EP1567631B1 - Detergent liquide a plusieurs composants - Google Patents

Detergent liquide a plusieurs composants Download PDF

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Publication number
EP1567631B1
EP1567631B1 EP03767666A EP03767666A EP1567631B1 EP 1567631 B1 EP1567631 B1 EP 1567631B1 EP 03767666 A EP03767666 A EP 03767666A EP 03767666 A EP03767666 A EP 03767666A EP 1567631 B1 EP1567631 B1 EP 1567631B1
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EP
European Patent Office
Prior art keywords
acid
sub
compositions
washing agent
composition
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EP03767666A
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German (de)
English (en)
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EP1567631A1 (fr
Inventor
Horst-Dieter Speckmann
Hermann Jonke
Helga Werner
Johannes Zipfel
Sabine Fabian
Eva-Maria Wikker
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046—Insoluble free body dispenser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Rigid or semi-rigid containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material or by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/04—Multi-cavity bottles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
    • B65D81/3283—Cylindrical or polygonal containers, e.g. bottles, with two or more substantially axially offset, side-by-side compartments for simultaneous dispensing
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present patent application relates to a liquid detergent composition consisting of at least two partial compositions held separately from each other.
  • a difficulty then arises, however, in that the minimum of the reactivity of the chemically active ingredients is not at the same pH, and therefore stabilization via the pH is not normally possible for all ingredients at the same time.
  • a further difficulty arises from the fact that the lowest possible minimum in the minimum of reactivity storage must change conditions of use of the agent, so that the reactivity of the chemically active ingredients under the washing conditions can be higher and they are thus enabled, their contribution to the washing result.
  • a liquid detergent which consists of at least two liquid partial compositions which are stored separately in a container with at least two chambers and at least one of which has an imine or oxaziridine bleach activator and at least one other an alkalizing agent, wherein at least one of the partial compositions contains a peroxygen bleach, and each part composition has a pH for stability.
  • the alkalizing agent increases the pH of the final composition so that bleach and bleach activator effectively react with each other.
  • the international patent application WO 94/15465 describes a two-pack system comprising on the one hand an aqueous aliphatic peracid and the second of an aqueous hydrogen peroxide solution containing corrosion inhibitor, peracid and / or hydrogen peroxide stabilizer. The two solutions are combined to produce a disinfectant.
  • German patent application DE 100 24 251 A1 It is proposed to store a bleaching agent which consists in a first component of an aqueous 1 to 40 weight percent aqueous imidoperoxycarboxylic acid dispersion and in a second component of a first component activating substance mixture separately in a double-chamber bottle and the two components only to mix during use.
  • the second component also referred to as pH-regulating buffer solution in this document, consists of an aqueous solution of sodium bicarbonate and sodium carbonate which has been thickened with the aid of methylcellulose.
  • the separation of the sub-compositions is preferably carried out in that they are in multi-chamber containers, wherein the number of chambers of the container corresponds to the number of sub-compositions and in each case one of the chambers only one of the sub-compositions is present.
  • Another object of the invention is therefore a combination of a liquid detergent composition defined herein, which consists of at least two, preferably exactly two liquid sub-compositions, and a multi-chamber container, wherein the number of chambers of the container corresponds to the number of sub-compositions and in each one of the chambers each one of the sub-compositions is present.
  • the chambers are either carried out separately and connected to each other or made integral with each other.
  • Each of the chambers has at least one, preferably exactly one outlet, from which the component composition can escape from the respective chamber. This can be done by the action of gravity, ie inclining the multi-chamber container so that the sub-compositions of the liquid detergent composition flow out.
  • the multi-chamber container is compressible, so that the outflow of the partial compositions can be accelerated by an example exerted by the hand of an operator pressure on the multi-chamber container.
  • the chambers may also be provided with pumping devices, which in the simplest case may consist of a tubular element which extends from just above the bottom of the chamber to its outlet.
  • the outlet of the each chamber may be formed as a simple opening, it may be provided with spouts or, for example, include a discharge or spray nozzle.
