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WO2007033743A1 - Composition de lessive ou de detergent en portions - Google Patents

Composition de lessive ou de detergent en portions Download PDF

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Publication number
WO2007033743A1
WO2007033743A1 PCT/EP2006/008273 EP2006008273W WO2007033743A1 WO 2007033743 A1 WO2007033743 A1 WO 2007033743A1 EP 2006008273 W EP2006008273 W EP 2006008273W WO 2007033743 A1 WO2007033743 A1 WO 2007033743A1
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WO
WIPO (PCT)
Prior art keywords
phase
weight
water
container
acid
Prior art date
Application number
PCT/EP2006/008273
Other languages
German (de)
English (en)
Inventor
Matthias Sunder
Salvatore Fileccia
Ingrid Kraus
Dieter Nickel
Peter Schmiedel
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO2007033743A1 publication Critical patent/WO2007033743A1/fr

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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
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid compositions
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof

Definitions

  • the present invention relates to portioned detergents or cleaning compositions, to processes for the preparation of portioned detergents or cleaning compositions and to the use of these portioned medium servings
  • Detergents or cleaning agents are now available to the consumer in a wide variety of forms. In addition to washing powders and granules, this range also includes detergent concentrates in the form of extruded or tableted compositions. These solid, concentrated or compacted forms are characterized by a reduced volume per dosage unit and thus lower the dosage Costs of packaging and transport In particular, the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing
  • solid or liquid detergents or cleaners which have a water-soluble or water-dispersible coating, such as films, are increasingly being described in recent years.
  • These compositions like the tablets, are characterized by a simplified dosage, because they can be dosed together with the water-soluble wrapper in the washing machine or dishwasher, on the other hand, but at the same time also allow the preparation of liquid or powdered detergents or cleaners, which are characterized over the compact data by a better resolution and faster effectiveness in this way
  • To individual dosing units packaged cleaning agents can be easily by inserting one or more bags directly into the washing machine or dishwasher or in the Einspulhunt, or by inserting into aries timmte amount of water, for example, in a bucket or hand basin or sink, be dosed
  • compositions of different consistency such as a powder or granules and one or morelvesstuckige solids (tablets, lozenges, balls, solidified melts, etc.), a liquid and one or morelvesstuckige solids or gel and one or more curtainsstuckige solids in a container and If the individual compositions are not separated by intermediate walls, the composition with the higher flowability will be distributed around the less adherent body, ie powders, liquids and gels will undermine large-scale solids.
  • the attractiveness of the portioned agent will decrease
  • the large-stucco solid can still be seen with the eye, but it is still possible to visualize the multifunctional properties of the product, but the agent does not look very attractive, as clear contours are no longer recognizable inside the container and the pu If the flowable composition has been distributed evenly and the large-solid mass is no longer recognizable by the packaging with the eye, the multifunctional advantages of the portioned agent become apparent to the consumer no longer perceived Notwithstanding these aesthetic problems, medium portions containing two different compositions within a compartment also suffer from a loss of washing or cleaning activity over time.
  • the process should be inexpensive and an optically attractive product which does not have the problems described above , deliver
  • portioned detergent or cleaner compositions in which a solidified melt comprising sugar, is adhesively bonded to a water-soluble or water-dispersible packaging, has a high degree of attractiveness and washing and cleaning compositions of the prior art in the washing or cleaning performance exceeds
  • the present invention is a portioned washing or makeskarzusammenam- composition
  • a water-soluble or water-dispersible container b) at least a first, adhesively bonded to Behaltermatenal, solid phase and c) at least one further phase, wherein the first phase a solidified melt which contains sugar
  • the solidified melt contains at least one washing or cleaning-active component
  • the first phase (s) and the second phase (s) are contained in the same compartment of the water-soluble or water-dispersible container It may be preferred that the container has only one compartment. Also the filling of a compartment of a multi-compartment container with at least one first and at least one second phase and the filling of one or more compartments with air, gas, a liquid, a gel, a shaped body It is also possible to fill several to all compartments of a multi-compartment container with one or more first and second phases and the remaining compartments with air, gas, a liquid, a gel, a shaped body or to fill a powder or granules
  • the first (s) and second (s) phases are in a closed container and have no contact with the outside atmosphere.
