[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO2002053695A2 - Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage contenant des tensioactifs - Google Patents

Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage contenant des tensioactifs Download PDF

Info

Publication number
WO2002053695A2
WO2002053695A2 PCT/EP2001/014810 EP0114810W WO02053695A2 WO 2002053695 A2 WO2002053695 A2 WO 2002053695A2 EP 0114810 W EP0114810 W EP 0114810W WO 02053695 A2 WO02053695 A2 WO 02053695A2
Authority
WO
WIPO (PCT)
Prior art keywords
detergent
water
cleaning agent
dishwashing
cleaning
Prior art date
Application number
PCT/EP2001/014810
Other languages
German (de)
English (en)
Other versions
WO2002053695A3 (fr
Inventor
Thomas Escher
Hans-Jürgen Riebe
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7669841&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2002053695(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP01991852A priority Critical patent/EP1348017B2/fr
Priority to DE50109183T priority patent/DE50109183D1/de
Publication of WO2002053695A2 publication Critical patent/WO2002053695A2/fr
Publication of WO2002053695A3 publication Critical patent/WO2002053695A3/fr

Links

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 detergent, detergent or cleaning agent portion containing surfactant and, in particular, relates to a detergent, detergent or cleaning agent portion containing surfactant, which is surrounded by a covering and contains a finely divided gas in its interior.
  • Preparations containing surfactants with finely divided gases contained therein 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
  • hair setting or other conditioning agents can be foamed
  • cleaners for glass surfaces and other hard surfaces for example in the bathroom and / or kitchen
  • cleaners for carpets and upholstery are advantageously applied or applied as foams.
  • cleaning agents or stains have been reported for textiles, which are applied in the form of a foam to areas or stains to be cleaned.
  • the foam allows a certain "service life" of the cleaning agent on the area to be cleaned or on the stain, without having to change the composition of the cleaning agent strongly in the direction of a high viscosity, which was previously a means of cleaning the cleaner Hold at the point where it was desired to act.
  • Foam containing surfactants are also described in WO 97/03176 (The Procter & Gamble Company).
  • the foams also referred to as "mousses" in the cited publication should be easy to dose and soluble, suspendable or emulsifiable in water if they have a bulk density ⁇ 250 g / l, stability (or collapse time) in air under conditions defined by standard measurement have half the foam volume) of> 15 s and have a stability of ⁇ 2 h - also under standard conditions - on water at a temperature of 20 ° C.
  • the publication does not take any measures to see how a low foam stability on water or a quick dissolving, suspending or emulsifying of the foam in water can be achieved.
  • a detergent, detergent or cleaning agent portion containing surfactant the content of which can be quickly dissolved, suspended or emulsified in an aqueous system or in water.
  • this should not be achieved with a foam removed or metered from a dispenser system, but with a detergent, detergent or cleaning agent portion which is fixed with respect to the outer shape, and in particular with a detergent or detergent containing surfactant. or detergent portion surrounded by a wrapper.
  • the present invention thus relates to a detergent, dishwashing or cleaning agent portion, the at least one surfactant, optionally together with one or more further detergent-active or detergent-active ingredient (s), and at least one ingredient that is compatible with the other ingredients finely divided gas, which does not converge into a single gas bubble, in at least one envelope disintegrable in water.
  • the invention also relates to a washing process, a rinsing process and a cleaning process using the detergent, rinsing agent or cleaning agent portion described in detail below.
  • the detergent, detergent or cleaning agent portion comprises at least one surfactant, optionally together with one or more further detergent-active, detergent-active or detergent-active ingredients, in a water-disintegrable coating.
  • One surfactant can be used, or several surfactants that are compatible with one another and preferably complementary in their properties (including their foaming behavior) can be used. All surfactants can belong to one type of surfactant; however, when using several surfactants, surfactants of different types are preferably used, 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 are clearly preferred for economic reasons and because of their performance spectrum and foaming behavior.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Suitable surfactants of the sulfonate type are preferably C thereby . ⁇ g 3 - alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, as obtained, for example, from C 12th 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • Alkanesulfonates which are derived from C 12 are also suitable.
  • esters of 2-sulfofatty acids for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production 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 become.
  • 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.
  • the alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 2 o- Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-alkyl sulfates which, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ® are suitable anionic surfactants.
  • 21 alcohols such as 2-methyl-branched C 9 n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 .
  • 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they can be used in detergent, dishwashing or cleaning agent portions according to the invention in relatively small amounts, for example in amounts of 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 especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can 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 also monoisopropylamine.
  • the anionic surfactants are preferably 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 cleaning agent portions are preferred which contain 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 surfactant (e), each based on the weight of the detergent, detergent or cleaning agent portion.
  • a preferred detergent, dishwashing or cleaning agent portion according to the invention has a soap content which exceeds 0.2% by weight, based on the total weight of the portion.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol (ether) sulfates, preferred portions being 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol (ether) sulfate (e), each based on the weight of the detergent, detergent or cleaning agent portion
  • a detergent, dishwashing or cleaning agent portion according to the invention can be used instead of the anionic surfactant (s) or in addition to the anionic surfactant (s) at least one non-ionic, cationic and / or zwitterionic surfactant.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or propylene oxide (PO) per mole of alcohol, in which the Alcohol residue may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched residues in the mixture, such as are usually present in oxo alcohol residues.
  • EO ethylene oxide
  • PO propylene oxide
  • alcohol ethoxylates and / or propoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms for example from 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 2 -C 4 alcohols with 3 EO or 4 EO, C 9 . 1 alcohol with 7 EO, C 13 . 15 - alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 . ⁇ 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, and mixtures of C 12 .
  • nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkyl polyglycosides which can be used satisfy the general formula RO (G) z , in which R represents a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • the detergent, dishwashing or cleaning agent portions according to the invention can preferably contain alkyl polyglycosides, with APG portions of more than 0.2% by weight, based on the total portion, being preferred.
