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EP1348017B2 - Portion of washing agent, rinsing agent or cleaning agent, containing surfactants - Google Patents

Portion of washing agent, rinsing agent or cleaning agent, containing surfactants Download PDF

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Publication number
EP1348017B2
EP1348017B2 EP01991852A EP01991852A EP1348017B2 EP 1348017 B2 EP1348017 B2 EP 1348017B2 EP 01991852 A EP01991852 A EP 01991852A EP 01991852 A EP01991852 A EP 01991852A EP 1348017 B2 EP1348017 B2 EP 1348017B2
Authority
EP
European Patent Office
Prior art keywords
detergent
water
cleaning composition
composition portion
cleaning
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01991852A
Other languages
German (de)
French (fr)
Other versions
EP1348017B1 (en
EP1348017A2 (en
Inventor
Thomas Escher
Hans-Jürgen Riebe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1348017A2 publication Critical patent/EP1348017A2/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29Sulfates of polyoxyalkylene ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • C11D2111/16Metals
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • C11D2111/18Glass; Plastics
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40Specific cleaning or washing processes
    • C11D2111/42Application of foam or a temporary coating on the surface to be cleaned

Definitions

  • the present invention relates to a surfactant-containing detergent, detergent or detergent portion and, in particular, relates to a surfactant-containing detergent, detergent or cleaning agent portion, which is surrounded by a casing and contains a finely divided gas in its interior.
  • Surfactant-containing preparations containing finely divided gases are known and can be present, for example, as surfactant-containing foams, as are available for many applications.
  • shaving creams can be provided as foams
  • the hair-setting or otherwise conditioning agents can be foamed
  • glass surface cleaners and other hard surfaces for example in the bathroom and / or kitchen area
  • cleansing agents have also been reported for textiles which are applied in the form of a foam to spots or spots to be cleaned.
  • the foam allows a certain "life" of the cleaning agent on the spot to be cleaned or on the spot, without having to change the composition of the cleaning agent strongly towards a high viscosity, which was previously a means to clean the cleaner at the To hold place where his action was desired.
  • foams are also in the document WO 97/03176 (The Procter & Gamble Company).
  • the foams referred to in the cited document as "mousses" should be readily dosable and soluble, suspendible or emulsifiable in water, if they have a bulk density ⁇ 250 g / l, a stability (or collapse time on) in the air under conditions defined by standard measurement 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.
  • CO 2 as a blowing agent the document no measures are to be taken to how a low foam stability to water or a rapid dissolving, suspending or emulsifying the foam can be achieved in water.
  • Another object of the present invention was to provide a surfactant-containing detergent, rinse or detergent portion whose contents can be rapidly dissolved, suspended or emulsified in an aqueous system or in water.
  • this should not be achieved with a foam taken from or dispensed from a dispensing system, but with a surfactant-containing detergent, detergent or detergent portion fixed in the outer form, and especially with a surfactant-containing detergent, Detergent or detergent portion surrounded by a wrapper.
  • the present invention thus relates to a detergent, dishwashing or cleaning agent portion according to claim 1.
  • the invention also relates to a washing method, a rinsing method and a cleaning method using the detergent, detergent or cleaning agent portion described in detail below.
  • the detergent, dishwashing or cleaning agent portion comprises a foam molding with at least one surfactant, optionally together with one or more further washing active, rinsing or cleaning active ingredient (s), in a water-disintegratable wrapper.
  • a surfactant may be used, or several surfactants which are compatible with one another and preferably complement each other in their properties (including in their foaming behavior) may be used. All surfactants may belong to a surfactant type; however, surfactants of different types are preferably used when using a plurality of surfactants. For example, one or more anionic surfactant (s) together with one or more nonionic surfactant (s).
  • anionic surfactants or anionic surfactant (s) containing surfactant mixtures or surfactant compounds for economic reasons and due to their power spectrum and foam behavior are clearly preferred.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Suitable surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of 2-sulfofatty acids for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • fatty acid glycerol esters are the Mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 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) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example 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 these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 which can be obtained as commercial products of the Shell Oil Company under the name DAN® are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they can be used in detergent, detergent or detergent portions according to the invention even in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • 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 in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine or monoisopropylamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • surfactants are used in the form of their magnesium salts.
  • detergent, detergent or cleaner portions which are 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 15 to 25% by weight, of one or more anionic surfactants are preferred (e), in each case based on the weight of the detergent, detergent or cleaning agent portion.
  • a preferred detergent, rinse or detergent portion according to the invention has a soap content that exceeds 0.2% by weight, based on the total weight of the portion.
  • Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol (ether) sulfates, with preferred portions containing 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 5 to 10 wt .-% fatty alcohol (ether) sulfate (E), in each case based on the weight of the detergent, detergent or cleaning agent portion
  • a detergent, dishwashing or cleaning agent portion according to the invention may contain at least one nonionic, cationic and / or anionic surfactant (s) or in addition to the anionic surfactant (s). or zwitterionic surfactant.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols having 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 used, in which Alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • PO propylene oxide
  • alcohol ethoxylates and / or propoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO and / or PO per mole of alcohol prefers.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols 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 , as well as mixtures of C 12-14 -alcohol with 3 EO and C 12-18- alcohol with 5 EO.
  • Corresponding propoxylated compounds can be used as well as compounds which contain PO in addition to EO.
  • the stated degrees of ethoxylation or degrees of propoxylation represent statistical averages, which for a particular product may be an integer or a fractional number.
  • Preferred alcohol ethoxylates and / or propoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols containing more than 12 EO or PO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO and / or PO.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as in the example Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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 that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
  • the detergent, detergent or cleaner portions of the invention may preferably contain alkylpolyglycosides, wherein contents of the portions of APG over 0.2 wt .-%, based on the total portion, are preferred.
  • Particularly preferred detergent, rinse or detergent portions according to the invention contain APG in amounts of from 0.2 to 10% by weight, preferably in amounts of from 0.2 to 5% by weight and in particular in amounts of 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated or propoxylated fatty alcohols, in particular not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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 the 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 having 2 to 8 carbon atoms
  • R 4 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • 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 the international application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettklaamide.
  • anionic and nonionic surfactants it may be preferable to use not only anionic and nonionic surfactants but also cationic surfactants. Their use is preferably carried out as Wasch maybesbooster, with only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably contained in the foam moldings in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 3.0% by weight.
  • the portions according to the invention are detergents
  • they usually contain one or more surfactants in total amounts of from 5 to 50% by weight, preferably in amounts of from 10 to 35% by weight, where
  • surfactants may be present in greater or lesser amounts.
  • the amount of surfactant is not the same in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.
  • the detergent, detergent or cleaner portions according to the invention are detergents, in particular dishwasher detergents
  • these usually contain one or more surfactants in total amounts of from 0.1 to 10% by weight. , preferably in amounts of 0.5 to 5 wt .-%, wherein in partial portions of the detergent or cleaner portions of the invention surfactants may be contained in greater or smaller amount.
  • the amount of surfactant is not the same for cleaning or dishwashing detergents in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.
  • gases for the content of the detergent, detergent or cleaner portions according to the invention may in principle be any conceivable gas whose use is economically justifiable, which is not disadvantageous with one or more other components of the inventive detergent, detergent or cleaner portions Interacting manner that are not harmful to the consumer during storage and use of the portions and that have no adverse effect on the laundry, items to be washed or to be cleaned.
  • gases are 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 (including mixtures in any proportions of the gases involved) among two or more of them.
  • the gas forms a foam together with other detergent-active, rinse-active or detergent-active components of the detergent, detergent or cleaner portions according to the invention.
  • the foam formed from the surfactant (s) or their solutions in water and the gas (s) is a dispersion of gas (s) in a relatively small liquid phase, the phase comprising the surfactant (s) comprising the continuous liquid phase and the gas phase is dispersed therein.
  • the dispersed phase gas bubbles have a more or less wide distribution of size;
  • the values of the bubble size can fluctuate in the range of 1 nm to 10 mm due to the production.
  • the mean bubble diameter is preferably in the range of 2 nm to 1 mm. Of course, smaller or larger gas bubbles can be realized.
  • the foam moldings according to the present invention comprise a water-disintegratable coating.
  • a water-disintegratable coating This is understood to mean a sheath which completely surrounds the other components of the detergent, detergent or cleaning agent portion and at least mechanically, more preferably also largely gas and moisture-tight, shielding it from the outside environment. This must be disintegratable in water, so either dissolve completely, which is preferred according to the invention, or depending on certain parameters such as temperature, electrolyte concentration, pH, enzyme concentration or other parameters in the washing, rinsing or cleaning liquor successively complete or partially solve.
  • the detergent, rinse or detergent portions comprise a water-soluble polymer material as the water-disintegratable wrapper.
  • the detergent, detergent or cleaning agent portion encloses an envelope of one or more water-soluble polymer material (s) or that more enclosures of the same or different materials are included.
  • the presence of an envelope is preferred, which brings advantages in the choice of materials and also with regard to the requirement that the water-soluble polymer material must ultimately dissolve residue-free in the washing, rinsing or cleaning fleet.
  • the wrapper (s) may be formed from a single water-soluble polymer material or may be formed from a plurality of different polymeric materials which may optionally have different solubility in water. In view of the present task, according to the invention, the use of several different polymer materials may be particularly preferred, which will be discussed separately below.
  • the particular form of the water-deintermissable envelope of the detergent, rinse or detergent portion of the present invention is not critical.
  • the sheaths may be formed flat or in the form of capsules or similar shaped bodies.
  • moldings which ensure a maximum contact surface between the liquor and the casing to be disintegrated are preferred.
  • the detergent, rinse or detergent portion comprises a water-soluble polymer of different layer thickness as the water-disintegratable wrapper. If the material remains the same, the regions of the coating with a smaller layer thickness dissolve faster than those with a greater layer thickness, so that a coating provided with pores or holes is formed in water as the dissolution process of the coating progresses. Through the pores or holes, water may enter the interior of the enclosure, gradually dissolve the contents of the detergent, detergent or detergent portion surrounded by the enclosure, and through the pores or holes to the outside, i. H. into the wash liquor, rinse liquor or cleaning liquor transport.
  • the detergent, rinse or detergent portion comprises as the water-disintegratable wrapper a polymer material having areas of good water solubility and areas of less good water solubility.
  • This may be the result of a different water solubility of the polymer itself, for example due to its different chemical nature (for example: polyvinyl alcohols with different degrees of acetalization), or may be the result of the fact that polymers with different water solubility are deliberately mixed or in polymer materials with, for example, less good water solubility other materials (for example, readily water-soluble inorganic or organic salts) are incorporated, which quickly go into contact with water in the wash liquor, wash liquor or cleaning liquor and thus also create a structure provided with pores or holes.
  • a different water solubility of the polymer itself for example due to its different chemical nature (for example: polyvinyl alcohols with different degrees of acetalization)
  • polymers with different water solubility are deliberately mixed or in polymer materials with, for example, less good water solubility other materials (for example, readily water-soluble inorganic or organic salts) are incorporated, which quickly go into contact with water in the wash liquor, wash liquor or cleaning liquor and thus also create a structure provided with pores or
  • water-soluble polymer materials are basically all polymer materials in question, which under the given conditions (temperature, pH, concentration of detergent components) in aqueous phase can more or less completely solve.
  • the polymer materials may particularly preferably belong to the groups (acetalised) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof and mixtures of said materials.
  • Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n 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, polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. By these technical methods, PVAL are also available which contain a predetermined residual amount of acetate groups.
  • PVAL eg Mowiol® grades from Hoechst
  • PVAL polyvinyl acetates having a residual content of acetyl groups, for example, about 1 to 2 or 11 to 13 mol%.
  • the water solubility of PVAL can be reduced by aftertreatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available under the name "SOLUBLON®” from Syntana bottlesgesellschaft E. Harke GmbH & Co. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.
  • Polyvinylpyrrolidones referred to as PVP for short, can be described by the following general formula: PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercially available PVP have molecular weights in the range of about 2500 to 750,000 g / mol and are available 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 alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
  • detergent, dishwashing or cleaning agent portions whose coating consists of water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000).
  • small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1200 glucose molecules as a result of the binding in the 1,4-position, the chain branches in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives which are obtainable by polymer-analogous reactions of starch.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, 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 is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • Preferred casings of water-soluble polymer material consist of a polymer with one molecular weight between 5,000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons.
  • the water-soluble polymer material forming the cladding preferably has a thickness of from 1 to 150 ⁇ m, preferably from 2 to 100 ⁇ m, more preferably from 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m.
  • These water-soluble films of polymer material can be produced by various manufacturing methods. Blow molding, calendering and casting processes should be mentioned here in principle.
  • the films are blown starting from a melt with air through a mandrel to a hose.
  • the calendering process which is likewise one of the preferred production processes
  • the raw materials plasticized by suitable additives are atomized to form the films.
  • an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film.
  • this film is additionally powdered before or during the removal.
  • Typical examples of organic crystalline materials are all water-soluble crystalline materials, especially sugars, while typical examples of inorganic crystalline materials are water-soluble salts, especially heavy metal-free salts.
  • Detergent, detergent or detergent portions may be particularly preferred, the sheaths of which consist of a crystalline material which can assume a special function in the washing, rinsing or cleaning process when it is in the wash liquor, rinsing liquor by the dissolution process or cleaning liquor has arrived.
  • An example of this is polyphosphates. These can complex calcium and magnesium ions contained in the water and thereby contribute to the fact that a softening of the water does not have to be carried out separately (for example by salt addition in the dishwasher).
  • Detergent, detergent or detergent portions whose density, depending on the components (eg of the foam), is in the range from 0.8 to 1.7 g / ml, preferably in the range from 0, are also preferred according to the invention , 9 to 1.5 g / ml.
  • Detergent, detergent or detergent portions with such a density can be produced inexpensively, since inexpensive available gases or gas mixtures can replace otherwise used solvents as a filler.
  • the resulting, relatively large volumes of the detergent, detergent or detergent portions thus prepared have the further advantage that the legal requirement is taken into account to produce such tablets in a size that swallowing the portions by children is impossible ,
  • the detergent, detergent or cleaner portions according to the invention may also contain one or more further wash-active, rinse-active or cleaning-active component (s).
  • wash-active component or “rinse-active component” or “cleansing-active component” is understood to mean all conceivable substances which are relevant in connection with a washing, rinsing or cleaning process. These are primarily the actual detergents, dishwashing detergents or cleaning agents with their individual components explained in the further course of the description.
  • active ingredients such as the surfactants (anionic, nonionic, cationic and amphoteric surfactants) described above, builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes , special polymers (for example those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the terms being restricted to these substance groups.
  • active ingredients such as the surfactants (anionic, nonionic, cationic and amphoteric surfactants) described above, builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes , special polymers (for example those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the terms being restricted to these substance groups.
  • washing-active components are also understood to mean washing auxiliaries, rinse aids or cleaning auxiliaries.
  • these are optical brighteners, UV protective substances, so-called soil repellents, ie polymers which counteract re-soiling of fibers or hard surfaces, and silver protectants.
  • Laundry-treating agents such as fabric softeners or dishwashing detergent additives, such as rinse aids, are also considered according to the invention as “wash-active components", “rinse-active components” or “cleaning-active components”.
  • builders are the most important ingredients of detergents and cleaners.
  • builders usually used in detergents and cleaning agents may be present, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - 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 x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514 described.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in International Patent Application WO-A-91/08171 is described.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 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, which Delayed and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in the German patent application DE-A-44 00 024 described.
  • Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • a fine crystalline, synthetic and bound water-containing zeolite optionally used is preferably zeolite A and / or P.
  • Zeolite MAP eg, commercial product: Doucil A24 from Crosfield
  • zeolite X is particularly preferred as the P-type zeolite.
  • zeolite X is particularly preferred as the P-type zeolite.
  • zeolite X is particularly preferred as the P-type zeolite.
  • mixtures of A, X and / or P are also suitable, however, are zeolite X and mixtures of A, X and / or P.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 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 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builders, if such use should not be avoided for ecological reasons.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided their use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of washing and cleaning agent portions according to the invention.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned in this context.
  • polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Due to their superior solubility, this group can again be the short-chain polyacrylates be preferred, the molecular weights of 2,000 to 10,000 g / mol, more preferably from 3,000 to 5,000 g / mol, have.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid or of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molar mass, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (foamy) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.
  • the polymers may also allylsulfonic acids, such as in the EP-B 0 727 448 , Allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units are also preferred DE-A 43 00 772 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C 42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those described in the German patent applications DE-A 43 03 320 and DE-A 44 17 734 are described and preferably contain as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives of which in the German patent application DE-A 195 40 086 is disclosed that they also have a bleach-stabilizing effect in addition to co-builder properties.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in US Pat European patent application EP-A 0 280 223 , Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which is a DE of 100 owns.
  • DE dextrose equivalent
  • 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.
  • 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 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 as well as from the international ones Patent Applications WO 92/18542 . WO 93/08251 . WO 93/16110 . WO 94/28030 . WO 95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to German patent application DE-A 196 00 018 , A product oxidized to C 6 of the
  • ethylenediamine-N, N'-disuccinate (EDDS) ethylenediamine-N, N'-disuccinate (EDDS)
  • EDDS ethylenediamine-N, N'-disuccinate
  • its synthesis for example, in the document US-A 3,158,615 is described, preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat US Patents US-A 4,524,009 and US-A 4,639,325 , in the European Patent Application EP-A 0 150 930 and in the Japanese Patent Application JP-A 93 / 339,896 to be discribed.
  • Suitable amounts are in zeolithumblen and / or silicate-containing formulations at 3 to 15 wt
  • organic co-builders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such co-builders are used, for example, in the international Patent Application WO 95/20029 described.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferred, especially when the detergent, detergent or cleaner portions according to the invention also contain bleach, to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.
  • the detergent, detergent or cleaner portions according to the invention may contain one or more further ingredients customary in detergents, dishwashing or cleaning compositions from the group of bleaches, bleach activators, enzymes, fragrances, perfume carriers, fluorescers, dyes , Foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidoperuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxya
  • chlorine or bromine-releasing substances As bleaching agents in automatic dishwashing compositions it is also possible to use chlorine or bromine-releasing substances.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • bleach activators can be incorporated into the detergent and cleaner portions.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts may also be incorporated into the detergent, rinse or detergent portions of the invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from 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, but in particular cellulase-containing Mixtures of particular interest. Peroxidases or oxidases have also proved suitable in some cases.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Enzymes are added according to the prior art primarily to a detergent composition, in particular a dishwashing agent, which is intended for the main rinse. Disadvantage was that the optimum effect of enzymes used limited the choice of temperature and also encountered problems in the stability of the enzymes in a strongly alkaline medium. With the detergent, detergent or cleaner portions according to the invention, it is possible to use enzymes in the pre-wash and thus to use the pre-rinse cycle in addition to the main rinse for an enzyme action on contaminants of the dishes.
  • enzymes to the detergent-active preparation or partial portion of a detergent portion intended for the pre-wash cycle.
  • the enzymes are more preferably optimized for use under the conditions of the pre-wash cycle, that is, for example, in cold water.
  • the detergent, detergent or cleaner portions according to the invention can then be when the enzyme preparations are liquid, as they are sometimes available commercially, because then a rapid effect can be expected, already in (relatively short and carried out in cold water ) Pre-rinse occurs.
  • the enzymes are used in solid form and they are provided with a sheath of a water-soluble material that is already soluble in cold water, the enzymes can unfold their effect even before the main wash or Hauptinstitutsgang.
  • Advantage of the use of an enclosure of water-soluble material, in particular of cold water-soluble material is that the enzyme / enzymes in cold water after dissolution of the enclosure comes to effect quickly / come. Thus, their duration of action can be extended, which benefits the washing or rinsing results.
  • the detergent, dishwashing or cleaning agent portions according to the invention also contain further additives, as are known from the prior art as additives for laundry or dishwashing detergent preparations. These can be added either to one or more, if necessary also to all partial portions (washing active preparations) of the detergent, dishwashing or cleaning agent portions according to the invention or, as described in copending patent application no. 199 29 098.9 with the title "active ingredient sachet" described - are incorporated into the water-soluble, the preparations enveloping materials, so for example in the water-soluble films, but also in the capsules or coatings according to the invention.
  • optical brighteners are used in the invention.
  • Examples of optical brighteners are derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable z. B.
  • alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) 4 '- (2 -sulfostyryl-) biphenyl can be used.
  • UV protection substances are substances that are released during the washing process or in the subsequent fabric softening process in the wash liquor and that accumulate accumulatively on the fiber, in order then to achieve a UV protection effect. Suitable are the products marketed under the name Tinosorb R Ciba Specialty Chemicals.
  • additives which are preferred in specific embodiments, are surfactants which in particular can influence the solubility of the water-soluble film, but can also control its wettability and foaming on dissolution, as well as foam inhibitors, but also bitter substances, which may inadvertently swallow such packaging or parts of such packaging prevent from children.
  • Another group of additives which is preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Dyes which are customarily used to improve the appearance of the optical product in detergents and cleaners are preferred here. The selection of such dyes is not difficult for a person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the detergent, detergent or cleaning agent portions and to light and no pronounced substantivity to textile fibers to not stain them.
  • the dyes according to the invention in the detergent, detergent or detergent portions in amounts of below 0.01 wt .-% present.
  • polymers which show washing or cleaning or rinsing Cobuilder properties, so for example polyacrylic acids, and modified polyacrylic acids or corresponding copolymers.
  • Another group of polymers are polyvinylpyrrolidone and other grayness inhibitors, such as copolymers of polyvinylpyrrolidone, cellulose ethers, and the like.
  • so-called soil repellents are also suitable as polymers, as are known to the washing and cleaning agent specialist and will be described in detail below.
  • bleach catalysts in particular bleach catalysts for automatic dishwashing detergents or detergents.
  • complexes of manganese and cobalt, especially with nitrogen-containing ligands are used.
  • silver protectants are a variety of mostly cyclic organic compounds, which are also familiar to the person skilled in the art and contribute to prevent the tarnishing of silver-containing objects in the cleaning process. Specific examples may be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.
  • the detergent, detergent or cleaning agent portions may also contain so-called soil repellents, ie polymers which are applied to fibers or hard surfaces (for example on porcelain and glass), have a positive effect on the oil and grease washability of textiles and thus specifically counteract re-soiling. This effect becomes particularly evident when a textile or a hard object (porcelain, glass) is contaminated, which has already been washed or cleaned several times with a portion according to the invention which contains this oil and fat-dissolving component.
  • soil repellents ie polymers which are applied to fibers or hard surfaces (for example on porcelain and glass)
  • nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and of hydroxypropoxy groups of 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • All of these additives are added to the inventive detergent, detergent or cleaner portions in amounts of at most 30 wt .-%, preferably 2 to 20 wt .-%.
  • the addition can also be made to a material of a water-soluble enclosure comprising the or one of the detergent-active preparation (s).
  • a material of a water-soluble enclosure comprising the or one of the detergent-active preparation (s).
  • Fragrances are added to the detergent, detergent or cleaner portions according to the invention in order to improve the aesthetic overall impression of the products and to provide the consumer in addition to the technical performance (fabric softening result) a sensory typical and distinctive product.
  • perfume oils or perfumes individual perfume compounds can be used, for example the synthetic products of the ester type, 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, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • Ethers include, for example, benzyl ethyl ether.
  • the aldehydes include, for. B. linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, purple and bourgeonal.
  • the ketones include the ionone, ⁇ -isomethylionone, and methyl cedryl ketone.
  • the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different odoriferous substances which are adapted to one another in such a way that together they produce an attractive fragrance note.
  • perfume oils may also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • the content of perfumes in the range up to 2 wt .-% of the total detergent, detergent or detergent portion.
  • the fragrances can be incorporated directly into the detergent, detergent or detergent portions become; but it may also be advantageous to apply the fragrances on carriers that enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven.
  • the cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.
  • the perfumes and fragrances can in principle be contained in each of the partial portions (washing-active preparations) of the detergent, dishwashing or cleaning agent portions according to the invention. However, it is particularly preferred that they are in a detergent in a provided for the post-wash cycle or fabric conditioning portion detergent portion or in a detergent, especially in a dishwashing detergent, in a provided for the final rinse or rinse cycle part-detergent portion, special partial-detergent portion, are included.
  • detergent, detergent or detergent portions are provided with a pressure of the foaming gas / foaming gases which is at least equal to the atmospheric pressure, inside the water-disintegratable casing. is greater than atmospheric pressure.
  • the water content of the components of the foam body according to the invention should be limited. In a particularly preferred embodiment, it is at most 15% by weight, more preferably from 1 to 10% by weight,
  • Particularly preferred is a method in which the components of the envelope after the chemical synthesis (formation of the bonds as described above) are extruded and processed into granules, for which - depending on the temperature stability of the compounds involved - also an elevated temperature can be applied.
  • the resulting granules are melted if necessary, optionally in the presence of a plasticizer, and are then z. B. processed by conventional methods known per se to tubular bags.
  • rotary die Another method which can be used according to the invention is known by the term "rotary die” method.
  • two previously produced films which may for example have the characteristics described above, at a more or less acute angle in the nip of a pair of rollers whose surfaces with z. B. hemispherical depressions are provided.
  • the mixture of wash-active, rinse-active or cleaning-active "content" components is filled in the converging films, which then - in the example hemispherical depressions - to a filled with the components spherical portion with a complete envelope of the Form foil.
  • this method is well known and therefore needs no further description at this point.
  • the invention also relates to a washing method, in particular a method for machine washing of laundry, in which the laundry is contacted with water and one or more detergent, detergent or detergent portion (s) according to the above detailed description.
  • the invention further relates to a rinsing method, in particular method for machine rinsing dishes, glass and metal, in which one brings the items to be contacted with water, in which one or more detergent, detergent or detergent portion (s) according to the above detailed description of the action of the water are exposed.
  • the invention also relates to a cleaning method, in particular a method for cleaning hard surfaces, in which the product to be cleaned is brought into contact with water and one or more detergent, detergent or cleaning agent portion (s) according to the above detailed description.
  • the invention further relates to a cleaning method, in particular a method for cleaning hard surfaces, in which the product to be cleaned is brought into contact with water, in which one or more detergent, detergent or cleaning agent portion (s) according to the above detailed description exposed to the action of the water.
  • the following detergent formulations were prepared in a conventional manner by combining and mixing the components shown in Table 1 below.
  • the formulations were filled into water-soluble PVA films.