  • contents of washing or cleaning agent portions according to the invention which form a completely closed container include, completely and controllably, loose or disperse and not prone to the formation of lumps or so-called gel phases
  • the container may have one or more openings up to 0.5 mm, preferably up to 0 3 mm and in particular up to 0.1 mm, and not completely closed to the outside atmosphere
  • the first phase adhesively bonded to the container material is solid.
  • solid phases are all those phases which have a shape stability and which therefore have their shape when placed on a surface within one week, preferably within one month and especially within a year, do not change noticeably
  • a solidified melt according to the invention solid or hard as a salt crystal, or even having elastic properties. With preference, however, the melt has a low elasticity and deforms under the action of pressure only in an imperceptible to the eye dimensions
  • the melt can be deformed by the action of pressure, but after removal of this pressure does not return to the original shape or an intermediate state, but retains the deformed shape
  • portioned washing or cleaning agent compositions have a more constant washing or cleaning performance over time if the melt contains sugar as the basic constituent.
  • the solidified melt contains from 10 to 99% by weight, preferably from 20 to 90 % By weight, particularly preferably 30 to 80% by weight, more preferably 35 to 70% by weight and in particular 40 to 65% by weight of sugar
  • sugar also means sugar derivatives such as sugar alcohols and / or sugar acids in the context of the application
  • Sugar alcohols are crystalline, readily water-soluble polyhydroxy compounds which are formed by reduction of the carbonyl group from sugars.
  • the monosaccharide sugar alcohols (C n H 2n + 2 O n ) include the compounds Xyht (a pentitol), d-sorbitol, which are important for foods (Also d-Gluc ⁇ t, a hexitol) and d-Mann ⁇ t (a hexitol) to the Disaccha ⁇ d sugar alcohols (C n H 2n O n - I ) maltitol, Palatmit® and lactitol sugar alcohols are less reactive than sugar because of the lack of carbonyl group
  • These are generally crystalline, water-soluble polyols according to the number of hydroxyl groups contained in the molecule Tetrite, Pentite, Hexite, etc.
  • Sugar acids are polyhydroxycarboxylic acids which tend to form lactones and are formed by oxidation of the aldehyde and / or the primary alcohol groups from simple sugars (monosaccharides) to carboxy groups. Some of the sugar acids occur as metabolites and / or are constituents of polymeric natural substances, such as Mild oxidation of sugars leads to the formation of aldonic acids when the aldehyde group is oxidized to the carboxy group.
  • sugars and sugar derivatives in particular the mono- and disaccharides and their derivatives, can be processed in the form of their melts, these melts having good looseness both for dyes as well as for many have washing or cleaning-active substances
  • the solid bodies resulting from the solidification of the sugar melts are also characterized by a smooth surface and an advantageous appearance, such as a high surface brilliance or a transparent appearance
  • the group of preferred as the material for the melt in the context of the present application are charged sugar from the group of mono- and Disacchande and derivatives of mono- and di- saccha ⁇ den especially glucose, fructose, ribose, maltose, lactose, sucrose, isomalt and Maltodextnn ® and mixtures of two, three, four or more mono- and / or Disacchanden and / or the derivatives of mono- and / or Disacchanden So are mixtures of isomalt ® and glucose, isomalt ® and lactose, isomalt ® and fructose, isomalt ® and ribose, isomalt ® and maltose, glucose and sucrose, isomalt or isomalt ® and Maltodextnn ® and sucrose as materials for the melt more preferably
  • melt particularly preferred as material for the melt are mixtures of maltodextrins and glucose, maltodextrins and lactose, maltodextrins and fructose, maltodexts and ribose, maltodextrins and maltose or maltodextes and sucrose
  • Maltodextnn be in the context of the present application by enzymatic degradation of starch derived water-soluble carbohydrates (dextrose equivalents, DE 3-20) with a chain length of 5-10 anhydroglucose units and a high proportion of maltose Maltodextnn be foods to improve the theological u calorischen properties added, taste little sweet and do not tend to retrogradation commercial products, for example, the company Cerestar, are usually offered as spray-dried free-flowing powders and have a water content of 3 to 5% by weight
  • isomalt ® is within the scope of the present application, a mixture of 6-O- ⁇ -D-glucopyranosyl-D-sorb ⁇ tol (1, 6-GPS) and 1-O- ⁇ -D-glucopyranosyl-D-mann ⁇ tol (1
  • the weight fraction of 1, 6-GPS in the total weight of the mixture is less than 57% by weight.