  • the outlet of a liquid detergent container is provided with a closure cap, in the case of the present invention, the outlet of each chamber may be provided with its own cap or the cap may be formed so that it can close several, in particular all outlets of the multi-chamber container.
  • the multi-chamber container may for ease of handling by the user grips or handles have, wherein the handle may be attached to one or more chambers, or may be part of a chamber, or more chambers each forming a handle and they are joined together so that the Multi-chamber container can be taken by the user's hand.
  • the multi-chamber container causes the partial compositions of the liquid detergent composition to mix only after leaving the outlets, for example, when pouring into a conventional dispensing compartment of a washing machine or into the washing drum of such a washing machine to be introduced with dispenser, or when spraying the agent on a textile surface requiring cleaning, for example in the context of laundry pretreatment.
  • the chambers of the multi-chamber container each have at least one, preferably exactly one ejection nozzle, and that the nozzle channels of the ejection nozzles are aligned substantially parallel to each other, but each case an asymmetrical to the total flow cross-section arranged cross-sectional constriction exhibit.
  • the cross-sectional constrictions are preferably arranged on the mutually facing sides of the nozzle channels in such a way that the partial compositions emerging under pressure have a mutually directed twist.
  • the application field of the application area may be, for example, a soiling on a laundry.
  • the multi-chamber container may consist of a material with a return characteristic and / or a provision in the Have original shape supporting shaping. In particular, it is recommended that the multi-chamber container be made of an elastically resetting plastic material.
  • the material from which the multichamber container is formed may be, for example, a polyolefin, in particular polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC) or polyethylene terephthalate (PET), in particular glycol-modified polyethylene terephthalate (PETG). , act. If desired, the material may also be one or more colors, wherein the individual chambers of the multi-chamber container may have the same color or the same colors or different colors among each other. Multi-chamber containers are for example from the international patent applications WO 02/22467 A1 . WO 97/23087 A1 . WO 96/12648 A1 . WO 95/16023 A1 . WO 91/04923 , the German patent application DE 32 20 693 A1 , the German utility model DE G 93 16 583 U1 or the Dutch patent specification NL 1 018 746 known.
  • PP polypropylene
  • PE polyethylene
  • PVC polyvinyl chloride
  • the liquid detergent composition of the invention does not contain a bleach activator.
  • the first part composition consists essentially of water and the organic peracid, which may be dissolved in water, but more preferably at least partially undissolved present in finely divided form.
  • the first part composition may also contain the corresponding organic peracid organic acid and small amounts of conventional stabilizers for the peracid, for example, from the European patent application EP 1 074 607 known vinyl ether-maleic acid copolymers as dispersants and / or from the European patent specification EP 0 497 337 known nonionic surfactants and / or complexing agents, which counteract the metal-catalyzed decomposition of the peracid.
  • the content of organic peracid is preferably 1 wt .-% to 25 wt .-%, in particular 2 wt .-% to 20 wt .-% and particularly preferably 3% to 15 wt .-%, each based on the first part composition.
  • the organic peracid may carry aliphatic and / or cyclic, including heterocyclic and / or aromatic, radicals.
  • peroxoic acid peroxoacetic acid, peroxopropionic acid, peroxohexanoic acid, peroxobenzoic acid and their substituted derivatives such as m-chloroperoxobenzoic acid, the mono- or di-peroxophthalic acids, 1,12-diperoxododecanedioic acid, Nonylamidoperoxoadipic acid, 6-hydroxyperoxohexanoic acid, 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid, N, N'-terephthaloyl-di-6-aminoperoxohexanoic acid, and mixtures of these.
  • m-chloroperoxobenzoic acid the mono- or di-peroxophthalic acids
  • Preferred peracids include 6-phthalimidoperoxohexanoic acid.
  • the first part composition preferably has an acidic pH, in particular in the range from pH 2.5 to pH 6 and more preferably from pH 3 to pH 5, which results from the presence of the organic peracid or can be adjusted by adding system-compatible acids ,
  • the first part composition contains no hydrogen peroxide. By this is meant to include at most such a small amount of hydrogen peroxide, which may eventually result from hydrolysis of the organic peracid.