  • Particularly preferred detergent, detergent or cleaning agent portions according to the Invention contain APG in amounts of 0.2 to 10% by weight, preferably in amounts of 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-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can 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 of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R ⁇ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R 2 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 3 is a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms
  • R 4 is a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C -alkyl or phenyl radicals being preferred
  • [Z] for is a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, 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 international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • cationic surfactants in addition to anionic and nonionic surfactants. They are preferably used as washing performance boosters, whereby only small amounts of cationic surfactants are required. If cationic surfactants are used, they are preferably contained in the foam moldings in amounts of 0.01 to 10% by weight, in particular 0.1 to 3.0% by weight.
  • the portions according to the invention are detergents
  • these usually contain one or more surfactant (s) in total amounts of 5 to 50% by weight, preferably in amounts of 10 to 35% by weight, where partial portions of the detergent, detergent or cleaning agent portions of surfactants according to the invention can be present in larger or smaller amounts.
  • the amount of surfactant is not the same in all portions; rather, partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided.
  • the detergent, dishwashing or cleaning agent portions according to the invention are cleaning agents, in particular dishwashing agents, they usually contain one or more surfactant (s) in total amounts of 0.1 to 10% by weight, preferably in amounts of 0.5 to 5% by weight, with partial portions of the detergent or cleaning agent portions of the invention containing surfactants in greater or lesser amounts.
  • the amount of surfactant is also not in the case of cleaning or dishwashing detergents all portions equal; rather, partial portions with a relatively larger and partial portions with a relatively smaller surfactant content can be provided.
  • Gases suitable for the contents of the detergent, dishwashing or cleaning agent portions according to the invention can in principle be all conceivable gases whose use is economically justifiable, which are not disadvantageous with one or more other components of the detergent, dishwashing or cleaning agent portions according to the invention Interact in ways that are not harmful to the consumer during storage and use of the portions and that have no adverse effect on the laundry, dishes or items to be cleaned.
  • Individual gases 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, for example, come as gases. Pentane or hexane in question.
  • the gases mentioned can be used individually or in any mixtures (also mixtures in any proportions of the gases involved with one another) by two or more of you.
  • the gas (s) form a foam together with other wash-active, rinse-active or cleaning-active components of the detergent, detergent or cleaning agent portions according to the invention.
  • the foam formed, for example, from the surfactant (s) or their solutions in water and the gas (s) is generally a dispersion of gas (s) in a relatively small liquid phase, which comprises the surfactant (s) Phase is the continuous liquid phase and the gas phase is dispersed therein.
  • the gas bubbles in the dispersed phase have a more or less wide distribution of size; the bubble size values can vary in the range of 1 nm to 10 mm due to the manufacturing process.
  • the average bubble diameter is preferably in the range from 2 nm to 1 mm. Of course, smaller or larger gas bubbles can also be realized.
  • the volume of the gas phase (gas fraction), based on the total volume, is advantageously 0.01 to 90%, preferably 0.1 to 50%, more preferably 0.5 to 20%.
  • the foam moldings according to the present invention comprise a water-disintegrable covering.
  • a water-disintegrable covering one becomes complete understood other components of the detergent, detergent or cleaning agent portion and at least mechanically, more preferably also largely gas and moisture proof from the outside environment shielding. This must be disintegrable in water, i.e. either completely dissolve, which is preferred according to the invention, or successively completely or depending on certain parameters such as temperature, electrolyte concentration, pH value, enzyme concentration or other parameters in the washing, rinsing or cleaning liquor partially solve.
  • the detergent, detergent or cleaning agent portions comprise a water-soluble polymer material as a water-disintegrable covering.
  • the detergent, detergent or cleaning agent portion surrounds an envelope made of one or more water-soluble polymer material (s) or that several enclosures made of the same or different materials are contained.
  • the presence of a covering is preferred, which brings advantages in the choice of material and also with regard to the requirement that the water-soluble polymer material must ultimately dissolve without residue in the washing, rinsing or cleaning liquor.
  • the sheath (s) can be made from a single water-soluble polymer material or can be made from several different polymer materials, which may have different solubility in water. In view of the present task, the use of a plurality of different polymer materials can be particularly preferred according to the invention, which will be dealt with separately below.
  • the particular form of the water-desinterable envelope of the detergent, dishwashing or cleaning agent portion of the present invention is not critical.
  • the envelopes can be flat or can also be in the form of capsules or similar shaped bodies. Shaped bodies which ensure a maximum contact area between the liquor and the casing to be disintegrated are of course preferred.
  • the detergent, detergent or cleaning agent portion as disintegrable in water Envelope comprises a water-soluble polymer of different layer thickness.
  • the areas of the covering with a smaller layer thickness dissolve faster than those with a larger layer thickness, so that with the progressive dissolving process of the covering in water a covering with pores or holes is formed.
  • Water can enter the interior of the casing through the pores or holes, gradually dissolve the contents of the detergent, detergent or cleaning agent portion surrounded by the casing, and out through the pores or holes, ie into the washing liquor, washing liquor or cleaning liquor, transport.
  • the detergent, dishwashing or cleaning agent portion comprises a polymer material with areas of good water solubility and with areas of less good water solubility as a water-disintegrable covering.
  • polymer materials which can dissolve more or less completely in the aqueous phase under the given conditions (temperature, pH value, concentration of detergent-active components) are suitable as water-soluble polymer materials.
  • the polymer materials can particularly preferably belong to the groups (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives and mixtures of the materials mentioned.
  • Polyvinyl alcohols are polymers of the general structure
  • polyvinyl alcohols are obtained via polymer-analogous reactions by hydrolysis, technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. These technical processes also make PVAL accessible which contain a predetermined residual proportion of acetate groups.
  • PVALs e.g. Mowiol ® types from Hoechst
  • PVALs are commercially available as white-yellow powders or granules with degrees of polymerization in the range from approx. 500 to 2,500 (corresponding to molar masses from approx. 20,000 to 100,000 g / mol) and have different degrees of hydrolysis, for example 98 to 99 or 87 to 89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of, for example, about 1 to 2 or 11 to 13 mol%.