  • Such mixtures can be incorporated, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the isomaltose obtained Formation of an odorless, colorless and crystalline solid produce
  • the melt comprises less than 50% by weight, preferably less than 30% by weight, more preferably less than 10% by weight, more preferably less than 5% by weight and in particular no sugar alcohols and / or sugar acids
  • the sugar (s) contained in the melt is selected from the group consisting of mono- and disaccharides, preferably from the group consisting of glucose, fructose, ribose, maltose, lactose and sucrose and also mixtures The use of glucose and / or maltose is particularly preferred.
  • glucose in these mixtures is preferably at least 30% by weight, preferably at least 45% by weight, more preferably at least 60% by weight, more preferably at least 75% by weight, very particularly preferably at least 90% by weight and in particular at least 99% by weight
  • portioned washing or Remungsmittel compositions which on the one hand melts, comprising 10 to 99 wt .-% glucose, fructose, ribose, maltose, lactose and / or sucrose and at least one further active, and on the other hand, one or more further also comprise active-containing phases, have a higher washing or cleaning effect than already known means
  • the washing or cleaning power of these sugar-containing agents does not change during storage and transport and does not decrease as always to observe with known means in the course
  • compositions according to the invention which contain bleaching agents, bleach catalysts and / or bleach activators in the first phase, ie the melt, and enzymes in the second phase (in a powder, granules, liquid or gel)
  • a lesser inactivation of the Enzymes as well as the other ingredients than with agents
  • particularly good results are obtained when glucose and / or maltose is used as sugar
  • bleach / perfume bleach / dye, nonionic / anionic surfactant, nonionic surfactant / polymer, antioxidant / nonionic surfactant, antioxidant / dye, antioxidant / perfume, antioxidant / Enzyme, bleach activator / perfume, bleach activator / dye, nonionic surfactant / bleach activator, bleach activator / polymer, antioxidants / bleach activator, lead activator / colorant, phosphates / phosphonates, pH adjuster / perfume, pH adjuster / enzyme, bleach catalyst / perfume , Bleach catalyst / dye, nonionic surfactant / bleach catalyst, bleach catalyst / polymer antioxidants / bleach catalyst, bleach catalyst / dye, and surfactant / builder
  • the melt may have a low melting point and to be processed at low temperatures. In special cases it may be preferred for the melt to be below 100 ° C. Preferably below 85 0 C, preferably below 70 0 C and especially below 55 ° C is flowable and can be processed A lowering of the melting point can be achieved by addition of suitable substances such as salts.
  • inventive means comprising at the temperatures mentioned processed melts, over the time show particularly stable washing or cleaning performance
  • melts contain, but which is solid at temperatures between 50 and 150 0 C, preferably at temperatures between 60 and 120 0 C f technicallyfahig, at 20 ° C / are in particular those are preferred in which the melting between 65 and 90 0 C and especially between 75 and 85 0 C from solid to flowable state
  • Preferred sugars have a melting point between 50 and 150 0 C and in particular between 65 and 115 0 C.
