DE10062585A1 - Particulate additives for compositions used in dishwashing or textile washing machines, have the active component(s) enclosed in a shell which is especially of a polymeric material - Google Patents

Abstract

Production of particulate additives for detergents and cleaning compositions is such that the active component is at least partly provided with a shell. An Independent claim is also included for particulate additives for detergents and cleaning compositions, the additives being at least partly covered with a shell of water-soluble, water-dispersible or meltable material.

Description

The present invention relates to a particulate additive for detergents and cleaning agents, containing common active ingredients, a machine dishwashing detergent that contains the additive, and a textile detergent that contains the additive.

The mechanical cleaning of dishes and also the washing of laundry in the household takes place in usual household dishwashers or washing machines. The cleaning or washing processes usually consist of several stages.

The automatic cleaning of dishes usually includes a pre-wash cycle, a main rinse cycle and a rinse cycle that are interrupted by intermediate rinse cycles. Both Most machines can be switched on with the pre-wash cycle for heavily soiled dishes. In the rinse aid rinse aid is added from a dosing tank in the machine, which is usually contain non-ionic surfactants as the main ingredient. Such rinse aids are in liquid form before and are widely described in the prior art. Your main task is Prevent limescale and deposits on the cleaned dishes. In addition to water and weak These rinse aids often also contain foaming nonionic surfactants, hydrotopes, pH regulators such as Citro Nenoic acid or scale-inhibiting polymers.

Household laundry usually includes a main wash cycle and several rinse cycles, a pre-wash cycle can also be activated here. The rinse aids are in the carried out only with water, with so-called post-wash treatment in the last rinse cycle detergents such as fabric softener components, etc. can be added.

Both in dishwashing and household washing are the components that after the actual cleaning or washing cycle are added via separate dosing chambers admitted. Dishwashers contain a storage tank, as well as in regular must be filled with rinse aid at intervals, a filling depending on the machine type for  10 to 50 rinse cycles are sufficient. In washing machines, the aftertreatment agents are in front of everyone Placing laundry in a dosing chamber provided for this purpose. Is filling the tank from Forgotten dishwashers, especially glasses with limescale stains and deposits unsightly. In washing machines, the desired textile aftertreatment is not carried out like that Fabric softener treatment and you get so-called hard laundry.

In the prior art there are therefore some proposed solutions, so-called post-treatment agents in to integrate the means for machine dishwashing or household detergents. These proposed solutions are tied to the offer form of compact shaped bodies.

The European patent application EP-A-0 851 024 (Unilever) describes two-layer Reini detergent tablets, the first layer of which contains peroxy bleach, builder and enzyme, while the second layer of acidifying agent and a continuous medium with a melting point contains between 55 and 70 ° C and scale inhibitors. Due to the high-melting continuous medium, the acid (s) and deposit inhibitor (s) should be released with a delay and a Effect rinse aid.

The disadvantage of the proposed solutions, the post-treatment agents and additives in the Integrating cleaning agents or detergents is because the aftertreatment used agents, which are often in liquid form or as aqueous solutions, in a solid form have to be transferred.

In particular, if the active substances are incorporated into a high-melting medium, so they are usually added to the melt, i.e. H. they become relatively high temperatures exposed. In particular with temperature-sensitive active substances, these temperatures can lead to a reduction in their activity.

The present invention was accordingly based on the object of a dosage form for Post-treatment agent for dishwashing detergent or textile detergent or so-called washing power to provide amplifiers, which may be in solid or liquid form, without the active substances themselves have to be converted into another physical form.

The present invention accordingly relates to a particulate additive for washing and Cleaning agent containing conventional active substances, which is characterized in that the additive at least partially with a water-soluble, water-dispersible and / or meltable Material is encased.

It was found that there are active substances that are used as aftertreatment agents in dishwashing or used in textile washing and are in solid or liquid form,  so-called washing power boosters or machine care products easily from water-soluble or water-dispersible materials can be encased, d. H. can be encapsulated. This opens up the possibility of liquid substances with solid washing and cleaning if necessary to combine means.

The active substances can be completely or partially encased. A partial wrapping is special then only suitable if it only serves to remove the active substances in the area of the wrapping Protect contact with other substances. Full wrapping is preferred if the Active substances are also to be separated from the ambient air or by wrapping one delayed release of the active substances should be stopped.

The coating of the additives according to the invention also offers the possibility of fusible sub punch or to give liquids or powders a defined shape that depends on the order can be specified.

The covering used in the present invention is water-soluble, water-dis pergeable and / or meltable. This means that the material from which the casing is made at least partially after a certain period of time after being placed in water dissolves or at least forms a dispersion or when a certain temperature is reached melts, so that the casing becomes permeable and an exchange of substances between the be container surrounding water and the contents enclosed by the container.

The selection of the wrapping materials is preferably dependent on the intended use the additives of the invention.

If the additive according to the invention is used as a so-called detergency booster, it should Dissolve the coating immediately afterwards and release the active substance. The cleaning process in a dishwasher is characterized in that the rinse cycle at a temperature temperature is above the temperature of the wash cycle, usually between 40 and 70 ° C. It has have therefore proven to be suitable if the covering does not or only during the rinse cycle little dissolves and melts at the temperature in the rinse cycle and the active releases substances. When used as a post-treatment agent in textile washing, that should Additive according to the invention have such a solution kinetics that the active substances only in Rinse aid, preferably only in the last rinse aid.

The casing preferably consists of a material that is at least one natural or synthetic polymer or a mixture of two or more thereof. Prefers contains the material from which the covering is made, gelatin, polyvinyl alcohol, polyethylene glycol, Cellulose ether, alginic acid and / or alginates or pectic acid or a mixture of two or  more of that. Furthermore, the material from which the casing is made up can contain additives, which affect elasticity and water solubility. The material preferably contains which the coating consists of, gelatin and a plasticizer, for example glycol. glycerin or sorbitol. The proportion of plasticizers in the material from which the casing is made is in typically about 10 to about 40% by weight.

