DE10148353A1 - Controlled release coatings on LCST polymer-coated shaped bodies, such as detergent tablets, are applied from aqueous dispersions containing a coating material, a dispersant and a co-dispersant - Google Patents

Abstract

Coatings on top of lower critical solution temperature (LCST) coatings on shaped bodies of dispersions, comprise (in wt.%): (a) a coating material solid at 20 deg C (10-80); (b) a dispersant (0.1-30); and (c) a co-dispersant (0.1-30) in water (15-99). The wt.% of (a)-(c) are based on the (a)-(c) mixture weight, the weight of water being based on the total dispersion and the ratio of (b):(c) being 0.5-20:1.

Description

The present invention relates to a method for producing retarded soluble Tablet coatings, such as those for the time-delayed or time-delayed controlled release of active ingredients are used. In a preferred one Embodiment, the present invention relates to a process for the production of delayed release soluble coatings for detergent tablets.

Detergent tablets are widely described in the prior art have compared to powder detergents due to their compact size Structure a number of advantages, such as storage and transportation. Washing and cleaning agent tablets are popular with consumers because of their simple nature (One-time) dosage increasing in popularity. As part of the progressive Development in the field of detergents and cleaning agents has always been a goal the manufacturer of these products by providing innovative washing and Detergent, various cleaning functions in one washing and Combine detergents and the cleaning process this way to make it more consumer-friendly. A problem with deploying combined Cleaning and care products is, however, the targeted release of certain ingredients that not immediately after delivery but only at a certain point in time Cleaning process should have their effect. To influence and control the Solution behavior of detergents and cleaning agents or their components, there is in State of the art a number of proposed solutions, also in German Language usage are increasingly referred to as "controlled release".

One starting point for the technical implementation of such "controlled release" concepts is the temperature dependence of the solubility of various ingredients or Coating materials, especially in those processes in which temperature curves run through, for example in the sterilization and pasteurization of Food or also in washing and cleaning processes that involve several heating and can have cooling phases. In washing and cleaning processes it can especially in the last stage of the process, e.g. B. the last rinse one Washing machine or in the last rinse of a dishwasher can be advantageous controls various active ingredients, such as fabric softener or rinse aid add.

A group of carrier or coating materials known as "inverse" Temperature switch "used with the aim of controlled release of materials have been the LCST polymers, substances that are better at low temperatures Have solubility than at higher temperatures. LCST polymers are also called Substances with lower critical segregation temperature (LCST) called. With the help of LCST polymer-containing coatings, it is possible to add active ingredients after a Heat treatment when the cooling phase begins and falls below the lower critical Release segregation temperature (LCST) in a controlled manner. To dissolve the LCST Avoid layering in the period prior to the onset of heat treatment optionally be provided with a further coating, which only becomes visible when the Heat treatment begins to dissolve or melt away.

International patent application WO 98/49910 (Instituut Voor Agrotechnological Onderzoek) is an encapsulated material, with at least part of the Material is encapsulated during a heat treatment in an aqueous environment and after cooling after this heat treatment is released. This material is with a layer of a material with a lower critical segregation temperature (LCST- Polymer), which is below the temperature of the heat treatment, and optionally one Provide layer of a hydrophobic film-forming material. As a hydrophobic Materials are vegetable, animal or semi-synthetic fats, paraffins, waxes or polymers are proposed. The encapsulated materials are in the Food industry used in sterilization processes.

German patent applications DE 199 58 471 and DE 199 58 472 (Henkel KGaA) disclose LCST substances as constituents of particulate active substances or Active substance preparations of detergents and cleaning agents for delayed release of these active ingredients in washing and cleaning processes. These documents also reveal the optional application of a coating to the LCST coating in order to do this preserve early dissolution. As possible coating materials are especially called paraffins, waxes and various polymers.

The application of a coating on moldings with LCST coating, which in the first Minutes of the cleaning cycle effectively soften or dissolve the functional layer should prevent and therefore only dissolve when the heat treatment is started or begins to melt, but is often problematic. While in Laboratory scale coatings by immersion by immersing the molded body in a Melt can be applied, this process is impractical on an industrial scale. The spraying of moldings with the melt of a coating material in A drum coater is very difficult to produce on a production scale master, since the coated moldings when cooling below the melting temperature of the coating material. Although this problem can be solved by Use of an organic solution of the coating material instead of a melt can be solved, but such an organic coating requires a high apparatus and Safety-related effort (explosion protection, solvent recovery).

A hydrophobization process for particulate material without LCST coating is Subject of the German application DE 196 33 421 (Henkel KGaA). It is revealed Coating particulate material with a PIT emulsion without, however, previously mentioned particular difficulties in the coating of moldings.

The present invention was based on the object of being a safe, reliable and economical process for coating detergent tablets with to provide an LCST functional layer.

• 1. 1 bis 80 Gew.-% eines bei 20°C festen Beschichtungsmittels,
• 2. 0,1 bis 30 Gew.-% eines Dispergators und
• 3. 0,1 bis 30 Gew.-% eines Co-Dispergators,

jeweils bezogen auf die Mischung der Komponenten (1) bis (3), in 15 bis 99 Gew.-% Wasser, bezogen auf die Dispersion, enthält. Hierbei ist es für die Herstellung der Dispersion wichtig, daß das Verhältnis der Komponenten (2) und (3) im Bereich von 0,5 : 1 bis 20 : 1 liegt. It has now surprisingly been found that detergent tablets having an external LCST coating can be provided with a coating without the use of an organic solvent or a melt by the coating material being in the form of a dispersion, preferably a PIT emulsion or a suspension is applied, the

• 1. 1 to 80% by weight of a coating agent which is solid at 20 ° C.,
• 2. 0.1 to 30% by weight of a dispersant and
• 3. 0.1 to 30% by weight of a co-dispersant,

each based on the mixture of components (1) to (3), in 15 to 99% by weight of water, based on the dispersion. It is important for the preparation of the dispersion that the ratio of components (2) and (3) is in the range from 0.5: 1 to 20: 1.

• 1. 10 bis 80 Gew.-% des bei 20°C festen Beschichtungsmittels,
• 2. 0,1 bis 30 Gew.-% eines Dispergators und
• 3. 0,1 bis 30 Gew.-% eines Co-Dispergators,

bezogen jeweils auf die Mischung der Komponenten (1) bis (3), in 15 bis 99 Gew.-% Wasser, bezogen auf die Dispersion, wobei das Verhältnis der Komponenten (2) und (3) im Bereich von 0,5 : 1 bis 20 : 1 liegt, zur Beschichtung von mit einem LCST-Coating versehenen Formkörpern The invention therefore relates to the use of dispersions, preferably of PIT emulsions or of suspensions

• 1. 10 to 80% by weight of the coating agent solid at 20 ° C.,
• 2. 0.1 to 30% by weight of a dispersant and
• 3. 0.1 to 30% by weight of a co-dispersant,

based in each case on the mixture of components (1) to (3), in 15 to 99% by weight of water, based on the dispersion, the ratio of components (2) and (3) in the range from 0.5: 1 is up to 20: 1, for coating molded articles provided with an LCST coating

PIT emulsions are emulsions that operate at certain temperatures (Phase inversion temperature, PIT) undergo phase inversion, the Phase inversion temperature the transition of the surfactant solubility from water to oil or from Features oil to water. For example, it is known that oil-in-water emulsions (O / W emulsions) that are produced and stabilized with non-ionic emulsifiers invert when heated to water-in-oil emulsions (W / O emulsions). This process is usually reversible, which means that when it cools down it becomes the original emulsion type regressed. It is known that emulsions that are used in their preparation Undergo phase inversion, are characterized by particular stability and fine-particle nature, while those made above the phase inversion temperature are less are finely divided. In the context of the present invention, it is particularly preferred if the dispersions intended for the coating (preferably PIT emulsions or Suspensions) a particle size between 0.05 and 10 microns, preferably between 0.1 and 5 microns and particularly preferably between 0.15 and 2 microns, the Particle size refers to the size of the dispersed phase particles.