  • the melt preferably contains one or more further active ingredients.
  • the use of any active ingredient of detergents or cleaning agents in inventive melts is conceivable.
  • a number of suitable active ingredients / washing or cleaning constituents for the preparation within the inventive melt are used in the course of
  • the first phase particularly preferably contains one or more actives from the field of detergent ingredients, preferably from the group of soil repellent polymers, optical brighteners, perfumes, bentonites, bleaches, bleach catalysts, bleach activators, preferably bleaches, bleach catalysts and / or bleach activators, preferably in amounts of from 1 to 90% by weight, more preferably in amounts of from 5 to 80% by weight, very particularly preferably in amounts of from 10 to 70% by weight and in particular in amounts from 15 to 60% by weight, based on di e first phase
  • solvent / salt mediators such as water, but also nonaqueous solvents
  • nonaqueous solvents which can be used according to the invention are, in particular, the organic solvents, of which only the most important can be mentioned here alcohols (methanol , Ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone , Butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and other nitrogen compounds (dimethylformamide, pyndin, N-methylpyrrohdone, acetonit
  • the container according to the invention contains at least one further, second phase.
  • This second phase is preferably in the form of a powder, in the form of granules, in the form of one or more extrudates, in the form of Compactates such as tablets or in the form of one or more casting bodies.
  • the second phase has the form of a powder or the form of granules.
  • these further phases can have the same consistency and Color, but also have different consistencies or colors Likewise, the other phases may contain the same composition, or even compositions which differ by one or more active ingredients
  • the second phase is liquid or gel-like
  • the volume ratio of first / first phase (s) and second / second phase (s) is preferably between 1100 and 21, more preferably between 150 and 11, more preferably between 120 and 12 and in particular between 10 and 10 and 1 3
  • the first phase preferably occupies between 5 and 90% by volume, preferably between 8 and 75% by volume, more preferably between 11 and 50% by volume and especially between 14 and 25% by volume of the compartment in which first and second phases
  • the container according to the invention is a one-compartment container and the first phase fills between 5 and 90% by volume, preferably between 8 and 75% by volume, more preferably between 11 and 50% by volume and in particular between 14 and 25% by volume of the container
  • an active substance or an active substance group can be contained both in the first phase and in the second phase.
  • the compositions of the first and the second phase can almost completely match.
  • the first phase and the second phase differ at least in one active substance or one active substance group.
  • the first and second phases contain mutually non-contractual active substances, which are thus "separated from one another" in the composition according to the invention.
  • the first phase comprises bleach, Bleach catalyst and / or bleach activator while the second phase contains one or more enzymes. It is also possible that the enzymes are contained in the first phase, while bleach-active compounds are exclusively part of the second phase
  • the first phase contains amylase Since it is advantageous to release certain detergent ingredients at different times into the detergent or clear rinse, it is preferred that the first phase (s) and the second phase (s) be in water loose different rates at 20 0 C or disperse, wherein the first (s) phase (s) preferably slowly lost / slower dis- persed / disperse as at least one of the second, preferably all the second phases
  • a water-soluble container of Polyvmylalkohol a melt which, based on the melt 35 to 70% by weight, preferably 40 to 65 wt % Glucose, maltose and / or fructose and 15 to 60% by weight, preferably 20 to 50% by weight and in particular 25 to 40% by weight of bleaching-active substances and a further solid or liquid, preferably particulate phase, preferably comprising enzyme and optional builder, wherein the melt is connected to the container wall, the melt is preferably self-adhesive and the ratio between the two phases is between 20 and 12
  • washing or cleaning agent portions have a higher "whitening effect", ie an improved ability to clean white laundry, than known agents
  • Bleaching agents, bleach catalysts and / or bleach activators are preferably present in the slower-releasing phase, preferably in the first phase.