  • the first part composition in one embodiment of the invention may contain anionic acid compatible with the organic peracid in amounts of up to 50% by weight, in particular 10% by weight to 30% by weight, based in each case on the first part composition.
  • the second part composition or each of the further optional subcompositions contains at least one enzyme, is free from oxidative bleaching agents and preferably also has surfactant, in particular anionic and / or nonionic surfactant. Mixtures of nonionic and anionic surfactant are particularly preferred, wherein the second part composition or any of the further sub-compositions may contain a mixture of nonionic and anionic surfactant or at least the second part composition nonionic surfactant and at least one further part composition may contain anionic surfactant.
  • enzyme mixtures may be included in the partial compositions or more enzymes may be distributed to the second and further partial compositions such that each of them contains only one enzyme.
  • the second part composition contains 8 wt .-% to 70 wt .-%, in particular 20 wt .-% to 55 wt .-% water.
  • the surfactants optionally present in the second sub-composition or sub-compositions include, in particular, anionic surfactants and nonionic surfactants, although cationic surfactants and amphoteric surfactants may also be suitable.
  • anionic surfactants preference is given to using one or more substances from the group of the carboxylic acids, the sulfuric acid half esters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
  • Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotinic acid (melissic acid) and the unsaturated Sezies 9c Hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c-oct
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14, 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 "), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C 12 , 15 wt .-% C 14, 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 , 1 wt .-% C 18 "), tallow fatty acid (about 3 Wt% C 14 , 26 wt% C 16 , 2 wt% C 16 -, 2 w
  • soybean oil fatty acid (about 2 wt .-% C 14 , 15 wt .-% C 16 , 5 G % by weight C, 8 , 25% by weight C 18- , 45% by weight C 18 " , 7% by weight C 18"' ).
  • Sulfuric acid semi-esters of longer-chain alcohols are also anionic surfactants and can be used in the context of the present invention.
  • Their alkali metal salts, in particular sodium salts, the so-called fatty alcohol sulfates are commercially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to give the corresponding alkyl sulfuric acids and subsequently neutralized.
  • the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
  • the quantitatively most important industrial process for the production of Fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in specific cascade, falling film, or tube bundle reactors.
  • alkyl ether sulfuric acids which can be used according to the invention are the alkyl ether sulfuric acids whose salts, the so-called alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
  • Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
  • Alkane sulfonic acids and oil finsulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
  • Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • alkanesulfonic acids Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
  • the reaction with unreacted paraffin yields an alkyl radical and the alkylpersulfonic acid which in an alkyl peroxysulfonyl radical and a hydroxyl radical decompose.
  • the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
  • Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
  • alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • linear alkylbenzenes which in turn are accessible from linear olefins.
  • C 8-16 preferably C 9-13 , alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content of less than 5 wt Alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C 8-16 -, preferably C 9-13 -alkyl benzene sulfonic acids used have a content of 2-phenyl isomer of less than 22% by weight. , based on the alkylbenzenesulfonic acid.
  • the said anionic surfactants may be used alone or in admixture with each other, mixtures of fatty acids and ether sulfates, in particular in weight ratios of 5: 1 to 1: 5, preferably 2: 1 to 1: 2, being particularly preferred.
  • the anionic surfactants described above in their acid form are usually used partially or fully neutralized. Suitable cations for the anionic surfactants are, in addition to the alkali metals (in particular Na and K salts), ammonium and mono-, di- or triethanolammonium ions. Instead of mono-, di- or triethanolamine, the analogous representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • 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 of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO Low-foaming nonionic surfactants may also be used which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical
  • each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical
  • the radical R 1 has an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • agents according to the invention are preferred in which R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • R 1 in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • alkylene oxide unit which may be contained in the nonionic surfactants in an alternating manner with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 , are suitable.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants which can be 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.