As a coating agent, i. H. Component (1), all substances that come into question 20 ° C solid (for example kneadable or coarse to fine crystalline) and only above about 40 ° C without decomposition into a pasty to flowable low viscous state pass. Preferred coating agents are especially lipids, in particular higher-chain hydrocarbons (e.g. Paraffinum durum) and / or wax esters (e.g. Cetyl palmitate).

Preferred dispersants, ie component (2), are hydrophilic nonionic dispersants, particularly preferably hydrophilic nonionic dispersants which have an HLB value of 8 to 18. The HLB value (hydrophile-lipophile balance) is to be understood as a value which according to

HLB = (100-L) / 5

can be calculated, where L is the percentage by weight of the lipophilic groups, ie the fatty alkyl or fatty acyl groups, in the ethylene oxide adducts. Ethylene oxide addition products on C _16-22 fatty alcohols are preferably suitable. Such commercially available products are mixtures of homologous polyglycol ethers of the starting fatty alcohols. Ethylene oxide addition products on partial esters of a polyol having 3 to 6 carbon atoms and C _14-22 fatty acids can also be used as dispersants. Particularly suitable as dispersants (2) are fatty alcohol polyglycol ethers of the general formula

R ¹ - (O-CH ₂ -CH ₂ ) _n -OH,

in which R ^{1 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 8 to 22 carbon atoms, preferably 12 to 22 carbon atoms and n is an integer from 10 to 50, preferably from 10 to 30, and addition products from 4 to 20 moles of ethylene oxide to one or more fatty acid partial glycerides.

Fatty acid partial glycerides of saturated or unsaturated fatty acids with 10 to 20 C atoms are technical mixtures of fatty acid mono-, di- and triglycerides, which are esterified by 1 mole of glycerol with 1 to 2 moles of a C _10-20 fatty acid or by Transesterification of 1 mole of a C _10-20 fatty acid triglyceride with 0.5 to 2 moles of glycerol can be obtained.

Addition products of 8 to 12 mol are particularly suitable as dispersants Ethylene oxide to saturated fatty alcohols with 16 to 22 carbon atoms.

In addition to the dispersant (2), the preparation of a dispersion required for the the method according to the invention is suitable, the presence of a co-dispersant (3), preferably a hydrophobic co-dispersant. Are special as co-dispersants those of the type of fatty alcohols with 16 to 22 carbon atoms, e.g. B. cetyl alcohol, stearyl alcohol, Arachidyl alcohol or behenyl alcohol or mixtures of these alcohols are preferred, as in the technical hydrogenation of vegetable or animal fatty acids with 16 to 22 C- Atoms or the corresponding fatty acid methyl ester can be obtained. More particularly preferred co-dispersants (3) are partial esters made of a polyol having 3 to 6 carbon atoms and fatty acids with 14 to 22 carbon atoms. Such partial esters are e.g. B. the monoglycerides of Palmitin and / or stearic acid, the sorbitan mono- and / or diesters of myristic acid, Palmitic acid, stearic acid or mixtures of these fatty acids, the monoesters Trimethylolpropane, erythritol or pentaerythritol and saturated fatty acids with 14 to 22 C- Atoms. Technical monoesters are also understood as monoesters Esterification of 1 mol of polyol with 1 mol of fatty acid can be obtained and which is a mixture of Represent monoesters, diesters and unesterified polyol.

Particularly preferred co-dispersants are cetyl alcohol, stearyl alcohol or a glycerol, Sorbitan or trimethylolpropane monoesters of a fatty acid with 14 to 22 carbon atoms or Mixtures of these substances.

As already mentioned, the ratio of components (2) and (3) is one for the production the dispersion of critical parameters. The ratio of (2) and (3) should be in the range of 0.5 1 to 20: 1, a range from 1: 1 to 10: 1 being preferred. In one particularly preferred variant of the method according to the invention is the ratio of Components (2) and (3) adjusted such that the phase inversion temperature of the total composition above the melting point of the solid Coating agent (1) and below 100 ° C.

To apply the dispersions, preferably the PIT emulsions or Suspensions on the respective substrates are suitable for all devices with which Coatings can be made from an aqueous solution. Larger objects can directly with spray nozzles, preferably two-substance nozzles, under simultaneous or subsequent drying can be sprayed. Smaller objects can be placed in drum coats, such as they are used, for example, in pharmacy, or spray coating pans become.

The homogeneity and diffusion tightness in this way using Dispersions (preferably PIT emulsions or suspensions) Coatings can be done by briefly melting the wax layer, for example under a heating lamp, can be increased further.

According to the present invention, the detergent tablet is preformed the application of the dispersion coating made up with an LCST substance. How Described at the beginning, LCST substances are substances which lower temperatures have a better solubility than at higher temperatures. They are also referred to as substances with a lower critical segregation temperature. These substances are usually polymers. Depending on the application conditions, the lower critical separation temperature between room temperature and the temperature of the Heat treatment. For example between 20 ° C, preferably 30 ° C and 100 ° C, especially between 30 ° C and 50 ° C. LCST substances are preferably suitable Cellulose derivatives, mono- or di-N-alkylated acrylamides, copolymers of mono- or di- N-substituted acrylamides with acrylamides and / or acrylates or acrylic acids and / or Polyvinylcaprolactam, in particular the alkylated and / or hydroxyalkylated Polysaccharides, cellulose ethers, polyisopropylacrylamides, copolymers of Polyisopropylacrylamids and blends of these substances are preferred.

Examples of alkylated and / or hydroxyalkylated polysaccharides are Methyl hydroxypropyl methyl cellulose (MHPC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), carboxymethyl cellulose (CMC), Carboxymethylmethylcellulose (CMMC), Hydroxybutylcellulose (HBC), Hydroxybutylmethylcellulose (HBMC), hydroxyethyl cellulose (HEC), hydroxyethyl carboxymethyl cellulose (HECMC), Hydroxyethyl ethyl cellulose (HEEC), hydroxypropyl cellulose (HPC), Hydroxypropylcarboxymethyl cellulose (HPCMC), hydroxyethyl methyl cellulose (HEMC), Methylhydroxyethyl cellulose (MHEC), methyl hydroxyethyl propyl cellulose (MHEPC), methyl cellulose (MC) and Propyl cellulose (PC) and mixtures thereof, carboxymethyl cellulose, methyl cellulose, Methylhydroxyethylcellulose and methylhydroxyproplcellulose as well as the alkali salts of the CMC and the slightly ethoxylated MC or mixtures of the foregoing are preferred.

Further examples of LCST substances are cellulose ethers and mixtures of Cellulose ethers with carboxymethyl cellulose (CMC). Other polymers that have a lower show critical separation temperature in water and which are also suitable Polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N- substituted acrylamides with acrylates and / or acrylic acids or mixtures of intertwined networks of the above (co) polymers. Are suitable also polyethylene oxide or copolymers thereof, such as Ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, Polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether Proteins such as poly (VATGVV), a repeating unit in the natural protein elastin and certain alginates. Mixtures of these polymers with salts or surfactants can can also be used as an LCST substance. Through such additions or through The LCST can copolymerize with more hydrophilic or more hydrophobic comonomers (lower critical separation temperature) can be modified accordingly.

