DE10100339A1 - Serving detergent, detergent or cleaning agent portion - Google Patents

Abstract

The invention relates to a portion of washing agent, rinsing agent or cleaning agent, containing at least one surfactant, optionally at least one other washing, rinsing or cleaning constituent, and at least one gas which is finely dispersed in the portion, is compatible with the other constituents and does not coalesce to form an individual gas bubble, in at least one coating which can disintegrate in water. The invention also relates to a method for washing, rinsing or cleaning, which can be carried out using the inventive portions of washing agent, rinsing agent, or cleaning agent.

Description

The present invention relates to a detergent or detergent containing surfactant Portion of detergent and relates in particular to a detergent containing surfactant, Serving of detergent or cleaning agent, which is surrounded by a wrapping and in contains a finely divided gas inside.

Preparations containing surfactants with finely divided gases contained therein are known and can be present, for example, as surfactant-containing foams, as is the case for many Applications are available. So shaving creams can be provided as foams hair firming or other conditioning agents can be foamed, cleaners for glass surfaces and other hard surfaces, for example in the bathroom and / or kitchen area, can be applied in foam form and cleaners for carpets and upholstery can advantageously be applied as foams or applied. More recently, there have also been cleaning or stains eliminating agents for textiles reported in the form of a foam to be cleaned Spots or stains are applied. The foam allows a certain "Service life" of the cleaning agent on the area to be cleaned or on the stain, without the composition of the detergent strongly towards a high Having to change viscosity, which used to be a means of getting the cleaner in place to hold at which its influence was desired.

Foam containing surfactants are also described in WO 97/03176 (The Procter & Gamble Company). The foams also referred to as "mousses" in the cited publication should be easy to dose and soluble, suspendable or emulsifiable in water, if they have a bulk density <250 g / l, in air under conditions defined by standard measurement, a stability (or collapse time) to half the foam volume) of ≧ 15 s and have a stability of <2 h on water at a temperature of 20 ° C - also under standard conditions. Apart from the choice of CO ₂ as a blowing agent, the publication does not contain any measures on how low foam stability on water or rapid dissolving, suspending or emulsifying the foam in water can be achieved.

Within the scope of the present invention, it was also an object to contain a surfactant Provide detergent, dish soap or detergent serving, the content of which dissolve, suspend or emulsify quickly in an aqueous system or water leaves. In contrast to the prior art, however, this should not be done with one Dispenser system removed or dosed foam can be achieved, but with a with regard to the outer shape, fixed detergent, detergent or Portion of detergent and especially with a detergent containing surfactant, Serving of detergent or detergent, which is surrounded by a wrapping.

The present invention thus relates to a detergent, detergent or Portion of detergent containing at least one surfactant, optionally together with one or more further washing-active, rinsing-active or cleaning-active Component (s), and at least one compatible with the other components, in the Portion of finely divided gas that does not converge into a single gas bubble comprises at least one casing which can be disintegrated in water.

The invention also relates to a washing method, a rinsing method and a Cleaning procedures using those detailed below Serving detergent, dish soap or detergent.

According to the invention, the detergent, detergent or cleaning agent portion comprises at least one surfactant, optionally together with one or more others active washing, rinsing or cleaning active ingredient (s), in one in water disintegratable wrapping. A surfactant can be used, or it can several compatible with each other, preferred in their properties (including in complementary surfactants can be used. Everyone can Surfactants belong to a type of surfactant; however, are preferred when in use  several surfactants surfactants of different types used, for example one or several anionic surfactants together with one or more nonionic surfactants.

According to the invention are anionic surfactants or anionic surfactant (s) containing Surfactant mixtures or surfactant compounds for economic reasons and due to their performance spectrum and foam behavior clearly preferred.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable 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 obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of 2-sulfofatty acids (ester sulfonates), e.g. B. the 2-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

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

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and 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 the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

Also the sulfuric acid monoesters of the ge chain-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _12-18 -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they can be used in detergent, detergent or cleaning agent portions according to the invention 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 the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine or also monoisopropylamine. The anioni are preferably located cal surfactants in the form of their sodium or potassium salts, in particular in the form of the sodium salt before. In a further embodiment of the invention, surfactants are in the form their magnesium salts.  

In the context of the present invention are detergent, dishwashing or Detergent portions preferred, the 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% and in particular 15 to 25% by weight of one or more anionic surfactant (s), included, each based on the weight of detergent, detergent or Cleaner portion.

When selecting the anionic surfactants used in the detergent, Detergent or detergent portions are used Freedom of formulation no restrictions to be observed in the way. A preferred one Serving detergent, detergent or detergent portion according to the invention however, a soap content of 0.2% by weight based on the total weight of the Serving, exceeds. The preferred anionic surfactants are Alkylbenzenesulfonates and fatty alcohol (ether) sulfates, preferred portions being 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight Fatty alcohol (ether) sulfate (s), each based on the weight of the detergent, or detergent serving

In a further, likewise preferred embodiment of the invention, a portion of detergent, dish soap or detergent according to the invention instead of the anionic surfactant (s) or in addition to the anionic surfactant (s) comprise at least one non-ionic, cationic and / or zwitterionic surfactant.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or propylene oxide (PO) per mole of alcohol, in which the Alcohol residue may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues. In particular, however, alcohol ethoxylates and / or propoxylates 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 and / or PO 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, and mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. Corresponding propoxylated compounds can also be used, as can compounds which also contain PO in addition to EO. The degrees of ethoxylation or degrees of propoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol holoxylates and / or propoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO or PO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO and / or PO.