  • 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.
  • polyhydroxy fatty acid amides of the following formula 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 in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants are the end-capped poly (oxyalkylated) surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • nonionic surfactants mixtures of alkoxylated fatty alcohols and alkyl glycosides are preferred. In them, the weight ratio of which is preferably 10: 1 to 1: 2, especially 10: 1 to 2: 1.
  • the weight ratio of anionic surfactant to nonionic surfactant is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. It is preferred if surfactant in amounts of 7.5 wt .-% to 70 wt .-%, particularly preferably from 10 wt .-% to 60 wt -% and in particular from 12.5 wt .-% to 50 wt. -%, is included.
  • the amounts and ratios indicated in one embodiment of the invention relate to the individual (second or further) partial compositions and, in a further embodiment, to the entire composition according to the invention.
  • Proteases amylase, lipase, cellulase and / or hemicellulase such as mannanase belong in particular to the enzymes contained in the second partial composition or the further partial compositions.
  • These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.
  • agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight, based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method (bisquinonic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method ( Gornall AG, CS Bardawill and MM David, J Biol. Chem. 177 (1948), pp. 751-766 ).
  • the first part composition is free of enzymes.
  • the second agent contains Partial composition protease, amylase and cellulase. In this case, further partial compositions (ie, except the first one) may be completely absent.
  • subtilisin type examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
  • the subtilisins 147 and 309 are sold under the trade names Esperase ® or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 (known from the international patent application WO 91/02792 ) derived from the name BLAP ® variants, in particular in the international patent applications WO 92/21760 . WO 95/23221 and in the German. patent applications DE 101 21 463 and DE 101 53 792 to be discribed. Other useful proteases from various Bacillus sp. and B. gibsonii are from the German patent applications DE 101 62 727 . DE 101 63 883 . DE 101 63 884 and DE 101 62 728 out.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym ®, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners.
  • the enzyme from B. licheniformis is obtainable from Novozymes under the name Termamyl ® and available from Genencor under the name Purastar® ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes. Furthermore, those in the international patent application WO 02/10356 disclosed ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and in the international patent application PCT / EP01 / 13278 highlighted cyclodextrin glucanotransferase (CGTase) from B.
  • CTTase cyclodextrin glucanotransferase
  • agaradherens DSM 9948
  • those belonging to the sequence space of ⁇ -amylases, in the German patent application DE 101 31 441 is defined.
  • fusion products of said molecules can be used, for example those from the German patent application DE 101 38 753 known.
  • the enhancements available under the trade names Fungamyl.RTM ® by Novozymes of ⁇ -amylase from Aspergillus niger and A. oryzae which are.
  • Another commercial product is, for example, the amylase LT® .
  • compositions according to the invention may contain lipases and / or cutinases.
  • lipases include, for example, the lipases originally obtainable from Humicola lanuginosa ( Thermomyces lanuginosus ) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens .
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. Genencor, for example, can be used for lipases or cutinases whose initial enzymes are originally from Pseudomonas mendocina and Fusarium solanii have been isolated.
  • compositions according to the invention may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.
  • EG endoglucanase
  • a useful fungal, endoglucanase (EG) -rich cellulase preparation and developments thereof are offered by Novozymes under the trade name Celluzyme ®.
  • the products are also available from Novozymes Endolase® and Carezyme ® based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® and Renozyme ®. Likewise, those in the international patent application WO 97/14804 disclosed cellulases used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ® and Biotouch ®. Other commercial products of AB Enzymes are Econase ® and Ecopulpo ® . Other suitable cellulases from Bacillus sp.
  • CBS 670.93 and CBS 669.93 are described in the international patent application WO 96/34092 disclosed, the Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ® is available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and IndiAge ® Neutra.
  • compositions of the invention may contain other enzymes, which are summarized under the term hemicellulases.
  • Suitable mannanases are available for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Robapec ® B1 from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, United States.
  • a suitable ⁇ -glucanase from a B. alcalophilus is that of the international patent application WO 99/06573 out.