  • PVAL water solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to desired values.
  • PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be adjusted to the degree, and films of this product series are available, which are soluble in the aqueous phase in all temperature ranges relevant to the application.
  • PVP Polyvinylpyrrolidones
  • PVP are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
  • detergent, dishwashing or cleaning agent portions whose wrapping is made of water-soluble film 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, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations.
  • starch derivatives are also obtainable from starch by polymer-analogous reactions.
  • Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H ⁇ oO 5 ) n and is formally considered a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • Preferred casings made of water-soluble polymer material consist of a polymer with a molecular weight between 5,000 and 500,000 daltons, preferably between 7,500 and 250,000 daltons and in particular between 10,000 and 100,000 daltons.
  • the water-soluble polymer material that forms the sheath preferably has a thickness of 1 to 150 ⁇ m, preferably 2 to 100 ⁇ m, particularly preferably 5 to 75 ⁇ m and in particular 10 to 50 ⁇ m.
  • These water-soluble films made of polymer material can be produced by various manufacturing processes.
  • blowing, calendering and casting processes should be mentioned here.
  • the films are blown from a melt with air through a blow mandrel to form a tube.
  • 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 water has evaporated, cooling is optional and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal.
  • detergent, detergent or cleaning agent portions which, as a water-disintegrable casing, comprise a casing made of a crystalline material, the crystalline material being organic or inorganic in nature.
  • organic crystalline materials are all water-soluble crystalline materials, especially sugar, while typical examples of inorganic crystalline materials are water-soluble salts, especially heavy metal-free salts.
  • Portions of detergent, dishwashing detergent or cleaning agent can be particularly preferred, the coatings of which consist of a crystalline material which can take on a special function in the washing, rinsing or cleaning process if it dissolves in water in the washing liquor, rinsing liquor or cleaning liquor has reached.
  • An example of this are polyphosphates. These can complex and calcium and magnesium ions contained in the water thereby contribute to the fact that softening of the water does not have to be carried out separately (for example by adding salt in the dishwasher).
  • detergent, detergent or cleaning agent portions the density of which - depending on the components (for example the foam) - is in the range from 0.8 to 1.7 g / ml, preferably in the range from 0 , 9 to 1.5 g / ml.
  • Detergent, detergent or cleaning agent portions with such a density can be produced inexpensively, since inexpensive gases or gas mixtures can replace solvents which are otherwise to be used as fillers.
  • the resulting, relatively large volumes of the detergent, dishwashing or cleaning agent portions thus produced have the further advantage that the legal requirement is taken to produce such shaped articles in a size that children cannot swallow the portions ,
  • the detergent, dishwashing or cleaning agent portions according to the invention can also contain one or more further wash-active, rinse-active or cleaning-active component (s).
  • wash-active component or “rinse-active component” or “cleaning-active component” is understood to mean preparations of all conceivable substances relevant in connection with a washing, rinsing or cleaning process.
  • Dishwashing detergents or cleaning agents with their individual components, which are explained in the further course of the description, including active substances such as the surfactants described above (anionic, nonionic, cationic and amphoteric surfactants), builder substances (inorganic and organic .builder substances), bleaching agents (such as, for example Peroxo bleaches and chlorine bleaches), bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and fragrances (perfumes), without the terms being on these substance groups are restricted.
  • active substances such as the surfactants described above (anionic, nonionic, cationic and amphoteric surfactants), builder substances (inorganic and organic .builder substances), bleaching agents (such as, for example Peroxo bleaches and chlorine bleaches), bleach activators, bleach stabilizers, bleach catalysts, enzymes, special polymers (for example those with cobuilder properties), graying inhibitors, dyes and
  • wash-active components are also understood to mean washing aids, rinsing aids or cleaning aids.
  • these are optical brighteners, UV Protective substances, so-called soil repellents, i.e. polymers that counteract re-soiling of fibers or hard surfaces, as well as silver protection agents.
  • Laundry treatment agents such as fabric softener or dishwashing detergent additives such as rinse aid are also considered according to the invention as “wash-active components”, “rinse-active components” or “cleaning-active components”.
  • builders are the most important ingredients in detergents and cleaning agents.
  • the detergent, dishwashing or cleaning agent portions according to the invention may contain builders typically used in washing and cleaning agents, in particular thus 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 + ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1, 9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 • yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but instead at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • An optionally used finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • Zeolite P-type is particularly preferred as zeolite MAP (e.g. commercial product: Doucil A24 from Crosfield).
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builder substances in the detergent, dishwashing or cleaning agent portions according to the invention, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to adjust a lower and milder pH value of detergent and cleaning agent portions according to the invention.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molar masses given 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.
  • GPC gel permeation chromatography
  • the measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights 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. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 2,000 to 10,000 g / mol, particularly preferably 3,000 to 5,000 g / mol, can in turn be preferred from this group. 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the foam moldings according to the invention is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • allylsulfonic acids such as, for example, in EP-B 0 727 448, allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units are preferred, for example those which, according to DE-A 43 00 772, are monomers as salts of acrylic acid and maleic acid and also vinyl alcohol or vinyl alcohol derivatives or according to DE-C 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those described in German patent applications DE-A 43 03 320 and DE-A 44 17 734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A 195 40 086 that, in addition to co-builder properties, they also have a bleach-stabilizing effect.
  • Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A 0 280 223.
  • Preferred polyacetals are derived from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • 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 processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol.
  • 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 capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known in particular from European patent applications EP-A 0 232 202, EP-A 0 427 349, EP-A 0 472 042 and EP-A 0 542 496 and from international patent applications WO 92/18542 , WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608.
