acylated phenol sulfonates (particularly n-nonanoyl- Or isononanoyloxybenzenesulfonate (n- or iso-NOBS)), carboxylic anhydrides (especially phthalic anhydride), acylated polyhydric alcohols (especially triacetin, ethylene glycol diacetate and 2,5- Diacetoxy-2,5-dihydrofuran).

  In addition to or instead of conventional bleach activators, so-called bleach catalysts can also be incorporated into the detergent according to the invention. These materials are transition metal salts or transition metal complexes that promote bleaching, such as Mn-, Fe-, Co-, Ru- or Mo-salen complexes or -carbonyl complexes. Complexes of N-containing tripodal ligands with Mn, Fe, Co, Ru, Mo, Ti, V and Cu, and Co-, Fe-, Cu- and Ru-ammine complexes can also be used as bleach catalysts.

  According to the invention, preferably from the group of bleach activators, in particular polyacylated alkylenediamines (especially tetraacetylethylenediamine (TAED)), N-acylimides (especially N-nonanoylsuccinimide (NOSI)). )), One or more from the group of acylated phenol sulfonates (especially n-nonanoyl- or isononanoyloxybenzene sulfonate (n- or iso-NOBS)) and n-methylmorpholinium acetonitrile methyl sulfate (MMA) In each case based on the total composition in an amount of 0.1 to 20% by weight, preferably 0.5 to 15% by weight and in particular 1 to 10% by weight.

  Suitable bleach activators within the scope of the present invention further include those of formula (XVIII)

Wherein R ¹ is from the group of —H, —CH ₃ , C _2-24 -alkyl group or C _2-24 -alkenyl group, —Cl, —Br, —OH, —NH ₂ and —CN. having at least one substituent, the substituted C _2-24 - alkyl group or a substituted C _2-24 - alkenyl, C _1-24 - alkenylaryl having an alkyl group - alkylaryl group or C _1-24 having an alkyl group Or a substituted alkylaryl group or a substituted alkenylaryl group having a C _1-24 -alkyl group and having at least one further substituent on the aromatic ring, wherein R ² and R ³ are independent of each other -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH _{2- CH 2 -OH, -CH (OH)} -CH 3, -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3, -CH (OH) -CH 2 -CH 3, -(CH ₂ CH ₂ -O) _n H (wherein n = 1, 2, 3, 4, 5 or 6 and X is an anion)
"Nitrilquats" represented by the above, and cationic nitriles.

The general formula (XVIII) includes a large number of cationic nitriles that can be used within the scope of the present invention. Particularly advantageously, the detergent and cleaner bodies according to the invention are those in which R ¹ is methyl, ethyl, propyl, isopropyl or n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl. , Cationic nitriles, which are n-hexadecyl or n-octadecyl groups. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, and one or both groups can also advantageously be a cyanomethylene group.

Since the synthesis is easier, it is preferable that the compounds in which the groups R ^{1 to} R ³ are the same, for example, (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CNX ⁻ , (CH ₃ CH ₂ ) ₃ N _{^{(+) CH 2 -CNX -,}} (CH 3 CH 2 CH 2) 3 N (+) CH 2 -CNX -, (CH 3 CH (CH 3)) 3 N (+) CH 2 -CNX - or (HO ^{_{-CH 2 -CH 2) 3 N (}} +) CH 2 -CNX - and the like. Here, X ⁻ is preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate.

  Dishwasher detergents or detergent auxiliaries suitable within the scope of the present invention comprise 0.1 to 20% by weight of the cationic nitrile of formula (XVIII), in each case based on the total weight of the composition. , Preferably in an amount of 0.25 to 15% by weight and in particular 0.5 to 10% by weight.