  • the obtained from B. subtilis ⁇ -glucanase is available under the name Cereflo ® from Novozymes.
  • the enzymes used in agents of the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • compositions according to the invention may contain enzyme stabilizers for this purpose.
  • enzyme stabilizers are reversible protease inhibitors.
  • benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including, in particular, derivatives with aromatic groups, for example according to the international patent application WO 95/12655 ortho-substituted, according to the international patent application WO 92/19707 metasubstituted and according to the US patent US 5,972,873 para-substituted phenylboronic acids or their salts or esters.
  • WO 98/13460 and the European patent application EP 583 534 For the same purpose, peptide aldehydes, that is, oligopeptides with reduced C-terminus, are disclosed.
  • Suitable peptidic protease inhibitors include ovomucoid (according to international patent application WO 93/00418 ) and leupeptin; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , for example from the European patent application EP 0 378 261 or the international patent application WO 97/05227 known, such as succinic acid, other dicarboxylic acids or salts of said acids.
  • end-capped fatty acid amide alkoxylates are disclosed.
  • Certain organic acids used as builders are capable of, as in the international patent application WO 97/18287 discloses additionally stabilizing a contained enzyme.
  • Lower aliphatic alcohols such as ethanol or propanol, but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other useful enzyme stabilizers.
  • EP 0 965 268 also protects di-glycerol phosphate against denaturation by physical influences.
  • peptide-aldehyde stabilizers is according to the international patent application WO 98/13462 increased by the combination with boric acid and / or boric acid derivatives and polyols and according to the international patent application WO 98/13459 further enhanced by the additional use of divalent cations, such as calcium ions.
  • the second partial composition or the further partial compositions may contain all ingredients customary in liquid detergents which do not unduly interact negatively with the abovementioned.
  • these include, for example, builder materials, heavy metal chelating agents, non-aqueous water-miscible solvents, thickeners, grayness inhibitors, foam control agents, color transfer inhibitors, antimicrobial agents, optical brighteners, dyes, and fragrances.
  • further ingredients may also be included in the first part composition, provided that they do not unreasonably affect the storage stability of the peracid component.
  • Builder materials which may be present in the compositions according to the invention are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 .yH 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 sheet silicates are described, for example, in the European patent application EP 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 process described in International Patent Application WO 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 delay dissolution are and have secondary washing properties.
  • the dissolution delay compared with 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 yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most 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 to the conventional water glasses, are described, for example, in the German patent application DE 44 00 024 described. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the optionally used finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is marketed by CONDEA Augusta SpA under the trade name VEGOBOND AX ⁇ ® and by the formula (n Na 2 O 1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 to 2.5) SiO 2 ⁇ ( 3.5-5.5) H 2 O can be described.
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 microns (volume distribution, measuring method, for example by means of Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.
  • phosphates as builders are possible, unless such use should not be avoided for environmental 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), if such 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 typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 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 can in principle be determined by means of gel permeation chromatography (GPC), a UV detector being used. The measurement is carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. These data deviate significantly from the molecular weight data in which polystyrenesulfonic acids are used as standard, the molar masses measured against polystyrenesulfonic acids generally being significantly higher.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol.
  • the short-chain polyacrylates the molecular weights of 2000 to 10,000 g / mol, and more preferably from 3000 to 5000 g / mol.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and 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.
  • the polymers may also allylsulfonic acids, such as from the European patent EP 0 727 448 B1 known allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • biodegradable polymers of more than two different monomer units for example those described in German Patent Application DE 43 00 772 A1 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the German patent DE 42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • organic builders polymeric aminodicarboxylic acids, their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred that they also have a bleach-stabilizing effect in addition to Cobuilder properties.
  • Further suitable builder substances are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as in the European patent application EP 0 280 223 described, can be obtained.
  • 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.
  • Further suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, 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 from 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 has a DE of 100 , is.
  • DE dextrose equivalent
  • Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.
  • a preferred dextrin is in the European patent application EP 0 703 292 A1 described.
