EP1348017B2 - Portion d'agent de lavage, d'agent de rincage ou d'agent de nettoyage contenant des tensioactifs - Google Patents

Portion d'agent de lavage, d'agent de rincage ou d'agent de nettoyage contenant des tensioactifs 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
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EP
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Prior art keywords
detergent
water
cleaning composition
composition portion
cleaning
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EP01991852A
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German (de)
English (en)
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EP1348017B1 (fr
EP1348017A2 (fr
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Thomas Escher
Hans-Jürgen Riebe
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/18—Glass; Plastics
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/42—Application 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (22)

  1. Portion d'agent de lavage, de rinçage ou de nettoyage, comprenant un corps façonné en mousse comprenant au moins un agent tensioactif, le cas échéant avec un ou plusieurs constituants actifs en lavage, en rinçage ou en nettoyage et au moins un gaz compatible avec les autres constituants, finement réparti dans la portion, qui ne se rassemble pas sous forme d'une seule bulle de gaz, dans au moins une enveloppe pouvant être désintégrée dans l'eau, dans laquelle la mousse est une dispersion de gaz dans une phase liquide relativement petite, la phase comprenant le ou les agents tensioactifs étant la phase liquide continue et une phase gazeuse étant dispersée dans celle-ci, la proportion de gaz par rapport au volume représentant de 20 à 90%.
  2. Portion d'agent de lavage, de rinçage ou de nettoyage selon la revendication 1, comprenant au moins un agent tensioactif anionique.
  3. Portion d'agent de lavage, de rinçage ou de nettoyage selon la revendication 1 ou la revendication 2, comprenant, comme agent tensioactif anionique un agent tensioactif du groupe constitué par les sulfates d'alcool gras, les éthersulfates d'alcool gras, les alkylbenzènesulfonates et les oléfinesulfonates.
  4. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 3, comprenant en plus d'un ou de plusieurs agents tensioactifs anioniques au moins un agent tensioactif non ionique, cationique et/ou zwittérionique.
  5. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 4, comprenant, en tant que gaz, un gaz ou un mélange de gaz du groupe constitué par l'air, l'azote, l'oxygène, le dioxyde de carbone, l'hélium, l'argon, le protoxyde d'azote, le monoxyde d'azote, les hydrocarbures fluorés et les alcanes.
  6. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 5, comprenant, comme enveloppe pouvant être désintégrée dans l'eau un matériau polymère soluble dans l'eau.
  7. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 5, comprenant comme enveloppe pouvant être désintégrée dans l'eau un matériau polymère soluble dans l'eau présentant différentes épaisseurs de couche.
  8. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 5, comprenant comme enveloppe pouvant être désintégrée dans l'eau un matériau polymère avec des zones présentant une bonne solubilité dans l'eau.
  9. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 8, comprenant comme enveloppe pouvant être désintégrée dans l'eau une enveloppe en poly(alcool vinylique) le cas échéant acétalisé.
  10. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 8, comprenant comme enveloppe pouvant être désintégrée dans l'eau une enveloppe en polyphosphate.
  11. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 10 présentant un diamètre moyen des bulles de gaz réparties dans la portion dans la plage de 2 nm à 1 mm.
  12. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 11 avec une densité dans la plage de 0,8 à 1,7 g/ml.
  13. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 12, contenant comme constituants supplémentaires actifs en lavage, en rinçage ou en nettoyage un ou plusieurs composants du groupe constitué par les agents tensioactifs, les builder, les agents de blanchiment, les activateurs de blanchiment, les enzymes, les inhibiteurs de mousse, les colorants et les parfums.
  14. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 13 avec une pression du gaz régnant à l'intérieur de l'enveloppe pouvant être désintégrée dans l'eau qui est au moins égale à la pression atmosphérique.
  15. Portion d'agent de lavage, de rinçage ou de nettoyage selon la revendication 14 avec une pression du gaz régnant à l'intérieur de l'enveloppe pouvant être désintégrée dans l'eau qui est supérieure à la pression atmosphérique.
  16. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 15, contenant en outre un ou plusieurs composants sous une forme protégée par un revêtement contre l'entrée d'eau ou d'humidité.
  17. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 16, contenant en outre un ou plusieurs composants dans l'enveloppe pouvant être désintégrée dans l'eau.
  18. Portion d'agent de lavage, de rinçage ou de nettoyage selon l'une quelconque des revendications 1 à 17, contenant de l'eau en une quantité d'au maximum 15% en poids, par rapport au poids total de la portion, de préférence en une quantité dans la plage de 1 à 10% en poids.
  19. Procédé de lavage, en particulier procédé pour le lavage en machine de linge, dans lequel on met en contact le linge avec de l'eau et une ou plusieurs portions d'agent de lavage selon l'une quelconque des revendications 1 à 18.
  20. Procédé de rinçage, en particulier procédé pour le lavage en machine de vaisselle, de verre et de métal, dans lequel on met en contact les objets à rincer avec de l'eau, dans lequel une ou plusieurs portions d'agent de rinçage selon l'une quelconque des revendications 1 à 18 sont soumises à l'effet de l'eau.
  21. Procédé de nettoyage, en particulier procédé pour le nettoyage de surfaces dures dans lequel on met en contact les objets à nettoyer avec de l'eau et une ou plusieurs portions d'agent de nettoyage selon l'une quelconque des revendications 1 à 18.
  22. Procédé de nettoyage, en particulier procédé pour le nettoyage de surfaces dures dans lequel on met les objets à nettoyer en contact avec de l'eau, dans lequel une ou plusieurs portions d'agent de nettoyage selon l'une quelconque des revendications 1 à 18 sont soumises à l'effet de l'eau.
EP01991852A 2001-01-05 2001-12-14 Portion d'agent de lavage, d'agent de rincage ou d'agent de nettoyage contenant des tensioactifs Expired - Lifetime EP1348017B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10100339A DE10100339A1 (de) 2001-01-05 2001-01-05 Tensidhaltige Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion
DE10100339 2001-01-05
PCT/EP2001/014810 WO2002053695A2 (fr) 2001-01-05 2001-12-14 Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage contenant des tensioactifs