Another class of preferably used nonionic surfactants, which either as sole nonionic surfactant or in combination with other nonionic Surfactants used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 become.

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

Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The detergent, detergent or cleaning agent portions according to the invention can preferably contain alkyl polyglycosides, the contents of the portions of APG over 0.2% by weight, based on the total portion, are preferred. Especially preferred detergent, detergent or cleaning agent portions according to the Invention contain APG in amounts of 0.2 to 10 wt .-%, preferably in amounts from 0.2 to 5% by weight and in particular in amounts of 0.5 to 3% by weight.  

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fat Acid alkanolamides may be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated or propoxylated fatty alcohol get, especially not more than half of it.

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

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

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

in which R ^{2 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{3 is} a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms and R ^{4 is} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl 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 propxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then, for example according to the teaching of international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.

It can also be preferred, in addition to anionic and nonionic surfactants use cationic surfactants. They are preferably used as Washing performance booster, whereby only small amounts of cationic surfactants are required are. If cationic surfactants are used, they are in the foam moldings preferably in amounts of 0.01 to 10% by weight, in particular 0.1 to 3.0% by weight contain.

In the cases in which the portions according to the invention are detergents deals, they usually contain one or more surfactant (s) in total amounts of 5 to 50 wt .-%, preferably in amounts of 10 to 35 wt .-%, the partial portions of Detergent, dishwashing or cleaning agent portions of surfactants according to the invention can be contained in larger or smaller quantities. In other words: the The amount of surfactant is not the same in all portions; rather, portions can be made with relatively larger and partial portions with a relatively smaller surfactant content.

In the cases where the detergent, dishwashing detergent or Detergent portions are detergents, in particular Dishwashing detergents usually contain one or more surfactants Total amounts from 0.1 to 10% by weight, preferably in amounts from 0.5 to 5% by weight, wherein in partial portions of the detergent or cleaning agent according to the invention Portions of surfactants can be contained in larger or smaller amounts. With others Words: The amount of surfactant is not in all of the cleaning or dishwashing detergents Partial portions equal; rather partial portions with relatively larger and partial portions with a relatively lower surfactant content.  

For the content of detergents, detergents or cleaning agents according to the invention Portions of suitable gases can in principle be all conceivable gases whose Use is economically justifiable, not with one or more others Components of the detergent, dishwashing or cleaning agent according to the invention Portions adversely interact, which contributes to the consumer Storage and use of the portions are not harmful and are not detrimental Have an effect on the items to be washed, items to be washed or items to be cleaned. Coming as gases for example individual substances from the group air, nitrogen, oxygen, carbon dioxide, Helium, argon, nitrous oxide, nitrogen monoxide, fluorocarbon (s) such as CFC, HCFC and HFC and alkane (s) such as methane, ethane, propane, butane, Pentane or hexane in question. The gases mentioned can be used individually or in any Mixtures (also mixtures in any proportions of the gases involved among each other) by two or more of you.

Under certain conditions the gas forms together with others wash-active, rinse-active or cleaning-active components of the inventive Portions of detergent, detergent or cleaning agent a foam. The for example from the surfactant (s) or their solutions in water and the / the Gas (s) formed foam is generally a dispersion of gas (s) in a relative small liquid phase, the phase comprising the surfactant (s) being the continuous is liquid phase and the gas phase is dispersed therein. Typically they have Gas bubbles of the dispersed phase have a more or less wide distribution of size; due to the manufacturing process, the values of the bubble size can range from 1 nm to 10 mm vary. The average bubble diameter is preferably in the range from 2 nm to 1 mm. Of course, smaller or larger gas bubbles can also be realized.

The volume of the gas phase (gas fraction) is advantageously based on the Total volume, 0.01 to 90%, preferably 0.1 to 50%, more preferably 0.5 to 20 %.

The foam molded articles according to the present invention comprise as a further component Invention a water disintegrable casing. Among them, one becomes complete other components of the detergent, detergent or cleaning agent portion surrounding and at least mechanically, more preferably also largely gas- and understood moisture-proof covering from the outside environment. This must be disintegrable in water, so it must either completely dissolve what  is preferred according to the invention, or depending on certain parameters such as temperature, electrolyte concentration, pH value, enzyme concentration or others Parameters in the washing, rinsing or cleaning fleet successively completely or partially to solve.

In a preferred embodiment of the invention, the detergent, Portions of detergent or cleaning agent as a water-disintegrable coating water soluble polymer material. There is a possibility that the detergent, Dishwashing detergent or detergent serving a wrapping of one or more water-soluble polymer material (ien) surrounds or that several enclosures same or different materials are included. As part of the present Invention is the presence of a wrapper preferred, which has advantages in the Choice of material and also with regard to the requirement that the water-soluble Polymer material ultimately leaves no residue in the washing, rinsing or cleaning liquor must solve. The envelope (s) can be made from a single water-soluble Polymer material or can be made from several different polymer materials be formed, which may have different solubility in water can. With regard to the present task, the Use of several different polymer materials may be particularly preferred, which will be dealt with separately below.

The special form of the detergent, The detergent or detergent portion of the present invention is not critical. So the envelopes can be flat or in the form of capsules or similar moldings are present. Of course, preference is given to moldings which have a maximum Ensure contact area between the liquor and the casing to be disintegrated.