The active ingredient preparation forming the shaped body can be packaged in a manner known per se and depends on the formulation of the finished agent. The tableting of a preparation, for example by simply mixing the individual ingredients (in the form of powders, granules and / or extrudates), as well as (co-) extrusion, injection molding and / or molding, is a preferred method for producing an Shown body usable according to the method, which is provided with an LCST coating. In a preferred embodiment, the LCST polymer of the coating simultaneously serves as a matrix material for another active ingredient. The moldings produced by the methods described above can be either single-phase or multi-phase. In the context of the present invention, such three-dimensional bodies are referred to as shaped bodies which have volumes of above 100 mm ³ , preferably above 250 mm ^3, in particular above 500 mm ³ and particularly preferably above 2000 mm ³ .

The active ingredients can also be produced in the form of capsules, the LCST The polymer itself can represent the capsule wall or can be added to the active ingredient contained capsule is applied. It doesn't just have to be a single capsule act. Likewise, a composite of capsules, the z. B. by gluing or pressing individual capsules are created, can be used.

Furthermore, it is possible to take one according to the method described above use according to the invention of a dispersion, preferably a PIT emulsion or a suspension, molded article produced with one or more further molded article (s), which can optionally also have an LCST and / or dispersion coating, for example by simply inserting or gluing the components together Combine combination product. In this context it can be advantageous if at least one of the shaped bodies has one or more recesses which are in their Dimension (s) the dimensions of the other molded body (s) corresponds / correspond.

In a further preferred embodiment, the LCST substance forms a matrix material. In this embodiment, e.g. B. an active ingredient-containing mixture that is coated with an LCST substance. The mixtures obtained can either be in Form of granules and then, if necessary in the presence of other ingredients, can be processed to a shaped body in a manner known per se, such as by pressing. On the other hand, it is also possible to use the mixture as a sol or as a melt further processing.

Moldings with a dispersion coating according to the invention can be used in particular Use advantageously in mechanical processes where the active ingredient (s) contained in one Rinse cycle should be released after the washing step. Examples are machine Textile washing and machine cleaning of dishes both in the household and in commercial area. Due to the assembly according to the invention with an LCST and The active ingredients remain in a dispersion coating even after the pre-rinse cycle and a subsequent heat treatment, e.g. B. the main rinse or wash in which the dispersion coating is melted, unchanged in a liquid medium and the active ingredient is only after cooling after the heat treatment, so in the rinse cycle, released.

In the context of the present invention, it is therefore preferred if the a dispersion coating of molded articles around detergents and cleaning agents, preferably textile detergents or dishwashing detergents which act as active ingredients or several components from the group of builders, cobuilders, surfactant (s), polymer (s), Disintegration aids, bleach, bleach activator (s), anti-aging components (s), enzyme (s), Fragrance (s), dye (s), silver protection agent, glass corrosion protection agent, fluorescent agent, optical brighteners, anti-shrink agents, anti-crease agents, antimicrobial agent (s), Germicide (s), fungicide (s), antioxidants, antistatic agents, ironing aids, repellents and Impregnating agent, UV absorber and / or any mixture of the above washing and cleaning-active substances and / or other usual components of washing and Detergents included.

A major advantage of such detergents and cleaning agents is that active ingredients contained in a process step to be released after a heating step, d. H. in Rinse aid, do not need to be added separately. Most washing and Go through cleaning processes both in the commercial sector and in the household different temperature levels. Especially in the case of machine processes, the So-called rinse cycles, which are a washing or cleaning stage at elevated temperature follow, usually added additional components. These are later stages of the process usually rinse aid rinses, in which the users, depending on the process, certain active ingredients enforce. These active ingredients are usually dosed either manually or using specially designed devices. With these processes, too Use of the active ingredients assembled according to the invention has a number of advantages.

The aforementioned, preferred in washing and cleaning agents according to the invention Active substances contained are described in more detail below.

Builder

According to the present invention, detergents and cleaning agents can all be used builders usually used in detergents and cleaning agents, in particular silicates, carbonates, organic cobuilders and also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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

Both the monoalkali metal salts and the dialkali metal salts of the Carbonic acid as well as sesquicarbonates can be included in the funds. preferred Alkali metal ions represent sodium and / or potassium ions. In one embodiment, it can be preferred, the carbonate and / or bicarbonate at least partially as further Mix component separately or subsequently. Also compounds from, for example Carbonate, silicate and optionally other auxiliaries such as anionic surfactants or other, especially organic builder substances, can be used as separate Component present in the finished funds.

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. Have among the variety of commercially available phosphates the alkali metal phosphates with particular preference for pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and Detergent industry the most important.

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

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

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

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the salt of water free of crystal water dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

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

builders

Organic cobuilders can be used in detergents and cleaning agents as part of the present invention in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are as follows described.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids which can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function. For example these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Methylglycinediacetic acid, sugar acids and mixtures thereof.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of washing or detergents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.

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

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 1000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol.

Both polyacrylates and also copolymers of unsaturated carboxylic acids containing sulfonic acid groups Monomers and optionally other ionic or nonionic monomers used. The copolymers containing sulfonic acid groups are described in detail below described.

• 1. ungesättigten Carbonsäuren
• 2. Sulfonsäuregruppen-haltigen Monomeren
• 3. gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

enthalten. If the cleaning agent according to the invention is a machine dishwashing detergent which, as a so-called "3 in 1" product, combines the conventional cleaners, rinse aid and a salt replacement function, then machine dishwashing agents according to the invention are preferred which additionally contain 0.1 to 70% by weight. -% of copolymers

• 1. unsaturated carboxylic acids
• 2. Monomers containing sulfonic acid groups
• 3. optionally further ionic or nonionic monomers

contain.

These copolymers cause the dishes treated with such agents subsequent cleaning processes become significantly cleaner than dishes that are washed with conventional agents were rinsed.

As an additional positive effect, the drying time is reduced with that Detergent treated dishes on d. H. the consumer can after the expiration of the cleaning program take the dishes out of the machine earlier and use again.

The invention is characterized by an improved "cleanability" of the treated Substrates in later cleaning processes and by significantly shortening the Drying time compared to comparable agents without the use Polymers containing sulfonic acid groups.

The drying time in the context of the teaching according to the invention is generally the understood the meaning in the sense of the word, i.e. the time that passes until one in one Dishwasher-treated dish surface is dried, but especially the Time that passes up to 90% in with a detergent or rinse aid concentrated or diluted form treated surface is dried.

In the context of the present invention, unsaturated carboxylic acids of the formula VII are preferred as the monomer,

R ¹ (R ² ) C = C (R ³ ) COOH (VII),

in which R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by formula I are in particular 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) preferred.

In the case of the monomers containing sulfonic acid groups, preference is given to those of the formula VIII

R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIII),

in which R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group , which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas VIIIa, VIIIb and / or VIIIc,

H ₂ C = CH-X-SO ₃ H (VIIIa),

H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIIb),

HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIIIc),

in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C ( O) -NH-CH (CH ₂ CH ₃ ) -.

Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₂ CH ₃ ) in formula IIa), 2-acrylamido-2-propanesulfonic acid (X = -C ( O) NH-C (CH ₃ ) ₂ in formula VIIIa), 2-acrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ - in formula VIIIa), 2 -Methacrylamido-2-methyl-1-propanesulfonic acid (X = -C (O) NH-CH (CH ₃ ) CH ₂ in formula VIIIb), 3-methacrylamido-2-hydroxy-propanesulfonic acid (X = -C (O) NH -CH ₂ CH (OH) CH ₂ - in formula VIIIb), allylsulfonic acid (X = CH ₂ in formula VIIIa), methallylsulfonic acid (X = CH ₂ in formula IIb), allyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula VIIIa), methallyloxybenzenesulfonic acid (X = -CH ₂ -OC ₆ H ₄ - in formula VIIIb), 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen-1-sulfonic acid (X = CH ₂ in formula VIIIb), styrene sulfonic acid (X = C ₈ H ₄ in formula VIIIa), vinyl sulfonic acid (X not present in formula VIIIa), 3-sulfopropyl acrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula VIIIa), 3-sulfopropyl methacrylate (X = -C (O) NH-CH ₂ CH ₂ CH ₂ - in formula VIIIb), sulfomethacrylamide (X = -C (O) NH- in formula VIIIb), sulfomethyl methacrylamide ( X = -C (O) NH-CH ₂ - in formula VIIIb) and water-soluble salts of the acids mentioned.