[enzyme]
Suitable enzymes are in particular those from hydrolases, for example protease, esterase, lipase and lipolytic enzymes, amylase, cellulase or other glycosyl hydrolase classes, and mixtures of said enzymes. In washing, all these hydrolases contribute to the removal of dirt (such as protein, fat or starch dirt) and graying. In addition, cellulases and other glycosyl hydrolases can contribute to color retention and increased fabric flexibility by removing pilling and microfibers. Redox enzymes can also be used for bleaching and for inhibiting color transfer. Particularly suitable enzyme active ingredients are strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and It can also be obtained from Humicola insolens and their genetically modified variants. Preference is given to using subtilisin type proteases, in particular proteases obtained from Bacillus lentus. Of particular interest in this regard are enzyme mixtures, such as mixtures of proteases and amylases, or mixtures of proteases and lipases or lipolytic enzymes, or mixtures of proteases and cellulases, or mixtures of cellulases and lipases or lipolytic enzymes, Or a mixture of protease and amylase and lipase or lipolytic enzyme, or a mixture of protease and lipase or lipolytic enzyme and cellulase, especially a protease and / or lipase-containing mixture or a mixture containing lipolytic enzyme . An example of such a lipolytic enzyme is a known cutinase.

  In some cases, peroxidase or oxidase has also been found suitable. Suitable amylases include, among others, α-amylase, isoamylase, pullulanase, and pectinase. The cellulase used is preferably cellobiohydrolase, endoglucanase and endoglucosidase (which may also be cellobiase) and mixtures thereof. Because different types of cellulases differ in their CMCase activity and avicelase activity, specific mixtures of cellulases can be used to establish the desired activity.

  Enzymes can be adsorbed on a carrier material or embedded in a coating material to protect them against premature degradation. Preferred compositions of the invention comprise the enzyme, preferably in the form of a liquid and / or solid enzyme preparation, in each case 0.1-10% by weight, preferably 0.5- In an amount of 8% by weight and in particular 1-5% by weight.

[dye]
In order to improve the aesthetic impression of dishwasher detergents or dishwasher detergent assistants, they can be colored with suitable dyes. Dyes that are suitable within the scope of the present invention (the choice of which does not give any difficulty to those skilled in the art) have a high degree of storage stability and a high degree of insensitivity to other components of the composition and to light. And has no significant substance to the product so as not to contaminate the product.

  For use in the dishwasher detergents or dishwasher detergent auxiliaries according to the invention, preferably all colorants which can be oxidatively disintegrated in the cleaning process and their suitable blue dyes (so-called blue dyes). A mixture of taste agents). It has been found advantageous to use colorants that are soluble in water or that are liquid organic substances at room temperature. An example of a suitable colorant is an anionic colorant (eg, an anionic nitroso dye). One possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020; this is, for example, Basacid® Green 970 as BASF (Ludwigshafen) From Germany) and their mixtures with suitable blue dyes. Further suitable colorants include Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamin EB400 (CI 45100), Basacid (registered trademark) Yellow 094 (CI 47005), Sicovit (registered trademark) Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI acid blue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI acid blue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI acid Yellow 218) and / or Sandolan® Blue (CI acid blue 182 CAS 12219-26-0).

[Fragrance]
Perfumes to improve the aesthetic impression of the composition and to provide consumers with not only the performance of the composition but also a “typical and unmistakable” composition visually and sensorially To the composition within the scope of the present invention.

  Perfume oils and fragrances that can be used within the scope of the present invention are individual odorant compounds such as synthetic compositions of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Ester-type odorant compounds include, for example, benzyl acetate, phenoxyethyl isobutanoate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbonate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl Glycinate, allyl cyclohexyl propionate, stearyl propionate and benzyl salicylate. Examples of ethers include benzyl ethyl ether; examples of aldehydes include, for example, straight chain alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitroneral, lyial and borage. Nal; ketones, for example, ionone, α-isomethylionone and methyl cedryl ketone; alcohols, anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; hydrocarbons, mainly terpenes (Such as limonene and pinene).