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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

Die vorliegende Erfindung betrifft eine tensidhaltige Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion und betrifft insbesondere eine tensidhaltige Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion, die von einer Umhüllung umgeben ist und in ihrem Innern ein feinverteiltes Gas enthält.The present invention relates to a surfactant-containing detergent, detergent or detergent portion and, in particular, relates to a surfactant-containing detergent, detergent or cleaning agent portion, which is surrounded by a casing and contains a finely divided gas in its interior.

Tensidhaltige Zubereitungen mit darin enthaltenen feinverteilten Gasen sind bekannt und können beispielsweise als tensidhaltige Schäume vorliegen, wie sie für viele Anwendungen erhältlich sind. So können Rasiercremes als Schäume bereitgestellt werden, können das Haar festigende oder anderweitig konditionierende Mittel aufgeschäumt werden, können Reiniger für Glasflächen und andere harte Oberflächen, beispielsweise im Bereich Bad und/oder Küche, in Schaum-Form aufgetragen werden und können Reiniger für Teppiche und Polster vorteilhafterweise als Schäume aufgetragen bzw. appliziert werden. In jüngerer Zeit wurde auch von reinigenden bzw. Flecken beseitigenden Mitteln für Textilien berichtet, die in Form eines Schaums auf zu reinigende Stellen bzw. Flecken aufgetragen werden. Der Schaum ermöglicht eine gewisse "Standzeit" des reinigenden Mittels auf der zu reinigenden Stelle bzw. auf dem Flecken, ohne die Zusammensetzung des reinigenden Mittels stark in Richtung auf eine hohe Viskosität verändern zu müssen, die früher ein Mittel dazu war, den Reiniger an der Stelle zu halten, an der seine Einwirkung erwünscht war.Surfactant-containing preparations containing finely divided gases are known and can be present, for example, as surfactant-containing foams, as are available for many applications. Thus, shaving creams can be provided as foams, the hair-setting or otherwise conditioning agents can be foamed, glass surface cleaners and other hard surfaces, for example in the bathroom and / or kitchen area, can be applied in foam form and can clean carpets and upholstery be advantageously applied or applied as foams. More recently, cleansing agents have also been reported for textiles which are applied in the form of a foam to spots or spots to be cleaned. The foam allows a certain "life" of the cleaning agent on the spot to be cleaned or on the spot, without having to change the composition of the cleaning agent strongly towards a high viscosity, which was previously a means to clean the cleaner at the To hold place where his action was desired.

Tensidhaltige Schäume sind auch in der Druckschrift WO 97/03176 (The Procter & Gamble Company) beschrieben. Die in der genannten Druckschrift auch als "mousses" bezeichneten Schäume sollen leicht dosierbar und in Wasser lösbar, suspendierbar oder emulgierbar sein, wenn sie eine Rohdichte < 250 g/l haben, an der Luft unter durch Standardmessung definierten Bedingungen eine Stabilität (oder Kollabierzeit auf das halbe Schaum-Volumen) von ≥ 15 s haben und auf Wasser einer Temperatur von 20 °C - ebenfalls unter Standard-Bedingungen - eine Stabilität von < 2 h haben. Außer durch die Wahl von CO2 als Treibmittel sind der Druckschrift keine Maßnahmen dazu zu entnehmen, wie eine geringe Schaumstabilität auf Wasser bzw. ein schnelles Lösen, Suspendieren oder Emulgieren des Schaums in Wasser erreicht werden kann.Surfactant-containing foams are also in the document WO 97/03176 (The Procter & Gamble Company). The foams referred to in the cited document as "mousses" should be readily dosable and soluble, suspendible or emulsifiable in water, if they have a bulk density <250 g / l, a stability (or collapse time on) in the air under conditions defined by standard measurement 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 document no measures are to be taken to how a low foam stability to water or a rapid dissolving, suspending or emulsifying the foam can be achieved in water.

Ferner sind aus der US 4,115,292 Reinigungsgegenstände bekannt, die Enzyme eingebettet in einen wasserlöslichen Film und Reinigungsmittel umhüllt von einem weiteren wasserlöslichen Film enthalten. Die Reinigungsmittel können dabei fest oder flüssig sein.Furthermore, from the US 4,115,292 Cleaning articles are known which contain enzymes embedded in a water-soluble film and detergent enveloped by another water-soluble film. The cleaning agents can be solid or liquid.

Im Rahmen der vorliegenden Erfindung war ebenfalls eine Aufgabe, eine tensidhaltigen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion bereitzustellen, deren Inhalt sich schnell in einem wäßrigen System oder in Wasser lösen, suspendieren oder emulgieren läßt. Im Gegensatz zum Stand cer Technik sollte dies jedoch nicht mit einem aus einem Spendersystem entnommenen bzw. dosierten Schaum erreicht werden, sondern mit einer hinsichtlich der äußeren Form fixierten, tensidhaltigen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion und insbesondere mit einer tensidhaltigen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion, die von einer Umhüllung umgeben ist.Another object of the present invention was to provide a surfactant-containing detergent, rinse or detergent portion whose contents can be rapidly dissolved, suspended or emulsified in an aqueous system or in water. In contrast to the state of the art, however, this should not be achieved with a foam taken from or dispensed from a dispensing system, but with a surfactant-containing detergent, detergent or detergent portion fixed in the outer form, and especially with a surfactant-containing detergent, Detergent or detergent portion surrounded by a wrapper.

Die vorliegende Erfindung betrifft somit eine Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion gemäß Anspruch 1.The present invention thus relates to a detergent, dishwashing or cleaning agent portion according to claim 1.

Weiter betrifft die Erfindung auch ein Waschverfahren, ein Spülverfahren und ein Reinigungsverfahren unter Verwendung der nachfolgend im einzelnen beschriebenen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion.Furthermore, the invention also relates to a washing method, a rinsing method and a cleaning method using the detergent, detergent or cleaning agent portion described in detail below.

Erfindungsgemäß umfaßt die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion einen Schaumformkörper mit mindestens einem Tensid, gegebenenfalls zusammen mit einem oder mehreren weiteren waschaktiven, spülaktiven oder reinigungsaktiven Bestandteil(en), in einer in Wasser desintegrierbaren Umhüllung. Es kann ein Tensid eingesetzt werden, oder es können mehrere miteinander kompatible, bevorzugt sich in ihren Eigenschaften (einschließlich in ihrem Schaumverhalten) ergänzende Tenside eingesetzt werden. Dabei können alle Tenside einem Tensid-Typ angehören; vorzugsweise werden jedoch bei Verwendung mehrerer Tenside Tenside unterschiedlichen Typs verwendet. beispielsweise ein oder mehrere Aniontensid(e) zusammen mit einem oder mehreren Niotensid(en).According to the invention, the detergent, dishwashing or cleaning agent portion comprises a foam molding with at least one surfactant, optionally together with one or more further washing active, rinsing or cleaning active ingredient (s), in a water-disintegratable wrapper. A surfactant may be used, or several surfactants which are compatible with one another and preferably complement each other in their properties (including in their foaming behavior) may be used. All surfactants may belong to a surfactant type; however, surfactants of different types are preferably used when using a plurality of surfactants. For example, one or more anionic surfactant (s) together with one or more nonionic surfactant (s).