Other ionic or nonionic monomers in particular are ethylenic unsaturated compounds. The content is preferably polymers used according to the invention on monomers of group iii) less than 20% by weight, based on the polymer. Polymers to be used with particular preference only from monomers of groups i) and ii).

• 1. ungesättigten Carbonsäuren der Formel VII.
  
  R¹(R²)C=C(R³)COOH (VII),
  
  in der R¹ bis R³ unabhängig voneinander für -H-CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettiger oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• 2. Sulfonsäuregruppen-haltigen Monomeren der Formel VIII
  
  R⁵(R⁶)C=C(R⁷)-X-SO₃H (VIII),
  
  in der R⁵ bis R⁷ unabhängig voneinander für -H-CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH-substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettiger oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH- C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• 3. gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren

besonders bevorzugt. In summary, copolymers are made of

• 1. unsaturated carboxylic acids of formula VII.
  
  R ¹ (R ² ) C = C (R ³ ) COOH (VII),
  
  in which R ¹ to R ³ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• 2. Monomers of the formula VIII containing sulfonic acid groups
  
  R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIII),
  
  in which R ⁵ to R ⁷ independently of one another are -H-CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH-substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X represents an optionally present spacer group is selected from - (CH ₂ ) - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH- C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -
• 3. optionally further ionic or nonionic monomers

particularly preferred.

• 1. einer oder mehrerer ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• 2. einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln VIIIa, VIIIb und/oder VIIIc:
  
  H₂C=CH-X-SO₃H (VIIIa),
  
  H₂C=C(CH₃)-X-SO₃H (VIIIb),
  
  HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H (VIIIc),
  
  in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂) mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH- C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• 3. gegebenenfalls weiteren ionischen oder nichtionogenen Monomeren.

Particularly preferred copolymers consist of

• 1. one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid
• 2. one or more monomers of the formulas VIIIa, VIIIb and / or VIIIc containing sulfonic acid groups:
  
  H ₂ C = CH-X-SO ₃ H (VIIIa),
  
  H ₂ C = C (CH ₃ ) -X-SO ₃ H (VIIIb),
  
  HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H (VIIIc),
  
  in which R ⁶ and R ⁷ are selected independently of one another from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X represents an optionally present spacer group which is selected from - (CH ₂ ) with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH- C (CH ₃ ) ₂ - and -C ( O) -NH-CH (CH ₂ CH ₃ ) -
• 3. optionally further ionic or nonionic monomers.

The copolymers contained in the agents according to the invention can be the monomers from the Groups i) and ii) and optionally iii) in varying amounts, wherein all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined. Particularly preferred Polymers have certain structural units, which are described below.

For example, agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula IX

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - (IX),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are produced by copolymerization of acrylic acid with a sulfonic acid group-containing acrylic acid derivative. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula X.

- [CH ₂ -C (CH ₃ ) COOH] _m - {CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Completely analogously, acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Agents according to the invention which contain one or more copolymers are structural units of the formula XI

- [CH ₂ -CHCOOH] _m - (CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p (XI),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are also preferred, a preferred embodiment of the present invention, just like agents are preferred, which are characterized in that they contain one or more copolymers, the structural units of formula XII

- [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] p- (XII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Instead of or in addition to acrylic acid and / or methacrylic acid, maleic acid can also be used as a particularly preferred monomer from group i). In this way, preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XIII

- [HOOCCH-CHCOOH] _m - (CH ₂ -CHC (O) -Y-SO ₃ H] _p - (XIII),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred and to agents which are characterized in that they contain one or more copolymers, the structural units of the formula XIV

- [HOOCCH-CHCOOH] _m - (CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p (XIV),

contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y represents -O- (CH ₂ ) _n with n = 0 to 4, represents -O- (C ₆ H4) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

In summary, automatic dishwashing agents according to the invention are preferred which contain, as ingredient b), one or more copolymers which have structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV

- [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) Y-SO ₃ H] _p - (IX),

- [CH ₂ -C (CH ₃ ) COOH] _m - (CH ₂ -CHC (O) -Y-SO ₃ H] _p - (X),

- [CH ₂ -CHCOOH) _m - (CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H) _p - (XI),

- [CH ₂ -C (CH ₃ ) COOH] _m - (CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - (XII),

- [HOOCCH-CHCOOH] _m [CH ₂ -CHC (O) Y-SO ₃ H] _p - (XIII),

- [HOOCCH-CHCOOH] _m [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - (XIV),

contain, in which m and p each represent an integer between 1 and 2000 and Y stands for a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -O- (CH ₂ ) with n = 0 to 4, represents -O- (C ₆ H ₄ ) -, represents -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

The sulfonic acid groups in the polymers can be wholly or partly in neutralized form are present, d. H. that the acidic hydrogen atom of the sulfonic acid group in some or all Sulphonic acid groups against metal ions, preferably alkali metal ions and in particular can be exchanged for sodium ions. Appropriate means of doing this are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.

The monomer distribution of the copolymers used in the agents according to the invention for copolymers containing only monomers from groups i) and ii), preferably each 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight Monomer from group i) and 10 to 50% by weight monomer from group ii), respectively based on the polymer.

In the case of terpolymers, those which contain 20 to 85% by weight of monomer from the Group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) included.

The molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use. Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 .

The content of one or more copolymers in the agents according to the invention may vary vary according to application and desired product performance, with preferred Machine dishwashing detergents according to the invention are characterized in that they or the copolymer (s) in amounts of 0.25 to 50% by weight, preferably 0.5 to 35 % By weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight % contain.

As already mentioned above, the agents according to the invention are special preferably both polyacrylates and the copolymers described above unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers are used. The Polyacrylates have been described in detail above. Are particularly preferred Combinations of the sulfonic acid groups described above Copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the trade name Sokalan® PA15 or Sokalan® PA25 (BASF) available.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid, 50 to 90 % By weight of acrylic acid and 50 to 10% by weight of maleic acid. Your relative Molecular weight, based on free acids, is generally 2000 to 100000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.

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

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

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

Further preferred copolymers preferably have acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives.

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

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and can be used Dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

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

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and are also preferred in this context Glycerol trisuccinates. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form can be present and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt the DTPMP. Preferred as a builder from the class of the phosphonates HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the means also contain bleach, may be preferred, aminoalkanephosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.

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

Agents according to the invention are thereby within the scope of the present application characterized in that they contain builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates in amounts of 0.1 to 99.5% by weight, preferably from 1 to 95% by weight, particularly preferably from 5 to 90% by weight and in particular from 10 to 80 wt .-%, each based on the agent.

surfactants

Preferred detergents and cleaning agents contain within the scope of the present application one or more surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

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

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerol with 1 to 3 Mole of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, Caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

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

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. The anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the sodium salts.

Another group of washing-active substances are the non-ionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferably used nonionic surfactants, which either as sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl ester.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Usable alkyl polyglycosides satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, which consist of a glucose residue and an n-alkyl chain, are preferably used.

Another class of preferably used nonionic surfactants, which either as sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

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


in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

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


in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder.