The covering can in principle have any shape, being rational and inexpensive forms that can be produced are generally preferred.

This includes, for example, all rotationally symmetrical with respect to at least one axis Shapes, for example the spherical shape, elliptical shapes or cylindrical shapes, where as Envelope a capsule in the form of a sealed at both ends by hemispherical shells Cylinder is preferred. The envelope can be formed in one piece or in several parts, the one-part or the two-part, openable and closable form, is preferred.

The envelope should have such a volume that a usual dosage for the desired application can be filled. It should also be borne in mind that when used in a dishwasher or washing machine, the additive does not have the The drain pump can be pumped out but through the existing sieves in the machine is held back. The volume for household applications is preferably between about 0.5 and about 300 ml, particularly preferably between about 0.8 and about 30 ml, and in particular the between 1 and about 20 ml. With an application in the industrial area it may also be useful to have a volume of more than 300 ml.

The additive according to the invention can contain, for example, such substances as active substances Show a reinforcing effect during the cleaning or washing process or only in an egg Afterwards, they take effect in a rinse aid. Particularly suitable active substances are surfactants, Builders, bleaches, bleach activators, dyes. Fragrances, optical brighteners, enzymes, Foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, color transfer inhibitors and corrosion inhibitors. The active ingredients are described in more detail below.

The active substances can be coated in a manner known per se, e.g. B. by applying the Envelope materials from the melt or from solutions or dispersions take place, the Lö Solution or emulsifier is removed by evaporation. Also an application as a fine powder, for example by electrostatic techniques, is possible, although this method is incorrect regular and poorly adhering coatings. The wrapping materials can be in Mixers, mixers and granulators are applied to particles. However, one is preferred Application of the casing materials in a fluidized bed, with a size classification at the same time the particles can take place.  

In the spraying process, all are well-established in pharmacy and food technology Process for the production of coated tablets, capsules and particles. The Polymersus Pension or solution is either sprayed on discontinuously in small portions, whereby the particles z. B. transported on a conveyor belt through a liquid curtain and then be dried in a stream of air or continuously with simultaneous drying by the blown air flow in fluidized bed, fluidized bed or flight bed wrapping devices sprayed. The coating process is also conceivable if the coating syrups are made of LCST polymers sufficiently high concentration can be added. The application of further layers can be carried out analogously respectively. Coating in commercially available drum coats is also possible. Suitable are z. B. commercially available coaters, e.g. B. the companies Lödige, Driam, Manesty, GS, Glatt.

If the wrapping materials lead to sticky products under certain circumstances, it can it makes sense to apply finely divided substances to the coated phases ("Ab powder "). All fine-particle substances can be used as powdering agents, including others Detergent ingredients such as builder substances can be used. Are preferred as additional powdering agents zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, Starch, cellulose derivatives, etc. used. Part of the buffer system, if present, can also be used can be used for powdering.

In a preferred embodiment, prefabricated capsules are used as the covering materials, which are commercially available, for example, as plug-in capsules.

If meltable substances are used as active substances, it has proven to be particularly advantageous proven to use half capsules, in which the active ingredients are filled in the form of their melt become. In this embodiment, substances are difficult to portion and thus to be dosed are converted into a well-dosed and easy-to-use form.

The additives can be used as independent products or in combination with dishwashing detergents or Textile detergents are used.

The additives according to the invention can be given directly to the consumer, so that he also adds them to the detergent or detergent as needed. by virtue of this additional dosing step would be in addition to the fixed dosage form and the addition minimized the advantages over liquid agents in the same dosing compartment. It is preferably the half, the additives according to the invention with particulate machine dishwashing detergents or Textile detergents, especially those that are in the form of moldings, to combine.  

Another object of the present invention is therefore also a particulate machine normal dishwashing detergent containing builders and at least one other ingredient the groups of surfactants, enzymes, bleaching agents, bleach activators, corrosion inhibitors, polymers re, dyes and fragrances and machine care products, characterized in that at least one further ingredient with a water-soluble, water-dispersible and / or meltable Material is encased.

The coated ingredient is preferably present in amounts of 0.5 to 30% by weight, preferably 1 up to 25% by weight and in particular from 2 to 15% by weight, in each case based on the total composition, in front.

Yet another object of the present invention is therefore also a particulate ma Fast textile detergent, containing builders and optionally other ingredients from the Groups of surfactants, enzymes, bleaches. Bleach activators, corrosion inhibitors, polymers, Dyes and fragrances and machine care products, characterized in that one or more of the other ingredients with a water-soluble, water-dispersible and / or fusible material are encased.

The ingredients of the automatic dishwashing detergent or textile detergent are as follows described. Some of these can also be used as active substances or carrier materials in the invention appropriate additives may be included.

Important ingredients of machine dishwashing detergents and also textile detergents are Ge rüststoffe. In the inventive agents for automatic dishwashing, everyone can Builders usually used in detergents and cleaning agents, in particular in particular, zeolites, silicates, carbonates, organic cobuilders, the phosphates. The below The builders mentioned are also used as carrier materials for active substances, such as rinse aid surfactants.

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 .yH2O are preferred.

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

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Cros field) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X), which was developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

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

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

It goes without saying that the generally known phosphates are also used as builder substances possible. Among the large number of commercially available phosphates, the alkali metal phos phate with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the detergent and cleaning agent industry.