  • An oxidized oligosaccharide according to German patent application DE-A 196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • ethylenediamine N, N'-disuccinate (EDDS) the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009 and 4,639,325, in European patent application EP-A 0 150 930 and in Japanese patent application JP-A 93 / 339,896 to be discribed.
  • Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic co-builders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be 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 described, for example, in international patent application WO 95/20029.
  • phosphonates are in particular hydroxyalkane or aminoalkanephosphonates.
  • Preferred aminoalkane phosphonates are examples
  • Ethylenediaminetetramethylenephosphonate (EDTMP)
  • Diethylene triamine pentamethylene phosphonate (DTPMP) as well as their higher homologues in question. They are preferably in the form of the neutral reacting sodium salts, e.g. used as the hexasodium salt of EDTMP or as the hepta- and octasodium salt of DTPMP.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the detergent, detergent or cleaning agent portions according to the invention also contain bleach, it may be preferred to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the detergent, dishwashing or cleaning agent portions according to the invention can contain one or more further ingredients from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, which are customary in detergents, dishwashing agents or cleaning agents , Foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. If cleaning or bleaching preparations for machine dishwashing are produced, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate; (b) the aliphatic or substituted aliphatic peroxyacids such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamido operadipic acid and N-nonenylamide; and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in compositions for machine dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts Cations such as potassium and sodium are considered.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • bleach activators can be incorporated into the detergent and cleaning agent portions.
  • Suitable bleach activators are compounds which form aliphatic peroxocarboxylic acids preferably provide with '1 to 10 C atoms, in particular 2 to 4 C-atoms, and / or optionally substituted perbenzoic acid, can be used.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • bleach catalysts can also be incorporated into the detergent, detergent or cleaning agent portions according to the invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably 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, in particular, however, cellulase-containing mixtures of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the compositions according to the invention can be, for example, approximately 0.1 to 5% by weight, preferably 0.1 to approximately 2% by weight.
  • enzymes are primarily added to a cleaning agent preparation, in particular a dishwashing agent which is intended for the main wash cycle.
  • the disadvantage here was that the optimum effect of the enzymes used restricted the choice of temperature and problems also occurred with the stability of the enzymes in a strongly alkaline environment.
  • the detergent, detergent or cleaning agent portions according to the invention it is possible to use enzymes in the pre-rinse cycle and thus to use the pre-rinse cycle in addition to the main rinse cycle for enzyme action on soiling of the wash ware.
  • enzymes to the washing-active preparation or partial portion of a detergent portion intended for the pre-rinse cycle.
  • the enzymes are furthermore preferably optimized for use under the conditions of the pre-rinse cycle, for example in cold water.
  • the detergent, dishwashing or cleaning agent portions according to the invention can be advantageous if the enzyme preparations are in liquid form, as are partly offered commercially, because then a quick effect can be expected, which has already been carried out in (relatively short and cold water) ) Pre-rinse occurs. Even if - as usual - the enzymes are used in solid form and these are coated with a water-soluble material that is already soluble in cold water, the enzymes can develop their effect before the main wash or main wash cycle.
  • the advantage of using a casing made of water-soluble material, in particular of a material soluble in cold water is that the enzyme (s) quickly comes into effect in cold water after the casing has been dissolved.
  • 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 washing or dishwashing or cleaning agent preparations. These can either be added to one or more portions of the detergent, dishwashing detergent or cleaning agent portions according to the invention, if necessary also to all partial portions (detergent-active preparations) or - as in the copending patent application No. 199 29 098.9 entitled “Active ingredient Portion pack "described - be incorporated into the water-soluble materials encasing the preparations, for example into the water-soluble films, but also into the capsules or coatings of the invention.
  • optical brighteners customary in detergents can be used here. These are added as an aqueous solution or as a solution in an organic solvent to the polymer solution which is converted into the film, or are added to a portion (detergent-active preparation) of a detergent, detergent or cleaning agent portion in solid or liquid form.
  • optical brighteners are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Are suitable for. B.
  • UV protection substances are substances which are released in the washing liquor during the washing process or during the subsequent fabric softening process and which accumulate on the fiber in order to then achieve a UV protection effect.
  • Products from Ciba Specialty Chemicals that are commercially available under the name Tinosorb R are suitable.
  • Other conceivable additives which are preferred in special embodiments are surfactants, which in particular can influence the solubility of the water-soluble film, but can also control its wettability and the foam formation when dissolved, and foam inhibitors, but also bitter substances, which inadvertently swallow such packaging or parts of such packaging prevent from children.
  • dyes in particular water-soluble or water-dispersible dyes.
  • Dyes are preferred here, as are usually used to improve the visual appearance of products in detergents and cleaning agents.
  • the choice of such dyes does not pose any difficulties for the person skilled in the art, in particular since such customary dyes have a high storage stability and insensitivity to the other constituents of the detergent, dishwashing detergent or cleaning agent portions and to light and have no pronounced substantivity to textile fibers in order not to dye them.
  • the dyes are present in the detergent, detergent or cleaning agent portions in amounts of less than 0.01% by weight.
  • polymers Another class of additives that can be added to the detergent, detergent or cleaning agent portions according to the invention are polymers.
  • polymers which show cobuilder properties during washing or cleaning or rinsing, for example polyacrylic acids, also modified polyacrylic acids or corresponding copolymers.
  • Another group of polymers are polyvinyl pyrrolidone and other graying inhibitors such as copolymers of polyvinyl pyrrolidone, cellulose ether and the like.
  • so-called soil repellents as are known to the person skilled in the detergent and cleaning agent and are described in detail below, are also suitable as polymers.
  • Another group of additives are bleaching catalysts, in particular bleaching catalysts for automatic dishwashing detergents or detergents. Complexes of manganese and cobalt are used here, especially with nitrogen-containing ligands.