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

In the case of detergents and cleaning agents for automatic dishwashing, all surfactants are generally suitable as surfactants. However, the nonionic surfactants described above, and above all the low-foaming nonionic surfactants, are preferred for this purpose. The alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. If desired, final etherification with short-chain alkyl groups, such as preferably the butyl group, can also give the class of "closed" alcohol ethoxylates, which can also be used for the purposes of the invention. For the purposes of the present invention, very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.

In the context of the present invention, weakly foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants. Among these, surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups. Here, automatic dishwashing agents according to the invention which contain surfactants of the general formula I as nonionic surfactant (s) are preferred


in which R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6.

The preferred nonionic surfactants of the formula XVII can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in formula I above can vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is generally unbranched, the linear radicals of alcohols of native origin having 12 to 18 carbon atoms, e.g. B. from coconut, palm, tallow or oleyl alcohol are preferred. Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, preferred dishwasher detergents according to the invention are those in which R ¹ in formula I for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.

In addition to propylene oxide, butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit. However, other alkylene oxides in which R ² or R ³ are selected independently of one another from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are also suitable. Preferred automatic dishwashing agents are characterized in that R ² or R ³ for a radical -CH ₃ , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, nonionic surfactants which have a C _9-15 alkyl radical with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, are particularly preferred for use in the agents according to the invention.

Low-foaming nonionic surfactants are preferred additional surfactants used. The machine tools according to the invention contain with particular preference Dishwashing detergent is a nonionic surfactant that has a melting point above Has room temperature. Accordingly, preferred means are characterized in that they preferably nonionic surfactant (s) with a melting point above 20 ° C. above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C included.

Suitable in addition to the nonionic surfactants contained in the agents according to the invention non-ionic surfactants, the melting or softening points in the above Temperature range are, for example, low-foaming nonionic Surfactants that can be solid or highly viscous at room temperature. Become at Room temperature highly viscous nonionic surfactants used, it is preferred that this one Viscosity above 20 Pa.s, preferably above 35 Pa.s and in particular have above 40 Pa.s. Also nonionic surfactants, which are waxy at room temperature Have consistency are preferred.

Preferred nonionic surfactants to be used as solid at room temperature originate from the Groups of alkoxylated nonionic surfactants, especially ethoxylated primary alcohols and Mixtures of these surfactants with structurally complicated surfactants such as Polyoxypropylene / Polyoxyethylene / Polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

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

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

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

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated Monohydroxyalkanols or alkylphenols, which are also polyoxyethylene-polyoxypropylene Have block copolymer units. The alcohol or alkylphenol part of such Nonionic surfactant molecules preferably make up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight such non-ionic surfactants. This makes them preferred automatic dishwashing detergents characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the Propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant make up, contain.

Other nonionic surfactants to be used with particular preference with melting points above Room temperature contain 40 to 70% of one Polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blends containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles Ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of Polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles Ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.

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

A further preferred automatic dishwashing agent according to the invention contains nonionic surfactants of the formula

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

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

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

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

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

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

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

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

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 'and R2 has 9 to 14 carbon atoms, R ^{3 represents} H and x assumes values from 6 to 15.

If the latter statements are summarized, dishwasher detergents according to the invention are preferred, the end group-capped poly (oxyalkylated) nonionic surfactants of the formula

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

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

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

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

In combination with the surfactants mentioned, anionic, cationic and / or amphoteric surfactants are used, which because of their foaming behavior in machine dishwashing detergents are only of minor importance and mostly only in Amounts below 10% by weight, mostly even below 5% by weight, for example from 0.01 to 2.5% by weight, based in each case on the agent. The Agents according to the invention can thus also be anionic, cationic as a surfactant component and / or contain amphoteric surfactants.

In a preferred embodiment of the present invention, the one with the LCST Substance made up active ingredient selected from the group of surfactants. The presence of surfactants in the rinse cycle of a machine dishwashing process has a positive effect the shine and the reduction of limescale. As active ingredients in the rinse aid only weakly foaming nonionic surfactants are usually used. The Use of other surfactants e.g. B. anionic surfactants is not excluded.

As stated above, in a preferred embodiment, the present Invention a molded body provided with a retardable soluble coating with or several other moldings, optionally also a coating (LCST, dispersion such as PIT, etc.) can have, for example, by inserting in a Recess or glue connected to a combination product. In this Context, it is particularly preferred if the aforementioned delayed soluble Molded surfactants, preferably low-foaming nonionic surfactants, contains.

explosives

To facilitate the disintegration of highly compressed tablets in order to shorten the disintegration times, it is possible to use disintegration aids, so-called tablet disintegrants, in these incorporate. Tablet disintegrants or disintegrants are used according to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184) understood auxiliary substances that are necessary for the rapid disintegration of Tablets in water or gastric juice and for the release of pharmaceuticals in absorbable Shape.

These substances, which are also known as "explosives" due to their effectiveness, increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, also other organic acids can be used. Swelling disintegration aids are for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural Polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives. All of the disintegration aids mentioned are according to the invention used.

In the context of the present invention, disintegration aids are preferred Cellulose-based disintegration aid is used and it is preferred that the two- or multi-phase detergent tablets according to the invention, containing surfactants, builders and other ingredients of detergents and cleaning agents, a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, each based on the tablet weight.

It is further preferred that the weight fraction of the disintegration aid and / or the disintegration aid in the phases of the washing and Detergent tablet by more than 0.25% by weight, preferably by more than 0.5% by weight and in particular differs by more than 1% by weight, the proportion by weight on relates the weight of the respective phase.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

The cellulose derivatives mentioned are preferably not used alone as disintegrants used on cellulose basis, but used in a mixture with cellulose. The salary these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the disintegrant Cellulose. Pure cellulose-based disintegrant is particularly preferred Cellulose used, which is free of cellulose derivatives. As another means of disintegration on cellulose basis or as a component of this component can be microcrystalline cellulose be used. This microcrystalline cellulose is obtained by partial hydrolysis of Celluloses obtained under such conditions that only the amorphous areas (approx. 30% of the Attack total cellulose mass) of the celluloses and completely dissolve the crystalline ones Leave areas (approx. 70%) undamaged. A subsequent disaggregation of the The microfine celluloses produced by hydrolysis yield the microcrystalline celluloses, which have primary particle sizes of approx. 5 µm and, for example, form granules an average particle size of 200 microns can be compacted.

In addition to the ingredients mentioned above, the washing agents according to the invention can and detergent tablets are a gas-releasing system of organic acids and Contain carbonates / bicarbonates.

As organic acids from the carbonates / hydrogen carbonates in aqueous solution Releasing carbon dioxide are, for example, the solid mono-, oligo- and polycarboxylic acids used. From this group citric acid, tartaric acid, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifying agent in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture, can also preferably be used from succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

The acids mentioned do not have to be stoichiometric to those contained in the tablets Carbonates or bicarbonates are used.

A preferred washing and Detergent tablet also contains an effervescent system.

The gas-developing shower system consists in the washing and Detergent tablets in addition to the above-mentioned organic acids from carbonates and / or Bicarbonates. The representatives of this class of substances are the ones for cost reasons Alkali metal salts clearly preferred. In the case of alkali metal carbonates or bicarbonates again, the sodium and potassium salts are different from the others for cost reasons Salts clearly preferred. Of course, the relevant ones do not have to be pure Alkali metal carbonates or bicarbonates are used; rather mixtures different carbonates and bicarbonates may be preferred.