  • Further constituents of detergents or cleaners such as soil repellent polymers, optical brighteners, perfume, bentonites, fluorescers, grayness inhibitors, anti-shrinkage agents, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, boring aids, repellents and impregnating agents, swelling and anti-slipping agents, UV absorbers or even clear-pulse substances are also preferably used ingredients of the late-release phase, which is preferably the first Phase is
  • one or more of these ingredients can also be contained in the second phase, which is preferably a powder / granulate which dissolves faster than the melt
  • compositions according to the invention are particularly suitable as detergents for domestic or industrial washing machines or as dishwashing agents for automatic dishwashing machines in the household or in the catering trade
  • inventive compositions described above are used as detergents, they preferably contain, in addition to the substances already mentioned, further active substances, preferably from the group of frameworks, surfactants, polymers, disintegration aids, fragrances and perfuming agents. These preferred ingredients are described in greater detail below. Suitable enzymes, bleaching agents, bleach catalysts and bleach activators, fluorescers, grayness inhibitors, anti-shrinkage agents, crease inhibitors, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, polishing aids, repellents and impregnating agents, swelling agents - and slip-resistant and UV absorbers are also listed
  • the zeolites, silicates, carbonates, organic co-builders and, where there are no ecological prejudices against their use, the phosphates pay
  • the inserted feinkristalhne, synthetic and bonded water Zeohth containing is preferably zeolite A and / or P zeolite P
  • zeolite MAP ® commercially available from Crosfield
  • zeolite X and mixtures of A, X and / or P Commercially available and preferably used in the context of the present invention is, for example, a Co Kr ⁇ stall ⁇ sat of zeolite X and zeolite A (about 80 wt -% zeolite X), which is represented by the formula
  • the zeolite can be used both as a scaffold in a granular compound, as well as for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used
  • Zeolites have an average particle size of less than 10 ⁇ m (volume distribution, Coulter Counter method) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water
  • crystalline layered silicates of the general formula NaMSi x O 2x + IyH 2 O in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred Values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the crystalline layered silicates of the formula NaMSi x O 2x + IyH 2 O are obtained, for example, from Cla ⁇ ant GmbH ( Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 .H 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .H 2 O , Magadnt), Na-SKS-3 (Na 2 Si 8 O 17 ⁇ H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ H 2 O, makatite)
  • both ⁇ - and ⁇ -sodium disilicates are Na 2 Si 2 O 5 y H 2 O and furthermore especially Na-SKS-5 (Cc-Na 2 Si 2 O 5 ), Na-SKS-7 (B-Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 H 2 O), Na-SKS-10 (NaHSi 2 O 5 3H 2 O, kanemite), Na-SKS 1 1 (t-Na 2 S ⁇ 2 0 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (5-Na 2 Si 2 O 5 ) is preferred
  • Washing or cleaning agents preferably contain a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x + 1 y H 2 O from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight and in particular from 0, 4 to 10% by weight, in each case based on the total weight of these agents
  • amorphous sodium silicates having a modulus Na 2 O SiO 2 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, which are preferably loosely entangled and have secondary wash properties
  • the Loseverzog für compared to conventional amorphous Nat ⁇ umsilikaten can thereby be caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying
  • the term "amorphous" understood that the silicates do not provide sharp X-ray reflections in Rontgenbeugungsexpenmenten , as typical of crystalline substances, but at most one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle, cause
  • X-ray amorphous silicates whose silicon particles exhibit blurred or even sharp diffraction maxima in electron diffraction phenomena. This is to be interpreted as meaning that the products have microcrystalline regions of sizes from 10 to a few hundred nm, with values of up to max 50 nm and in particular up to 20 nm are preferred
  • Such Rontgenamorphe silicates also have a Loseverzog für compared to the conventional waterglass
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acid (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives
  • the phosphates combine several Advantages in itself They act as alkali storage, prevent limescale on machine parts or Kalkinkrustationen in tissues and also contribute to the cleaning performance
  • phosphates are the pentasodium t ⁇ phosphate, Na 5 P 3 Oi 0 (Nat ⁇ umt ⁇ - polyphosphate) and the corresponding potassium salt Pentakaliumt ⁇ phosphat, K 5 P 3 O 10 (Kaliumt ⁇ polyphosphat) According to the invention are preferably still used the Nat ⁇ umkaliumt ⁇ poly lyphosphate
  • phosphates are used as washing or cleaning-active substances in detergents or also in cleaners
  • preferred agents include dicloses (s) phosphate (s), preferably alkali metal metal phosphate (s), particularly preferably pentanatomium or pentapotassium phosphate (sodium). or Kaliumt ⁇ polyphosphat), in amounts of 5 to 80% by weight, preferably from 15 to 75% by weight and in particular from 20 to 70% by weight, each based on the weight of the washing or cleaning agent
  • alkali carriers examples include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the alkali silicates, alkali metal catechols and mixtures of the abovementioned substances.