  • Another preferred group of additives in the sense of the invention are silver protection agents. These are a large number of mostly cyclic organic compounds which are likewise familiar to the person skilled in the art and which help to prevent tarnishing of silver-containing objects during the cleaning process. Specific examples can 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 can also contain so-called soil repellents, that is to say polymers which build up on fibers or hard surfaces (for example on porcelain and glass) and have a positive influence on the oil and fat washability from textiles and thus counteract re-soiling in a targeted manner.
  • soil repellents that is to say polymers which build up on fibers or hard surfaces (for example on porcelain and glass) and have a positive influence on the oil and fat washability from textiles and thus counteract re-soiling in a targeted manner. This effect is particularly evident when a textile or a hard object (porcelain, glass) is soiled that has already been washed or cleaned several times beforehand with a portion according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups 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 the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • All of these additives are added to the detergent, detergent or cleaning agent portions according to the invention in amounts of up to at most 30% by weight, preferably 2 to 20% by weight.
  • the addition can also be made to a material of a water-soluble enclosure, which comprises one or more of the wash-active preparation (s).
  • a person skilled in the art it is therefore possible for a person skilled in the art to either increase the weight of the plastic material for the enclosure, in order to exploit the depot effect which is achieved according to the invention, or to add at least some of the additives mentioned to keep the remaining portion. However, this is less preferred.
  • Fragrances are added to the detergent, detergent or cleaning agent portions according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (fabric softener result), to provide the consumer with a sensorially typical and distinctive product.
  • Individual perfume compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, pt-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate,
  • the ethers include, for example, benzyl ethyl ether.
  • the aldehydes include e.g. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.
  • the ketones include the ionones, ⁇ -isomethyl ionone and methyl cedryl ketone.
  • Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different fragrances are preferably used which are coordinated with one another in such a way that together they produce an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-yang oil.
  • the fragrance content is usually in the range up to 2% by weight of the total detergent, dishwashing or cleaning agent portion.
  • the fragrances can be incorporated directly into the detergent, detergent or cleaning agent portions; However, it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance for the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven themselves as such carrier materials. There the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • the perfumes and fragrances can be contained in each of the partial portions (active detergent preparations) of the detergent, dishwashing or cleaning agent portions according to the invention.
  • they are in a detergent portion in a partial detergent portion intended for the post-wash or softener stage or in a detergent, especially in a dishwashing detergent, in a partial detergent portion provided for the post-rinse stage or rinse cycle, special portion of detergent portion are included.
  • they must therefore be comprised of a material which is water-soluble only under the conditions (in particular at the temperature) of the post-wash or rinse cycle, and water-insoluble under the conditions (in particular at the temperature) of the preceding wash or rinse cycles, in particular by a corresponding film or capsule ,
  • this can be done, for example, with a pouch consisting of a plurality of compartments made of foils of different water solubility.
  • detergent, dishwashing or cleaning agent portions are created with a pressure of the foaming gas / gases in the interior of the water-disintegrable casing which is at least equal to the atmospheric pressure, but which - more preferably - is greater than atmospheric pressure.
  • This advantageously makes it possible for the penetration of moisture into the interior of the casing to be made more difficult and for the components of the portion contained inside to be better protected against a damaging influence.
  • this can also be achieved by adding one or more components contained in the detergent, dishwashing or cleaning agent portion that are at risk of partial or complete loss of activity in the presence of moisture Access to water or moisture protected by a coating.
  • the water content of the components of the foam should Shaped body are limited according to the invention. In a particularly preferred embodiment, it is at most 15% by weight, more preferably from 1 to 10% by weight,
  • a method is particularly preferred in which the components of the casing are extruded after chemical synthesis (formation of the bonds as described above) and processed into granules, for which — depending on the temperature stability of the compounds involved — an elevated temperature can also be used.
  • the granules obtained are melted if necessary, optionally in the presence of a plasticizer, and are then z.
  • a further procedure which can be used according to the invention is known under the name "rotary die".
  • two previously produced foils which for example can have the characteristics described above, run at a more or less acute angle in the nip of a pair of rollers, the surfaces of which At the height of the nip, the mixture of wash-active, rinse-active or cleaning-active “content” components is filled into the converging foils, which then - in the hemispherical depressions, for example - become one with the components Allow the filled portion of ball to be formed from the film with a complete covering, this method is also generally known and therefore does not require any further description at this point.
  • the invention also relates to a washing method, in particular a method for machine washing laundry, in which the items to be washed are brought into contact with water and one or more portions of detergent, dishwashing detergent or cleaning agent) in accordance with the detailed description above.
  • the invention further relates to a washing method, in particular a method for machine washing dishes, glass and metal, in which the items to be washed are brought into contact with water, in which one or more detergent, detergent or cleaning agent portion (s) according to the above detailed description of the effects of water.
  • the invention also relates to a cleaning method, in particular a method for cleaning hard surfaces, in which the material to be cleaned is brought into contact with water and one or more detergent, detergent or cleaning agent portions) according to the detailed description above.
  • the invention further relates to a cleaning method, in particular a method for cleaning hard surfaces, in which the material to be cleaned is brought into contact with water, in which one or more portions of detergent, dishwashing liquid or cleaning agent) according to the above detailed description of the action are exposed to water.
  • Cognis Lutensol AO7 C13C15 oxo alcohol ethoxylate with 7 moles EO
  • Cognis Dehydol LS5 C12-C14 fatty alcohol ethoxylate with 5 mol EO ex.
  • Wacker Marlox MO 154 C12-C14 fatty alcohol ethoxylate / propoxylate with 5 mol EO and
  • Marlinat 242 / 90M C12-C14 fatty alcohol polyethylene glycol (2EO) ether sulfate -
  • LAS-Mipa linear alkylbenzenesulfonate monoisopropylamine salt ex Condea
  • the detergent portions produced in this way could be used successfully in the washing process and produced excellent washing performance.