Erfindungsgemäß sind anionische Tenside oder Aniontensid(e) enthaltende Tensidmischungen oder Tensidcompounds aus ökonomischen Gründen und aufgrund ihres Leistungsspektrums und Schaumverhaltens deutlich bevorzugt.According to the invention, anionic surfactants or anionic surfactant (s) containing surfactant mixtures or surfactant compounds for economic reasons and due to their power spectrum and foam behavior are clearly preferred.

Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsufonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, in Betracht, wie man sie beispielsweise aus C12-18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält. Geeignet sind auch Alkansulfonate, die aus C12-18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Ebenso sind auch die Ester von 2-Sulfofettsäuren (Estersulfonate), z.B. die 2-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren geeignet.As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Suitable surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure.Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are the Mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-Patentschriften 3,234,258 oder 5,075,041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete Aniontenside.Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example 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 these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 which can be obtained as commercial products of the Shell Oil Company under the name DAN® are suitable anionic surfactants.

Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie können in Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen gemäß der Erfindung aufgrund ihres hohen Schaumverhaltens bereits in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt werden.The sulfuric acid monoesters of straight-chain or branched C 7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they can be used in detergent, detergent or detergent portions according to the invention even in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden, und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8-18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Further 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 in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische.As further anionic surfactants are particularly soaps into consideration. Suitable are 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin oder auch Monoisopropylamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor. In einer weiteren Ausführungsform der Erfindung werden Tenside in Form ihrer Magnesiumsalze eingesetzt.The anionic surfactants including the soaps may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine or monoisopropylamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. In a further embodiment of the invention, surfactants are used in the form of their magnesium salts.

Im Rahmen der vorliegenden Erfindung sind Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen bevorzugt, die 5 bis 50 Gew.-%, vorzugsweise 7,5 bis 40 Gew.-% und insbesondere 15 bis 25 Gew.-% eines oder mehrerer anionischer Tensid(e), enthalten, jeweils bezogen auf das Gewicht der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion.In the context of the present invention, detergent, detergent or cleaner portions which are 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 15 to 25% by weight, of one or more anionic surfactants are preferred (e), in each case based on the weight of the detergent, detergent or cleaning agent portion.

Bei der Auswahl der anionischen Tenside, die in der erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion zum Einsatz kommen, stehen der Formulierungsfreiheit keine einzuhaltenden Beschränkungen im Weg. Eine bevorzugte Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion gemäß der Erfindung weist jedoch einen Gehalt an Seife auf, der 0,2 Gew.-%, bezogen auf das Gesamtgewicht der Portion, übersteigt. Bevorzugt einzusetzende anionische Tenside sind dabei die Alkylbenzolsulfonate und Fettalkohol(ether)sulfate, wobei bevorzugte Portionen 2 bis 20 Gew.-%, vorzugsweise 2,5 bis 15 Gew.-% und insbesondere 5 bis 10 Gew.-% Fettalkohol(ether)sulfat(e), jeweils bezogen auf das Gewicht der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion, enthaltenWhen selecting the anionic surfactants which are used in the detergent, dishwashing detergent or cleaning agent portion according to the invention, there are no restrictions to be kept in the way of freedom from formulation. However, a preferred detergent, rinse or detergent portion according to the invention has a soap content that exceeds 0.2% by weight, based on the total weight of the portion. Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol (ether) sulfates, with preferred portions containing 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 5 to 10 wt .-% fatty alcohol (ether) sulfate (E), in each case based on the weight of the detergent, detergent or cleaning agent portion

In einer weiteren, ebenfalls bevorzugten Ausführungsform der Erfindung kann eine erfindungsgemäße Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion anstelle des/der anionischen Tenside(s) oder zusätzlich zu dem/den anionischen Tensid(en) wenigstens ein nicht-ionisches, kationisches und/oder zwitterionisches Tensid umfassen.In a further, likewise preferred embodiment of the invention, a detergent, dishwashing or cleaning agent portion according to the invention may contain at least one nonionic, cationic and / or anionic surfactant (s) or in addition to the anionic surfactant (s). or zwitterionic surfactant.

Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte und/oder propoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) und/oder Propylenoxid (PO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate und/oder -propoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO und/oder PO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, sowie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO. Auch entsprechende propoxylierte Verbindungen sind verwendbar, genauso wie auch Verbindungen, die neben EO auch PO enthalten. Die angegebenen Ethoxylierungsgrade bzw. Propoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate und/oder -propoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO bzw. PO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO und/oder PO.As nonionic surfactants are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols having 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 used, in which Alcohol radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, are alcohol ethoxylates and / or propoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO and / or PO per mole of alcohol prefers. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols 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 , as well as mixtures of C 12-14 -alcohol with 3 EO and C 12-18- alcohol with 5 EO. Corresponding propoxylated compounds can be used as well as compounds which contain PO in addition to EO. The stated degrees of ethoxylation or degrees of propoxylation represent statistical averages, which for a particular product may be an integer or a fractional number. Preferred alcohol ethoxylates and / or propoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols containing more than 12 EO or PO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO and / or PO.

Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nicht-ionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90/13533 beschriebenen Verfahren hergestellt werden.Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as in the example Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.

Eine weitere Klasse von nichtionischen Tensiden, die vorteilhaft eingesetzt werden kann, sind die Alkylpolyglycoside (APG). Einsetzbare Alkylpolyglycoside genügen der allgemeinen Formel RO(G)z, in der R für einen linearen oder verzweigten, insbesondere in 2-Stellung methylverzweigten, gesättigten oder ungesättigten, aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen steht und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Glycosidierungsgrad z liegt dabei zwischen 1,0 und 4,0, vorzugsweise zwischen 1,0 und 2,0 und insbesondere zwischen 1,1 und 1,4.Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable alkylpolyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably 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.

Bevorzugt eingesetzt werden lineare Alkylpolyglucoside, also Alkylpolyglycoside, in denen der Polyglycosylrest ein Glucoserest und der Alkylrest ein n-Alkylrest ist.Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

Die erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen können bevorzugt Alkylpolyglycoside enthalten, wobei Gehalte der Portionen an APG über 0,2 Gew.-%, bezogen auf die gesamte Portion, bevorzugt sind. Besonders bevorzugte Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen gemäß der Erfindung enthalten APG in Mengen von 0,2 bis 10 Gew.-%, vorzugsweise in Mengen von 0,2 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 3 Gew.-%.The detergent, detergent or cleaner portions of the invention may preferably contain alkylpolyglycosides, wherein contents of the portions of APG over 0.2 wt .-%, based on the total portion, are preferred. Particularly preferred detergent, rinse or detergent portions according to the invention contain APG in amounts of from 0.2 to 10% by weight, preferably in amounts of from 0.2 to 5% by weight and in particular in amounts of 0.5 to 3% by weight.

Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten bzw. propoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated or propoxylated fatty alcohols, in particular not more than half thereof.

Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (I),

Figure imgb0001
in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)
Figure imgb0001
wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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.

Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II),

Figure imgb0002
in der R2 für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R3 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R4 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
Figure imgb0002
in the 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 having 2 to 8 carbon atoms and R 4 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielweise nach der Lehre der internationalen Anmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.[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 the international application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

Weiterhin kann es bevorzugt sein, neben anionischen und nichtionischen Tensiden auch kationische Tenside einzusetzen. Ihr Einsatz erfolgt dabei bevorzugt als Waschleistungsbooster, wobei nur kleine Mengen an kationischen Tensiden erforderlich sind. Werden kationische Tenside eingesetzt, so sind sie in den Schaum-Formkörpern bevorzugt in Mengen von 0,01 bis 10 Gew.-%, insbesondere von 0,1 bis 3,0 Gew.-% enthalten.Furthermore, it may be preferable to use not only anionic and nonionic surfactants but also cationic surfactants. Their use is preferably carried out as Waschleistungsbooster, with only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably contained in the foam moldings in amounts of from 0.01 to 10% by weight, in particular from 0.1 to 3.0% by weight.

In den Fällen, in denen es sich bei den erfindungsgemäßen Portionen um Waschmittel handelt, enthalten diese üblicherweise ein oder mehrere Tensid(e) in Gesamtmengen von 5 bis 50 Gew.-%, bevorzugt in Mengen von 10 bis 35 Gew.-%, wobei in Teilportionen der erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen Tenside in größerer oder kleinerer Menge enthalten sein können. Mit anderen Worten: Die Tensidmenge ist nicht in allen Teilportionen gleich; vielmehr können Teilportionen mit relativ größerem und Teilportionen mit relativ kleinerem Tensidgehalt vorgesehen werden.In cases in which the portions according to the invention are detergents, they usually contain one or more surfactants in total amounts of from 5 to 50% by weight, preferably in amounts of from 10 to 35% by weight, where In some portions of the detergent, detergent or cleaner portions of the invention, surfactants may be present in greater or lesser amounts. In other words: the amount of surfactant is not the same in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.

In den Fällen, in denen es sich bei den erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen um Reinigungsmittel handelt, insbesondere um Geschirrspülmittel, enthalten diese üblicherweise ein oder mehrere Tensid(e) in Gesamtmengen von 0,1 bis 10 Gew.-%, bevorzugt in Mengen von 0,5 bis 5 Gew.-%, wobei in Teilportionen der erfindungsgemäßen Spülmittel- oder Reinigungsmittel-Portionen Tenside in größerer oder kleinerer Menge enthalten sein können. Mit anderen Worten: Die Tensidmenge ist auch bei Reinigungs- bzw. Geschirrspülmitteln nicht in allen Teilportionen gleich; vielmehr können Teilportionen mit relativ größerem und Teilportionen mit relativ kleinerem Tensidgehalt vorgesehen werden.In the cases in which the detergent, detergent or cleaner portions according to the invention are detergents, in particular dishwasher detergents, these usually contain one or more surfactants in total amounts of from 0.1 to 10% by weight. , preferably in amounts of 0.5 to 5 wt .-%, wherein in partial portions of the detergent or cleaner portions of the invention surfactants may be contained in greater or smaller amount. In other words, the amount of surfactant is not the same for cleaning or dishwashing detergents in all partial portions; Rather, partial portions can be provided with relatively larger and partial portions with relatively smaller surfactant content.

Für den Inhalt der erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen geeignete Gase können grundsätzlich alle denkbaren Gase sein, deren Verwendung ökonomisch vertretbar ist, die nicht mit einer oder mehreren anderen Komponenten der erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen in nachteiliger Weise in Wechselwirkung treten, die für den Verbraucher bei Lagerung und Gebrauch der Portionen nicht schädlich sind und die keine nachteilige Wirkung auf das Waschgut, Spülgut oder zu reinigende Gut haben. Als Gase kommen beispielsweise Einzelstoffe aus der Gruppe Luft, Stickstoff, Sauerstoff, Kohlendioxid, Helium, Argon, Distickstoffoxid, Stickstoffmonoxid, Fluorkohlenstoff(e) wie beispielsweise CFC, HCFC und HFC und Alkan(e) wie beispielsweise Methan, Ethan, Propan, Butan, Pentan oder Hexan infrage. Die genannten Gase können einzeln oder in beliebigen Mischungen (auch Mischungen in beliebigen Mengenverhältnissen der beteiligten Gase untereinander) von zwei oder mehr von Ihnen Verwendung finden.Suitable gases for the content of the detergent, detergent or cleaner portions according to the invention may in principle be any conceivable gas whose use is economically justifiable, which is not disadvantageous with one or more other components of the inventive detergent, detergent or cleaner portions Interacting manner that are not harmful to the consumer during storage and use of the portions and that have no adverse effect on the laundry, items to be washed or to be cleaned. Examples of gases are 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 (including mixtures in any proportions of the gases involved) among two or more of them.

Unter bestimmten Bedingungen bildet das Gas/bilden die Gase zusammen mit anderen waschaktiven, spülaktiven oder reinigungsaktiven Komponenten der erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen einen Schaum. Der aus dem/den Tensid(en) bzw. ihren Lösungen in Wasser und dem/den Gas(en) gebildete Schaum ist eine Dispersion von Gas(en) in einer relativ kleinen flüssigen Phase, wobei die die Tensid(e) umfassende Phase die kontinuierliche flüssige Phase ist und die Gasphase hierin dispergiert ist. Typischerweise haben die Gasblasen der dispergierten Phase eine mehr oder weniger breite Verteilung der Größe; die Werte der Blasengröße können herstellungsbedingt im Bereich von 1 nm bis 10 mm schwanken. Die mittlere Blasendurchmesser liegt bevorzugt im Bereich von 2 nm bis 1 mm. Natürlich können auch kleinere oder größere Gasblasen realisiert werden.Under certain conditions, the gas forms a foam together with other detergent-active, rinse-active or detergent-active components of the detergent, detergent or cleaner portions according to the invention. The foam formed from the surfactant (s) or their solutions in water and the gas (s) is a dispersion of gas (s) in a relatively small liquid phase, the phase comprising the surfactant (s) comprising the continuous liquid phase and the gas phase is dispersed therein. Typically, the dispersed phase gas bubbles have a more or less wide distribution of size; The values of the bubble size can fluctuate in the range of 1 nm to 10 mm due to the production. The mean bubble diameter is preferably in the range of 2 nm to 1 mm. Of course, smaller or larger gas bubbles can be realized.

Als weitere Komponente umfassen die Schaum-Formkörper gemäß der vorliegenden Erfindung eine in Wasser desintegrierbare Umhüllung. Darunter wird eine vollständig die anderen Komponenten der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion umgebende und diese zumindest mechanisch, weiter bevorzugt auch weitgehend gas- und feuchtigkeitsdicht von der Außenumgebung abschirmende Umhüllung verstanden. Diese muß in Wasser desintegrierbar sein, also sich entweder ganz auflösen, was erfindungsgemäß bevorzugt ist, oder sich in Abhängigkeit von bestimmten Parametern wie Temperatur, Elektrolytkonzentration, pH-Wert, Enzymkonzentration oder anderer Parameter in der Wasch-, Spül- oder Reinigungsflotte sukzessive vollständig oder partiell lösen.As a further component, the foam moldings according to the present invention comprise a water-disintegratable coating. This is understood to mean a sheath which completely surrounds the other components of the detergent, detergent or cleaning agent portion and at least mechanically, more preferably also largely gas and moisture-tight, shielding it from the outside environment. This must be disintegratable in water, so either dissolve completely, which is preferred according to the invention, or depending on certain parameters such as temperature, electrolyte concentration, pH, enzyme concentration or other parameters in the washing, rinsing or cleaning liquor successively complete or partially solve.

In einer bevorzugten Ausführungsform der Erfindung umfassen die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen als in Wasser desintegrierbare Umhüllung ein wasserlösliches Polymer-Material. Dabei besteht die Möglichkeit, daß die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion eine Umhüllung aus einem oder mehreren wasserlöslichen Polymer-Material(ien) umgibt oder daß mehrere Umfassungen aus gleichen oder unterschiedlichen Materialien enthalten sind. Im Rahmen der vorliegenden Erfindung ist das Vorhandensein einer Umhüllung bevorzugt, was Vorteile bei der Materialwahl und auch im Hinblick auf das Erfordernis bringt, daß sich das wasserlösliche Polymer-Material letzten Endes rückstandsfrei in der Wasch-, Spül- oder Reinigungsflotte lösen muß. Die Umhüllung(en) kann/können aus einem einzigen wasserlöslichen Polymer-Material oder kann/können aus mehreren verschiedenen Polymer-Materialien gebildet sein, die gegebenenfalls unterschiedliche Löslichkeit in Wasser aufweisen können. Im Hinblick auf die vorliegende Aufgabenstellung kann erfindungsgemäß die Verwendung mehrerer verschiedenen Polymer-Materialien besonders bevorzugt sein, worauf nachfolgend gesondert eingegangen wird.In a preferred embodiment of the invention, the detergent, rinse or detergent portions comprise a water-soluble polymer material as the water-disintegratable wrapper. There is the possibility that the detergent, detergent or cleaning agent portion encloses an envelope of one or more water-soluble polymer material (s) or that more enclosures of the same or different materials are included. In the context of the present invention, the presence of an envelope is preferred, which brings advantages in the choice of materials and also with regard to the requirement that the water-soluble polymer material must ultimately dissolve residue-free in the washing, rinsing or cleaning fleet. The wrapper (s) may be formed from a single water-soluble polymer material or may be formed from a plurality of different polymeric materials which may optionally have different solubility in water. In view of the present task, according to the invention, the use of several different polymer materials may be particularly preferred, which will be discussed separately below.