It corresponds to a further preferred embodiment of the invention that the Serving detergent, detergent or cleaning agent as disintegrable in water Envelope comprises a water-soluble polymer of different layer thickness. at the same material, the areas of the covering dissolve with less Layer thickness faster than those with greater layer thickness, so that with progressive dissolving process of wrapping in water with pores or holes provided wrapping forms. Water can enter the interior through the pores or holes the wrapping, the contents of the detergent, Dissolve the detergent or detergent portion successively and through the pores or  Holes outwards, d. H. into the washing liquor, rinsing liquor or cleaning liquor, transport.

A similar effect can occur in a further, likewise preferred embodiment of the invention according to which the detergent, dishwashing or cleaning agent Portion as a water-disintegrable coating, a polymer material with areas good water solubility and with areas less good water solubility. This can be the result of different water solubility of the polymer itself, for example due to its different chemical nature (example: polyvinyl alcohols with different degrees of acetalization), or may be the result of the fact that Polymers with different water solubility are mixed specifically or that in Polymer materials with less good water solubility, for example, others Materials (for example, water-soluble inorganic or organic salts) are stored, which quickly come into contact with water in the wash liquor, rinse liquor or Cleaning solution go into solution and so also one with pores or holes create the provided structure.

In principle, all polymer materials come as water-soluble polymer materials in question under the given conditions (temperature, pH, concentration on active detergent components) more or less completely in the aqueous phase can. The polymer materials can particularly preferably be the groups (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives and mixtures of the materials mentioned.

Polyvinyl alcohols (PVAL for short) are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

those in small quantities also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ -]

contain. Since the corresponding monomer (vinyl alcohol) is not stable in free form, become polyvinyl alcohols via polymer-analogous reactions by hydrolysis, technical in particular by alkaline-catalyzed transesterification of polyvinyl acetates with  Alcohols, preferably with methanol, are obtained. Through these technical processes are also available PVAL, which contain a predetermined residual proportion of acetate groups.

Commercial PVAL (e.g. Mowiol® grades from Hoechst) come as white yellowish powder or granules with degrees of polymerization in the range of about 500 to 2,500 (corresponding to molar masses of approx. 20,000 to 100,000 g / mol) in the trade and have different degrees of hydrolysis, for example 98 to 99 or 87 to 89 mol. %. They are therefore partially saponified polyvinyl acetates with a residual content of acetyl groups from, for example, about 1 to 2 or 11 to 13 mol%.

The water solubility of PVAL can be checked by post-treatment with aldehydes (Aceta lization), by complexing with Ni or Cu salts or by treatment with Reduce dichromates, botany acid, borax and thus adjust them to the desired values. PVAL films are largely impenetrable for gases such as oxygen, nitrogen, Helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

Examples of suitable water-soluble PVAL films are those under designation "SOLUBLON®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. available PVAL films. Their solubility in water can be adjusted to the degree and there are films in this range available, all for use relevant temperature ranges are soluble in the aqueous phase.

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVP are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH ₂ -CH ₂ ] _n -OH

the technically by basic catalyzed polyaddition of ethylene oxide (oxirane) in mostly systems containing small amounts of water with ethylene glycol as the starting molecule getting produced. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to <100,000. Have polyethylene oxides an extremely low concentration of reactive hydroxy end groups and only show still weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to <250,000 g / mol), which is primarily by hydrolysis of the collagen contained in the skin and bones of animals under acid or alkaline conditions. The amino acid composition of the Gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as Water-soluble shell material is particularly in the form of hard or pharmaceutical Soft gelatin capsules extremely common. Gelatin is found in the form of foils their low price compared to the above-mentioned polymers Use.

In the context of the present invention, detergents, dishwashing detergents are also preferred. or detergent portions, the wrapping of which is made of water-soluble film at least one polymer from the group starch and starch derivatives, cellulose and Cellulose derivatives, especially methyl cellulose and mixtures thereof.

Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW approx. 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW. approx. 300,000 to 2,000,000). Next to it are still contain small amounts of lipids, phosphoric acid and cations. During the amylose Due to the binding in the 1,4 position, long, helical, intertwined chains with forms about 300 to 1200 glucose molecules, the chain branches at amylopectin after an average of 25 glucose units through 1,6-binding to a knot-like one Formations with about 1,500 to 12,000 molecules of glucose. In addition to pure starch Production of water-soluble casings for detergents, detergents or Detergent portions in the context of the present invention also starch derivatives,  which can be obtained from starch by polymer-analogous reactions. Such chemically modified starches include products from esterifications or Etherifications in which hydroxy hydrogen atoms have been substituted. But also Strengths in which the hydroxy groups versus functional groups that do not have one Oxygen atoms are bound, have been replaced, can be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, Carboxymethyl starch (CMS), starch esters and ethers and amino starches.

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

Preferred casings made of water-soluble polymer material consist of a Polymer with a molecular weight between 5,000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons and especially between 10,000 and 100,000 daltons. The water-soluble polymer material that forms the sheath preferably has one Thickness from 1 to 150 microns, preferably from 2 to 100 microns, particularly preferably from 5 to 75 µm and in particular from 10 to 50 µm.