Landscapes

  • 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)

Abstract

L'invention concerne une portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage qui contient au moins un tensioactif, éventuellement avec au moins un autre composant de lavage, de rinçage ou de nettoyage, et au moins un gaz finement divisé dans la portion, compatible avec les autres composants, qui ne se concentre pas pour former une seule bulle de gaz, dans au moins une enveloppe pouvant se désintégrer dans l'eau. L'invention concerne également un procédé de lavage, de rinçage ou de nettoyage qui peut être mis en oeuvre à l'aide des portions d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage selon l'invention.
PCT/EP2001/014810 2001-01-05 2001-12-14 Portion d'agent de lavage, d'agent de rinçage ou d'agent de nettoyage contenant des tensioactifs WO2002053695A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP01991852A 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
DE50109183T DE50109183D1 (de) 2001-01-05 2001-12-14 Tensidhaltige waschmittel-, spülmittel- oder reinigungsmittelportion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10100339.0 2001-01-05
DE10100339A DE10100339A1 (de) 2001-01-05 2001-01-05 Tensidhaltige Waschmittel-, Spülmittel- oder Reinigungsmittel-Portion

Publications (2)

Publication Number Publication Date
WO2002053695A2 true WO2002053695A2 (fr) 2002-07-11
WO2002053695A3 WO2002053695A3 (fr) 2002-11-07