Alkali metal phosphates is the summary 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 lime incrustations in tissues 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, very easily soluble in water powder, which lose the 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 trime taphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to 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), KH2PO4, is a white salt with a density of 2.33 gcm ^-3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in Water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 melting point 35 ° with loss of 5H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated to a greater extent. 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 set that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition) as dodecahydrate, and as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (accordingly 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under 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 three-phase 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). In the case of substances, there are colorless crystals which are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating disodium phosphate to <200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, graham 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 a non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n which crystallizes with 6H ₂ O and is water-free -Na with n = 3. In 100 g of water about 17 g dissolve at room temperature, at 60 ° approx. 20 g, at 100 ° about 32 g of the water free of crystal water; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mi combinations of these two can be used; also mixtures of sodium tripolyphosphate and natri umkaliumtripolyphosphat or mixtures of potassium tripolyphosphate and sodium potassium tripoly phosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium Umtripolyphosphate can be used according to the invention.

As organic cobuilders in the dishwasher detergents according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used become. These classes of substances are described below.  

Useful organic builders are, for example, those in the form of their sodium salts settable polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, adipin acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acid ren, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their builder, the acids possess typically also have the property of an acidifying component and are therefore also used for Setting a lower pH value for detergents or cleaning agents. In particular are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any Mi. names from these.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metals tall salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 500 to 70,000 g / mol.

For the purposes 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 made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. These figures deviate significantly from the molecular weight figures for which polystyrene sulfonic acids are used as the 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 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acid ren, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and ins special 30,000 to 40,000 g / mol.  

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

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

Also particularly preferred are biodegradable polymers made from more than two different ones NEN monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those which are preferably monomers acrolein and acrylic have acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their Salts or their precursors to name, for example polyaspartic acids or their Salts and derivatives.

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

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. The hydrolysis products are preferably of medium molar mass range from 400 to 500000 g / mol. A polysaccharide with a dextrose Equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being one common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.

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

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine di succinate, are other suitable cobuilders. Here, ethylenediamine-N, N'-disuccinate (EDDS) be preferably used in the form of its sodium or magnesium salts. Also preferred are in in this connection also glycerol disuccinates and glycerol trisuccinates. Suitable use Quantities in formulations containing zeolite and / or silicate are 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the hydroxyal Kanphosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). As aminoalkane phosphonates occur preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) as well as their higher homologues in question. They are preferably in shape the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta and Octa sodium salt of DTPMP, used. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also contains lead che contain, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to form complexes with alkaline earth ions to be used as cobuilders.

Anionic, nonionic, cationic and / or amphoteric surfactants can be used as surfactant (s) mixtures of these are used.

From an application point of view, preference is given to mixtures of anionic and nonionic Surfactants. The total surfactant content of the detergents in the case of detergents is 5 to 60% by weight, based on the weight of the agent, with surfactant contents above 15% by weight being preferred rend detergent for automatic dishwashing, preferably less than 5% by weight of surfactant (s) contain.  

Examples of anionic surfactants used are 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 an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce Rinestern are the mono-, di- and triesters as well as their mixtures as they are to be understood in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the order esterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. Preferred sulfated fat Acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbons Substance atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid re, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and especially the sodium salts of sulfuric acid are half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example made 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 ge-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and 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 ten side (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. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hy third 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, available. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

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

In addition, alkyl glycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular in the 2-position methyl branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

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

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

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

in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. 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 II

in which R ³ for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁴ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ⁵ for a linear, branched or cyclic alkyl radical or is an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, at 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 star in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.

In the context of the present invention, additives which are anionic (s) and nonionic are preferred contain (s) surfactant (s), with application advantages from certain quantitative Ratios in which the individual classes of surfactants are used can result.

Only low-foaming nonionic surfactants are usually used in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance. Agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is branched linearly or preferably in the 2-position methyl may or may contain linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues. 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 of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In the case of agents according to the invention for machine dishwashing in particular, it is preferred that the agents contain a nonionic surfactant that has a melting point above room temperature  having. Accordingly, at least one of the deformable masses in the invention The process preferably uses a nonionic surfactant with a melting point above 20 ° C. Nonionic surfactants to be used preferably have melting points above 25 ° C. nonionic surfactants to be used with particular preference have melting points between 25 and 60 ° C, especially between 26.6 and 43.3 ° C.

Suitable non-ionic surfactants, the melting or softening points in the tempera mentioned have low-foaming nonionic surfactants, which at Room temperature can be solid or highly viscous. Become highly viscous at room temperature Nonionic surfactants used, it is preferred that these have a viscosity above 20 Pas, preferably have above 35 Pas and in particular above 40 Pas. Also non-ionic surfactants that are used in Room temperature waxy consistency are preferred.

Preferred nonionic surfactants to be used as solid at room temperature come from the groups of alkoxylated nonionic surfactants, especially the ethoxylated primary alcohols and mixtures thereof Surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxy ethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out furthermore by good foam control.

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

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

The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the Molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally contain polyoxyethylene-polyoxypropylene block copolymer units point. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferred more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight the total molecular weight of such nonionic surfactants.  

Other nonionic surfactants to be used with particular preference with melting points above space temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene Block polymer blends, which is 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block Copolymers of polyoxyethylene and polyoxypropylene, initiated with and containing trimethylolpropane tend 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

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

Another preferred surfactant can be represented by formula III

R ⁶ O [CH ₂ CH (CH ₃ ) O] _x (CH ₂ CH ₂ O) _y [CH ₂ CH (OH) R ⁷ ] (III)

describe in which R ^{6 represents} a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R ⁷ 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 represents a value of at least 15.