Sodium carbonate forms a white powder with a density of 2.532 gcm ^-3 . A distinction is made between lightly calcined soda with a bulk density of 0.5-0.55 kg / l and heavily calcined soda with 1.0-1.1 kg / l. Sodium carbonate forms three hydrates with water: sodium carbonate decahydrate (crystal soda), Na ₂ CO ₃ .10H ₂ O, colorless, monoclinic, ice-like looking crystals with a density of 1.44 gcm ^-3 melting point 32-34 °; Sodium carbonate heptahydrate, Na ₂ CO ₃ .7H ₂ O, rhombic crystals of density 1.51 gcm ^-3 melting point 32-35 °; Sodium carbonate monohydrate, Na ₂ CO ₃ .H ₂ O, rhombic crystals with a density of 2.25 gcm ^-3 _, melting point 100 °.

Sodium bicarbonate is a white, alkaline-tasting, odorless, dry air-resistant powder (monoclinic crystals) with a density of 2.159 gcm ^-3 , which decomposes into CO ₂ , H ₂ O and sodium carbonate when heated to over 65 °.

Potassium carbonate (potash) is a white, non-toxic, hygroscopic, granular with a density of 2.428 gcm ^-3 that forms various hydrates. If one leads in conc. Potassium carbonate solution a lot of carbon dioxide, so the less soluble potassium bicarbonate precipitates. In addition, potassium carbonate shows great similarities in its properties to the closely related soda. Potassium carbonate-1,5-water ("potash hydrate") is the stable phase of the potassium carbonate in contact with the saturated solution in the range from 0 ° C to approx. 110 ° C and can be obtained by crystallization from supersaturated potassium carbonate solutions. It crystallizes in shiny, practically dust-free crystals, has a density of 2.155 gcm ^-3 and completely loses its crystal water at temperatures of 130 to 160 ° C. Most large-scale manufacturing processes for potassium carbonate initially lead to potassium carbonate-1,5-water, which is calcined in rotary kilns at 200 to 350 ° C to 98 to 100% potassium carbonate. If this calcination is omitted, the crystallized potassium carbonate 1,5 hydrate is dried at 110 to 120 ° C. and sold as a potash hydrate. Technically common manufacturing processes for the products mentioned are, for example, the process with continuous crystallization (starting materials: KOH and CO ₂ ), the fluidized bed process (starting materials: KOH and CO ₂ ), the amine process (KOH / CO ₂ in the presence of isopropylamine: Mines de Potasse d'Alsace or KOH / CO ₂ in the presence of triethylamine: Kali-Chemie AG) or the nepheline digestion process (mainly former USSR). The ion exchange process (starting materials: KCl and (NH4) 2CO ₃ ), the magnesia process (Engel-Precht process, Neustaßfurt process; of secondary importance; starting materials: KCl, MgCO ₃ .3 H ₂ O and CO ₂ ), the formate potash process (raw materials: potassium sulfate, calcium hydroxide and carbon monoxide), the Piesteritz process (raw materials: potassium sulfate and calcium cyanamide) and the Le Blanc process (raw materials: potassium sulfate, calcium carbonate and carbon).

Trona, a mixed salt of sodium carbonate and sodium bicarbonate, which is also referred to as sodium sesquicarbonate or sodium carbonate sesquihydrate, can also be used as the second component of the shower system. Sodium carbonate sesquihydrate is found in nature as a mineral (Trona) and is described by the formula Na ₂ CO ₃ NaHCO ₃ .2H ₂ O. Large Trona deposits are found, for example, in the USA (Green River / Wyoming), Kenya (Lake Magadi) and the Republic of Sudan (Dongola). While the deposits in Africa can be exploited in the open-cast mine, the Trona is mined in the USA. Trona has a density of 2.17 gcm ^-3 and a Mohs hardness of 2.5. Trona is usually used for the production of pure soda, but pure Na ₂ CO ₃ .NaHCO ₃ .2H ₂ O can also be produced by the sodium sesquicarbonate process, which is sold. Pure sodium sesquicarbonate is also formed from sodium bicarbonate by standing in humid air with the release of carbon dioxide or by introducing carbon dioxide into a sodium carbonate solution.

bleach

Bleaching agents and bleach activators are important components of detergents and cleaning agents, and a detergent and cleaning agent can contain one or more substances from the groups mentioned within the scope of the present invention. Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H ₂ O ₂ in water. Further bleaching agents which can be used are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.

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

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a Obtained solution of sodium carbonate in hydrogen peroxide, but mistakenly as Peroxycarbonate viewed. It was not until 1909 that the compound was Attachment connection recognized, nevertheless has the historical designation "Sodium percarbonate" has become established in practice.

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

Detergents for automatic dishwashing can also use bleach from the Group of organic bleaches included. Typical organic bleaches used as Ingredients can be used in the present invention are Diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaches are Peroxyacids, examples being especially the alkylperoxyacids and Arylperoxyacids are called. Preferred representatives are (a) peroxybenzoic acid and their ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α- Naphtoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, Phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o- Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N- nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, Diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyidiperoxybutane-1,4-diacid, N, N- Terephthaloyl-di (6-aminopercaproic acid) can be used.

As a bleaching agent for automatic dishwashing, according to the present invention chlorine or bromine-releasing substances can also be used. Among the appropriate chlorine or bromine-releasing materials come, for example, heterocyclic N-bromine and N- Chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5- dimethylhydanthoin are also suitable.

Advantageous agents in the context of the present invention contain one or more Bleaching agents, preferably from the group of oxygen or halogen bleaching agents, especially chlorine bleach, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40% by weight, preferably of 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20 wt .-%, each based on the total agent.

Bleach activators

To improve the bleaching effect when cleaning at temperatures of 60 ° C and below To achieve cleaning agents within the scope of the present invention Bleach activators included. As bleach activators, compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 C- Atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result are used. Suitable substances are O- and / or N- Acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (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 the conventional bleach activators or in their place, according to the The present invention also includes so-called bleaching catalysts in the cleaning agents be incorporated. These fabrics are bleach-enhancing Transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

According to the invention, agents are preferred, one or more substances from the group of Bleach activators, especially from the groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, especially N- Nonanoylsuccinimide (NOSI), the acylated phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), in amounts of 0.1 to 20% by weight, preferably 0.5 to 15% by weight and in particular from 1 to 10% by weight, based in each case on the total composition.

The bleach activators preferred in the context of the present invention also include the "nitrile quats", cationic nitriles of the formula (XVIII),


in which R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH , -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C _1-24 alkyl group, or for a substituted alkyl or alkenylaryl radical with a C _1-24 alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -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 (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6 and X is an anion.

The general formula (XVIII) includes a large number of cationic nitriles which can be used in the context of the present invention. The detergent tablets according to the invention particularly advantageously contain cationic nitriles in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n- Tetradecyl, n-hexadecyl or n-octadecyl radical. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical.

For reasons of easier synthesis, compounds are preferred in which the radicals R ¹ to R ^{3 are} identical, 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 ^- , where X ^{- is} preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate.

Preferred detergents and cleaning agents in the context of the present invention are characterized in that it contains the cationic nitrile of the formula (XVIII) in amounts of 0.1 up to 20% by weight, preferably from 0.25 to 15% by weight and in particular from 0.5 to 10 % By weight, based in each case on the molding weight.

enzymes

Enzymes in particular come from the hydrolase classes such as that Proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these Hydrolases contribute to the removal of stains such as protein, fat or in the laundry starchy stains and graying. Cellulases and others Glycosyl hydrolases can also be removed by removing pilling and Microfibrils help maintain color and increase the softness of the textile. to Bleaching or to inhibit color transfer can also use oxidoreductases become. Bacterial strains or fungi such as Bacillus are particularly suitable subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic derived from their genetically modified variants Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and Lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for such lipolytic enzymes are the well-known cutinases.