These water-soluble films made of polymer material can be used in various ways Manufacturing processes are manufactured. Here are basically blowing, calendering and To call casting process. In a preferred method, the foils are used starting from a melt with air via a blow mandrel to a hose blown. In the calendering process, which is also one of the preferred ones Manufacturing process belongs, the raw materials plasticized by suitable additives Forming the foils atomized. In particular, it may be necessary to contact the  Spray to connect drying. In the casting process, that too one of the preferred manufacturing methods, an aqueous polymer preparation on a heatable drying roller given, after evaporation of the water becomes optional cooled and the film pulled off as a film. If necessary, this film will be in front of or additionally powdered during peeling.

It corresponds to a further, likewise preferred embodiment of the invention, Provide detergent, dish soap or detergent servings as in Water-disintegrable coating is a coating made of a crystalline material comprise, wherein the crystalline material may be organic or inorganic in nature. Typical examples of organic crystalline materials are all water-soluble crystalline materials, especially sugar, while typical examples of inorganic crystalline materials are water soluble salts, especially heavy metal free salts. Detergent, dishwashing detergent or cleaning agent Be portions, the wrappings of which consist of a crystalline material which in the Washing, rinsing or cleaning process can take on a special function if it by dissolving it in water into the wash liquor, rinse liquor or cleaning liquor has arrived. An example of this are polyphosphates. These can be contained in the water Calcium and magnesium ions complex and thereby contribute to the fact that a Do not soften the water separately (e.g. by adding salt in the Dishwasher) must be carried out.

According to the invention, detergents, detergents or cleaning agents are further preferred. Portions whose density - depending on the components (e.g. the foam) - in Range is 0.8 to 1.7 g / ml, preferably in the range 0.9 to 1.5 g / ml. Detergent, detergent or cleaning agent portions with such a density can be produced inexpensively, since gases are available at low cost or gas mixtures to replace solvents to be used as fillers can. The resulting, relatively large volumes of detergent, Detergent or detergent portions also have the other Advantage that the legal requirement is taken into account, such moldings to be made in a size that children cannot swallow is.

The detergent, detergent or cleaning agent portions according to the invention can, in a further preferred embodiment, one or more  further wash-active, rinse-active or cleaning-active component (s) contain. Under the term "wash-active component" or "rinse-active component" or "cleaning-active component" within the scope of the present invention Preparations of all conceivable, in connection with a washing, rinsing or Relevant substances cleaning process understood. These are primarily those actual detergents, dishwashing detergents or cleaning agents with their further course the description of individual components explained in more detail. This includes active substances such as the surfactants (anionic, nonionic, cationic and amphoteric surfactants), builder substances (inorganic and organic Builders), bleaches (such as peroxo bleach and chlorine Bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), Graying inhibitors, dyes and fragrances (perfumes) without the terms on these substance groups are restricted.

Under the term "wash-active components", rinse-active components " or "cleaning-active components" but also washing aids, rinsing aids or Understanding cleaning aids. Examples of these are optical brighteners, UV Protective substances, so-called soil repellents, i.e. polymers that prevent re-contamination counteracting fibers or hard surfaces, as well as silver protection agents. Also Laundry treatment agents such as fabric softener or dishwasher detergent additives such as According to the invention, rinse aids are called "wash-active components", "rinse-active components Components "or" active cleaning components "considered.

The portions of detergent, dishwashing detergent or cleaning agent according to the invention usable surfactants have already been described in detail above.

In addition to the surfactants, builders are the most important ingredients in washing and Detergents. In the detergent, detergent or Servings of detergent can usually be found in detergents and cleaning agents used builders may be included, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use exist - also phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for × 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

An optionally used finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. Zeolite P-type is particularly preferred as zeolite MAP (e.g. commercial product: Doucil A24 from Crosfield). However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), 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) on and included preferably 18 to 22% by weight, in particular 20 to 22% by weight of bound Water.

Of course, in the detergent or dishwashing detergent according to the invention Servings of detergent also include use of the well known phosphates Builder substances possible, provided that such use is not from ecological Reasons should be avoided. The sodium salts are particularly suitable Orthophosphate, the pyrophosphate and especially the tripolyphosphate.

Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that its use is not due to ecological reasons is objectionable, and mixtures of these. Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these. Even the acids themselves can be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to adjust one according to the lower and milder pH of detergent and cleaning agent portions the invention. In this context, citric acid, Succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of to call this.

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

In the context of the present invention, the molar masses given for polymeric polycarboxylates are weight-average molar masses M _{W of} the particular acid form, which were basically determined 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. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene acids are generally significantly higher than the molar masses specified in the context of the present invention.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2,000 to 20,000 g / mol. Because of their superior solubility, can In this group, the short-chain polyacrylates, the molecular weights of 2,000 to 10,000 g / mol, particularly preferably from 3,000 to 5,000 g / mol.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid or acrylic acid or methacrylic acid with maleic acid. As Copolymers of acrylic acid with maleic acid have proven particularly suitable Contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molar mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

To improve water solubility, the polymers can also allylsulfonic acids, such as for example in EP-B 0 727 448, allyloxybenzenesulfonic acid and Contain methallylsulfonic acid as a monomer.

In particular, biodegradable polymers of more than two are preferred various monomer units, for example those described in DE-A 43 00 772 as monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or  Vinyl alcohol derivatives or according to DE-C 42 21 381 as monomer salts of Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

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

Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives, of which in the German Patent application DE-A 195 40 086 discloses that in addition to co-builder Properties also have a bleach-stabilizing effect.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dialdehydes can be obtained with polyol carboxylic acids, the 5 to 7 Have carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A 0 280 223. Preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde and terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or Obtain glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol. there is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, preferably, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which is a DE out of 100. Both maltodextrins with a DE between 3 and 20 can be used 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 2,000 to 30,000 g / mol. A preferred dextrin is in British patent application 94 19 091 described.  