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

R ⁸ O [CH ₂ CH (R ¹⁰ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ⁹ (IV)

in which R ⁸ and R ^{9 represent} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{10 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. When the value x ≧ 2, each R ¹⁰ in the above formula can be different. R ⁸ and R ⁹ 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. For the radical R ¹⁰ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ¹⁰ 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 ¹⁰ 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 ⁸ O [CH ₂ CH (R ¹⁰ ) O] _x CH ₂ CH (OH) CH ₂ OR ⁹

simplified. In the last-mentioned formula, R ⁸ , R ⁹ and R ^{17 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 ⁸ and R ^{9 have} 9 to 14 C atoms, R ¹⁰ stands for H and x assumes values from 6 to 15.

The use of surfactants is preferably limited in detergents for machine dishwashing indicate the use of nonionic surfactants in small quantities. As part of the present Agents preferably used as dishwashing agents are characterized in that they total surfactant contents below 5 wt .-%, preferably below 4 wt .-%, particularly ders preferably below 3 wt .-% and in particular below 2 wt .-%, each bezo on their total weight.

If the agent according to the invention is a textile detergent, the additive preferably contains textile softening substances, especially cationic surfactants.

Examples of cationic surfactants are, in particular, quaternary ammonium compounds, cationic Polymers and emulsifiers.

Suitable examples are quaternary ammonium compounds of the formulas (VII) and (VIII),

where in (I) R ^a and R ^{b are} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{c is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{d is} either equal to R ^a , R ^b or R ^c or stands for an aromatic residue. X ^- represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these. Examples of cationic compounds of the formula (VII) are didecyldimethylammonium chloride, ditallow dimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (VIII) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here R ^e stands for an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ^f stands for H, OH or O (CO) R ^h , R ^g independently of R ^{f stands} for H, OH or O (CO) R ⁱ , where R ^h and R ⁱ independently of one another each represent an aliphatic acyl radical with 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently have the value 1, 2 or 3. X ^- can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof. Compounds are preferred which contain the group O (CO) R ^h for R ^f and alkyl radicals having 16 to 18 carbon atoms for R ^c and R ^h . Connections in which R ^g also stands for OH are particularly preferred. Examples of compounds of the formula (VIII) are methyl-N- (2-hydroxyethyl) -N, N-di (tallow acyl-oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl-methyl-ammonium methosulfate or methyl -N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (VIII) are used which have unsaturated alkyl chains, preference is given to the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30. Typical commercial examples are the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold by Stepan under the trademark Stepantex® or the products from Cognis known under Dehyquart® or the products from Goldschmidt-Witco known under Rewoquat®. Further preferred compounds are the diesterquats of the formula (IX), which are available under the name Rewoquat® W 222 LM or CR 3099 and, in addition to their softness, also ensure stability and color protection.

R ^k and R ^l each independently represent an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazolinium compounds of the formula (X),

where R ^{m is} H or a saturated alkyl radical with 1 to 4 carbon atoms, R ⁿ and R ^o independently of one another each represent an aliphatic, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms, R ⁿ alternatively also for O (CO) R ^p may, where R ^{p is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ^{- is} an anion. q can take integer values between 1 and 4.

Further suitable quaternary compounds are described by formula (XI)

where R ^q , R ^r and R ^s independently of one another represent a C _1-4 alkyl, alkenyl or hydroxyalkyl group, R ^t and R ^u each independently represent a C _8-28 alkyl group and r is a number between 0 and 5 is.

In addition to the compounds of formulas VII to XI, short-chain, water-soluble, quaternary Ammonium compounds are used, such as trihydroxyethylmethylammonium methosulfate or the alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methylammonium chloride, e.g. B. cetyltrimethylammonium chloride, stearyltrimethylammonium chloride,  Distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzyl ammonium chloride and tricetylmethylammonium chloride.

Protonated alkylamine compounds, which have a softening effect, and also not quaternized, protonated precursors of the cationic emulsifiers are suitable.

The quaternized Pro are further cationic compounds which can be used according to the invention teinhydrolysate.

Suitable cationic polymers include the polyquaternium polymers as used in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the polyquaternium-6, polyquaternium-7, polyquaternium-10- also known as merquats Polymers (Ucare Polymer IR 400; Amerchol), polyquaternium 4 copolymers, such as graft copolymers re with a cellulose backbone and quaternary ammonium groups that over allyldimethylammonium chloride-bound, cationic cellulose derivatives, such as cationic guar, such as guar hydroxypropyltriammonium chloride, and similar quaternized guar derivatives (e.g. Cosmedia guar, Manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), e.g. B. the commercial product Glucquat®100, according to the CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride ", copolymers of PVP and dimethylaminomethacrylate, Copo polymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers,

Polyquaternized polymers (e.g. Luviquat Care from BASF) can also be used cationic chitin-based biopolymers and their derivatives, for example that under the Han Product name Chitosan® (manufacturer: Cognis) available polymer.

Cationic silicone oils such as those commercially available are also suitable according to the invention available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modified sili con, also known as amodimethicone), SM-2059 (manufacturer: General Electric), SLM- 55067 (manufacturer: Wacker) Abil®-Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquartare Polydimethylsiloxanes, Quaternium-80), and Siliconquat Rewoquat® SQ 1 (Tegopren® 6922, Her Steller: Goldschmidt-Rewo).

Compounds of the formula (XII)

the alkylamidoamines can be in their non-quaternized or, as shown, their quaternized form. R ^v can be an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5. R ^w and R ^x each independently represent H, C _1-4 alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid®S 18 or the 3-tallowamidopropyl trimethylammonium methosulfate available under the name Stepantex®X 9124, which, in addition to having a good conditioning effect, are also characterized by an ink transfer inhibiting action and especially by their good biodegradability.