Peroxidases or oxidases have also proven to be suitable in some cases. To the suitable amylases include in particular alpha-amylases, iso-amylases, Pullulanases and pectinases. Cellobiohydrolases are preferably used as cellulases, Endoglucanases and glucosidases, which are also called cellobiases, or Mixtures of these are used. Because different types of cellulase are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures of the Cellulases the desired activities can be set.

The enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition. Contain preferred agents according to the invention Enzymes, preferably in the form of liquid and / or solid enzyme preparations, in quantities from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5 % By weight, based in each case on the total composition. The enzymes can be found in washing and Cleaning process both during heat treatment and in the rinse cycle after the heat treatment, i.e. in a mixture with the LCST substance.

dyes

To improve the aesthetic impression of detergents and cleaning agents, they can be dyed with suitable dyes. Within the scope of the present invention preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the rest Ingredients of the agents and against light as well as no pronounced substantivity Textile fibers so as not to stain them.

Are preferred for use in the washing and cleaning agents according to the invention all colorants that can be oxidatively destroyed in the washing process as well as mixtures the same with suitable blue dyes, so-called blue tones. It has proven to be beneficial proven to use colorants in water or at room temperature in liquid organic substances are soluble. For example, anionic colorants are suitable, z. B. anionic nitroso dyes. A possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is a commercial product for example as Basacid® Green 970 from BASF, Ludwigshafen, and Mixtures of these with suitable blue dyes. Coming as additional colorants Pigmosol® Blue 6900 (CI 74160), Pigmosol Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).

When choosing the colorant, it must be ensured that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of readily water-soluble colorants, e.g. For example, the above-mentioned Basacid "green or the above-mentioned Sandolan® blue, colorant concentrations in the range from a few 10 ^-2 to 10 ^-3 % by weight are typically chosen. In the case of those which are particularly preferred on account of their brilliance, but less so In contrast, readily water-soluble pigment dyes, for example the Pigmosol® dyes mentioned above, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^-3 to 10 ^-4 % by weight.

fragrances

Fragrances are added to the agents in the context of the present invention in order to improve aesthetic impression of the products and the consumer in addition to performance of the product a visually and sensory "typical and distinctive" product for To make available.

Individual perfume oils or fragrances can be used in the context of the present invention Fragrance compounds, e.g. B. the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol, the hydrocarbons mainly include terpenes such as limonene and Pinene.

However, preference is given to using mixtures of different fragrances that work together create an appealing fragrance. Such perfume oils can also be natural Fragrance mixtures contain, as they are accessible from plant sources, for. B. Pine, Citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the cleaning agents according to the invention be, but it can also be advantageous to apply the fragrances to carriers that the Increase the perfume's adhesion to the laundry and by slower fragrance release ensure long-lasting fragrance of the textiles. As such carrier materials have become For example, cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries. It is also possible to use the fragrances to be made up with an LCST substance so that it is only released in the rinse cycle become, which leads to a scent impression when opening the machine.

electrolytes

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

pH adjusters

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents may be indicated. All of them can be used here known acids or alkalis, provided that their use does not result from application technology or ecological reasons or for reasons of consumer protection. The amount of these steeping agents usually exceeds 1% by weight of the total formulation Not.

foam inhibitors

As foam inhibitors in the washing and cleaning agents according to the invention can be used in particular in textile cleaning, for example Soaps, paraffins or silicone oils, which may be based on carrier materials may be upset. Suitable anti-redeposition agents that are also said to be repellents are referred to, for example, nonionic cellulose ethers such as methyl cellulose and Methyl hydroxypropyl cellulose with a methoxy group content of 15 to 30% by weight and on hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ethers and the polymers of phthalic acid known from the prior art and / or terephthalic acid or derivatives thereof, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, particularly preferred are sulfonated derivatives of phthalic and terephthalic polymers.

Optical brighteners

Optical brighteners (so-called "whiteners") can be the agents of the invention can be added to cause graying and yellowing of the treated textiles remove. These substances absorb on the fiber and cause a lightening and feigning bleaching effect by turning invisible ultraviolet radiation into visible convert longer wave light, whereby the ultraviolet absorbed from sunlight Light is emitted as a weak bluish fluorescence and with the yellow tone of the greyed or yellowed laundry produces pure white. Suitable compounds are derived for example from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids (Flavonic acids), 4,4'-distyryl-biphenylene, methylumbelliferone, coumarins, Dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems and the pyrene derivatives substituted by heterocycles.

graying

Graying inhibitors in textile cleaning agents have the task of that of the fiber to keep detached dirt suspended in the fleet and thus the re-opening of the To prevent dirt. For this purpose, water-soluble colloids are mostly organic in nature suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, Salts of ether sulfonic acids of starch or cellulose or salts of acidic Sulfuric acid esters of cellulose or starch. Also water-soluble, acidic groups containing polyamides are suitable for this purpose. Furthermore, soluble ones Use starch preparations and starch products other than the above, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. As Graying inhibitors can also be used cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures.

Crease agents

Because textile fabrics, especially from rayon, rayon, cotton and their Mixtures that can be creased because the individual fibers prevent bending, kinking. Pressing and squeezing across the grain are sensitive Washing and cleaning agents according to the invention contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, Fettsäureestern. Fatty acid amides, alkyl esters, alkyl olamides or fatty alcohols, the are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Antimicrobial agents

Are the washing and cleaning agents according to the invention Textile cleaning agents, these can be used to combat microorganisms contain antimicrobial agents. A distinction is made here depending on the antimicrobial Spectrum and mechanism of action between bacteriostatics and bactericides, Fungistatics and fungicides etc. Important substances from these groups are for example Benzalkoniumchloride, Alkylarlylsulfonate, Halogenphenole and Phenolmercuriacetat, whereby these compounds are also completely dispensed with in the agents according to the invention can.

antioxidants

To unwanted, caused by oxygen and other oxidative processes Changes to the detergent tablets and / or the treated To prevent textiles, the agents can contain antioxidants. To this Compound classes include, for example, substituted phenols, hydroquinones, Pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, Dithiocarbamates, phosphites and phosphonates.

antistatic agents

Increased comfort can result from the additional use of antistatic agents, which are additionally added to the washing and cleaning agents according to the invention. Antistatic agents increase the surface conductivity and thus enable an improved one Drainage of formed charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligand and give one more on the surfaces or less hygroscopic film. Leave these mostly surface-active antistatic agents into nitrogenous (amines, amides, quaternary ammonium compounds), phosphorus (Phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents divide. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional one Finishing effect is achieved.

softener

To care for the textiles and to improve the textile properties like a softer one "Handle" (avivage) and reduced electrostatic charge (increased comfort) can the agents according to the invention contain fabric softener. The active ingredients in Fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues such as the disteraryldimethylammonium chloride, which however, due to its insufficient biodegradability, it is increasingly becoming quaternary Ammonium compounds is replaced, the ester groups in their hydrophobic residues as Breakpoints for biodegradation included.

UV absorbers

Finally, the washing and cleaning agents according to the invention, in particular Textile cleaning agents, also contain UV absorbers, on the treated textiles and improve the lightfastness of the fibers. Connections this Desired properties are, for example, by radiation-free Deactivating active compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Substituted benzotriazoles are also in the 3-position Phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in 2- Position, salicylates, organic Ni complexes and natural products such as umbelliferone and the body's own urocanic acid.

Corrosion inhibitors

Detergents for machine dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing. The known substances of the prior art can be used. In general, silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface. In chlorine-free cleaners, especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Salt-like and complex-like inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used. Preferred here are the transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes
[Me-TACN) Mn ^IV (m - 0) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-MeTACN) Mn ^IV (m - 0) ₃ Mn ^IV (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂
[Me-TACN) Mn ^III (m - 0) (m - 0Ac) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and
[Me-MeTACN) Mn ^III (m - 0) (m-OAc) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ , where Me-TACN is 1,4,7-trimethyl-1, 4,7-triazacyclononane and Me-MeTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Zinc compounds can also be used to prevent corrosion on the wash ware.