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. Such oxidized dextrins and processes for their preparation are known in particular from European patent applications EP-A 0 232 202, EP-A 0 427 349, EP-A 0 472 042 and EP-A 0 542 496 and from international patent applications WO 92/18542 , WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608. An oxidized oligosaccharide according to German patent application DE-A 196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable co-builders. Here, ethylenediamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615 is described, preferably in the form of its sodium or magnesium salts used. Glycerol disuccinates are also preferred in this context and glycerol trisuccinates, as described, for example, in US Pat. No. 4,524,009 and US-A 4,639,325, in European patent application EP-A 0 150 930 and described in Japanese Patent Application JP-A 93 / 339,896. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.

Other useful organic co-builders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups. Such co-builders are described, for example, in international patent application WO 95/20029 described.

Another class of substances with co-builder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkane phosphonates. Among the hydroalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt used, the disodium salt neutral and the tetrasodium salt alkaline (pH = 9) responding. Preferred aminoalkane phosphonates are Ethylenediaminetetramethylenephosphonate (EDTMP),  Diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in Question. They are preferably in the form of neutral sodium salts, e.g. B. as Hexasodium salt of EDTMP or as hepta and octasodium salt of DTPMP, used. HEDP is preferred as the builder from the phosphonate class used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the Detergent, dishwashing or cleaning agent portions according to the invention also Contain bleach, be preferred, aminoalkanephosphonates, in particular DTPMP, use or use mixtures of the phosphonates mentioned.

In addition, all compounds that are able to complex with To form alkaline earth metal ions can be used as co-builders.

In addition to the ingredients mentioned surfactant and builder, the inventive Detergent, detergent or cleaning agent portions one or more more in Detergents, dishwashing detergents or cleaning agents are common ingredients from the group of Bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, Graying inhibitors, color transfer inhibitors and corrosion inhibitors included.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. If cleaning or bleaching preparations for machine dishwashing are produced, 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) 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 peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamido operadipic acid and N-nonenylamide; and (c) aliphatic and araliphatic peroxy dicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di ( aminopercaproic).

Can also be used as bleach in machine dishwashing compositions Chlorine or bromine releasing substances are used. Among the appropriate chlorine or bromine-releasing materials come, for example, heterocyclic N-bromine and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5- dimethylhydantoin are also suitable.

To be one when washing or cleaning at temperatures of 60 ° C and below To achieve improved bleaching effects, bleach activators can be used in the washing and Servings of detergent are incorporated. Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or result in optionally substituted perbenzoic acid can be used. Are suitable Substances containing O and / or N-acyl groups with the number of carbon atoms mentioned and / or against also carry substituted benzoyl groups. Multiple acylates are preferred Alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 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, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, Ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

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

Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Bak are particularly well suited strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus-derived enzymatic agents. Proteases are preferably from Subtilisin type and in particular proteases obtained from Bacillus lentus, used. There are enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, in particular, however, cellulase-containing mixtures of particular interest. Also Peroxidases or oxidases have proven to be suitable in some cases. The Enzymes can be adsorbed on carriers and / or embedded in coating substances, to protect them against premature decomposition. The proportion of enzymes, En enzyme mixtures or enzyme granules in the compositions according to the invention can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-% bet protrude.

According to the state of the art, enzymes are primarily used Preparation added, especially added to a dishwashing detergent for the Main wash is determined. The disadvantage was that the optimum effect used Enzymes limited the choice of temperature and also problems with the stability of the Enzymes appeared in a strongly alkaline environment. With the detergent, Servings of detergent or detergent are possible, enzymes also in the pre-rinse cycle to use and thus the pre-wash in addition to the main wash for one To use enzyme action on soiling of the dishes.

According to the invention, it is particularly preferred that the one provided for the pre-rinse cycle active detergent preparation or portion of a detergent portion of enzymes add. The enzymes are further preferred for use under the conditions the pre-rinse cycle, e.g. in cold water.

The detergents, detergents or Servings of detergent when the enzyme preparations are in liquid form, like some of them are offered in stores, because then a quick effect is expected that can already be carried out in (relatively short and cold water) Pre-rinse occurs. Even if - as usual - the enzymes are used in solid form and they are provided with a covering made of a water-soluble material,  which is already soluble in cold water, the enzymes can Main wash or main wash cycle take effect. Advantage of Use of an enclosure made of water-soluble material, in particular from cold water soluble material is that the enzyme (s) after in cold water Dissolving the enclosure quickly comes into effect. So that can Effectiveness are extended, which benefits the washing or rinsing result.

The detergent, detergent or cleaning agent portions according to the invention according to a particularly preferred embodiment, contain further additives, as they are known from the prior art as additives for washing or rinsing or Detergent preparations are known. These can be either one or several, if necessary also all portions (washing-active preparations) of Detergent, dishwashing or cleaning agent portions according to the invention added are or - as in the copending patent application No. 199 29 098.9 with the Title "Active ingredient portion pack" described - in the water-soluble, the Preparations encasing materials, for example in the water-soluble Films, but also incorporated into the capsules or coatings according to the invention become.