Of the compounds used as bleaching agents and providing H ₂ O ₂ in water, sodium percarbonate is of particular importance. "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 .3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm ^-3 which is slightly decomposed into sodium carbonate and has a bleaching or oxidizing effect and the oxygen decays.

Sodium carbonate peroxohydrate was first made in 1899 by precipitation with ethanol from a solution obtained from sodium carbonate in hydrogen peroxide, but mistakenly referred to as peroxy carbonate hen. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, nevertheless, the historical name "sodium percarbonate" has become established in practice.

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

Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthlo-looperoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the agents. If cleaning or bleaching agents are produced for machine dishwashing, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxy lauric acid, peroxystearic acid, ε-phthalimidanoic acid paprooxyaproacid acid )], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenyl amidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1 , 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Chlorine or bromine can also be used as bleaching agents in machine dishwashing releasing substances are used. Among the appropriate chlorine or bromine releases Materials come for example heterocyclic N-bromo- and N-chloramides, for example Trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or its salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

To improve when washing or cleaning at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be incorporated. Bleach activators, the supporting the action of the bleaching agents are, for example, compounds that have one or more re contain N- or O-acyl groups, such as substances from the class of anhydrides, the esters, the Imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine (TAED),  Tetraacetylmethylene diamine (TAMD) and tetraacetylhexylene diamine (TAHD), but also Pentaace tylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) and isatoic anhydride (ISA).

As bleach activators, compounds which are aliphatic under perhydrolysis conditions oxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or result in optionally substituted perbenzoic acid can be used. Substans are suitable zen, the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substi tuated 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, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, ins special n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid hydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triace tin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile- Methyl sulfate (MMA), enol esters and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, especially pentaacetyl glucose (PAG), pen taacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N- alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N- Benzoyl. Hydrophilically substituted acylacetals and acyllactams are also considered trains used. Combinations of conventional bleach activators can also be used.

In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts are incorporated. These fabrics are bleaching enhancers de 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 tripod ligands containing N as well as Co, Fe, Cu and Ru amine complexes are as Bleaching catalysts can be used.

Bleach activators from the group of multi-acylated alkylenediamines, in particular, are preferred special tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in men gene up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and be particularly preferably 2 to 6 wt .-% based on the total agent used.

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

The corrosion inhibitors mentioned can protect the dishes or the machine are also incorporated into the masses to be processed, whereby in the area of ma rapid dishwashing silver protection agents have a special meaning. Can be used the known substances of the prior art. In general, Sil protective agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes be set. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. In addition, active chlorine-containing agents, the corro, are often found in detergent formulations dieren the silver surface significantly reduce. In chlorine-free cleaners, other oxygen and nitrogen-containing organic redox-active compounds, such as two and three term phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Be The transition metal salts selected from the group of manganese are preferred and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or Man goose and manganese sulfate. Zinc compounds can also be used to prevent corrosion be used on the wash ware.

If anti-corrosive agents are used, which are multi-phase moldings, it is be prefers to separate them from the bleaching agents. Detergent tablets, at where one part contains bleach while another contains anti-corrosion agents therefore preferred.

The separation of the bleaching agents from other ingredients can also be advantageous. OF INVENTION Agents according to the invention, which are in the form of multi-phase moldings and in which one Phase containing bleach while another contains enzymes are also preferred.

Enzymes in particular come from the hydrolase classes such as the protea sen, esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry in laundry to remove stains such as protein, fat or starchy stains cuts and graying. Cellulases and other glycosyl hydrolases can also be used  by removing pilling and microfibrils to preserve color and increase softness of the textile. Oxi can also be used to bleach or inhibit the transfer of color doreductases are used. Bacterial strains or fungi are particularly suitable such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humi cola insolens and enzymatic derived from their genetically modified variants Agents. Proteases of the subtilisin type and in particular proteases which are preferred are obtained from Bacillus lentus. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic 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 lipa Se-containing mixtures or mixtures with lipolytically active enzymes of special In teresse. Known cutinases are examples of such lipolytically active enzymes. Also Peroxidases or oxidases have proven to be suitable in some cases. To the suitable Amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrofases, endoglucanases and glucosidases that also called cello bias, or mixtures of these are used. Because there are different Differentiate cellulase types by their CMCase and avicelase activities targeted mixtures of the cellulases the desired activities can be set.

Other enzymes are naturally used in machine dishwashing detergents to take into account the different treated substrates and soiling. Here come in particular those from the classes of hydrolases such as proteases, esterases, Li pasen or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of ge called enzymes in question. All of these hydrolases help remove soils like stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching be used. Bacterial strains or fungi such as Bacillus are particularly suitable subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants. before proteases of the subtilisin type and in particular proteases derived from Bacillus lentus are used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytically active enzymes or from protease, Amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic acting enzymes, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. Examples of such The well-known cutinases are lipolytic enzymes. Also peroxidases or oxidases ha have proven to be suitable in some cases. Suitable amylases include in particular right alpha-amylases, iso-amylases, pullulanases and pectinases.  

The enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or En zymgranulate can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, each based on the uncompressed part.

Other ingredients that may be included are, for example, dyes, optical brighteners, Fragrances, soil release compounds, soil repellents, antioxidants, fluorescent agents, foams inhibitors, silicone and / or paraffin oils, color transfer inhibitors, graying inhibitors, Detergent booster etc. These substances are described below.

To improve the aesthetic impression of the agents according to the invention, they can be whole or partially colored with suitable dyes. Special optical effects can be thereby achieve in the case of moldings, in particular if in the case of the production of moldings from several masses, the masses to be processed are colored differently. preferred Dyes, the selection of which is not difficult for the person skilled in the art, have a high level Storage stability and insensitivity to the other ingredients of the agent and to Light and no pronounced substantivity towards the treated substrates as in for example textile fibers or dishes, so as not to stain them.