Family

ID=7669841

Family Applications (1)

Application Number Title Priority Date Filing Date
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

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)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004016233A1 (fr) * 2002-07-22 2004-02-26 Sasol Germany Gmbh Microemulsion contenant des filtres anti-uv et/ou des agents antipelliculaires
WO2007105162A1 (fr) * 2006-03-14 2007-09-20 Scott Allan Kuehl Materiau a base de mousse destine a eteindre les incendies
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
EP2486117B1 (fr) 2009-10-09 2017-07-19 Reckitt Benckiser Finish B.V. Composition détergente
WO2022128369A1 (fr) * 2020-12-14 2022-06-23 Unilever Ip Holdings B.V. Composition
WO2023025761A1 (fr) * 2021-08-25 2023-03-02 Unilever Ip Holdings B.V. Composition de détergent
CN116601276A (zh) * 2020-12-14 2023-08-15 联合利华知识产权控股有限公司 组合物
WO2023237412A1 (fr) 2022-06-09 2023-12-14 Unilever Ip Holdings B.V. Composition détergente liquide concentrée

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10246713A1 (de) * 2002-10-07 2004-04-15 Henkel Kgaa Portioniertes Flüssigwaschmittel
WO2022128370A1 (fr) * 2020-12-14 2022-06-23 Unilever Ip Holdings B.V. Composition

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB955896A (en) * 1962-02-09 1964-04-22 Colgate Palmolive Co Bleaching packets
US3198740A (en) * 1960-06-22 1965-08-03 Procter & Gamble Packet of water-soluble film of polyvinyl alcohol filled with detergent composition
US3277009A (en) * 1961-10-03 1966-10-04 Gen Aniline & Film Corp Water-soluble package and method for making and using same
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
EP0337568A2 (fr) * 1988-04-11 1989-10-18 Colgate-Palmolive Company Article détergent
EP0388105A2 (fr) * 1989-03-13 1990-09-19 Dai-Ichi Kogyo Seiyaku Co., Ltd. Détergent préalablement dosé
WO1992001037A1 (fr) * 1990-07-03 1992-01-23 Ecolab Inc. Article de film soluble dans l'eau contenant un systeme detersif
FR2666349A1 (fr) * 1990-08-28 1992-03-06 Nln Sa Detergent en sachet-dose pour le nettoyage de la vaisselle.
US5234615A (en) * 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
DE19521140A1 (de) * 1995-06-09 1996-12-12 Weber Rudolf Dipl Ing Wasserlösliche Beutel mit Wandmittelbestandteilen (Baukastenprinzip)
US6133214A (en) * 1998-07-15 2000-10-17 Henkel Kommanditgesellschaft Auf Aktien Portioned detergent composition
WO2001000781A1 (fr) * 1999-06-25 2001-01-04 Henkel Kommanditgesellschaft Auf Aktien Emballage-portion de matiere active

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4126563A (en) † 1974-07-08 1978-11-21 Graham Barker Composition for treating fabrics, method for making and using the same
US4176079A (en) † 1977-04-20 1979-11-27 The Procter & Gamble Company Water-soluble enzyme-containing article
US4374035A (en) * 1981-07-13 1983-02-15 The Procter & Gamble Company Accelerated release laundry bleach product
US4619710A (en) * 1984-04-20 1986-10-28 Badger Pharmacal, Inc. Disposer cleaner
US4973416A (en) † 1988-10-14 1990-11-27 The Procter & Gamble Company Liquid laundry detergent in water-soluble package
EP0846754A1 (fr) † 1996-12-06 1998-06-10 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
CA2296354C (fr) † 1997-11-10 2003-05-27 The Procter & Gamble Company Composition de detergent
WO1999064555A1 (fr) * 1998-06-05 1999-12-16 The Procter & Gamble Company Compositions detergentes en forme de granules, de poudres et de comprimes contenant une substance particulaire gazeifiee
JP2002528654A (ja) † 1998-10-23 2002-09-03 ザ、プロクター、エンド、ギャンブル、カンパニー 布地色保護方法
GB2355008A (en) † 1999-10-05 2001-04-11 Procter & Gamble Foam matrix coating material
BR0014549A (pt) † 1999-10-05 2002-06-04 Procter & Gamble Artigo elástico
GB2355014A (en) † 1999-10-05 2001-04-11 Procter & Gamble Foams and compositions containing these foams