A preferred group of additives used according to the invention are optical brighteners. The optical brighteners customary in detergents can be used here. This are as an aqueous solution or as a solution in an organic solvent Polymer solution, which is converted into the film, or a partial Portion (active washing preparation) of a detergent, dish soap or cleaning agent Portion added in solid or liquid form. Examples of optical brighteners are Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B. Salts of 4,4'-bis (2-anilino-4-morpholino1,3,5-triazinyl-6-amino-) stilbene-2,2'- disulfonic acid or compounds of a similar structure which instead of the morpholino Group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Brighteners of the type of substituted Diphenylstyryle in the partial portions (washing-active preparations) of the Serving detergent or cleaning agent portions according to the invention, z. 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-) diphenyls. Mixtures of the aforementioned Brighteners can be used.  

Another group of additives preferred according to the invention are UV protection substances. These are substances which are released in the washing liquor during the washing process or during the subsequent fabric softening process and which accumulate on the fiber in order to then achieve a UV protection effect. Products from Ciba Specialty Chemicals that are commercially available under the name Tinosorb ^R are suitable.

Other conceivable additives which are preferred in special embodiments are surfactants, which in particular can influence the solubility of the water-soluble film, but can also control their wettability and foam formation when dissolved, and Foam inhibitors, but also bitter substances that prevent accidental swallowing Can prevent packaging or parts of such packaging from children.

Another group of additives preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Are preferred here Dyes, such as those used to improve the optical product appearance in washing and Cleaning agents are usually used. The selection of such dyes poses no difficulties for the person skilled in the art, in particular since such customary ones Dyes have a long shelf life and are insensitive to the rest Ingredients of the detergent, detergent or cleaning agent portions and against To have light as well as no pronounced substantivity towards textile fibers not to stain. The dyes are according to the invention in the detergent, dishwashing or cleaning agent portions in amounts of less than 0.01% by weight.

Another class of additives which, according to the invention, detergent, dishwashing or portions of detergent can be added are polymers. Under these On the one hand, polymers come into question polymers which, during washing or cleaning or Rinsing also shows cobuilder properties, for example polyacrylic acids modified polyacrylic acids or corresponding copolymers. Another group of Polymers are polyvinyl pyrrolidone and other graying inhibitors, such as copolymers of polyvinyl pyrrolidone, cellulose ether and the like. After another Embodiments of the invention also come as so-called soil repellents as polymers question how they are known to the detergent and cleaning agent and are described in detail below.  

Another group of additives are bleaching catalysts, especially bleaching catalysts for automatic dishwashing detergents or detergents. Be used here complexes of manganese and cobalt, especially those containing nitrogen Ligands.

Another preferred group of additives for the purposes of the invention is silver retardants. This is a large number of mostly cyclic organic ones Compounds which are also familiar to the person skilled in the art addressed here and to this contribute to the tarnishing of silver-containing objects during the cleaning process to prevent. Specific examples can be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.

The detergent, dishwashing or Detergent portions also contain so-called soil repellents, i.e. polymers, who pull on fibers or hard surfaces (for example on porcelain and glass) Oil and fat washability from textiles positively influence and thus one Counteract re-soiling in a targeted manner. This effect is particularly evident if a textile or a hard object (porcelain, glass) is soiled, the already several times before with a portion according to the invention that this oil and fat contains solvent component, washed or cleaned. Among 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 methoxy groups from 15 to 30% by weight and of hydroxypropoxy groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether, and those from the prior art known polymers of phthalic acid and / or terephthalic acid or of their Derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.

All of these additives are the detergent, dishwashing or Detergent portions in amounts up to a maximum of 30% by weight, preferably 2 to 20% by weight, added. As already mentioned, the addition to a material can also water-soluble enclosure that the or one of the wash-active (n) Preparation (s) includes. To maintain the balance of the recipe, it is Specialist therefore possible to use the plastic material for encasing either in his  To increase weight so as to achieve the depot effect which is achieved according to the invention, exploit or the additives mentioned at least partially in the to keep the remaining portion. However, this is less preferred.

Fragrances are the detergent, detergent or Servings of detergent added to the overall aesthetic impression of the products improve and consumer in addition to technical performance (Fabric softener result) a sensorially typical and distinctive product for To make available. As perfume oils or fragrances, individual fragrance Compounds are used, for example the synthetic products of the type Esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. fragrance Compounds of the ester type are, for example, benzyl acetate, Phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylyl carbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and Benzyl salicylate. The ethers include, for example, benzyl ethyl ether. To the aldehydes count z. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lileal and Bourgeonal.

The ketones include the ionones, α-isomethyl ionone, and methyl cedryl ketone. To the Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Terpineol. The hydrocarbons mainly include terpenes such as limonene and Pinene. Mixtures of different fragrances are preferably used, which are coordinated so that together they produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures such as those from vegetable sources are accessible. Examples are pine, citrus, jasmine, patchouli, Rose or ylang ylang oil. Nutmeg oil, 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 labdanumö) as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The fragrance content is usually in the range up to 2% by weight of the total Serving detergent, dish soap or detergent.

The fragrances can be added directly to detergents, detergents or cleaning agents. Portions are incorporated; but it can also be advantageous to apply the fragrances  Apply carriers that increase and adhere the perfume to the laundry a slower fragrance release ensures a long-lasting fragrance of the textiles. As such Carrier materials have proven themselves, for example, cyclodextrins. The Cyclodextrin-perfume complexes additionally coated with other auxiliaries become.