Preferred for use in agents according to the invention are all colorants which are used in the washing process can be destroyed by oxidation and mixtures thereof with suitable blue dyes, so-called blue tones. It has proven to be advantageous to use colorants in water or are soluble in liquid organic substances at room temperature. For example, are suitable se anionic colorants, e.g. B. anionic nitroso dyes. A possible colorant is with for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a trade product is available, for example, as Basacid® Green 970 from BASF, Ludwigshafen, so like mixtures of these with suitable blue dyes. Pig mosol® 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® Blau (CI Acid Blue 182, CAS 12219-26-0) for use.

When choosing the colorant, care must be taken to ensure 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 coloring agent in the washing or cleaning agents varies. In the case of readily water-soluble colorants, e.g. B. the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the preferred because of their brilliance, but less water-soluble pigment dyes, for. B. the above-mentioned Pigmosol® dyes, the suitable concentration of the colorant in washing or cleaning agents, on the other hand, is typically a few 10 ^-3 to 10 ^-4 wt .-%.

The agents according to the invention can contain one or more optical brighteners. This Fabrics that are also called "whiteners" are used in modern detergents because even freshly washed and bleached white laundry has a slight yellow tinge. optical Brighteners are organic dyes that form part of the invisible UV radiation from the sun convert light into longer-wave blue light. The emission of this blue light complements the "Gap" in the light reflected from the textile, so that a textile treated with an optical brightener Eye appears whiter and lighter. Because the mechanism of action of brighteners is their pulling up on the fibers, one differentiates depending on the "dyed" fibers, for example Brightener for cotton, polyamide or polyester fibers. The commercial ones for incorporation brighteners suitable in detergents essentially comprise five structural groups Stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline group and the group the combination of benzoxazole or benzimidazole with conjugated systems. An overview of Common brightener is for example in G. Jakobi, A. Löhr "Detergents and Textile Washing", VCH-Verlag, Weinheim, 1987, pages 94 to 100. Are suitable for. B. salts of 4,4'- Bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or the like built compounds that instead of the morpholino group a diethanolamino group, a methyl wear amino group, an anilino group or a 2-methoxyethylamino group. Can continue Brighteners of the substituted diphenylstyryl type may be present, e.g. B. the alkali salts of 4,4'- Bis (2-sulfostyryl) diphenyl, 4,4-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). Mixtures of the aforementioned brighteners can also be used.

Fragrances are added to the agents according to the invention in order to give the aesthetic impression of Improve products and provide consumers with a visual and visual performance to provide sensory "typical and distinctive" product. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the type the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. olfactory Compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert.- Butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbylacetate, phenylethyl acetate, linalylbene zoat, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and  Benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen alde hyd, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, Phe nylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as Lime and pinene. However, mixtures of different fragrances are preferably used, which 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. Also suitable are 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 as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.

The fragrance content of the agents according to the invention is usually up to 2% by weight of the entire wording. The fragrances can be incorporated directly into the agents according to the invention tet, but it can also be advantageous to apply the fragrances to carriers that the Haf Increase the perfume on the laundry and slow down the fragrance release for longer lasting fragrance of the textiles. Such carrier materials have, for example Cyclodextrins have proven their worth, with the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.

In addition, the agents can also contain components that can be washed out of the oil and fat influence textiles positively (so-called soil repellents). This effect becomes special clearly, if a textile is soiled, which has previously been repeatedly with an inventive moderate detergent containing this oil and fat-dissolving component. To the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, and the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonio nisch modified derivatives of these. Of these, the sulfonated ones are particularly preferred Derivatives of phthalic acid and terephthalic acid polymers.

As foam inhibitors that can be used in the agents produced according to the invention NEN, for example, soaps, paraffins or silicone oils come into consideration, which if necessary Carrier materials can be applied.  

Graying inhibitors have the task of removing the dirt detached from the fibers in the liquor to keep suspended and thus prevent the dirt from re-opening. For this are Suitable water-soluble colloids mostly organic, for example the water-soluble sal ze 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 what Serum-soluble polyamides containing acidic groups are suitable for this purpose. Continue reading soluble starch preparations and starch products other than those mentioned above are used, z. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Prefers However, cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyal kylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, Me thylcarboxymethylcellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the means used

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

To combat microorganisms, the agents prepared in accordance with the invention can be antimi contain crobial agents. A distinction is made depending on the antimicrobial spectrum and Mechanism of action between bacteriostatics and bactericides, fungiostatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsul fonate, halophenols and phenol mercuriacetate, being entirely based on these compounds can be dispensed with.

Unwanted changes caused by oxygen and other oxidative processes To prevent changes to the agents and / or the treated textiles, the agents can be anti contain oxidants. This class of compounds includes, for example, substituted phenols, Hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, Dithiocarbamates, phosphites and phosphonates.

An increased wearing comfort can result from the additional use of antstatics, which be additionally added to the agents produced according to the invention. Antistatic agents increase the Surface conductivity and thus enable an improved flow of charges. External antistatic agents are generally substances with at least one hydrophilic molecule and give a more or less hygroscopic film on the surfaces. This mostly  Surface-active antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary ammoni umverbindungen), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, Al subdivide antistatic agents. The lauryl (or stearyl) dimethylbenzylam disclosed here monium chlorides are suitable as antistatic agents for textiles or as an additive to detergents in addition, a finishing effect is achieved.

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

Finally, the agents produced according to the invention can also contain UV absorbers which are based on pull up the treated textiles and improve the lightfastness of the fibers. Verbindun conditions that have these desired properties are, for example, those due to radiation-free Deactivating active compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Also substituted are benzotriazoles in the 3-position phenylsub substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid suitable.