  However, a mixture of different odorants that together produce a satisfactory fragrance note is preferred. Such perfume oils may also contain natural odorant mixtures, such as are available from plant sources. Examples are pine oil, citrus oil, jasmine oil, patchouli oil, rose oil or ylang-ylang oil. Similarly suitable are clary sage oil, chamomile oil, clove oil, balsam oil, mint oil, cinnamon oil, lime blossom oil, juniper berry oil, vetiver oil, olive oil, galvanum oil and labdanum oil, and orange blossom oil. Orange flower oil, orange peel oil and sandalwood oil.

[Corrosion protectant]
The dishwasher detergent may include a corrosion inhibitor to protect the product or machine. Silver protectants are particularly important in the field of mechanical dishwashing. Prior art known materials can be used. In general, it is possible to use, in particular, a silver protective agent selected from the triazole group, the benzotriazole group, the bisbenzotriazole group, the aminotriazole group, the alkylaminotriazole group, and the transition metal salt or complex group. it can. Particular preference is given to using benzotriazole and / or alkylaminotriazole. Further, active chlorine containing agents are frequently encountered in cleaning formulations. This can significantly reduce the corrosion of the silver surface. In chlorine-free cleaners, in particular oxygen- and nitrogen-containing organic redox active compounds (such as dihydric and trihydric phenols) such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, and these Derivatives of this class of compounds are used. Inorganic compounds in the form of salts and complexes (such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce) are often used. Here, preferred are transition metal salts selected from the group of manganese and / or cobalt salts and / or complexes, and particularly preferred are cobalt (ammine) complexes, cobalt (acetato) complexes, cobalt (carbonyl). ) Complexes, cobalt chloride or manganese chloride, and manganese sulfate, and manganese complexes

[In the formula, Me-TACN is 1,4,7-trimethyl-1,4,7-triazacyclononane, and Me-Me-TACN is 1,2,4,7-tetramethyl-1, 4,7-triazacyclononane)
Is mentioned. Similarly, zinc compounds can be used to prevent corrosion on the product.

  Within the scope of the present invention, preferably at least one silver protective agent selected from the group of triazole, benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, preferably benzotriazole and / or alkylaminotriazole is used. A dishwasher detergent or dishwasher further comprising, in any case, in an amount of 0.001-1% by weight, preferably 0.01-0.5% by weight and especially 0.05-0.25% by weight, based on the total composition And detergent aids.

  Further, the present application provides the use of the dishwasher detergent or dishwasher detergent aid of the present invention to reduce glass corrosion during mechanical dishwashing.

Unstained glasses were washed in a continuously operated dishwasher using a standard commercial dishwasher detergent with a water hardness of 0-1 ° (German hardness). In Comparative Example V1, only 24.5 g of standard commercial dishwasher detergent was administered for each wash cycle. In Comparative Examples V2 and V3, 250 mg zinc acetate and 400 mg crystalline sheet-like silicate Na-SKS-6 (σ-Na ₂ Si ₂ O ₅ ), respectively, 24.5 g of standard commercially available It was administered at the same time as the dishwasher detergent. In Example E1 of the present invention, 250 mg zinc acetate and 400 mg Na-SKS-6 were further administered separately from the final dishwasher detergent. The washing operation was repeated 50 times under the above conditions. The overall appearance of the product was evaluated with reference to the evaluation criteria described below.

  The results are shown in the table below:

評価基準：T0 = 曇りなし〜T4 = ひどい曇り

Evaluation criteria: T0 = no cloudiness ~ T4 = heavy cloudy

  The table shows that the dishwasher detergent of the present invention containing a combination of zinc salt and crystalline sheet-like silicate, under certain conditions, only contains a dishwasher detergent or silicate containing only a zinc salt. It shows significantly better glass corrosion properties than the dishwasher detergent it contains. The corrosion inhibition effect of the combination of zinc salt and silicate active ingredients is significantly greater than the sum of the effects observed for the individual substances.