The perfumes and fragrances can basically in each of the portions (washing active Preparations) of detergents, dishwashing detergents or cleaning agents according to the invention Servings included. However, it is particularly preferred that they are in one Detergent in a part intended for the post-wash or fabric softener Serving detergent or in a cleaning agent, especially in one Dishwashing detergent, in a part provided for the rinse or rinse cycle Portion of detergent, especially portion of detergent, are included. You need to therefore according to the invention only in the conditions (especially in the Temperature) of the post-wash cycle or rinse cycle, water-soluble at which Conditions (in particular at the temperature) of the preceding wash cycles or Rinse cycles of water-insoluble material, especially from a suitable film or capsule may be included. According to the invention, this is done, for example, with one Multi-chamber bags made of foils of different water solubility makeable.

According to two further preferred embodiments of the invention Detergent, detergent or cleaning agent portions with an inside of the in Water disintegrable wrapping prevailing pressure of the foaming Gases / the foaming gases created that are at least equal to that Atmospheric pressure, which - however, more preferably - is greater than atmospheric pressure. This advantageously enables moisture to penetrate into the Interior of the envelope is difficult and the components contained in the interior Portion is better protected from a damaging influence. This can be done in one alternative embodiment of the invention can also be achieved by using one or several contained in the detergent, detergent or cleaning agent portion Components that are at risk in the presence of moisture, either partially or complete loss of activity before entering water or Protects moisture through a coating.  

In view of the need to disintegrate the detergent, Portions of detergent or cleaning agent before premature disintegration To protect water, the water content of the components of the foam Shaped body are limited according to the invention. He is in a special one preferred embodiment at at most 15 wt .-%, more preferably at 1 to 10 wt .-%.

In the manufacture of the casings of detergents, detergents or cleaning agents Portions can be, for example, two foils of different compositions Let it run in parallel and from it the two different materials Put the foils together. The general procedure is as such well known in the art and requires no further explanation.

A method is particularly preferred in which the components follow the casing chemical synthesis (formation of bonds as described above) extruded and processed into granules, for which - depending on the temperature stability of the compounds involved - an elevated temperature can also be applied. The granules obtained are melted, if necessary, in Presence of a plasticizer, and then z. B. conventional, per se known methods processed into tubular bags.

Another procedure that can be used according to the invention is under the name "rotary die" process known. In this run two previously made films, the for example, have the characteristics described above in one more or less acute angle in the nip of a pair of rolls, the Surfaces with e.g. B. hemispherical depressions are provided. At the height of the Nip into the converging foils, the mixture of wash-active, flush-active or cleaning-active "content" components are filled, which then - in the, for example, hemispherical depressions - one with the components Allow the filled portion of ball to be formed from the foil with a complete coating. This method is also generally known and therefore does not require any at this point further description.

The invention also relates to a washing process, in particular Process for machine washing laundry, in which the laundry is washed  Water and one or more detergents, detergents or cleaning agents Portion (s) according to the detailed description above.

The invention further relates to a rinsing method, in particular a method for mechanical Rinse dishes, glass and metal by putting the dishes in contact with water in which one or more detergents, detergents or cleaning agents Portion (s) according to the detailed description of the effects of water above are exposed.

Finally, the invention also relates to a cleaning method, in particular Process for cleaning hard surfaces, in which the goods to be cleaned with Water and one or more detergents, detergents or cleaning agents Portion (s) according to the detailed description above.

The invention also relates to a cleaning method, in particular a method for Cleaning hard surfaces by contacting the material to be cleaned with water in which one or more detergents, detergents or cleaning agents Portion (s) according to the detailed description of the effects of water above are exposed.

The invention is further illustrated by the following examples, but without reference to this being limited.

Examples 1 to 5

The following recipes for detergents were carried out in a manner known per se combine and mix those given in Table 1 below Components manufactured. The formulations were filled into water-soluble PVA films.

The detergent portions produced in this way were successful in the washing process used and provided excellent washing performance.  

Table 1

The trade names given stand for products with the following chemical composition:
ABS powder = alkyl benzene sulfonate 90% ex Unger
Sulfopon 1218 G = C12-C18 fatty alcohol sulfate granules ex Cognis
Lutensol AO7 = C13C15 oxo alcohol ethoxylate with 7 moles of EO
Lutensol AO5 = C13C15 oxo alcohol ethoxylate with 5 moles of EO
Lutensol AO3 = C13C15 oxo alcohol ethoxylate with 3 moles of EO
Dehydol LT7 = C12-C18 fatty alcohol ethoxylate with 7 mol EO ex Cognis
Dehydol LS5 = C12-C14 fatty alcohol ethoxylate with 5 mol EO ex. Cognis
Dehypon LS54 = C12-C14 fatty alcohol ethoxylate propoxylate with 5 moles of EO and 4 moles of PO from Cognis
Dehypon LS 52R = C12-C14 fatty alcohol ethoxylate / propoxylate random with 5 mol EO and 2 mol PO ex from Cognis
Tixogel MP 250 = organically modified layered silicate ex Südchemie
Thixatrol Plus = diamide wax mixture ex Rheox
TAED = tetraacetyl diamine ex Warwick
Triacetin = glycerol triacetate ex Cognis
Na-SKS-6 = ex Clariant
Sokalan CP 5 = polycarboxylate ex BASF
Turpinal 2NZ = hydroxyethane diphosphonic acid di-sodium salt ex. Cognis
Velvetol 251 C = terephthalic acid ethyl glycol PEG polyester ex Rhodia
Tinopal CBS-X = opt. Brightener ex Ciba
Tinosorb FD = UV absorber ex Ciba
VP1132 = silicone defoamer ex. Wacker
Marlox MO 154 = C12-C14 fatty alcohol ethoxylate / propoxylate with 5 moles of EO and 4 moles of PO ex Condea
Marlinat 242 / 90M = C12-C14 fatty alcohol polyethylene glycol (2EO) ether sulfate monoisopropanolamine salt from Condea
LAS-Mipa = linear alkylbenzenesulfonate monoisopropylamine salt ex Condea
Edenor K12-18 = C12-C18 fatty acid ex Cognis