Publications (3)

Publication Number Publication Date
EP1348017A2 EP1348017A2 (fr) 2003-10-01
EP1348017B1 EP1348017B1 (fr) 2006-03-08
EP1348017B2 true EP1348017B2 (fr) 2009-11-11

Family

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EP01991852A Expired - Lifetime EP1348017B2 (fr) 2001-01-05 2001-12-14 Portion d'agent de lavage, d'agent de rincage ou d'agent de nettoyage contenant des tensioactifs

Country Status (6)

Country Link
EP (1) EP1348017B2 (fr)
AT (1) ATE319798T1 (fr)
DE (2) DE10100339A1 (fr)
ES (1) ES2260322T5 (fr)
PT (1) PT1348017E (fr)
WO (1) WO2002053695A2 (fr)

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DE10233330B4 (de) * 2002-07-22 2007-04-26 Sasol Germany Gmbh Mikroemulsion enthaltend UV-Lichtschutzfilter und/oder Antischuppenmittel
DE10246713A1 (de) * 2002-10-07 2004-04-15 Henkel Kgaa Portioniertes Flüssigwaschmittel
WO2007105162A1 (fr) * 2006-03-14 2007-09-20 Scott Allan Kuehl Materiau a base de mousse destine a eteindre les incendies
GB0917740D0 (en) 2009-10-09 2009-11-25 Reckitt Benckiser Nv Detergent composition
CN106635470A (zh) * 2016-09-30 2017-05-10 东莞市蓝鲸化工科技有限公司 车身表面免水清洁去污防污保护喷剂及其制备方法
US20240060008A1 (en) * 2020-12-14 2024-02-22 Conopco, Inc., D/B/A Unilever Composition
WO2022128369A1 (fr) * 2020-12-14 2022-06-23 Unilever Ip Holdings B.V. Composition
WO2023025740A1 (fr) * 2021-08-25 2023-03-02 Unilever Ip Holdings B.V. Composition détergente
WO2023237412A1 (fr) 2022-06-09 2023-12-14 Unilever Ip Holdings B.V. Composition détergente liquide concentrée

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WO1999024547A1 (fr) † 1997-11-10 1999-05-20 The Procter & Gamble Company Composition de detergent
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WO2001025393A1 (fr) † 1999-10-05 2001-04-12 The Procter & Gamble Company Produit elastique
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Also Published As

Publication number Publication date
ES2260322T3 (es) 2006-11-01
WO2002053695A2 (fr) 2002-07-11
DE10100339A1 (de) 2002-07-18
ATE319798T1 (de) 2006-03-15
WO2002053695A3 (fr) 2002-11-07
ES2260322T5 (es) 2010-03-12
EP1348017B1 (fr) 2006-03-08
DE50109183D1 (de) 2006-05-04
PT1348017E (pt) 2006-07-31
EP1348017A2 (fr) 2003-10-01

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