Die spezielle Form der in Wasser desinterierbaren Umhüllung der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion der vorliegenden Erfindung ist nicht kritisch. So können die Umhüllungen flächig ausgebildet sein oder auch in Form von Kapseln oder ähnlichen Formkörpern vorliegen. Bevorzugt sind natürlich Formkörper, die eine maximale Kontaktfläche zwischen der Flotte und der zu desintegrierenden Umhüllung sicherstellen.The particular form of the water-deintermissable envelope of the detergent, rinse or detergent portion of the present invention is not critical. Thus, the sheaths may be formed flat or in the form of capsules or similar shaped bodies. Of course, moldings which ensure a maximum contact surface between the liquor and the casing to be disintegrated are preferred.

Es entspricht einer weiteren bevorzugten Ausführungsform der Erfindung, daß die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion als in Wasser desintegrierbare Umhüllung ein wasserlösliches Polymer unterschiedlicher Schichtdicke umfaßt. Bei gleichbleibendem Material lösen sich die Bereiche der Umhüllung mit geringerer Schichtdicke schneller als diejenigen mit größerer Schichtdicke, so daß sich mit fortschreitendem Lösungsprozeß der Umhüllung in Wasser eine mit Poren oder Löchern versehene Umhüllung ausbildet. Durch die Poren oder Löcher kann Wasser in das Innere der Umhüllung eintreten, den von der Umhüllung umgebenen Inhalt der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion sukzessive lösen und durch die Poren oder Löcher nach außen, d. h. in die Waschflotte, Spülflotte oder Reinigungsflotte, transportieren.It is another preferred embodiment of the invention that the detergent, rinse or detergent portion comprises a water-soluble polymer of different layer thickness as the water-disintegratable wrapper. If the material remains the same, the regions of the coating with a smaller layer thickness dissolve faster than those with a greater layer thickness, so that a coating provided with pores or holes is formed in water as the dissolution process of the coating progresses. Through the pores or holes, water may enter the interior of the enclosure, gradually dissolve the contents of the detergent, detergent or detergent portion surrounded by the enclosure, and through the pores or holes to the outside, i. H. into the wash liquor, rinse liquor or cleaning liquor transport.

Ein ähnlicher Effekt kann sich bei einer weiteren, ebenfalls bevorzugten Ausführungsform der Erfindung einstellen, gemäß der die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion als in Wasser desintegrierbare Umhüllung ein Polymer-Material mit Bereichen guter Wasserlöslichkeit und mit Bereichen weniger guter Wasserlöslichkeit umfaßt. Dies kann Resultat einer unterschiedlichen Wasserlöslichkeit des Polymers selbst sein, beispielsweise durch seine unterschiedliche chemische Natur (Beispiel: Polyvinylalkohole mit unterschiedlichem Acetalisierungsgrad), oder kann Resultat der Tatsache sein, daß Polymere mit unterschiedlicher Wasserlöslichkeit gezielt gemischt werden oder daß in Polymer-Materialien mit beispielsweise weniger guter Wasserlöslichkeit andere Materialien (beispielsweise gut wasserlösliche anorganische oder organische Salze) eingelagert sind, die bei Kontakt mit Wasser schnell in der Waschflotte, Spülflotte oder Reinigungsflotte in Lösung gehen und so ebenfalls eine mit Poren oder Löchern versehene Struktur schaffen.A similar effect may be obtained in a further, likewise preferred embodiment of the invention, according to which the detergent, rinse or detergent portion comprises as the water-disintegratable wrapper a polymer material having areas of good water solubility and areas of less good water solubility. This may be the result of a different water solubility of the polymer itself, for example due to its different chemical nature (for example: polyvinyl alcohols with different degrees of acetalization), or may be the result of the fact that polymers with different water solubility are deliberately mixed or in polymer materials with, for example, less good water solubility other materials (for example, readily water-soluble inorganic or organic salts) are incorporated, which quickly go into contact with water in the wash liquor, wash liquor or cleaning liquor and thus also create a structure provided with pores or holes.

Als wasserlösliche Polymer-Materialien kommen grundsätzlich alle Polymer-Materialien infrage, die sich unter den gegebenen Bedingungen (Temperatur, pH-Wert, Konzentration an waschaktiven Komponenten) in wäßriger Phase mehr oder weniger vollständig lösen können. Die Polymer-Materialien können besonders bevorzugt den Gruppen (acetalisierter) Polyvinylalkohol, Polyvinylpyrrolidon, Polyethylenoxid, Gelatine, Cellulose und deren Derivate und Mischungen der genannten Materialien zugehören.As water-soluble polymer materials are basically all polymer materials in question, which under the given conditions (temperature, pH, concentration of detergent components) in aqueous phase can more or less completely solve. The polymer materials may particularly preferably belong to the groups (acetalised) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof and mixtures of said materials.

Polyvinylalkohole (abgekürzt PVAL) sind Polymere der allgemeinen Struktur

        [-CH2-CH(OH)-]n

die in geringen Mengen auch Struktureinheiten des Typs

        [-CH2-CH(OH)-CH(OH)-CH2-]

enthalten. Da das entsprechend Monomer (Vinylalkohol) in freier Form nicht beständig ist, werden Polyvinylalkohole über polymeranaloge Reaktionen durch Hydrolyse, technisch insbesondere durch alkalisch katalysierte Umesterung von Polyvinylacetaten mit Alkoholen, vorzugsweise mit Methanol, erhalten. Durch diese technischen Verfahren sind auch PVAL zugänglich, die einen vorbestimmten Restanteil an Acetat-Gruppen enthalten.
Polyvinyl alcohols (abbreviated PVAL) are polymers of the general structure

[-CH 2 -CH (OH) -] n

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, polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. By these technical methods, PVAL are also available which contain a predetermined residual amount of acetate groups.

Handelsübliche PVAL (z.B. Mowiol®-Typen der Firma Hoechst) kommen als weißgelbliche Pulver oder Granulate mit Polymerisationsgraden im Bereich von ca. 500 bis 2.500 (entsprechend Molmassen von ca. 20.000 bis 100.000 g/mol) in den Handel und haben unterschiedliche Hydrolysegrade von beispielsweise 98 bis 99 bzw. 87 bis 89 Mol-%. Sie sind also teilverseifte Polyvinylacetate mit einem Restgehalt an Acetyl-Gruppen von beispielsweise etwa 1 bis 2 bzw. 11 bis 13 Mol-%.Commercially available PVAL (eg Mowiol® grades from Hoechst) are commercially available as white-yellowish powders or granules with degrees of polymerization in the range of about 500 to 2,500 (corresponding to molar masses of about 20,000 to 100,000 g / mol) and have different degrees of hydrolysis, for example 98 to 99 or 87 to 89 mol%. So they are partially hydrolyzed polyvinyl acetates having a residual content of acetyl groups, for example, about 1 to 2 or 11 to 13 mol%.

Die Wasserlöslichkeit von PVAL kann man durch Nachbehandlung mit Aldehyden (Acetalisierung), durch Komplexierung mit Ni- oder Cu-Salzen oder durch Behandlung mit Dichromaten, Borsäure, Borax verringern und so gezielt auf gewünschte Werte einstellen. Folien aus PVAL sind weitgehend undurchdringlich für Gase wie Sauerstoff, Stickstoff, Helium, Wasserstoff, Kohlendioxid, lassen jedoch Wasserdampf hindurchtreten.The water solubility of PVAL can be reduced by aftertreatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values. Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Beispiele geeigneter wasserlöslicher PVAL-Folien sind die unter Bezeichnung "SOLUBLON®" von der Firma Syntana Handelsgesellschaft E. Harke GmbH & Co. erhältlichen PVAL-Folien. Deren Löslichkeit in Wasser läßt sich Grad-genau einstellen, und es sind Folien dieser Produktreihe erhältlich, die in allen für die Anwendung relevanten Temperaturbereichen in wäßriger Phase löslich sind.Examples of suitable water-soluble PVAL films are the PVAL films available under the name "SOLUBLON®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.

Polyvinylpyrrolidone, kurz als PVP bezeichnet, lassen sich durch die folgende allgemeine Formel beschreiben:

Figure imgb0003
PVP werden durch radikalische Polymerisation von 1-Vinylpyrrolidon hergestellt. Handelsübliche PVP haben Molmassen im Bereich von ca. 2500 bis 750.000 g/mol und werden als weiße, hygroskopische Pulver oder als wäßrige Lösungen angeboten.Polyvinylpyrrolidones, referred to as PVP for short, can be described by the following general formula:
Figure imgb0003
PVP are prepared by radical polymerization of 1-vinylpyrrolidone. Commercially available PVP have molecular weights in the range of about 2500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.

Polyethylenoxide, kurz PEOX, sind Polyalkylenglykole der allgemeinen Formel

        H-[O-CH2-CH2]n-OH

die technisch durch basisch katalysierte Polyaddition von Ethylenoxid (Oxiran) in meist geringe Mengen Wasser enthaltenden Systemen mit Ethylenglykol als Startmolekül hergestellt werden. Sie haben Molmassen im Bereich von ca. 200 bis 5.000.000 g/mol, entsprechend Polymerisationsgraden n von ca. 5 bis >100.000. Polyethylenoxide besitzen eine äußerst niedrige Konzentration an reaktiven Hydroxy-Endgruppen und zeigen nur noch schwache Glykol-Eigenschaften.
Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH 2 -CH 2 ] n -OH

the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

Gelatine ist ein Polypeptid (Molmasse: ca. 15.000 bis >250.000 g/mol), das vornehmlich durch Hydrolyse des in Haut und Knochen von Tieren enthaltenen Kollagens unter sauren oder alkalischen Bedingungen gewonnen wird. Die Aminosäuren-Zusammensetzung der Gelatine entspricht weitgehend der des Kollagens, aus dem sie gewonnen wurde, und variiert in Abhängigkeit von dessen Provenienz. Die Verwendung von Gelatine als wasserlösliches Hüllmaterial ist insbesondere in der Pharmazie in Form von Hart- oder Weichgelatinekapseln äußerst weit verbreitet. In Form von Folien findet Gelatine wegen ihres im Vergleich zu den vorstehend genannten Polymeren hohen Preises nur geringe Verwendung.Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.

Bevorzugt sind im Rahmen der vorliegenden Erfindung auch Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen, deren Umhüllung aus wasserlöslicher Folie aus mindestens einem Polymer aus der Gruppe Stärke und Stärkederivate, Cellulose und Cellulosederivate, insbesondere Methylcellulose und Mischungen hieraus besteht.Also preferred within the scope of the present invention are detergent, dishwashing or cleaning agent portions whose coating consists of water-soluble film of at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.

Stärke ist ein Homoglykan, wobei die Glucose-Einheiten α-glykosidisch verknüpft sind. Stärke ist aus zwei Komponenten unterschiedlichen Molekulargewichts aufgebaut: aus ca. 20 bis 30% geradkettiger Amylose (MG. ca. 50.000 bis 150.000) und 70 bis 80% verzweigtkettigem Amylopektin (MG. ca. 300.000 bis 2.000.000). Daneben sind noch geringe Mengen Lipide, Phosphorsäure und Kationen enthalten. Während die Amylose infolge der Bindung in 1,4-Stellung lange, schraubenförmige, verschlungene Ketten mit etwa 300 bis 1200 Glucose-Molekülen bildet, verzweigt sich die Kette beim Amylopektin nach durchschnittlich 25 Glucose-Bausteinen durch 1,6-Bindung zu einem astähnlichen Gebilde mit etwa 1.500 bis 12.000 Molekülen Glucose. Neben reiner Stärke sind zur Herstellung wasserlöslicher Umhüllungen der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen im Rahmen der vorliegenden Erfindung auch Stärke-Derivate, die durch polymeranaloge Reaktionen aus Stärke erhältlich sind. Solche chemisch modifizierten Stärken umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Stärken, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Stärke-Derivate einsetzen. In die Gruppe der Stärke-Derivate fallen beispielsweise Alkalistärken, Carboxymethylstärke (CMS), Stärkeester und -ether sowie Aminostärken.Starch is a homoglycan, wherein the glucose units are linked α-glycosidically. Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000). In addition, small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1200 glucose molecules as a result of the binding in the 1,4-position, the chain branches in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, for the production of water-soluble coatings of detergent, detergent or detergent portions in the context of the present invention are also starch derivatives which are obtainable by polymer-analogous reactions of starch. Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, 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.

Reine Cellulose weist die formale Bruttozusammensetzung (C6H10O5)n auf und stellt formal betrachtet ein β-1,4-Polyacetal von Cellobiose dar, die ihrerseits aus zwei Molekülen Glucose aufgebaut ist. Geeignete Cellulosen bestehen dabei aus ca. 500 bis 5000 Glucose-Einheiten und haben demzufolge durchschnittliche Molmassen von 50.000 bis 500.000. Als Desintegrationsmittel auf Cellulosebasis verwendbar sind im Rahmen der vorliegenden Erfindung auch Cellulose-Derivate, die durch polymeranaloge Reaktionen aus Cellulose erhältlich sind. Solche chemisch modifizierten Cellulosen umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Cellulosen, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Cellulose-Derivate einsetzen. In die Gruppe der Cellulose-Derivate fallen beispielsweise Alkalicellulosen, Carboxymethylcellulose (CMC), Celluloseester und -ether sowie Aminocellulosen.Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

Bevorzugte Umhüllungen aus wasserlöslichem Polymer-Material bestehen aus einem Polymer mit einer Molmasse zwischen 5.000 und 500.000 Dalton, vorzugsweise zwischen 7.500 und 250.000 Dalton und insbesondere zwischen 10.000 und 100.000 Dalton. Das wasserlösliche Polymer-Material, das die Umhüllung bildet, weist vorzugsweise eine Dicke von 1 bis 150 µm, vorzugsweise von 2 bis 100 µm, besonders bevorzugt von 5 bis 75 µm und insbesondere von 10 bis 50 µm, auf.Preferred casings of water-soluble polymer material consist of a polymer with one molecular weight between 5,000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons. The water-soluble polymer material forming the cladding preferably has a thickness of from 1 to 150 μm, preferably from 2 to 100 μm, more preferably from 5 to 75 μm and in particular from 10 to 50 μm.

Diese wasserlöslichen Folien aus Polymer-Material können nach verschiedenen Herstellverfahren hergestellt werden. Hier sind prinzipiell Blas-, Kalandrier- und Gießverfahren zu nennen. Bei einem bevorzugten Verfahren werden die Folien dabei ausgehend von einer Schmelze mit Luft über einen Blasdorn zu einem Schlauch geblasen. Bei dem Kalandrierverfahren, das ebenfalls zu den bevorzugt eingesetzten Herstellverfahren gehört, werden die durch geeignete Zusätze plastifizierten Rohstoffe zur Ausformung der Folien verdüst. Hier kann es insbesondere erforderlich sein, an die Verdüsungen eine Trocknung anzuschließen. Bei dem Gießverfahren, das ebenfalls zu den bevorzugten Herstellverfahren gehört, wird eine wäßrige Polymerzubereitung auf eine beheizbare Trockenwalze gegeben, nach dem Verdampfen des Wassers wird optional gekühlt und die Folie als Film abgezogen. Gegebenenfalls wird dieser Film vor oder während des Abziehens zusätzlich abgepudert.These water-soluble films of polymer material can be produced by various manufacturing methods. Blow molding, calendering and casting processes should be mentioned here in principle. In a preferred method, the films are blown starting from a melt with air through a mandrel to a hose. In the case of the calendering process, which is likewise one of the preferred production processes, the raw materials plasticized by suitable additives are atomized to form the films. In particular, it may be necessary to attach drying to the atomizations. In the casting process, which is also one of the preferred production methods, an aqueous polymer preparation is placed on a heatable drying roller, after the evaporation of the water is optionally cooled and the film is peeled off as a film. Optionally, this film is additionally powdered before or during the removal.