  • 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 methods of their preparation are, for example, from the European patent applications EP 0 232 202 . EP 0 427 349 . EP0472042 and EP 0 542 496 as well as the 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 known.
  • Oxydisuccinates and other derivatives of disuccinates are also other suitable builder materials.
  • ethylenediamine-N, N'-disuccinate (EDDS) the synthesis of which, for example, in US 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 4,524,009 .
  • Such builders are described, for example, in the international patent application WO 95/20029 described.
  • Builder substances, and among these, in particular water-soluble materials, are preferably present in agents according to the invention in amounts of from 1% by weight to 20% by weight, in particular from 1% by weight to 8% by weight, the first part composition preferably being free of builder materials.
  • the complexing agents for heavy metals optionally contained in the compositions include phosphoric acid, aminocarboxylic acids and optionally functionally modified phosphonic acids, for example hydroxy- or aminoalkanephosphonic acids.
  • useful aminocarboxylic acids include nitrilotriacetic acid, methylglycinediacetic acid and diethylenetriaminepentaacetic acid.
  • phosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or the disodium salt or tetrasodium salt of this acid, 2-phosphonobutane-1,2,4-tricarboxylic acid or the trisodium salt of this acid, ethylenediamine tetramethylenephosphonic acid (EDTMP).
  • the N-oxides corresponding to the nitrogen-containing compounds mentioned can also be used.
  • the useful complexing agents include ethylenediamine-N, N'-disuccinic acid (EDDS).
  • EDDS ethylenediamine-N, N'-disuccinic acid
  • the complexing agents mentioned in their acid form can be used as such or in the form of their alkali metal salts, in particular the sodium salts. Preference is given to the use of mixtures of aminocarboxylic acids with phosphonic acids.
  • Complexing agents for heavy metals are preferably contained in agents according to the invention in amounts of from 0.05% by weight to 1% by weight, it being possible for them to be present in the first part composition and / or in the second or the further part compositions.
  • Non-aqueous solvents which can be used in the compositions according to the invention originate, for example, from the group of monohydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range intended for use.
  • the solvents are selected from ethanol, n- or 1-propanol, the butanols, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl, or ethyl ether, di-isopropylene glycol monomethyl, or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1 Butoxyethoxy-2-propanol, 3-methyl-3-me
  • nonaqueous solvents can be used in the liquid detergents according to the invention in amounts of up to 40% by weight, preferably from 0.5 to 20% by weight and in particular from 1% by weight to 10% by weight Solvents, the amounts of those which also act as enzyme stabilizers, are included.
  • Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils.
  • silicone oils are used.
  • Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether ,
  • nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether
  • 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 of these.
  • Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic
  • Optical brighteners can be added to the compositions according to the invention in order to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting the ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure with the yellowness of the grayed or yellowed wash White results.
  • Suitable compounds are derived, for example from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalsimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • the optical brighteners are usually used in amounts between 0.05 and 0.3 wt .-%, based on the finished composition.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions
  • compositions according to the invention may contain synthetic crease inhibitors which, however, preferably do not contain the first part composition are included.
  • synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • compositions of the invention may contain antimicrobial agents.
  • antimicrobial agents For controlling microorganisms, the compositions of the invention may contain antimicrobial agents.
  • antimicrobial agents Here one differentiates depending upon antimicrobial Spectrum and mechanism of action between bacteriostats and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercuriacetate, wherein the compounds according to the invention can be used entirely without these compounds.
  • Thickening agents which can be used in the partial compositions according to the invention are, for example, those from the class of polyurethanes, polyacrylates which may also be present at least partially crosslinked, polyacrylamides and / or polysaccharides or their derivatives.
  • an optionally modified polymer of saccharides such as glucose, galactose, mannose, gulose, altrose, allose, etc.
  • a water-soluble xanthan as it is commercially available, for example, under the product names Kelzan®, Rhodopol®, Ketrol® or Rheozan®.