Examples 6 to 9

Further detergent recipes for detergents without solid content according to the Table 2 below was prepared as described above. The ones in the table The specified components are the chemical components listed above.

The detergent portions produced in this way were successful in the washing process used and provided excellent washing performance.  

Table 2

Claims (23)

1. Detergent, dish soap or detergent portion, comprising at least one Surfactant, optionally together with one or more further washing-active, active or cleaning active ingredient (s), and at least one with the other constituents compatible, in the portion of finely divided gas that is not too a single gas bubble converges, in at least one in water disintegratable wrapping. 2. Detergent, dish soap or detergent portion according to claim 1, comprising at least one anionic surfactant. 3. Detergent, dish soap or detergent portion according to claim 1 or Claim 2, comprising as the anionic surfactant a surfactant from the group Fatty alcohol sulfate, fatty alcohol ether sulfate, alkylbenzenesulfonate and olefin sulfonate. 4. Detergent, detergent or cleaning agent portion according to one of claims 1 to 3, comprising in addition to one or more anionic surfactant (s) at least one non-ionic, cationic and / or zwitterionic surfactant. 5. Detergent, detergent or cleaning agent portion according to one of claims 1 to 4, comprising as a gas a gas or a mixture of gases from the group Air, nitrogen, oxygen, carbon dioxide, helium, argon, nitrous oxide, Nitric oxide, fluorocarbon (e) and alkane (e). 6. Detergent, detergent or cleaning agent portion according to one of claims 1 to 5, comprising a water-soluble coating as a water-disintegrable coating Polymer material. 7. Detergent, detergent or cleaning agent portion according to one of claims 1 to 5, comprising a water-soluble coating as a water-disintegrable coating Polymer material of different layer thicknesses.   8. detergent, detergent or cleaning agent portion according to one of claims 1 to 5, comprising a polymer material as a water-disintegrable coating Areas of good water solubility. 9. detergent, detergent or cleaning agent portion according to one of claims 1 to 8, comprising a casing as a casing disintegrable in water optionally acetalized polyvinyl alcohol. 10. Detergent, detergent or cleaning agent portion according to one of claims 1 to 8, comprising a casing as a casing disintegrable in water Polyphosphate. 11. Detergent, detergent or cleaning agent portion according to one of claims 1 to 10 with an average diameter of the gas bubbles distributed in the portion Range from 2 nm to 1 mm. 12. Detergent, detergent or cleaning agent portion according to one of claims 1 to 11 with a density in the range of 0.8 to 1.7 g / l. 13. detergent, detergent or cleaning agent portion according to one of claims 1 to 12 with a gas content, based on volume, of 0.01 to 90%, preferably from 0.1 to 50%, more preferably from 0.5 to 20%. 14. Detergent, detergent or cleaning agent portion according to one of claims 1 to 13, containing as additional wash-active, rinse-active or cleaning-active Components one or more components from the group consisting of Surfactants, builders, bleaching agents, bleach activators, enzymes, foam inhibitors, Dyes and fragrances. 15. Detergent, detergent or cleaning agent portion according to one of claims 1 to 14 with a ruling inside the water disintegrable enclosure Pressure of the gas that is at least equal to atmospheric pressure.   16. detergent, detergent or cleaning agent portion according to claim 15 with a inside the pressure of the Gas that is greater than atmospheric pressure. 17. Detergent, detergent or cleaning agent portion according to one of claims 1 to 16, additionally containing one or more components in one before entry protected from water or moisture by a coating. 18. Detergent, detergent or cleaning agent portion according to one of claims 1 to 17, additionally containing one or more components in the in water disintegratable wrapping. 19. Detergent, dishwashing or cleaning agent portion according to one of claims 1 to 18, containing water in an amount of at most 15 wt .-%, based on the total weight of the portion, preferably in an amount ranging from 1 to 10% by weight. 20. washing processes, in particular processes for machine washing laundry, by washing the laundry with water and one or more detergent Portion (s) according to any one of claims 1 to 19 in contact. 21. Washing method, in particular method for machine washing dishes, glass and metal, in which the dishes are brought into contact with water, in which one or several portions of detergent according to one of claims 1 to 19 of the action of Are exposed to water. 22. Cleaning methods, in particular methods for cleaning hard surfaces, in which you can clean with water and one or more Detergent portion (s) according to any one of claims 1 to 19 in contact. 23. Cleaning methods, in particular methods for cleaning hard surfaces, in which one brings the goods to be cleaned into contact with water, in which one or several detergent portion (s) according to one of claims 1 to 19 Exposed to water.