Es entspricht einer weiteren, ebenfalls bevorzugten Ausführungsform der Erfindung, Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen bereitzustellen, die als in Wasser desintegrierbare Umhüllung eine Umhüllung aus einem kristallinen Material umfassen, wobei das kristalline Material organischer oder anorganischer Natur sein kann. Typische Beispiele organischer kristalliner Materialien sind alle wasserlöslichen kristallinen Materialien, insbesondere Zucker, während typische Beispiele anorganischer kristalliner Materialien wasserlösliche Salze, insbesondere Schwermetall-freie Salze sind. Besonders bevorzugt können dabei Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen sein, deren Umhüllungen aus einem kristallinen Material bestehen, das im Wasch-, Spül- oder Reinigungsprozeß eine spezielle Funktion übernehmen kann, wenn es durch den Lösevorgang in Wasser in die Waschflotte, Spülflotte oder Reinigungsflotte gelangt ist. Ein Beispiel hierfür sind Polyphosphate. Diese können im Wasser enthaltene Calcium- und Magnesium-Ionen komplexieren und dadurch dazu beitragen, daß eine Enthärtung des Wassers nicht separat (beispielsweise durch Salz-Zusatz in der Geschirrspülmaschine) durchgeführt werden muß.It is another, yet preferred embodiment of the invention to provide detergent, rinse or detergent portions which comprise a water-disintegratable wrapper as a crystalline material wrapper wherein the crystalline material may be organic or inorganic in nature. Typical examples of organic crystalline materials are all water-soluble crystalline materials, especially sugars, while typical examples of inorganic crystalline materials are water-soluble salts, especially heavy metal-free salts. Detergent, detergent or detergent portions may be particularly preferred, the sheaths of which consist of a crystalline material which can assume a special function in the washing, rinsing or cleaning process when it is in the wash liquor, rinsing liquor by the dissolution process or cleaning liquor has arrived. An example of this is polyphosphates. These can complex calcium and magnesium ions contained in the water and thereby contribute to the fact that a softening of the water does not have to be carried out separately (for example by salt addition in the dishwasher).

Weiter bevorzugt sind erfindungsgemäß Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen, deren Dichte - abhängig von den Komponenten (z. B. des Schaums) - im Bereich von 0,8 bis 1,7 g/ml liegt, vorzugsweise im Bereich von 0,9 bis 1,5 g/ml liegt. Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen mit einer derartigen Dichte können kostengünstig hergestellt werden, da preiswert zur Verfügung stehende Gase oder Gasgemische ansonsten zu verwendende Lösungsmittel als Füllstoff ersetzen können. Die resultierenden, relativ großen Volumina der so hergestellten Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen haben darüber hinaus noch den weiteren Vorteil, daß dem gesetzlichen Erfordernis Rechnung getragen wird, derartige Formkörper in einer Größe herzustellen, daß ein Verschlucken der Portionen durch Kinder unmöglich ist.Detergent, detergent or detergent portions whose density, depending on the components (eg of the foam), is in the range from 0.8 to 1.7 g / ml, preferably in the range from 0, are also preferred according to the invention , 9 to 1.5 g / ml. Detergent, detergent or detergent portions with such a density can be produced inexpensively, since inexpensive available gases or gas mixtures can replace otherwise used solvents as a filler. The resulting, relatively large volumes of the detergent, detergent or detergent portions thus prepared have the further advantage that the legal requirement is taken into account to produce such tablets in a size that swallowing the portions by children is impossible ,

Die erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen können in einer weiteren bevorzugten Ausführungsform noch einen oder mehrere weitere(n) waschaktive(n), spülaktive(n) oder reinigungsaktive(n) Komponente(n) enthalten. Unter dem Begriff "waschaktive Komponente" oder "spülaktive Komponente" oder "reinigungsaktive Komponente" werden im Rahmen der vorliegenden Erfindung Zubereitungen aller denkbaren, im Zusammenhang mit einem Wasch-, Spül- oder Reinigungsvorgang relevanten Substanzen verstanden. Dies sind in erster Linie die eigentlichen Waschmittel, Spülmittel oder Reinigungsmittel mit ihren im weiteren Verlauf der Beschreibung näher erläuterten Einzelkomponenten. Darunter fallen Aktivstoffe wie die oben näher beschriebenen Tenside (anionische, nicht-ionische, kationische und amphotere Tenside), Buildersubstanzen (anorganische und organische Buildersubstanzen), Bleichmittel (wie beispielsweise Peroxo-Bleichmittel und Chlor-Bleichmittel), Bleichaktivatoren, Bleichstabilisatoren, Bleichkatalysatoren, Enzyme, spezielle Polymere (beispielsweise solche mit Cobuilder-Eigenschaften), Vergrauungsinhibitoren, Farbstoffe und Duftstoffe (Parfums), ohne daß die Begriffe auf diese Substanzgruppen beschränkt sind.In a further preferred embodiment, the detergent, detergent or cleaner portions according to the invention may also contain one or more further wash-active, rinse-active or cleaning-active component (s). In the context of the present invention, the term "wash-active component" or "rinse-active component" or "cleansing-active component" is understood to mean all conceivable substances which are relevant in connection with a washing, rinsing or cleaning process. These are primarily the actual detergents, dishwashing detergents or cleaning agents with their individual components explained in the further course of the description. These include active ingredients such as the surfactants (anionic, nonionic, cationic and amphoteric surfactants) described above, builders (inorganic and organic builders), bleaches (such as peroxy bleach and chlorine bleach), bleach activators, bleach stabilizers, bleach catalysts, enzymes , special polymers (for example those with cobuilder properties), grayness inhibitors, dyes and fragrances (perfumes), without the terms being restricted to these substance groups.

Es werden unter dem Begriff "waschaktive Komponenten", "spülaktive Komponenten" oder "reinigungsaktive Komponenten" jedoch auch Waschhilfsmittel, Spülhilfsmittel oder Reinigungshilfsmittel verstanden. Beispiele für diese sind optische Aufheller, UV-Schutzsubstanzen, sog. Soil Repellents, also Polymere, die einer Wiederanschmutzung von Fasern oder harten Oberflächen entgegenwirken, sowie Silberschutzmittel. Auch Wäsche-Behandlungsmittel wie Weichspüler bzw. Geschirrspülmittel-Zusätze wie Klarspüler werden erfindungsgemäß als "waschaktive Komponenten", "spülaktive Komponenten" oder "reinigungsaktive Komponenten" betrachtet.However, the term "washing-active components", "rinse-active components" or "cleaning-active components" are also understood to mean washing auxiliaries, rinse aids or cleaning auxiliaries. Examples of these are optical brighteners, UV protective substances, so-called soil repellents, ie polymers which counteract re-soiling of fibers or hard surfaces, and silver protectants. Laundry-treating agents, such as fabric softeners or dishwashing detergent additives, such as rinse aids, are also considered according to the invention as "wash-active components", "rinse-active components" or "cleaning-active components".

Die in den erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen verwendbaren Tenside wurden bereits oben im Detail beschrieben.The surfactants which can be used in the detergent, dishwashing or cleaning agent portions according to the invention have already been described in detail above.

Neben den Tensiden sind Gerüststoffe die wichtigsten Inhaltsstoffe von Wasch- und Reinigungsmitteln. In den erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen können üblicherweise in Wasch- und Reinigungsmitteln eingesetzte Gerüststoffe enthalten sein, insbesondere also Zeolithe, Silicate, Carbonate, organische Cobuilder und - wo keine ökologischen Vorurteile gegen ihren Einsatz bestehen - auch Phosphate.In addition to the surfactants, builders are the most important ingredients of detergents and cleaners. In the detergent, detergent or cleaner portions according to the invention builders usually used in detergents and cleaning agents may be present, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also phosphates.

Geeignete kristalline, schichtförmige Natriumsilicate besitzen die allgemeine Formel NaMSixO2x+1 .H2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilicate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilicate Na2Si2O5 · yH2O bevorzugt, wobei β-Natriumdisilicat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO-A-91/08171 beschrieben ist.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 are 2, 3 or 4. Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514 described. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in International Patent Application WO-A-91/08171 is described.

Einsetzbar sind auch amorphe Natriumsilicate mit einem Modul Na2O :SiO2 von 1 : 2 bis 1 : 3,3, vorzugsweise von 1 : 2 bis 1 : 2,8 und insbesondere von 1 : 2 bis 1 : 2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilicaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, daß die Silicate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silicatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, daß die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige sogenannte röntgenamorphe Silicate, welche ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern aufweisen, werden beispielsweise in der deutschen Patentanmeldung DE-A- 44 00 024 beschrieben. Insbesondere bevorzugt sind verdichtete/kompaktierte amorphe Silicate, compoundierte amorphe Silicate und übertrocknete röntgenamorphe Silicate.It is also possible to use amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 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, which Delayed and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments, the silicates do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in the German patent application DE-A-44 00 024 described. Especially preferred are densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Ein gegebenenfalls eingesetzter feinkristalliner, synthetischer und gebundenes Wasser enthaltender Zeolith ist vorzugsweise Zeolith A und/oder P. Als Zeolith des P-Typs wird Zeolith MAP (z. B. Handelsprodukt: Doucil A24 der Firma Crosfield) besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus A, X und/oder P. Kommerziell erhältlich und im Rahmen der vorliegenden Erfindung bevorzugt einsetzbar ist beispielsweise auch ein Co-Kristallisat aus Zeolith X und Zeolith A (ca. 80 Gew.-% Zeolith X), das von der Firma CONDEA Augusta S.p.A. unter dem Markennamen VEGOBOND AX® vertrieben wird und durch die Formel

        nNa2O·(1-n)K2O·Al2O3·(2-2,5)SiO2·(3,5-5,5)H2O

beschrieben werden kann. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 µm (Volumenverteilung; Meßmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22 Gew.-%, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.
A fine crystalline, synthetic and bound water-containing zeolite optionally used is preferably zeolite A and / or P. Zeolite MAP (eg, commercial product: Doucil A24 from Crosfield) is particularly preferred as the P-type zeolite. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula

nNa 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, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Selbstverständlich ist in den erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen möglich, sofern ein derartiger Einsatz nicht aus ökologischen Gründen vermieden werden sollte. Geeignet sind insbesondere die Natriumsalze der Orthophosphate, der Pyrophosphate und insbesondere der Tripolyphosphate.Of course, in the detergents, dishwashing or cleaning agent portions according to the invention, it is also possible to use the generally known phosphates as builders, if such use should not be avoided for ecological reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern deren Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- und Reinigungsmittel-Portionen gemäß der Erfindung. Insbesondere sind in diesem Zusammenhang Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen von diesen zu nennen.Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided their use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of washing and cleaning agent portions according to the invention. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these are to be mentioned in this context.

Als Builder sind weiter polymere Polycarboxylate geeignet. Dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70.000 g/mol.As builder further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70,000 g / mol.

Bei den für polymere Polycarboxylate angegebenen Molmassen handelt es sich im Rahmen der vorliegenden Erfindung um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt wurden, wobei ein UV-Detektor eingesetzt wurde. Die Messung erfolgte dabei gegen einen externen Polyacrylsäure-Standard, der aufgrund seiner strukturellen Verwandtschaft mit den untersuchten Polymeren realistische Molgewichtswerte liefert. Diese Angaben weichen deutlich von den Molgewichtsangaben ab, bei denen Polystyrolsulfonsäuren als Standard eingesetzt werden. Die gegen Polystyrolsäuren gemessenen Molmassen sind in der Regel deutlich höher als die im Rahmen der vorliegenden Erfindung angegebenen Molmassen.In the context of the present invention, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrene acids are generally significantly higher than the molecular weights specified in the context of the present invention.

Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molmasse von 2.000 bis 20.000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate bevorzugt sein, die Molmassen von 2.000 bis 10.000 g/mol, besonders bevorzugt von 3.000 bis 5.000 g/mol, aufweisen.Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Due to their superior solubility, this group can again be the short-chain polyacrylates be preferred, the molecular weights of 2,000 to 10,000 g / mol, more preferably from 3,000 to 5,000 g / mol, have.

Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure oder der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2.000 bis 70.000 g/mol, vorzugsweise 20.000 bis 50.000 g/mol und insbesondere 30.000 bis 40.000 g/mol.Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid or of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molar mass, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wäßrige Lösung eingesetzt werden. Der Gehalt der erfindungsgemäßen Schaum-Formkörper an (co-)polymeren Polycarboxylaten beträgt vorzugsweise 0,5 bis 20 Gew.-%, insbesondere 3 bis 10 Gew.-%.The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (foamy) polymeric polycarboxylates according to the invention is preferably from 0.5 to 20% by weight, in particular from 3 to 10% by weight.

Zur Verbesserung der Wasserlöslichkeit können die Polymere auch Allylsulfonsäuren, wie beispielsweise in der EP-B 0 727 448 , Allyloxybenzolsulfonsäure und Methallylsulfonsäure als Monomer enthalten.To improve the water solubility, the polymers may also allylsulfonic acids, such as in the EP-B 0 727 448 , Allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Insbesondere bevorzugt sich auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die gemäß der DE-A 43 00 772 als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder gemäß der DE-C 42 21 381 als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten.In particular, biodegradable polymers of more than two different monomer units, for example those which are suitable according to the invention, are also preferred DE-A 43 00 772 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C 42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Weiter bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE-A 43 03 320 und DE-A 44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat enthalten.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 preferably contain as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Ebenso sind als weitere bevorzugte Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate, von denen in der deutschen Patentanmeldung DE-A 195 40 086 offenbart wird, daß sie neben Co-Builder-Eigenschaften auch eine bleichstabilisierende Wirkung aufweisen.Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE-A 195 40 086 is disclosed that they also have a bleach-stabilizing effect in addition to co-builder properties.

Weitere geeignete Buildersubstanzen sind Polyacetale, die durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren erhalten werden können, die 5 bis 7 Kohlenstoffatome und mindestens 3 Hydroxygruppen aufweisen, beispielsweise wie beschrieben in der europäischen Patentanmeldung EP-A 0 280 223 . Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids having 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in US Pat European patent application EP-A 0 280 223 , Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500.000 g/mol. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30, bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose ist, welche ein DE von 100 besitzt. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2.000 bis 30.000 g/mol. Ein bevorzugtes Dextrin ist in der britischen Patentanmeldung 94 19 091 beschrieben.Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which is a DE of 100 owns. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2,000 to 30,000 g / mol. A preferred dextrin is in the British Patent Application 94 19 091 described.

Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, die in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren. Derartige oxidierte Dextrine und Verfahren zu ihrer Herstellung sind insbesondere aus den europäischen Patentanmeldungen EP-A 0 232 202 , EP-A 0 427 349 , EP-A 0 472 042 und EP-A 0 542 496 sowie aus den internationalen Patentanmeldungen WO 92/18542 , WO 93/08251 , WO 93/16110 , WO 94/28030 , WO 95/07303 , WO 95/12619 und WO 95/20608 bekannt. Ebenfalls geeignet ist ein oxidiertes Oligosaccharid gemäß der deutschen Patentanmeldung DE-A 196 00 018 . Ein an C6 des Saccharidrings oxidiertes Produkt kann besonders vorteilhaft sein.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 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 as well as from the international ones Patent Applications WO 92/18542 . WO 93/08251 . WO 93/16110 . WO 94/28030 . WO 95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to German patent application DE-A 196 00 018 , A product oxidized to C 6 of the saccharide ring may be particularly advantageous.

Auch Oxydisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisuccinat sind weitere geeignete Co-Builder. Dabei wird Ethylendiamin-N,N'-disuccinat (EDDS), dessen Synthese beispielsweise in der Druckschrift US-A 3,158,615 beschrieben wird, bevorzugt in Form seiner Natrium- oder Magnesiumsalze verwendet. Weiterhin bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate, wie sie beispielsweise in den US-Patentschriften US-A 4,524,009 und US-A 4,639,325 , in der europäischen Patentanmeldung EP-A 0 150 930 und in der japanischen Patentanmeldung JP-A 93/339,896 beschrieben werden. Geeignete Einsatzmengen liegen in zeolithhaltigen und/oder silicathaltigen Formulierungen bei 3 bis 15 Gew.-%.Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS), its synthesis, for example, in the document US-A 3,158,615 is described, preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat US Patents US-A 4,524,009 and US-A 4,639,325 , in the European Patent Application EP-A 0 150 930 and in the Japanese Patent Application JP-A 93 / 339,896 to be discribed. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Weitere brauchbare organische Co-Builder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und wenigstens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten. Derartige Co-Builder werden beispielsweise in der internationalen Patentanmeldung WO 95/20029 beschrieben.Other useful organic co-builders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are used, for example, in the international Patent Application WO 95/20029 described.