  • the alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate
  • the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt %, preferably below 6% by weight, more preferably below 4% by weight and in particular below 2% by weight, in each case based on the total weight of the washing or cleaning
  • used are particularly preferred agents, which contain based on their total weight less than 0.5% by weight and in particular no alkali metal hydroxides
  • organic cobuilders include polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrinates and phosphonates. These classes of substances are described below
  • Useful organic framework substances are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or 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, Ammocarbonsauren, Nitnlotriessigsaure (NTA), if such use is not objectionable for environmental reasons, and mixtures of these
  • the free acids have in addition to their builder effect typically also the property of an acid component and thus serve to set a lower and milder pH value of detergents or cleaning agents
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures thereof may be mentioned here
  • polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol
  • the molecular weights given for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form which were basically determined by means of gel permeation chromatography (GPC) using a UV detector. The measurement was carried out against an external polyacrylic acid Standard, which provides realistic molecular weight values due to its structural relationship to the polymers studied
  • 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, this group can in turn comprise the short-chain polyacrylates, the molar masses of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol, have, be preferred
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and 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 particularly suitable
  • Their relative molecular mass, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of detergents or cleaning agents in (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight and in particular from 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives as monomers
  • copolymers are those which have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers
  • polymeric aminodicarboxylic acids their salts or their precursors
  • Substances are particularly preferred Polyasparagmsauren or their salts
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are prepared from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as Gluconic acid and / or glucoheptonic acid
  • organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • the hydrolysis products have average molecular weights in the region of 400 up 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 customary measure of the reducing action of a polysaccharide in comparison with dextrose Usable are both Maltodext ⁇ ne with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range of 2000 to 30,000 g / mol
  • 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
  • Ethylendiamindisucci- nat preferably Ethylendiamindisucci- nat
  • co-builders preferably Ethylend ⁇ am ⁇ n-N, N '-d ⁇ succ ⁇ nat (EDDS) is preferably in the form of its sodium or magnesium salts thereof
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups
  • nonionic, anionic, cationic and amphoteric surfactants are included in the group of surfactants
  • Nonionic surfactants which may be used are all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants. Particular preference is given to washing or cleaning agents containing nonionic surfactants from the group of alkoxylated alcohols.
  • Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, especially primary alcohols preferably used with 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or methyl branched preferably in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they
  • alcohol ethoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example coconut oil, palm oil, tallow fatty acid or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are particularly preferred
  • Preferred ethoxylated alcohols include, for example, C 12 -i 4 alcohols containing 3 EO or 4 EO, C9-11 alcohol containing 7 EO, C 3 -i 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12 -i 8 -alcohols with 3 EO
  • ethoxy ether degrees represent statistical averages which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homology distribution (NRE)
  • fatty alcohols containing more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO
  • 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 methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and glycosides, is any number between 1 and 10, preferably x 1, 2 to 1, 4
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dimethylhydroxylamine, and fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols. especially not more than half of them
  • surfactants are polyhydroxy fatty acid amides of the formula
  • R 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
  • [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 amming 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
  • 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 oxy-alkyl radical having 1 to 8 carbon atoms
  • Ci 4 alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxyherte, preferably ethoxylated or propoxylated Derivatives of this residue
  • [Z] is preferably obtained by reductive ammination 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-aryl-oxy-substituted compounds can be prepared by reaction with fatty acid methyl esters in the presence of an alkoxide be converted as a catalyst into the desired polyhydroxy fatty acid amides
  • Nonionic surfactants from the group of alkoxylated alcohols more preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO / AO / EO N ⁇ otens ⁇ de, or the PO / AO / PO N ⁇ otens ⁇ de, especially the PO / EO / PO N ⁇ otens ⁇ de are particularly preferred
  • Such PO / EO / PO N ⁇ otens ⁇ de are characterized by good foam control
  • anionic surfactants used in detergents are those of the sulfonate and sulfates type.
  • Sulfonate surfactants preferably comprise C 9-13 -alkylbenzenesulfonates, olefmsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 -i obtained 8 -Monoolef ⁇ nen with terminal or mnenstandiger double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products are also suitable Alkansul- sulfonates, from C 12 18 alkanes, for example by Sulfochlo ⁇ réelle or sulfoxidation and subsequent hydrolysis Likewise, the esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut
  • sulfonated fatty acid glycyl esters are sulfonated fatty acid glycyl esters.
  • Fatty acid glycine esters are to be understood as meaning the mono-, di- and tern esters and mixtures thereof, as used in the preparation of
  • the sulfonated products of saturated fatty acids having 6 to 22 carbon atoms, for example, are the preferred sulfonated fatty acid esters Caproic acid, caprylic acid, capnic acid, my ⁇ stic acid, lauric acid, palmitic acid, stearic acid or behenic acid
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelhoffreschester the C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl ristyl-, cetyl or stearyl alcohol, or Cio-C 2 o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are also preferred.
  • Alk (en) ylsulfates of said chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical which has an analogous decomposition behavior to the adequate compounds based on oleochemicals raw materials of washing technology are the C 12 - C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates preferably 2,3-alkyl sulfates, which obtained as commercial products from Shell Oil Company under the name DAN ® are suitable anionic surfactants
  • 2 i-alcohols such as 2-methyl-branched C 9 .n-alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci 2 .i 8 fatty alcohols having 1 to 4 EO, are suitable They are in washing or Detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5% by weight used
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular e-thoxylated fatty alcohols represent Preferred sulfosuccinates contain C 8 . 18 fatty alcohol radicals or mixtures thereof These particularly preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols which in themselves constitute nonionic surfactants.
  • alk (en) ylbernostic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof
  • Suitable further anionic surfactants are, in particular, soaps.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myroleic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids
  • the anionic surfactants including the soaps may be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or ethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form sodium salts
  • cationic active substances for example, cationic compounds of the following formulas can be used
  • each group R 1 is independently selected from C 1-6 alkyl, alkenyl or hydroxyalkyl groups
  • each group R 2 is independently selected from C 8-2 ⁇ -alkyl or alkenyl groups
  • R 3 R 1 or (CH 2 ) n -TR 2
  • R 4 R 1 or R 2 or (CH 2 ) n -TR 2
  • T -CH 2 -, -O-CO- or -CO-O- and n is one integer from 0 to 5 is
  • Textile-softening compounds can be used to care for the textiles and to improve the textile properties such as a softer handle and reduced electrostatic charge (increased wearing comfort).
  • the active compounds of these formulations are quaternary ammonium compounds having two hydrophobic radicals, such as, for example, Disteriardi - Methylammoniumchlo ⁇ d, which, however, due to its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation
  • Such "esterquats" having improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents.