Claims (14)

At least one zinc salt and at least one general formula (I)

[Wherein A is an alkali metal and / or hydrogen,
B is an alkaline earth metal and / or subgroup element, preferably an element from the group consisting of zinc, iron and manganese,
C is the third main group element and / or subgroup element of the periodic table, preferably iron, and
D is a fifth main group element and / or subgroup element of the periodic table,
The following also applies:
0 ≦ a ≦ 1; 0 ≦ b ≦ 0.5; 0 ≦ c / x ≦ 0.05; 0 ≦ d / x ≦ 0.25; 1.9 ≦ x ≦ 22; 0 ≦ f ≦ 40]
A dishwasher detergent or a dishwasher detergent aid comprising a crystalline sheet-like silicate represented by Crystalline sheet-like silicates have the general formula (Ia)

[Wherein M is sodium or hydrogen,
x is a number from 1.9 to 22, preferably 1.9 to 4, and
y is a number from 0 to 33)
The detergent for a dishwasher or the detergent adjuvant for a dishwasher of Claim 1 which has these.   A zinc salt and a crystalline sheet-like silicate of the general formula (I) or general formula (Ia) are used in a ratio of 10: 1 to 1:50, preferably 5: 1 to 1:30, in particular 3: 3. The dishwasher detergent or dishwasher detergent aid according to claim 1 or 2, comprising a ratio of 1 to 1:10.   A group of inorganic zinc salts, preferably a group of soluble inorganic zinc salts, in particular comprising at least one zinc salt selected from the group consisting of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The detergent for dishwashers or the detergent for dishwashers in any one of 1-3.   A group of organic zinc salts, preferably a group of soluble organic zinc salts, particularly preferably a group of soluble zinc salts of organic acid monomers or organic acid polymers, in particular zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate And at least one zinc salt selected from the group consisting of zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietic acid, zinc valerate and zinc p-toluenesulfonate. Dishwasher detergent or detergent for dishwashers.   6. The weight percentage of zinc salt based on the total weight of the composition is 0.1 to 10% by weight, preferably 0.2 to 7% by weight, in particular 0.4 to 4% by weight. Dishwasher detergent.   The weight fraction of the crystalline sheet-like silicate represented by the general formula (I) or the general formula (Ia) based on the total weight of the composition is 0.1 to 20% by weight, preferably 0.2 to 15% by weight, particularly The detergent for dishwashers in any one of Claims 1-6 which is 0.4-10 weight%.   The zinc salt and / or crystalline sheet-like silicate is formulated in particulate form with one or more further active and / or builder substances and is present as a formulation. Dishwasher detergent or dishwasher detergent aid.   The crystalline sheet-like silicate represented by the general formula (I) or the general formula (Ia) comprises one or more further active substances and / or builder substances, preferably organic monocarboxylic acids or organic polycarboxylic acids, hydroxypolyesters. Dishwasher detergent according to any of the preceding claims, formulated in particulate form with one or more further active substances and / or builder substances from the group of carboxylic acids and phosphonic acids and present as a formulation. Or a detergent aid for dishwashers.   Dishwasher detergent or dishwasher detergent aid according to any of claims 1 to 7, wherein the zinc salt and / or the crystalline sheet-like silicate are present in a polymer matrix.   8. A dimensional stability and having a penetration of 200 to 1000 g, preferably 250 to 900 g, particularly preferably 300 to 800 g and in particular 350 to 700 g. Detergents for dishwashers or detergent aids for dishwashers as described in 1.   Dishwasher detergent or detergent aid for a dishwasher according to any of claims 1 to 7, having a viscosity of 500 to 500,000 mPas, preferably 900 to 200,000 mPas and in particular 1300 to 100,000 mPas.   The detergent for a dishwasher or the detergent adjuvant for a dishwasher in any one of Claims 1-12 packaged in the water-soluble inclusion body.   14. Use of a dishwasher detergent or dishwasher detergent aid according to any of claims 1 to 13 to reduce glass corrosion during mechanical dishwashing.