Eine weitere Substanzklasse mit Co-Builder-Eigenschaften stellen die Phosphonate dar. Dabei handelt es sich insbesondere um Hydroxyalkan- bzw. Aminoalkanphosphonate. Unter den Hydroalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung als Co-Builder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH = 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutralreagierenden Natriumsalze, z.B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octanatriumsalz der DTPMP, eingesetzt. Als Builder wird dabei aus der Klasse der Phosphonate bevorzugt HEDP verwendet. Die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwermetallbindevermögen. Dementsprechend kann es, insbesondere wenn die erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen auch Bleiche enthalten, bevorzugt sein, Aminoalkanphosphonate, insbesondere DTPMP, einzusetzen oder Mischungen aus den genannten Phosphonaten zu verwenden.Another class of substances with co-builder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroalkane phosphonates, the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH = 9). As aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably used in the form of the neutral-reacting sodium salts, for example as the hexasodium salt of EDTMP or as hepta- and octasodium salt of DTPMP. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferred, especially when the detergent, detergent or cleaner portions according to the invention also contain bleach, to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.

Darüber hinaus können alle Verbindungen, die in der Lage sind, Komplexe mit Erdalkalimetallionen zu bilden, als Co-Builder eingesetzt werden.In addition, all compounds capable of forming complexes with alkaline earth metal ions can be used as co-builders.

Neben den genannten Bestandteilen Tensid und Builder können die erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen einen oder mehrere weitere in Wasch-, Spül- oder Reinigungsmitteln übliche Inhaltsstoffe aus der Gruppe der Bleichmittel, Bleichaktivatoren, Enzyme, Duftstoffe, Parfümträger, Fluoreszenzmittel, Farbstoffe, Schauminhibitoren, Siliconöle, Antiredepositionsmittel, optischen Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren und Korrosionsinhibitoren enthalten.In addition to the constituents surfactant and builder, the detergent, detergent or cleaner portions according to the invention may contain one or more further ingredients customary in detergents, dishwashing or cleaning compositions from the group of bleaches, bleach activators, enzymes, fragrances, perfume carriers, fluorescers, dyes , Foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors.

Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborat-tetrahydrat und das Natriumperborat-monohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Werden Reinigungs- oder Bleichmittel-Zubereitungen für das maschinelle Geschirrspülen hergestellt, so können auch Bleichmittel aus der Gruppe der organischen Bleichmittel eingesetzt werden. Typische organische Bleichmittel sind die Diacylperoxide, wie z.B. Dibenzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Bevorzugte Vertreter sind (a) die Peroxybenzoesäure und ihre ringsubstituierten Derivate, wie Alkylperoxybenzoesäuren, aber auch Peroxy-α-Naphtoesäure und Magnesiummonoperphthalat; (b) die aliphatischen oder substituiert aliphatischen Peroxysäuren, wie Peroxylaurinsäure, Peroxystearinsäure, ε-Phthalimidoperoxy-capronsäure [Phthaloiminoperoxyhexansäure (PAP)], o-Carboxybenzamido-peroxycapronsäure, N-Nonenylamidoperadipinsäure und N-Nonenylamidoper-succinate; und (c) aliphatische und araliphatische Peroxydicarbonsäuren, wie 1,12-Diperoxycarbonsäure, 1,9-Diperoxyazelainsäure, Diperocysebacinsäure, Diperoxybrassylsäure, die Diperoxyphthalsäuren, 2-Decyldiperoxybutan-1,4-disäure, N,N-Terephthaloyl-di(6-aminopercapronsäure).Among the compounds serving as bleaches in water H 2 O 2 , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. When cleaning or bleaching preparations for automatic dishwashing are prepared, it is also possible to use bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. 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 peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxy-caproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidoperuccinate; and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid ).

Als Bleichmittel in Zusammensetzungen für das maschinelle Geschirrspülen können auch Chlor oder Brom freisetzende Substanzen eingesetzt werden. Unter den geeigneten Chlor oder Brom freisetzenden Materialien kommen beispielsweise heterocyclische N-Brom- und N-Chloramide, beispielsweise Trichlorisocyanursäure, Tribromisocyanursäure, Dibromisocyanursäure und/oder Dichlorisocyanursäure (DICA) und/oder deren Salze mit Kationen wie Kalium und Natrium in Betracht. Hydantoinverbindungen, wie 1,3-Dichlor5,5-dimethylhydantoin sind ebenfalls geeignet.As bleaching agents in automatic dishwashing compositions it is also possible to use chlorine or bromine-releasing substances. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Um beim Waschen oder Reinigen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Wasch- und Reinigungsmittel-Portionen eingearbeitet werden. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran.In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C and below, bleach activators can be incorporated into the detergent and cleaner portions. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.

Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können auch sogenannte Bleichkatalysatoren in die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen gemäß der Erfindung eingearbeitet werden. Bei diesen Stoffen handelt es sich um bleichverstärkende Übergangsmetallsalze bzw. Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -carbonylkomple-xe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar.In addition to or in place of the conventional bleach activators, so-called bleach catalysts may also be incorporated into the detergent, rinse or detergent portions of the invention. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere jedoch Cellulase-haltige Mischungen von besonderem Interesse. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate in den erfindungsgemäßen Zusammensetzungen kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,1 bis etwa 2 Gew.-% betragen.Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are enzyme mixtures, for example from 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, but in particular cellulase-containing Mixtures of particular interest. Peroxidases or oxidases have also proved suitable in some cases. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of the enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

Enzyme werden nach dem Stand der Technik in erster Linie einer Reinigungsmittel-Zubereitung zugesetzt, insbesondere einem Geschirrspülmittel zugesetzt, das für den Hauptspülgang bestimmt ist. Nachteil war dabei, daß das Wirkungsoptimum verwendeter Enzyme die Temperaturwahl beschränkte und auch Probleme bei der Stabilität der Enzyme im stark alkalischen Milieu auftraten. Mit den erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen ist es möglich, Enzyme auch im Vorspülgang zu verwenden und damit den Vorspülgang zusätzlich zum Hauptspülgang für eine Enzymeinwirkung auf Verschmutzungen des Spülguts zu nutzen.Enzymes are added according to the prior art primarily to a detergent composition, in particular a dishwashing agent, which is intended for the main rinse. Disadvantage was that the optimum effect of enzymes used limited the choice of temperature and also encountered problems in the stability of the enzymes in a strongly alkaline medium. With the detergent, detergent or cleaner portions according to the invention, it is possible to use enzymes in the pre-wash and thus to use the pre-rinse cycle in addition to the main rinse for an enzyme action on contaminants of the dishes.

Erfindungsgemäß besonders bevorzugt ist also, der für den Vorspülgang vorgesehenen waschaktiven Zubereitung oder Teilportion einer Reinigungsmittel-Portion Enzyme zuzusetzen. Die Enzyme sind weiter bevorzugt für den Einsatz unter den Bedingungen des Vorspülgangs, also beispielsweise in kaltem Wasser, optimiert.It is therefore particularly preferred according to the invention to add enzymes to the detergent-active preparation or partial portion of a detergent portion intended for the pre-wash cycle. The enzymes are more preferably optimized for use under the conditions of the pre-wash cycle, that is, for example, in cold water.

Vorteilhaft können die erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen dann sein, wenn die Enzymzubereitungen flüssig vorliegen, wie sie teilweise im Handel angeboten werden, weil dann eine schnelle Wirkung erwartet werden kann, die bereits im (relativ kurzen und in kaltem Wasser durchgeführten) Vorspülgang eintritt. Auch wenn - wie üblich - die Enzyme in fester Form eingesetzt werden und diese mit einer Umhüllung aus einem wasserlöslichen Material versehen sind, das bereits in kaltem Wasser löslich ist, können die Enzyme bereits vor dem Hauptwaschgang bzw. Hauptreinigungsgang ihre Wirkung entfalten. Vorteil der Verwendung einer Umfassung aus wasserlöslichem Material, insbesondere aus kaltwasserlöslichem Material ist, daß das Enzym/die Enzyme in kaltem Wasser nach Auflösen der Umfassung schnell zur Wirkung kommt/kommen. Damit kann deren Wirkungszeit ausgedehnt werden, was dem Wasch- bzw. Spülergebnis zugute kommt.Advantageously, the detergent, detergent or cleaner portions according to the invention can then be when the enzyme preparations are liquid, as they are sometimes available commercially, because then a rapid effect can be expected, already in (relatively short and carried out in cold water ) Pre-rinse occurs. Even if - as usual - the enzymes are used in solid form and they are provided with a sheath of a water-soluble material that is already soluble in cold water, the enzymes can unfold their effect even before the main wash or Hauptreinigungsgang. Advantage of the use of an enclosure of water-soluble material, in particular of cold water-soluble material is that the enzyme / enzymes in cold water after dissolution of the enclosure comes to effect quickly / come. Thus, their duration of action can be extended, which benefits the washing or rinsing results.

Die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen gemäß der Erfindung enthalten gemäß einer besonders bevorzugten Ausführungsform noch weitere Additive, wie sie aus dem Stand der Technik als Additive für Wasch- bzw. Spül- bzw. Reinigungsmittel-Zubereitungen bekannt sind. Diese können entweder einer oder mehreren, im Bedarfsfall auch allen Teil-Portionen (waschaktiven Zubereitungen) der erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen zugesetzt werden oder - wie in der parallel anhängigen Patentanmeldung Nr. 199 29 098.9 mit dem Titel "Wirkstoff-Portionspackung" beschrieben - in die wasserlöslichen, die Zubereitungen umhüllenden Materialien, also beispielsweise in die wasserlöslichen Folien, aber auch in die erfindungsgemäßen Kapseln oder Coatings eingearbeitet werden.According to a particularly preferred embodiment, the detergent, dishwashing or cleaning agent portions according to the invention also contain further additives, as are known from the prior art as additives for laundry or dishwashing detergent preparations. These can be added either to one or more, if necessary also to all partial portions (washing active preparations) of the detergent, dishwashing or cleaning agent portions according to the invention or, as described in copending patent application no. 199 29 098.9 with the title "active ingredient sachet" described - are incorporated into the water-soluble, the preparations enveloping materials, so for example in the water-soluble films, but also in the capsules or coatings according to the invention.

Eine bevorzugte Gruppe erfindungsgemäß verwendeter Additive sind optische Aufheller. Verwendet werden können hier die in Waschmitteln üblichen optischen Aufheller. Diese werden als wäßrige Lösung oder als Lösung in einem organischen Lösungsmittel der Polymerlösung beigegeben, die in die Folie umgewandelt wird, oder werden einer TeilPortion (waschaktiven Zubereitung) einer Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion in fester oder flüssiger Form zugesetzt. Beispiele für optische Aufheller sind Derivate von Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze. Geeignet sind z. B. Salze der 4, 4'-Bis(2-anilino-4-morpholino1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolamino-Gruppe, eine Methylamino-Gruppe, eine Anilino-Gruppe oder eine 2-Methoxyethylamino-Gruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle in den Teil-Portionen (waschaktiven Zubereitun-gen) der erfindungsgemäßen Wasch- oder Reinigungsmittel-Portionen enthalten sein, z. B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl-)diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl-)diphenyls oder 4-(4-Chlorstyryl-)4'-(2-sulfostyryl-)diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden.A preferred group of additives used in the invention are optical brighteners. Can be used here, the usual in detergents optical brightener. These are added to the polymer solution as an aqueous solution or as a solution in an organic solvent, which is converted into the film, or are added to a TeilPortion (detergent preparation) a detergent, detergent or cleaning agent portion in solid or liquid form. Examples of optical brighteners are derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable z. B. salts of 4, 4'-bis (2-anilino-4-morpholino1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar construction, which instead of the morpholino group Diethanolamino Group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of substituted diphenylstyrene may be present in the partial portions (washing-active preparations) of the washing or cleaning agent portions according to the invention, eg. For example, 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-) biphenyl. Mixtures of the aforementioned brightener can be used.

Eine weitere erfindungsgemäß bevorzugte Gruppe von Additiven sind UV-Schutz-Substanzen. Dabei handelt es sich um Stoffe, die beim Waschprozeß oder bei dem nachfolgenden Weichspülprozeß in der Waschflotte freigesetzt werden und die sich auf der Faser akkumulativ anhäufen, um dann einen UV-Schutz-Effekt zu erzielen. Geeignet sind die unter der Bezeichnung TinosorbR im Handel befindlichen Produkte der Firma Ciba Speciality Chemicals.Another group of additives which is preferred according to the invention are UV protection substances. These are substances that are released during the washing process or in the subsequent fabric softening process in the wash liquor and that accumulate accumulatively on the fiber, in order then to achieve a UV protection effect. Suitable are the products marketed under the name Tinosorb R Ciba Specialty Chemicals.

Weitere denkbare und in speziellen Ausführungsformen bevorzugte Additive sind Tenside, die insbesondere die Löslichkeit der wasserlöslichen Folie beeinflussen können, aber auch deren Benetzbarkeit und die Schaumbildung beim Auflösen steuern können, sowie Schauminhibitoren, aber auch Bitterstoffe, die ein versehentliches Verschlucken solcher Verpackungen oder Teile solcher Verpackungen von Kindern verhindern können.Further conceivable additives, which are preferred in specific embodiments, are surfactants which in particular can influence the solubility of the water-soluble film, but can also control its wettability and foaming on dissolution, as well as foam inhibitors, but also bitter substances, which may inadvertently swallow such packaging or parts of such packaging prevent from children.

Eine weitere erfindungsgemäß bevorzugte Gruppe von Additiven sind Farbstoffe, insbesondere wasserlösliche oder wasserdispergierbare Farbstoffe. Bevorzugt sind hier Farbstoffe, wie sie zur Verbesserung der optischen Produktanmutung in Wasch- und Reinigungsmitteln üblicherweise eingesetzt werden. Die Auswahl derartiger Farbstoffe bereitet dem Fachmann keine Schwierigkeiten, insbesondere da derartige übliche Farbstoffe eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen und gegen Licht sowie keine ausgeprägte Substantivität gegenüber Textilfasern haben, um diese nicht anzufärben. Die Farbstoffe sind erfindungsgemäß in den Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen in Mengen von unter 0,01 Gew.-% zugegen.Another group of additives which is preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Dyes which are customarily used to improve the appearance of the optical product in detergents and cleaners are preferred here. The selection of such dyes is not difficult for a person skilled in the art, especially since such conventional dyes have a high storage stability and insensitivity to the other ingredients of the detergent, detergent or cleaning agent portions and to light and no pronounced substantivity to textile fibers to not stain them. The dyes according to the invention in the detergent, detergent or detergent portions in amounts of below 0.01 wt .-% present.

Eine weitere Klasse von Additiven, die erfindungsgemäß den Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen zugesetzt werden kann, sind Polymere. Unter diesen Polymeren kommen zum einen Polymere in Frage, die beim Waschen oder Reinigen bzw. Spülen Cobuilder-Eigenschaften zeigen, also zum Beispiel Polyacrylsäuren, auch modifizierte Polyacrylsäuren oder entsprechende Copolymere. Eine weitere Gruppe von Polymeren sind Polyvinylpyrrolidon und andere Vergrauungsinhibitoren, wie Copolymere von Polyvinylpyrrolidon, Cellulose-Ether und dergleichen. Nach einer weiteren Ausführungsform der Erfindung kommen als Polymere auch sogenannte Soil Repellents in Frage, wie sie dem Wasch- und Reinigungsmittel-Fachmann bekannt sind und nachfolgend im einzelnen beschrieben werden.Another class of additives which may be added to the detergent, rinse or detergent portions in accordance with the invention are polymers. Among these polymers are on the one hand polymers in question, which show washing or cleaning or rinsing Cobuilder properties, so for example polyacrylic acids, and modified polyacrylic acids or corresponding copolymers. Another group of polymers are polyvinylpyrrolidone and other grayness inhibitors, such as copolymers of polyvinylpyrrolidone, cellulose ethers, and the like. According to a further embodiment of the invention, so-called soil repellents are also suitable as polymers, as are known to the washing and cleaning agent specialist and will be described in detail below.

Eine weitere Gruppe von Additiven sind Bleichkatalysatoren, insbesondere Bleichkatalysatoren für maschinelle Geschirrspülmittel oder Waschmittel. Verwendet werden hier Komplexe des Mangans und des Cobalts, insbesondere mit stickstoffhaltigen Liganden.Another group of additives are bleach catalysts, in particular bleach catalysts for automatic dishwashing detergents or detergents. Here are used complexes of manganese and cobalt, especially with nitrogen-containing ligands.