  • xanthan is meant a polysaccharide corresponding to that produced by the bacterial strain Xanthomonas campestris from aqueous solutions of glucose or starch ( J. Biochem. Microbiol. Technol. Engineer. Vol. III (1961), pp. 51 to 63 ). It consists essentially of glucose, mannose, glucuronic acid and their acetylation products and also contains minor amounts of chemically bound pyruvic acid.
  • water-soluble polysaccharide derivatives as can be obtained, for example, by alkoxylation with, for example, ethylene oxide, propylene oxide and / or butylene oxide, by alkylation with, for example, methyl halides and / or dimethyl sulfate, by acylation with carboxylic acid halides or by saponifying deacetylation from the corresponding polysaccharides, is possible .
  • Thickening agents are present in the inventive compositions in amounts of preferably 0.05 wt .-% to 2.5 wt .-%, in particular 0.1 wt .-% to 2 wt .-%, wherein the proportion is not the same in all sub-compositions has to be big.
  • the individual partial compositions are preferably used in equal proportions. This can be done in a simple manner by adjusting the viscosity of the partial compositions and / or the type of outflow openings of the chambers of the multi-chamber container, in particular the Adjustment of the diameter of the outflow openings, can be achieved so that the user of the agent receives by simply pouring or expressing the multi-chamber container a readily usable amount, for example, the necessary for a wash in a washing machine amount of liquid detergent. It is preferred if the first and / or each further part composition has a viscosity (determined, for example, using a Brookfield rotary viscometer, spindle No. 3, 20 revolutions per minute, room temperature) in the range from 700 mPa.s to 1000 mPa.s.
  • surfactant- and enzyme-containing partial compositions T1 and T2 were prepared. These were each filled into a chamber of a polyethylene chamber composed of two chambers of equal size (each volume 750 ml), and the second chamber of the bottle was filled with the same amount of a 5% by weight aqueous phthalimidoperoxohexanoic acid preparation P (Eureco® L, manufacturer Ausimont). filled.

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Claims (18)

  1. Composition d'agent de lavage liquide, contenant un agent tensioactif en des quantités de 7,5% en poids à 80% en poids, constituée par au moins deux compositions partielles contenant de l'eau, conservées séparément l'une de l'autre, une première composition partielle contenant un peracide organique et une deuxième composition partielle contenant une enzyme.
  2. Composition d'agent de lavage selon la revendication 1, caractérisée en ce que la première composition partielle contient 1% en poids à 25% en poids, en particulier 2% en poids à 20% en poids de peracide organique.
  3. Composition d'agent de lavage selon la revendication 1 ou 2, caractérisée en ce que la première composition partielle contient de l'acide 6-phtalimidoperoxohexanoïque.
  4. Composition d'agent de lavage selon l'une quelconque des revendications 1 à 3, caractérisée en ce que la première composition partielle présente un pH acide, en particulier dans la plage de 2,5 à 6 et de manière particulièrement préférée de 3 à 5.
  5. Composition d'agent de lavage selon l'une quelconque des revendications 1 à 4, caractérisée en ce que la deuxième composition partielle ou chacune des autres compositions partielles éventuelles contient un agent tensioactif, en particulier un agent tensioactif anionique et/ou non-ionique.
  6. Composition d'agent de lavage selon la revendication 5, caractérisée en ce que la deuxième composition partielle ou chacune des autres compositions partielles éventuelles contient un mélange d'agent tensioactif non-ionique et anionique ou au moins la deuxième composition partielle contient un agent tensioactif non-ionique et au moins une autre composition partielle contient un agent tensioactif anionique.
  7. Composition d'agent de lavage selon la revendication 6, caractérisée en ce que le rapport pondéral d'agent tensioactif anionique à agent tensioactif non-ionique est situé entre 10:1 et 1:10, de préférence entre 7,5:1 et 1:5 et en particulier entre 5:1 et 1:2.