For all of the above-mentioned ingredients, advantageous properties can be derived therefrom sult to separate them from other ingredients or with certain other ingredients to assemble together. In the case of multi-phase moldings, the individual phases can also have a different content of the same ingredient, which achieves advantages can be.

Examples of machine care products are water softeners and decalcifiers. As a water softener All substances known from the prior art are suitable which are able to approx Ions to complex. Descaler are substances that are able to remove limescale dissolve and preferably also to keep in solution, such as. B. organic and inorganic Acids.  

Examples of suitable acids that can be used as decalcifying agents are boric acid as well Alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts as well as solid mono-, oligo- and polycarboxylic acids and -hydroxycarboxylic acids, such as citric acid, Malic acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, ox Acid and polyacrylic acid, organic sulfonic acids such as amidosulfonic acid commercially available Lich and is also preferably used as an acid in the context of the present invention kalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), embers aric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

If the agents according to the invention are in the form of moldings, they can be used as further constituents Disintegrant and a shower system are included.

To facilitate the disintegration of highly compressed moldings, it is possible to disintegrate tools, so-called tablet disintegrants, to incorporate into them in order to reduce the disintegration times Shorten. These substances are suitable, for example, for the release of individual forms to accelerate body areas compared to other areas. Under tablet disintegrants or decay accelerators are according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184) auxiliaries understood for the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in a resorbable form.

These substances, which are also called "explosives" due to their effectiveness, enlarge their volume in the event of water ingress, with the volume on the one hand increasing (swelling) and the other on the other hand, a pressure can be generated via the release of gases, which the tablet in lets smaller particles disintegrate. Well-known disintegration aids are, for example, carbo nat / citric acid systems, whereby other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrro lidon (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or Ca 13795 00070 552 001000280000000200012000285911368400040 0002010062585 00004 13676 sein derivatives.

In the context of the present invention, desin Cellulose-based detergent.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally considered, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxy 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 a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferred as a cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not in finely divided form used, but before mixing into the premixes to be pressed into a coarser one Form transferred, for example granulated or compacted. Washing and cleaning shaped agent, the disintegrants in granular or optionally cogranulated form are contained in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel) ben. These writings are also more detailed information on the production of granulated, compacted or cogranulated cellulose disintegrant. The particle sizes of such disintegration medium are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm. The above mentioned coarser disintegration aids and described in more detail in the cited documents cellulose-based are preferred in the context of the present invention as disintegration use tools and in the trade, for example, under the name Arbocel® TF-30-HG available from Rettenmaier.

As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial Hydrolysis of celluloses obtained under conditions that only the amorphous areas (approx. Attack and completely dissolve 30% of the total cellulose mass) of the celluloses, which crystallize leave areas (approx. 70%) undamaged. A subsequent disaggregation of the the hydrolysis of the microfine celluloses produces the microcrystalline celluloses, the Pri have particle sizes of about 5 µm and, for example, granules with a medium Particle size of 200 microns can be compacted.

Preferred detergent tablets in the context of the present invention ent additionally hold a disintegration aid, preferably a disintegration aid Cellulose base, preferably in granular, cogranulated or compacted form, in quantities  from 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 weight of the molded body.

The detergent tablets according to the invention can moreover a ga Developing shower system included that in one or more of the masses to be processed is incorporated. The gas-developing shower system can consist of a single substance, which releases a gas on contact with water. Among these connections is particularly that To name magnesium peroxide, which releases oxygen on contact with water. Usually be however, the gas-releasing bubble system itself consists of at least two components, that react with each other to form gas. While here a multitude of systems think and is executable, which release nitrogen, oxygen or hydrogen, for example Bubble system used in the detergent tablets according to the invention Let you choose based on both economic and ecological considerations. Preferred shower systems consist of alkali metal carbonate and / or bicarbonate as well an acidifying agent which is suitable from the alkali metal salts in aqueous solution Koh to release lime dioxide.

In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are out Cost reasons clearly preferred over the other salts. Needless to say the pure alkali metal carbonates or bicarbonates concerned are not used; rather, mixtures of different carbonates and hydrogen carbonates from washtech African interest may be preferred.

In preferred detergent tablets, 2 to 20% by weight are used as the shower system. %, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 parts by weight. % of an acidifying agent, based in each case on the entire molded body. The The content of individual substances in the substances mentioned may well be higher.

As acidifying agents that release carbon dioxide from the alkali salts in aqueous solution for example boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, organic acidification is preferred agent used, the citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. From this group tartaric acid, succinic acid, malonic acid, adipic acid are preferred right, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as ami Dosulfonic acid can also be used. Commercially available and as an acidifier in Sokalan® DCS (trademark  from BASF), a mixture of succinic acid (max. 31 wt.%), glutaric acid (max. 50 wt. %) and adipic acid (max. 33% by weight).

In the context of the present invention, detergent tablets are preferred, in which a substance from the group of organic di-, Tri- and oligocarboxylic acids or mixtures of these are used.

The combination products can be produced in a manner known per se.

In one possible embodiment, the agents according to the invention are in the form of moldings. The Shaped bodies and the coated additives can be produced separately and then together connected, the moldings can be prefabricated recesses for the coated additives stanchions, such as troughs or through holes. The connection can for example by simply inserting or inserting into a hole or a recess and / or gluing of the two fixed components.

In a further embodiment, the coated additives are prepared in a suitable tablet direction with the premix for the dishwashing detergent or textile detergent to form articles processed.