Eine weitere im Sinne der Erfindung bevorzugte Gruppe von Additiven sind Silberschutzmittel. Es handelt sich hier um eine Vielzahl von meist cyclischen organischen Verbindungen, die ebenfalls dem hier angesprochen Fachmann geläufig sind und dazu beitragen, das Anlaufen von Silber enthaltenden Gegenständen beim Reinigungsprozeß zu verhindern. Spezielle Beispiele können Triazole, Benzotriazole und deren Komplexe mit Metallen wie beispielsweise Mn, Co, Zn, Fe, Mo, W oder Cu sein.Another preferred group of additives within the meaning of the invention are silver protectants. These are a variety of mostly cyclic organic compounds, which are also familiar to the person skilled in the art and contribute to prevent the tarnishing of silver-containing objects in the cleaning process. Specific examples may be triazoles, benzotriazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.

Als weitere erfindungsgemäße Zusätze können die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen auch sogenannte Soil Repellents enthalten, also Polymere, die auf Fasern oder harte Flächen (beispielsweise auf Porzellan und Glas) aufziehen, die Öl- und Fettauswaschbarkeit aus Textilien positiv beeinflussen und damit einer Wiederanschmutzung gezielt entgegenwirken. Dieser Effekt wird besonders deutlich, wenn ein Textil oder ein harter Gegenstand (Porzellan, Glas) verschmutzt wird, das/der bereits vorher mehrfach mit einer erfindungsgemäßen Portion, das diese öl- und fettlösende Komponente enthält, gewaschen oder gereinigt wurde. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxypropylcellulose mit einem Anteil an Methoxy-Gruppen von 15 bis 30 Gew.-% und an Hydroxypropoxy-Gruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder der Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylenglykolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen. Besonders bevorzugt von diesen sind die sulfonierten Derivate der Phthalsäure- und der Terephthalsäure-Polymere.As further additives according to the invention, the detergent, detergent or cleaning agent portions may also contain so-called soil repellents, ie polymers which are applied to fibers or hard surfaces (for example on porcelain and glass), have a positive effect on the oil and grease washability of textiles and thus specifically counteract re-soiling. This effect becomes particularly evident when a textile or a hard object (porcelain, glass) is contaminated, which has already been washed or cleaned several times with a portion according to the invention which contains this oil and fat-dissolving component. Examples of preferred oil and fat dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and of hydroxypropoxy groups of 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Alle diese Additive werden den erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen in Mengen bis höchstens 30 Gew.-%, vorzugsweise 2 bis 20 Gew.-%, zugesetzt. Wie bereits gesagt, kann der Zusatz auch zu einem Material einer wasserlöslichen Umfassung erfolgen, das die oder eine der waschaktive(n) Zubereitung(en) umfaßt. Um die Ausgewogenheit der Rezeptur zu erhalten, ist es dem Fachmann daher möglich, das Kunststoffmaterial für die Umfassung entweder in seinem Gewicht zu steigern, um so den Depot-Effekt der gemäß Erfindung erzielt wird, auszunutzen oder aber die genannten Additive zusätzlich zumindest anteilsweise in der restlichen Portion zu halten. Dies ist jedoch weniger bevorzugt.All of these additives are added to the inventive detergent, detergent or cleaner portions in amounts of at most 30 wt .-%, preferably 2 to 20 wt .-%. As already stated, the addition can also be made to a material of a water-soluble enclosure comprising the or one of the detergent-active preparation (s). To obtain the balance of the recipe, it is therefore possible for the skilled person to increase the plastic material for the enclosure either in its weight so as to achieve the depot effect of the invention, exploit or additionally said additives at least partially in the to keep the remaining portion. However, this is less preferred.

Duftstoffe werden den erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen zugesetzt, um den ästhetischen Gesamteindruck der Produkte zu verbessern und dem Verbraucher neben der technischen Leistung (Weichspülergebnis) ein sensorisch typisches und unverwechselbares Produkt zur Verfügung zu stellen. Als Parfümöle oder Duftstoffe können einzelne Riechstoff-Verbindungen verwendet werden, beispielsweise die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe. Riechstoff-Verbindungen vom Typ der Ester sind beispielsweise Benzyl-acetat, Phenoxyethylisobutyrat, p-t-Butylcyclohexylacetat, Linalylacetat, Dimethylbenz-ylcarbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether. Zu den Aldehyden zählen z. B. lineare Alkanale mit 8 bis 18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lileal und Bourgeonal.Fragrances are added to the detergent, detergent or cleaner portions according to the invention in order to improve the aesthetic overall impression of the products and to provide the consumer in addition to the technical performance (fabric softening result) a sensory typical and distinctive product. As perfume oils or perfumes, individual perfume compounds can be used, for example the synthetic products of the ester type, 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, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. Ethers include, for example, benzyl ethyl ether. The aldehydes include, for. B. linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, purple and bourgeonal.

Zu den Ketonen zählen die lonone, α-Isomethylionon, und Methylcedrylketon. Zu den Alkoholen zählen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol. Zu den Kohlenwasserstoffen zählen hauptsächlich Terpene wie Limonen und Pinen. Bevorzugt werden Mischungen verschie-dener Riechstoffe verwendet, die so aufeinander abgestimmt sind, daß sie gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoff-Gemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind. Beispiele sind Pine-, Citrus-, Jasmin-, Patchouli-, Rosen- oder Ylang-Ylang-Öl. Ebenfalls geeignet sind Muskatöl, Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl und Labdanumöl sowie Orangenblütenöl, Neroliol, Orangenschalenöl und Sandelholzöl.The ketones include the ionone, α-isomethylionone, and methyl cedryl ketone. The alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Preference is given to using mixtures of different odoriferous substances which are adapted to one another in such a way that together they produce an attractive fragrance note. Such perfume oils may also contain natural fragrance mixtures as are available from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.

Üblicherweise liegt der Gehalt an Duftstoffen im Bereich bis zu 2 Gew.-% der gesamten Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion.Usually, the content of perfumes in the range up to 2 wt .-% of the total detergent, detergent or detergent portion.

Die Duftstoffe können direkt in die Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen eingearbeitet werden; es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen, die die Haftung des Parfüms auf der Wäsche verstärken und durch eine langsamere Duftfreisetzung für langanhaltenden Duft der Textilien sorgen. Als solche Trägermaterialien haben sich beispielsweise Cyclodextrine bewährt. Dabei können die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden.The fragrances can be incorporated directly into the detergent, detergent or detergent portions become; but it may also be advantageous to apply the fragrances on carriers that enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles. As such carrier materials, for example, cyclodextrins have been proven. The cyclodextrin-perfume complexes can additionally be coated with other auxiliaries.

Die Parfüm- und Duftstoffe können grundsätzlich in jeder der Teil-Portionen (waschaktive Zubereitungen) der erfindungsgemäßen Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen enthalten sein. Besonders bevorzugt ist es jedoch, daß sie in einem Waschmittel in einer für den Nachwaschgang oder Weichspülgang vorgesehenen Teil-Waschmittel-Portion bzw. in einem Reinigungsmittel, besonders in einem Geschirrspülmittel, in einer für den Nachspülgang bzw. Klarspülgang vorgesehenen Teil-Reinigungsmittel-Portion, speziell Teil-Spülmittel-Portion, enthalten sind. Sie müssen daher erfindungsgemäß von einem nur bei den Bedingungen (insbesondere bei der Temperatur) des Nachwaschgangs bzw. Nachspülgangs wasserlöslichen, bei den Bedingungen (insbesondere bei der Temperatur) der vorangehenden Waschgänge bzw. Spülgänge wasserunlöslichen Material, insbesondere von einer entsprechenden Folie oder Kapsel umfaßt sein. Erfindungsgemäß ist dies beispielsweise mit einem aus mehreren Kammern bestehenden Beutel aus Folien unterschiedlicher Wasserlöslichkeit machbar.The perfumes and fragrances can in principle be contained in each of the partial portions (washing-active preparations) of the detergent, dishwashing or cleaning agent portions according to the invention. However, it is particularly preferred that they are in a detergent in a provided for the post-wash cycle or fabric conditioning portion detergent portion or in a detergent, especially in a dishwashing detergent, in a provided for the final rinse or rinse cycle part-detergent portion, special partial-detergent portion, are included. They must therefore according to the invention of a water-insoluble only in the conditions (especially at the temperature) of the Nachwaschgangs or Nachspülgangs, under the conditions (especially at the temperature) of the previous washes or rinses water-insoluble material, in particular of a corresponding film or capsule , According to the invention this is feasible, for example, with a bag consisting of several chambers made of films of different water solubility.

Gemäß zwei weiteren bevorzugten Ausführungsformen der Erfindung werden Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen mit einem in Innern der in Wasser desintegrierbaren Umhüllung herrschenden Druck des aufschäumenden Gases/der aufschäumenden Gase geschaffen, der mindestens gleich dem Atmosphärendruck ist, der jedoch - weiter bevorzugt - größer als Atmosphärendruck ist. Damit wird in vorteilhafter Weise ermöglicht, daß ein Eindringen von Feuchtigkeit in das Innere der Umhüllung erschwert wird und die im Innern enthaltenen Komponenten der Portion besser vor einem schädigenden Einfluß geschützt ist. Dies kann in einer alternativen Ausführungsform der Erfindung auch erreicht werden, indem man eine oder mehrere in der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion enthaltene Komponenten, die in Gefahr sind, in Gegenwart von Feuchtigkeit einem teilweisen oder vollständigen Aktivitätsverlust zu unterliegen, vor dem Zutritt von Wasser oder Feuchtigkeit durch ein Coating schützt.According to two further preferred embodiments of the invention detergent, detergent or detergent portions are provided with a pressure of the foaming gas / foaming gases which is at least equal to the atmospheric pressure, inside the water-disintegratable casing. is greater than atmospheric pressure. This advantageously makes it possible to prevent the penetration of moisture into the interior of the casing and to better protect the components of the portion contained in the interior from harmful influence. This can also be achieved in an alternative embodiment of the invention by subjecting one or more components contained in the detergent, rinse or detergent portion, which are in danger of undergoing a partial or complete loss of activity in the presence of moisture, before Access of water or moisture by a coating protects.

Im Hinblick auf die Notwendigkeit, die desintegrierbare Umhüllung der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen vor einer vorzeitigen Desintegration durch Wasser zu schützen, sollte der Wassergehalt der Komponenten des Schaum-Formkörpers gemäß der Erfindung beschränkt werden. Er liegt in einer besonders bevorzugten Ausführungsform bei höchstens 15 Gew.-%, weiter bevorzugt bei 1 bis 10 Gew.-%,In view of the need to protect the disintegratable envelope of the detergent, detergent or detergent portions from premature disintegration by water, the water content of the components of the foam body according to the invention should be limited. In a particularly preferred embodiment, it is at most 15% by weight, more preferably from 1 to 10% by weight,

Bei der Herstellung der Umhüllungen der Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen kann man beispielsweise zwei Folien unterschiedlicher Zusammensetzung parallel ablaufen lassen und daraus die aus den beiden verschiedenen Materialien gebildeten Folien zusammensetzen. Die allgemeine Vorgehensweise ist als solche aus dem Stand der Technik wohlbekannt und bedarf keiner weiteren Erläuterung.In the production of the wraps of detergent, detergent or detergent portions, for example, two films of different composition can be run in parallel and composed of the films formed from the two different materials. The general procedure is well known as such from the prior art and needs no further explanation.

Besonders bevorzugt ist ein Verfahren, bei dem die Komponenten der Umhüllung nach der chemischen Synthese (Ausbildung der Bindungen wie vorstehend beschrieben) extrudiert und zu Granulaten verarbeitet werden, wofür - je nach der Temperaturstabilität der beteiligten Verbindungen - auch eine erhöhte Temperatur angewendet werden kann. Die erhaltenen Granulate werden bei Bedarf aufgeschmolzen, gegebenenfalls in Gegenwart eines Plastifiziermittels, und werden dann z. B. nach herkömmlichen, an sich bekannten Verfahren zu Schlauchbeuteln verarbeitet.Particularly preferred is a method in which the components of the envelope after the chemical synthesis (formation of the bonds as described above) are extruded and processed into granules, for which - depending on the temperature stability of the compounds involved - also an elevated temperature can be applied. The resulting granules are melted if necessary, optionally in the presence of a plasticizer, and are then z. B. processed by conventional methods known per se to tubular bags.

Eine weitere, erfindungsgemäß anwendbare Verfahrensweise ist unter der Bezeichnung "rotary die"-Verfahren bekannt. Bei diesem laufen zwei vorher hergestellte Folien, die beispielsweise die vorstehend beschriebenen Charakteristiken haben können, in einem mehr oder weniger spitzen Winkel in den Walzenspalt eines Walzenpaares, dessen Oberflächen mit z. B. halbkugelförmigen Vertiefungen versehen sind. Auf der Höhe des Walzenspaltes wird in die zusammenlaufenden Folien die Mischung aus waschaktiven, spülaktiven oder reinigungsaktiven "Inhalts-"Komponenten eingefüllt, die sich dann - in den beispielsweise halbkugelförmigen Vertiefungen - zu einer mit den Komponenten gefüllten Kugel-Portion mit einer vollständigen Umhüllung aus der Folie formen lassen. Auch dieses Verfahren ist allgemein bekannt und bedarf daher an dieser Stelle keiner weiteren Beschreibung.Another method which can be used according to the invention is known by the term "rotary die" method. In this run two previously produced films, which may for example have the characteristics described above, at a more or less acute angle in the nip of a pair of rollers whose surfaces with z. B. hemispherical depressions are provided. At the height of the nip, the mixture of wash-active, rinse-active or cleaning-active "content" components is filled in the converging films, which then - in the example hemispherical depressions - to a filled with the components spherical portion with a complete envelope of the Form foil. Also, this method is well known and therefore needs no further description at this point.

Die Erfindung betrifft darüber hinaus auch noch ein Waschverfahren, insbesondere Verfahren zum maschinellen Waschen von Wäsche, in dem man das Waschgut mit Wasser und einer oder mehreren Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion(en) gemäß der obigen detaillierten Beschreibung in Kontakt bringt.In addition, the invention also relates to a washing method, in particular a method for machine washing of laundry, in which the laundry is contacted with water and one or more detergent, detergent or detergent portion (s) according to the above detailed description.

Die Erfindung betrifft weiter ein Spülverfahren, insbesondere Verfahren zum maschinellen Spülen von Geschirr, Glas und Metall, in dem man das Spülgut mit Wasser in Kontakt bringt, in dem eine oder mehrere Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion(en) gemäß der obigen detaillierten Beschreibung der Einwirkung des Wassers ausgesetzt sind.The invention further relates to a rinsing method, in particular method for machine rinsing dishes, glass and metal, in which one brings the items to be contacted with water, in which one or more detergent, detergent or detergent portion (s) according to the above detailed description of the action of the water are exposed.

Die Erfindung betrifft abschließend auch ein Reinigungsverfahren, insbesondere Verfahren zur Reinigung harter Oberflächen, in dem man das zu reinigende Gut mit Wasser und einer oder mehreren Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion(en) nach der obigen detaillierten Beschreibung in Kontakt bringt.Finally, the invention also relates to a cleaning method, in particular a method for cleaning hard surfaces, in which the product to be cleaned is brought into contact with water and one or more detergent, detergent or cleaning agent portion (s) according to the above detailed description.

Die Erfindung betrifft weiter auch ein Reinigungsverfahren, insbesondere Verfahren zur Reinigung harter Oberflächen, in dem man das zu reinigende Gut mit Wasser in Kontakt bringt, in dem eine oder mehrere Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion(en) gemäß der obigen detaillierten Beschreibung der Einwirkung des Wassers ausgesetzt sind.The invention further relates to a cleaning method, in particular a method for cleaning hard surfaces, in which the product to be cleaned is brought into contact with water, in which one or more detergent, detergent or cleaning agent portion (s) according to the above detailed description exposed to the action of the water.

Die Erfindung wird weiter durch die nachfolgenden Beispiele erläutert, ohne jedoch auf diese beschränkt zu sein.The invention is further illustrated by, but not limited to, the following examples.

Beispiele 1 bis 5Examples 1 to 5

Es wurden die folgenden Rezepturen für Waschmittel auf an sich bekannem Weg durch zusammengeben und Mischen der in der nachfolgenden Tabelle 1 angegebenen Komponenten hergestellt. Die Rezepturen wurden in wasserlösliche PVA-Folien abgefüllt.The following detergent formulations were prepared in a conventional manner by combining and mixing the components shown in Table 1 below. The formulations were filled into water-soluble PVA films.