  8. Composition d'agent de lavage selon l'une quelconque des revendications 1 à 7, caractérisée en ce qu'elle contient l'agent tensioactif en des quantités de 7,5% en poids à 70% en poids, de préférence de 10% en poids à 60% en poids et en particulier de 12,5% en poids à 50% en poids.
  9. Composition d'agent de lavage selon l'une quelconque des revendications 1 à 8, caractérisée en ce que la deuxième composition partielle contient des protéases, des amylases et des cellulases.
  10. Composition d'agent de lavage selon l'une quelconque des revendications 1 à 9, caractérisée en ce que la deuxième composition partielle est alcaline.
  11. Composition d'agent de lavage selon l'une quelconque des revendications 1 à 10, caractérisée en ce qu'elle se trouve dans un conteneur à plusieurs chambres, le nombre de chambres du conteneur correspondant au nombre de compositions partielles et seulement une des compositions partielles étant à chaque fois présente dans une des chambres.
  12. Combinaison d'une composition d'agent de lavage selon l'une quelconque des revendications 1 à 10 et d'un conteneur à plusieurs chambres, le nombre de chambres du conteneur correspondant au nombre de compositions partielles et seulement une des compositions partielles étant à chaque fois présente dans une des chambres.
  13. Combinaison selon la revendication 12, caractérisée en ce que les chambres du conteneur à plusieurs chambres sont soit réalisées séparément et reliées les unes aux autres, soit réalisées en une pièce les unes avec les autres.
  14. Combinaison selon la revendication 12 ou 13, caractérisée en ce que chacune des chambres présente au moins une, en particulier exactement une, sortie, via laquelle peut sortir la composition partielle de chaque chambre.
  15. Combinaison selon l'une quelconque des revendications 12 à 14, caractérisée en ce que le conteneur à plusieurs chambres peut être écrasé par compression.
  16. Combinaison selon l'une quelconque des revendications 12 à 14, caractérisée en ce que les chambres du conteneur à plusieurs chambres sont équipées de dispositifs à pompe.
  17. Combinaison selon l'une quelconque des revendications 12 à 16, caractérisée en ce que les chambres du conteneur à plusieurs chambres présentent au moins une, de préférence exactement une, buse d'expulsion et en ce que les canaux à buse des buses d'expulsion sont orientés de manière essentiellement parallèle les uns aux autres tout en présentant toutefois un rétrécissement de section disposé asymétriquement par rapport à la section d'écoulement totale.
  18. Combinaison selon l'une quelconque des revendications 12 à 17, caractérisée en ce que le conteneur à plusieurs chambres est constitué par un matériau présentant une caractéristique de résilience et/ou présente une forme favorisant un retour à la forme de départ.
EP03767666A 2002-12-06 2003-11-26 Detergent liquide a plusieurs composants Revoked EP1567631B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10257387 2002-12-06
DE10257387A DE10257387A1 (de) 2002-12-06 2002-12-06 Mehrkomponenten-Flüssigwaschmittel
PCT/EP2003/013285 WO2004053042A1 (fr) 2002-12-06 2003-11-26 Detergent liquide a plusieurs composants

Publications (2)

Publication Number Publication Date
EP1567631A1 EP1567631A1 (fr) 2005-08-31
EP1567631B1 true EP1567631B1 (fr) 2013-01-16

Family

ID=32336133

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03767666A Revoked EP1567631B1 (fr) 2002-12-06 2003-11-26 Detergent liquide a plusieurs composants

Country Status (6)

Country Link
US (1) US20050227896A1 (fr)
EP (1) EP1567631B1 (fr)
AU (1) AU2003292123A1 (fr)
DE (1) DE10257387A1 (fr)
ES (1) ES2400460T3 (fr)
WO (1) WO2004053042A1 (fr)

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Also Published As

Publication number Publication date
DE10257387A1 (de) 2004-06-24
EP1567631A1 (fr) 2005-08-31
ES2400460T3 (es) 2013-04-10
WO2004053042A1 (fr) 2004-06-24
AU2003292123A1 (en) 2004-06-30
US20050227896A1 (en) 2005-10-13

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