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3198740A (en) * 1960-06-22 1965-08-03 Procter & Gamble Packet of water-soluble film of polyvinyl alcohol filled with detergent composition
US3277009A (en) * 1961-10-03 1966-10-04 Gen Aniline & Film Corp Water-soluble package and method for making and using same
GB955896A (en) * 1962-02-09 1964-04-22 Colgate Palmolive Co Bleaching packets
US4115292A (en) * 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US5234615A (en) * 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
EP0337568A2 (fr) * 1988-04-11 1989-10-18 Colgate-Palmolive Company Article détergent
EP0388105A2 (fr) * 1989-03-13 1990-09-19 Dai-Ichi Kogyo Seiyaku Co., Ltd. Détergent préalablement dosé
WO1992001037A1 (fr) * 1990-07-03 1992-01-23 Ecolab Inc. Article de film soluble dans l'eau contenant un systeme detersif
FR2666349A1 (fr) * 1990-08-28 1992-03-06 Nln Sa Detergent en sachet-dose pour le nettoyage de la vaisselle.
DE19521140A1 (de) * 1995-06-09 1996-12-12 Weber Rudolf Dipl Ing Wasserlösliche Beutel mit Wandmittelbestandteilen (Baukastenprinzip)
US6133214A (en) * 1998-07-15 2000-10-17 Henkel Kommanditgesellschaft Auf Aktien Portioned detergent composition
WO2001000781A1 (fr) * 1999-06-25 2001-01-04 Henkel Kommanditgesellschaft Auf Aktien Emballage-portion de matiere active

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1348017A2 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004016233A1 (fr) * 2002-07-22 2004-02-26 Sasol Germany Gmbh Microemulsion contenant des filtres anti-uv et/ou des agents antipelliculaires
WO2007105162A1 (fr) * 2006-03-14 2007-09-20 Scott Allan Kuehl Materiau a base de mousse destine a eteindre les incendies
EP2486117B1 (fr) 2009-10-09 2017-07-19 Reckitt Benckiser Finish B.V. Composition détergente
EP2486117B2 (fr) † 2009-10-09 2022-12-21 Reckitt Benckiser Finish B.V. Composition détergente
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
WO2022128369A1 (fr) * 2020-12-14 2022-06-23 Unilever Ip Holdings B.V. Composition
CN116601276A (zh) * 2020-12-14 2023-08-15 联合利华知识产权控股有限公司 组合物
WO2023025761A1 (fr) * 2021-08-25 2023-03-02 Unilever Ip Holdings B.V. Composition de détergent
WO2023237412A1 (fr) 2022-06-09 2023-12-14 Unilever Ip Holdings B.V. Composition détergente liquide concentrée

Also Published As

Publication number Publication date
ES2260322T3 (es) 2006-11-01
EP1348017B1 (fr) 2006-03-08
DE10100339A1 (de) 2002-07-18
EP1348017B2 (fr) 2009-11-11
PT1348017E (pt) 2006-07-31
DE50109183D1 (de) 2006-05-04
EP1348017A2 (fr) 2003-10-01
ES2260322T5 (es) 2010-03-12
WO2002053695A3 (fr) 2002-11-07
ATE319798T1 (de) 2006-03-15

Similar Documents

Publication Publication Date Title
EP1194523B1 (fr) Portion de detergent ou nettoyant
WO2001019948A1 (fr) Agent de rinçage
WO2001000781A1 (fr) Emballage-portion de matiere active
DE19941480B4 (de) Wasch- oder Reinigungsmittel-Portion mit wasserdurchlässiger Umfassung
DE10066036B4 (de) Kompartiment-Hohlkörper
WO2001007560A1 (fr) Portion d'agent de lavage ou de nettoyage et emballage pour agent de lavage ou de nettoyage
DE19961661A1 (de) Wirkstoffportionspackung
EP1348017B1 (fr) Portion d'agent de lavage, d'agent de rincage ou d'agent de nettoyage contenant des tensioactifs
DE10032612A1 (de) Klarspülmittel II
DE10225116A1 (de) Maschinelles Geschirrspülmittel mit verbessertem Glaskorrosionsschutz II
EP1005524A1 (fr) Corps moules parfumes a haute dose
WO2002062937A1 (fr) Produits detergents et nettoyants possedant des microparticules fines qui renferment des constituants de produits nettoyants
WO2001029173A1 (fr) Detergents ou nettoyants a base de gaz inerte en portions
WO2001040432A1 (fr) Doses de detergent ou de produit de nettoyage emballees
DE10100338A1 (de) Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen mit funktioneller Umhüllung
DE10053329A1 (de) Enzymhaltige Umhüllung für Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen
DE20019913U1 (de) Klarspülmittel II
WO2001029174A1 (fr) Detergents ou nettoyants en portions contenant un delitant
DE20023763U1 (de) Kompartiment-Hohlkörper
WO2001032821A1 (fr) Portion de produit de lavage ou de nettoyage contenant un agent de blanchiment
WO2007131529A1 (fr) Agent de traitement pour textiles
DE10062857A1 (de) Waschmittel-, Spülmittel- oder Reinigungsmittel-Portionen mit transparenter Umhüllung
WO2003044082A1 (fr) Polymeres a solubilite amelioree
DE10327878A1 (de) Beschichtete plastische Silikate
WO2003054133A1 (fr) Composes de silicate de soude en tant que materiaux enveloppants

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AU BR CA CN CZ DZ HU ID IL IN JP KR MX PL RO RU SG SI SK UA US ZA

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

AK Designated states

Kind code of ref document: A3

Designated state(s): AU BR CA CN CZ DZ HU ID IL IN JP KR MX PL RO RU SG SI SK UA US ZA

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2001991852

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2001991852

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP

WWG Wipo information: grant in national office

Ref document number: 2001991852

Country of ref document: EP