In the agents according to the invention, the coated additives can contain the aforementioned The other parts protrude from the matrix of the other particulate ingredients kel can also have sizes that are in the range mentioned, so that overall a detergent or textile detergent is formulated, which consists of large detergent and Additive particles exist. In particular, if the coated additives are colored, for example So have a red, blue, green or yellow color, it is for the appearance of the pro ducts, d. H. of the entire agent is advantageous if the coated additives are visibly larger than the matrix of the particles of the other ingredients of the agent. Here are part of the invention Chen-shaped machine dishwashing detergent or textile detergent preferred (without consideration supply of the coated additives) particle sizes between 200 and 3000 microns, preferably between Have 300 and 2500 microns and in particular between 400 and 2000 microns.

If the agents according to the invention are formulated as a powder mixture, it can be used, in particular with greatly different sizes of coated additives and detergent or textile detergent matrix - on the one hand partial separation occurs when the package is shaken ten, on the other hand, the dosage in two successive cleaning cycles be different because the consumer does not always necessarily have the same amount of cleaning or textile detergent and additives dosed. Should be desired, technically always the same amount per To use the cleaning cycle, this can be done via the packaging of the inventive packaging familiar to the person skilled in the art  Means can be realized in bags made of water-soluble film. Also particulate machine dishwashing detergent or textile detergent, in which a dosing unit in a bag is packaged from water-soluble film, are the subject of the present invention.

As a result, the consumer only has one bag which, for example, contains a detergent or dishwashing powder and contains several optically prominent rinse aid particles, in insert the dosing compartment of his dishwasher or washing machine. This execution Form of the present invention is therefore a visually attractive alternative to conventional Means.

The agents according to the invention can be produced in a manner known per se. A procedure for Manufacture of powdered automatic dishwashing detergents with a rinse effect, in which a Known powdered dishwasher detergent with rinse aid part according to the invention keln is mixed, is therefore a further object of the present invention.

The desired retention of additives in the machine described above also applies to In addition to the above-mentioned enlargement of the additive particles, water changes can also be carried out by reduce the size of the holes in the sieve insert. In this way you can machine Formulate dishwashing detergent or textile detergent that have a uniform mean particle size have which is smaller than, for example, 4 to 12 mm. For this purpose, the invention Product, in which the additives also have smaller particle sizes, include a sieve insert ben that replaces or covers the insert in the machine. Another item The present invention is therefore a kit-of-parts, which is a powdered according to the invention machine dishwashing detergent or textile detergent and a sieve insert for household items includes dishwashers or washing machines.

As already mentioned, the combination of agent and sieve insert according to the invention allows Formulation of agents in which the additives also have smaller particle sizes. OF INVENTION kits-of-parts according to the invention, in which the particle sizes of the agent according to the invention (under Consideration of the additive particles) in the range from 400 to 2500 µm, preferably from 500 to 1600 µm and in particular from 600 to 1200 µm are preferred.

In order to prevent the enclosed sieve insert from becoming blocked due to dirt residues etc. the mesh size or hole size should not be chosen too small. Here are inventive kits-of-parts are preferred where the mesh size or hole size of the sieve insert is 1 to 4 mm and the additives are larger than this mesh size or hole size of the sieve insert zes.  

The kit of parts according to the invention is not restricted to the specific shape of the sieve insert, where it replaces or covers the insert in the machine. It is fictional also possible and preferred according to the kit-of-parts to include a sieve insert, the shape of a basket, which in a known manner in the dishwasher - for example on the cutlery basket - can be hung or placed in the drum of the washing machine can be. In this way, a sieve insert designed in this way replaces the dosing chamber, d. H. the consumer doses the agent according to the invention directly into this sieve insert, which acts in the cleaning and rinse cycle in the manner described above.

Claims (12)

1. Particulate additive for detergents and cleaning agents containing customary active substances, characterized in that the additive is at least partially coated with a water-soluble, water-dispersible and / or meltable material. 2. Additive according to claim 1, characterized in that the wrapping material is selected is natural or synthetic polymers or mixtures thereof. 3. Additive according to claim 2, characterized in that the polymers are selected from gelatin, polyvinyl alcohol, polyethylene glycol, cellulose ether, alginic acid and / or Al ginate or pectic acid. 4. Additive according to one of claims 1 to 3, characterized in that the coating has a volume of 0.5 to 300 ml. 5. Additive according to one of claims 1 to 4, characterized in that the active substances are selected from surfactants, builders, bleaching agents, bleach activators, dyes, Fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, antirede positioners, graying inhibitors, color transfer inhibitors and corrosion inhibitors bitters, machine care products and any mixtures of the above. 6. Process for producing a particulate additive for washing and cleaning with tel, containing customary active substances, characterized in that the active substances at least at least partially be provided with a covering in a manner known per se. 7. The method according to claim 6, characterized in that the covering as a melt or applied from solutions or dispersions. 8. The method according to claim 6, characterized in that a plug as a covering capsule is used, in which the active substance is filled. 9. The method according to claim 8, characterized in that a half as a plug capsule capsule is used. 10. Particulate automatic dishwashing detergent containing builders and min at least one other ingredient from the groups of surfactants, enzymes, bleaches, Bleach activators, corrosion inhibitors, polymers, dyes and fragrances and machine care products,  characterized in that at least one other ingredient with egg nem water-soluble, water-dispersible and / or meltable material is encased. 11. Particulate machine dishwashing detergent according to claim 10, characterized records that the coated ingredient in amounts of 0.5 to 30 wt .-%, preferably from 1 to 25 wt .-% and in particular from 2 to 15 wt .-%, each based on the ge entire means is included. 12. Particulate machine laundry detergent containing builders and min at least one other ingredient from the group of surfactants, enzymes, bleaches, Bleach activators, corrosion inhibitors, polymers, colors and fragrances and machines care products, characterized in that one or more of the other ingredients with a with a water-soluble, water-dispersible and / or meltable Ma are covered.