In the context of the present invention, automatic dishwashing detergents are preferred which additionally have at least one silver protective agent selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1% by weight, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total mean.

In agents coated according to the invention, the active ingredient is incorporated in such a way that it Main rinse or wash cycle (and also in optional pre-rinse cycles) not or only in released to a minor extent. This ensures that the active ingredients only in Rinse a dishwasher or in the rinse cycle Textile washing machines are effective. In addition to this chemical packaging depending on the type of dishwasher or textile washing machine, a physical one Packaging required so that the active ingredient-containing particles when changing water in the The machine cannot be pumped out and is therefore no longer available for the rinse aid stand.

Domestic dishwashers contain, for example, in front of the drain pump, which the water or the cleaning solution after the individual cleaning cycles the machine pumps, a strainer insert that clogs the pump due to dirt residues should prevent. The packaging of the active ingredient used is in terms of its Size and shape preferably designed so that it is the sieve insert Dishwasher after the cleaning cycle, d. H. after exercise stress the machine and the cleaning solution, does not happen. This ensures that the active ingredient is present in the rinse cycle and only in this rinse cycle is released and brings the desired rinse aid effect. As part of the present Automatic dishwashing agents preferred according to the invention are characterized in that the molded article containing the active ingredient with dispersion coating at least in two Spatial dimensions above 4 mm, preferably above 8 mm and in particular above 12 mm.

• 1. 10 bis 80 Gew.-% des bei 20°C festen Beschichtungsmittels,
• 2. 0,1 bis 30 Gew.-% eines Dispergators und
• 3. 0,1 bis 30 Gew.-% eines Co-Dispergators,

bezogen jeweils auf die Mischung der Komponenten (1) bis (3), in 15 bis 99 Gew.% Wasser, bezogen auf die Dispersion, wobei das Verhältnis der Komponenten (2) und (3) im Bereich von 0,5 : 1 bis 20 : 1 liegt, zur Beschichtung von mit einem LCST-Coating versehenen Formkörpern. Another object of the present invention is a method for coating a shaped body which has an LCST coating by applying a dispersion, preferably a PIT emulsion or suspension

• 1. 10 to 80% by weight of the coating agent solid at 20 ° C.,
• 2. 0.1 to 30% by weight of a dispersant and
• 3. 0.1 to 30% by weight of a co-dispersant,

based in each case on the mixture of components (1) to (3), in 15 to 99% by weight of water, based on the dispersion, the ratio of components (2) and (3) in the range from 0.5: 1 to Is 20: 1, for coating molded articles provided with an LCST coating.

With regard to the components (1) to (3) preferably used in the process according to the invention, their preferred weight ratio, and the preferred size, shape and ingredients of the coated shaped body, reference is made to the above to avoid repetition. EXAMPLES I. To prepare a dispersion according to the invention (here a PIT emulsion) 45% by weight of paraffin (mp: 57-60 ° C., Merck), 7.5% by weight of Mergital B10 (fatty alcohol polyglycol ether, Cognis), 2.5% by weight of Cutina GMS (glycerol partial ester, Cognis) and 45% by weight of water heated to 95 ° C. with stirring. When the mixture was subsequently cooled, which was likewise carried out with stirring, the phase inversion temperature was exceeded in the range between 81 ° C. and 89 ° C. The particle size of the emulsion was between 0.18 µm and 0.3 µm.
II. Using the dispersion described above (here a PIT emulsion), a three-layer coating is applied to a shaped body (for a formulation of the shaped body, see Table 1).
Layer 1: 75 mg of a mixture of Erkol-M-051140 (polyvinyl alcohol, Cognis) and HPMC (Methocel, Dow) in a ratio of 4.3 5.4 as a 5% solution in water (LCST layer)
Layer 2: 30 mg Luviscol Plus (polyvinylcaprolactam, BASF)
Layer 3: 40 mg of a wax layer using the dispersion described above Table 1

Claims (13)

1. Use of dispersions 1. 10 to 80% by weight of the coating agent solid at 20 ° C., 2. 0.1 to 30% by weight of a dispersant and 3. 0.1 to 30% by weight of a co-dispersant, based in each case on the mixture of components (1) to (3), in 15 to 99% by weight of water, based on the dispersion, the ratio of components (2) and (3) in the range from 0.5: 1 is up to 20: 1, for coating molded articles provided with an LCST coating. 2. Use according to claim 1, characterized in that it is in the Dispersion around an emulsion, preferably around a PIT emulsion and / or around a Suspension acts. 3. Use according to one of claims 1 or 2, characterized in that as Coating agents lipids, in particular higher-chain hydrocarbons and / or Wax esters can be used. 4. Use according to claim 1 or 3, characterized in that as a dispersant preferably a hydrophilic nonionic dispersant, particularly preferred hydrophilic nonionic dispersants with an HLB value of 8 to 18 is used. 5. Use according to one of claims 1 to 4, characterized in that as Co-dispersants preferably a hydrophobic co-dispersant, especially preferably cetyl alcohol, stearyl alcohol or a glycerol, sorbitan or Trimethylpropane mono- or diester of a fatty acid with 14 to 22 carbon atoms or Mixtures of these substances can be used. 6. Use according to one of claims 1 to 5, characterized in that the Ratio of (2): (3) is in the range of 1: 1 to 10: 1. 7. Use according to one of claims 1 to 6, characterized in that LCST polymer is selected from cellulose derivatives, mono- or di-N-alkylated Acrylamides, copolymers of mono- or di-N-substituted acrylamides with Acrylamides and / or acrylates or acrylic acids and / or polyvinylcaprolactam. 8. Use according to one of claims 1 to 7, characterized in that the LCST polymer is selected from cellulose ethers, polyisopropylacrylamide, Copolymers of polyisopropylacrylamide and blends of these substances. 9. Use according to one of claims 1 to 8, characterized in that the Shaped body is produced by tableting, extrusion and / or casting. 10. Use according to one of claims 1 to 9, characterized in that the LCST coating in addition to the LCST polymer, another substance, preferably one contains washing and cleaning active substance. 11. Use according to one of claims 1 to 10, characterized in that it the molding is a detergent and cleaning agent, preferably a Textile detergent or dishwashing detergent is one or the active ingredients several components from the group of builders, cobuilders, surfactant (s), polymer (s), Disintegration aid, bleach, bleach activator (s), anti-aging component (s), Enzyme (s), fragrance (s), dye (s), silver protection agent, glass corrosion protection agent, Fluorescent agents, optical brighteners, anti-shrink agents, anti-crease agents, antimicrobial agent (s), germicide (s), fungicide (s), antioxidants, Antistatic agents, ironing aids, phobing and impregnating agents, UV absorbers and / or any mixtures of the above washing and cleaning substances and / or contains other common constituents of washing and cleaning agents. 12. Use according to one of claims 1 to 11, characterized in that the coated molded body with a further molded body by gluing and / or Inserting into a recess is combined to form a combination product. 13. A process for coating a molded article which has an LCST coating by applying a dispersion, preferably a PIT emulsion or suspension 1. 10 to 80% by weight of the coating agent solid at 20 ° C., 2. 0.1 to 30% by weight of a dispersant and 3. 0.1 to 30% by weight of a co-dispersant, based in each case on the mixture of components (1) to (3), in 15 to 99% by weight of water, based on the dispersion, the ratio of components (2) and (3) in the range from 0.5 l to 20: 1, for coating molded articles provided with an LCST coating.