Die so hergestellten Waschmittel-Portionen konnten erfolgreich im Waschprozeß verwendet werden und erbrachten hervorragende Waschleistungen. Tabelle 1 Rezepturbeispiele für Waschmittel-Portionen Beispiel Nr. 1 2 3 4 5 ABS-Pulver - 20 15,5 - 20 Sulfopon 1218 G - - - 1,5 - Lutensol AO 7 - - - - 10 Lutensol AO 5 - - - - 15 Lutensol AO 3 - - - - 10 Dehydol LT 7 - 35 27,6 - - Dehydol LS 5 38 - - - - Dehypon LS 54 17,73 21,85 - - - Dehypon LS 52 R - - - 61,6 - Tixogel MP 250 = modifiziertes Schichtsilicat - - - 0,6 - Propylencarbonat 1,14 0,92 - 1,8 0,8 Thixatrol Plus 0,29 0,23 - - 0,2 Perborat-monohydrat 15 - 19,3 14 - TAED-Granulat 5 - - 5,5 - Propylenglykol - - - - 19 Triethylacetylcitrat - - 22,1 - - Tri-Natriumcitrat wasserfrei 15 10 - 10 - Na-SKS-6 - - 6,9 - - Soda - - - - 13,2 Sokalan CP 5-Pulver 3,2 5,2 5,5 - 5 Turpinal 2 NZ (HEDP 2Na-Salz) 1 1,2 1,1 1 1,2 Velvetol 251C = Soil repellant - - - 0,2 - UV-Absorber Tinosorb FD - - 0,1 - - opt Aufheller Tinopal CBS-X 0,1 0,1 - 0,1 0,1 Siliconentschäumer VP1132 0,5 0,5 0,3 0,2 0,5 Parfüm + + + + + Protease + + - + + Amylase + + - + + Farbstoff + + - + + Restsalze Auf 100 Auf 100 Auf 100 Auf 100 Auf 100 The detergent portions thus prepared were successfully used in the washing process and gave excellent washing performance. <b> Table 1 </ b> Formulation examples for detergent portions Example no. 1 2 3 4 5 ABS powder - 20 15.5 - 20 Sulfopone 1218 G - - - 1.5 - Lutensol AO 7 - - - - 10 Lutensol AO 5 - - - - 15 Lutensol AO 3 - - - - 10 Dehydrol LT 7 - 35 27.6 - - Dehydrol LS 5 38 - - - - Dehypon LS 54 17.73 21.85 - - - Dehypon LS 52 R - - - 61.6 - Tixogel MP 250 = modified phyllosilicate - - - 0.6 - propylene carbonate 1.14 0.92 - 1.8 0.8 Thixatrol Plus 0.29 0.23 - - 0.2 Perborate monohydrate 15 - 19.3 14 - TAED granules 5 - - 5.5 - propylene glycol - - - - 19 triethyl - - 22.1 - - Tri-sodium citrate anhydrous 15 10 - 10 - Na-SKS-6 - - 6.9 - - soda - - - - 13.2 Sokalan CP 5 powder 3.2 5.2 5.5 - 5 Turpinal 2 NZ (HEDP 2Na salt) 1 1.2 1.1 1 1.2 Velvetol 251C = Soil repellant - - - 0.2 - UV absorber Tinosorb FD - - 0.1 - - opt Brightener Tinopal CBS-X 0.1 0.1 - 0.1 0.1 Silicone defoamer VP1132 0.5 0.5 0.3 0.2 0.5 Perfume + + + + + protease + + - + + amylase + + - + + dye + + - + + residual salts At 100 At 100 At 100 At 100 At 100

Die angegebenen Handelsnamen stehen für Produkte der folgenden chemischen Zusammensetzung:

ABS-Pulver =
Alkylbenzolsulfonat 90%ig ex Fa. Unger
Sulfopon 1218 G =
C12-C18 Fettalkoholsulfat Granulat ex Fa. Cognis
Lutensol AO7 =
C13C15-Oxoalkoholethoxylat mit 7 Mol EO
Lutensol AO5 =
C13C15-Oxoalkoholethoxylat mit 5 Mol EO
Lutensol AO3 =
C13C15-Oxoalkoholethoxylat mit 3 Mol EO
Dehydol LT7 =
C12-C18-Fettalkoholethoxylat mit 7 Mol EO ex Fa. Cognis
Dehydol LS5 =
C12-C14-Fettalkoholethoxylat mit 5 Mol EO ex Fa. Cognis
Dehypon LS54 =
C12-C14-Fettalkoholethoxylat/propoxylat mit 5 Mol EO und 4 Mol PO ex Fa. Cognis
Dehypon LS 52R =
C12-C14-Fettalkoholethoxylat/propoxylat random mit 5 Mol EO und 2 Mol PO ex Fa. Cognis
Tixogel MP 250 =
organisch modifiziertes Schichtsilikat ex Fa. Südchemie
Thixatrol Plus =
Diamidwachsmischung ex Fa. Rheox
TAED =
Tetraacetyldiamin ex Fa. Warwick
Triacetin =
Glycerintriacetat ex Fa. Cognis
Na-SKS-6 =
ex Fa. Clariant
Sokalan CP 5 =
Polycarboxylat ex Fa. BASF
Turpinal 2NZ =
Hydroxyethandiphosphonsäure-di-Natrium-Salz ex. Fa. Cognis
Velvetol 251 C =
Terephthalsäure-Ethyleglycol-PEG-Polyester ex Fa. Rhodia
Tinopal CBS-X =
opt. Aufheller ex Fa. Ciba
Tinosorb FD =
UV-Absorber ex Fa. Ciba
VP1132 =
Siliconentschäumer ex. Fa. Wacker
Marlox MO 154 =
C12-C14-Fettalkoholethoxylat/propoxylat mit 5 Mol EO und 4 Mol PO ex Fa. Condea
Marlinat 242/90M =
C12-C14 Fettalkoholpolyethylenglycol-(2EO)-ethersulfat - Monoisopropanolaminsalz ex Fa. Condea
LAS-Mipa =
Lineares Alkylbenzolsulfonat Monoisopropylamin-Salz ex Fa. Condea
Edenor K12-18 =
C12-C18 Fettsäure ex Fa. Cognis
The given trade names stand for products of the following chemical composition:
ABS powder logo CNRS logo INIST
Alkylbenzenesulfonate 90% ex Fa. Unger
Sulfopone 1218 G =
C12-C18 fatty alcohol sulfate granules ex Fa. Cognis
Lutensol AO7 logo CNRS logo INIST
C13C15 oxo alcohol ethoxylate with 7 moles EO
Lutensol AO5 logo CNRS logo INIST
C13C15 oxo alcohol ethoxylate with 5 moles EO
Lutensol AO3 logo CNRS logo INIST
C13C15 oxo alcohol ethoxylate with 3 moles EO
Dehydrol LT7 logo CNRS logo INIST
C12-C18 fatty alcohol ethoxylate with 7 moles of EO ex Fa. Cognis
Dehydrol LS5 logo CNRS logo INIST
C12-C14 fatty alcohol ethoxylate with 5 moles of EO ex Fa. Cognis
Dehypon LS54 =
C12-C14 fatty alcohol ethoxylate / propoxylate with 5 moles of EO and 4 moles of PO ex Cognis
Dehypon LS 52R =
C12-C14 fatty alcohol ethoxylate / propoxylate random with 5 moles EO and 2 moles PO ex Cognis
Tixogel MP 250 =
organically modified phyllosilicate ex Fa. Südchemie
Thixatrol Plus
Diamid wax mixture ex Fa. Rheox
TAED =
Tetraacetyldiamine ex Fa. Warwick
Triacetin logo CNRS logo INIST
Glycerol triacetate ex Fa. Cognis
Na-SKS-6 =
ex Fa. Clariant
Sokalan CP 5 =
Polycarboxylate ex Fa. BASF
Turpinal 2NZ =
Hydroxyethanediphosphonic acid di-sodium salt ex. Fa. Cognis
Velvetol 251 C =
Terephthalic acid-ethylene glycol-PEG polyester ex Fa. Rhodia
Tinopal CBS-X =
opt. Brightener ex Fa. Ciba
Tinosorb FD logo CNRS logo INIST
UV absorber ex Fa. Ciba
VP1132 =
Silicone defoamer ex. Fa. Wacker
Marlox MO 154 =
C12-C14 fatty alcohol ethoxylate / propoxylate with 5 moles EO and 4 moles PO ex Fa. Condea
Marlinat 242 / 90M =
C12-C14 fatty alcohol polyethylene glycol (2EO) ether sulfate monoisopropanolamine salt ex Fa. Condea
LAS-Mipa logo CNRS logo INIST
Linear alkylbenzenesulfonate monoisopropylamine salt ex Fa. Condea
Edenor K12-18 =
C12-C18 fatty acid ex Cognis

Beispiele 6 bis 9Examples 6 to 9

Weitere Waschmittel-Rezepturen für Waschmittel ohne Feststoff-Anteil gemäß der nachfolgenden Tabelle 2 wurden wie oben beschrieben hergestellt. Die in der Tabelle angegebenen Komponenten sind die vorstehend aufgeführten chemischen Komponenten.Further detergent formulations for detergents without a solids content according to the following Table 2 were prepared as described above. The components listed in the table are the chemical components listed above.

Die so hergestellten Waschmittel-Portionen konnten erfolgreich im Waschprozeß verwendet werden und erbrachten hervorragende Waschleistungen. Tabelle 2 Komponente / Beispiel Nr. 6 7 8 9 Marlox MO 154 26 26 - 22,5 Lutensol AO 3 - - 18,2 - Lutensol AO 7 - - 40 - LAS-Mipa - - 20 28 Marlinat 242/90M 24 24 - - Edenor K12-18 15 15 - 22,3 Ethanol - - - 3,5 Glycerin - 21,8 - 1 Propylenglycol 8,3 - - 15 Polyethylenglycol 400 20 - - - Triethanolamin - 10,2 - - Monoethanolamin 4,2 - - 6,3 Triacetin - 18,2 - Hydroxyethandiphosphonsäure - 0,5 - - Tinopal CBS-X - - 0,1 0,1 Siliconentschäumer - - + - Parfüm + + + + Protease + + + + Amylase + + + - Cellulase + + + + Farbstoff + + + + The detergent portions thus prepared were successfully used in the washing process and gave excellent washing performance. <b> Table 2 </ b> Component / example no. 6 7 8th 9 Marlox MO 154 26 26 - 22.5 Lutensol AO 3 - - 18.2 - Lutensol AO 7 - - 40 - LAS Mipa - - 20 28 Marlinat 242 / 90M 24 24 - - Edenor K12-18 15 15 - 22.3 ethanol - - - 3.5 glycerin - 21.8 - 1 propylene glycol 8.3 - - 15 Polyethylene glycol 400 20 - - - triethanolamine - 10.2 - - Monoethanolamine 4.2 - - 6.3 triacetin - 18.2 - hydroxyethane - 0.5 - - Tinopal CBS-X - - 0.1 0.1 silicone defoamers - - + - Perfume + + + + protease + + + + amylase + + + - cellulase + + + + dye + + + +

Claims (22)

  1. Laundry detergent, dishwasher detergent or cleaning composition portion comprising a foam moulding with at least one surfactant, optionally together with one or more further laundering, dishwashing or cleaning constituent(s), and at least one gas which is finely divided in the portion, is compatible with the other constituents and does not combine to give a single gas bubble, in at least one coating disintegrable in water, wherein the foam is a dispersion of gas(es) in a relatively small liquid phase, in which the phase comprising the surfactant(s) is the continuous liquid phase and the gas phase is dispersed therein, the proportion of gas, based on the volume, amounting to 20 to 90%.
  2. Laundry detergent, dishwasher detergent or cleaning composition portion according to Claim 1, comprising at least one anionic surfactant.
  3. Laundry detergent, dishwasher detergent or cleaning composition portion according to Claim 1 or Claim 2, comprising, as the anionic surfactant, a surfactant from the group of fatty alcohol sulphate, fatty alcohol ether sulphate, alkylbenzenesulphonate and olefinsulphonate.
  4. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 3, comprising, in addition to one or more anionic surfactant(s), at least one nonionic, cationic and/or zwitterionic surfactant.
  5. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 4, comprising, as the gas, a gas or a mixture of gases from the group of air, nitrogen, oxygen, carbon dioxide, helium, argon, dinitrogen oxide, nitrogen monoxide, fluorocarbon(s) and alkane(s).
  6. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 5, comprising, as the coating disintegrable in water, a water-soluble polymer material.
  7. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 5, comprising, as the coating disintegrable in water, a water-soluble polymer material of different layer thicknesses.
  8. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 5, comprising, as the coating disintegrable in water, a polymer material with regions of good water solubility.
  9. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 8, comprising, as the coating disintegrable in water, a coating composed of optionally acetalized polyvinyl alcohol.
  10. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 8, comprising, as the coating disintegrable in water, a coating composed of polyphosphate.
  11. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 10, having an average diameter of the gas bubbles distributed in the portion in the range of 2 nm to 1 mm.
  12. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 11, having a density in the range of 0.8 to 1.7 g/ml.
  13. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 12, comprising, as additional laundering, dishwashing or cleaning constituents, one or more components from the group consisting of surfactants, builders, bleaches, bleach activators, enzymes, foam inhibitors, dyes and fragrances.
  14. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 13, having a pressure of the gas within the interior of the coating disintegrable in water which is at least equal to atmospheric pressure.
  15. Laundry detergent, dishwasher detergent or cleaning composition portion according to Claim 14, having a pressure of the gas within the interior of the coating disintegrable in water which is greater than atmospheric pressure.
  16. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 15, comprising additionally one or more components in a form protected by a coating before the entry of water or moisture.
  17. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 16, comprising additionally one or more components in the coating disintegrable in water.
  18. Laundry detergent, dishwasher detergent or cleaning composition portion according to one of Claims 1 to 17, comprising water in an amount of at most 15% by weight based on the total weight of the portion, preferably in an amount in the range of 1 to 10% by weight.
  19. Washing process, especially process for machine washing of laundry, in which the laundry is brought into contact with water and one or more laundry detergent portion(s) according to one of Claims 1 to 18.
  20. Dish washing process, especially process for machine washing of dishware, glass and metal, in which the ware is brought into contact with water, in which one or more dishwasher detergent portions according to one of Claims 1 to 18 are exposed to the action of water.
  21. Cleaning process, especially process for cleaning hard surfaces, in which the ware to be cleaned is brought into contact with water and one or more cleaning composition portion(s) according to one of Claims 1 to 18.
  22. Cleaning process, especially process for cleaning hard surfaces, in which the ware to be cleaned is brought into contact with water, in which one or more cleaning composition portion(s) according to one of Claims 1 to 18 is/are exposed to the action of water.
EP01991852A 2001-01-05 2001-12-14 Portion of washing agent, rinsing agent or cleaning agent, containing surfactants Expired - Lifetime EP1348017B2 (en)

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DE10100339A DE10100339A1 (en) 2001-01-05 2001-01-05 Serving detergent, detergent or cleaning agent portion
DE10100339 2001-01-05
PCT/EP2001/014810 WO2002053695A2 (en) 2001-01-05 2001-12-14 Portion of washing agent, rinsing agent or cleaning agent, containing surfactants

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AT (1) ATE319798T1 (en)
DE (2) DE10100339A1 (en)
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DE10233330B4 (en) * 2002-07-22 2007-04-26 Sasol Germany Gmbh Microemulsion containing UV photoprotective filter and / or anti-dandruff agent
DE10246713A1 (en) * 2002-10-07 2004-04-15 Henkel Kgaa Portioned detergent, cleanser, textile care agent or cosmetic in a hollow body, contains an anionic surfactant as an ammonium salt in which the cationic nitrogen has at least one alk(en)yl chain with at least three carbon atoms
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CN116601276A (en) * 2020-12-14 2023-08-15 联合利华知识产权控股有限公司 Composition and method for producing the same
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EP1348017B1 (en) 2006-03-08
EP1348017A2 (en) 2003-10-01
ATE319798T1 (en) 2006-03-15
DE50109183D1 (en) 2006-05-04
ES2260322T3 (en) 2006-11-01
WO2002053695A2 (en) 2002-07-11
ES2260322T5 (en) 2010-03-12
PT1348017E (en) 2006-07-31
DE10100339A1 (en) 2002-07-18

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