  • Dimethylolethyleneurea is also suitable as finish
  • the group of polymers includes, in particular, the washing- or cleaning-active polymers and / or polymers which are effective as softeners.
  • cationic, anionic and amphoteric polymers can also be used in detergents or cleaners in addition to nonionic polymers
  • “Cationic polymers” in the context of the present invention are polymers which carry a positive charge in the polymer molecule. This can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers are derived from the groups of the quaternized CeIIuIo - Se-De ⁇ vate, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, the Vinylpyrrolidone-Methoimidazoliniumchlo ⁇ d- copolymers, the quaternized polyvinyl alcohols or specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyqua
  • Amphoteric polymers within the meaning of the present invention also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids
  • Detergents or cleaning agents contain the abovementioned cationic and / or amphoteric polymers, preferably in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the detergent or cleaning agent.
  • the bleaching agents are a washing or cleaning substance which is used with particular preference.
  • the sodium carbonate, sodium borate tetrahydrate and sodium borate monohydrate are of particular importance.
  • Further bleaches which can be used are, for example, peroxypyrophosphates, Citrate perhydrates and H 2 O 2 supplying peracid salts or peracids, such as perbenzoates, Peroxophthalate, Diperazelainsaure, Phthaloiminopersaure or Diperdodecandikla
  • Typical organic bleaching agents are the diacyl peroxides, such as, for example, dibenzoyl peroxide.
  • Other typical organic bleaching agents are the peroxyacids, examples of which are the alkyl polyoxysaurs and the aryl peroxyacids
  • Chlorine or bromine-releasing substances can also be used as the bleaching agent.
  • suitable chlorine or bromine-releasing materials are heterocyclic N-bromo- and N-chloramides, for example trichlorocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloicocyanuric acid (DICA) and / or their derivatives Salts with cations such as potassium and sodium into consideration Hydantoinverbmditch, such as 1, 3-D ⁇ chlor-5,5-d ⁇ methylhydantho ⁇ n are also suitable
  • washing or cleaning agents which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably sodium carbonate to the entire portioned detergent composition
  • Bleach activators are used in detergents or in detergents, for example, in order to achieve cleaning at temperatures of 60 0 C and below, an improved bleaching effect as bleaching activators, compounds which under perhydrolysis aliphatic specific Peroxocarbonsauren preferably having 1 to 10 carbon atoms, in particular Suitable are substances which carry O- and / or N-acyl groups of said carbon atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated Triazinde ⁇ vate, in particular 1, 5-D ⁇ acetyl-2,4-d ⁇ oxohexahydro-1, 3,5-tr ⁇ az ⁇ n (DADHT), acylated Glycolunle, especially Tetraacetylglykolunl (TAGU), N-Acyl ⁇ m ⁇ de, in particular N-Nonanoylsucc ⁇ n ⁇ m ⁇ d (NOSI ), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfone at (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular trimellactin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-diphrahydrofuran,
  • bleach activators are preferably used in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, especially 2 to 8% by weight and more preferably 2 to 6% by weight, based in each case on the total weight of the bleach activator-containing agents That is, used on the total weight of the inventive compositions
  • bleach activators which are preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitrites of the formula
  • R 1 is -H, -CH 3, a C 2-24 -alkyl or -alkenyl radical, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-4 alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-4 alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH
  • bleach catalysts can also be used. These substances are bleaching-intensifying transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • bleach catalysts Bleach-enhancing transition metal complexes, in particular having the central atoms Mn 1 Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt ( amm ⁇ n) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in customary amounts, preferably in an amount of up to 5% by weight, in particular of 0, From 0025% by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, based in each case on the total weight of the inventive compositions.
  • more bleach catalysts in particular having the central atoms Mn 1 Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and /
  • complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S.
  • lead compound (s) in the agents according to the invention which are macromolecular ligands 1, 4,7-tri-methyl-1, 4,7-triazacyclononane (Me-TACN), 1, 4,7-triazacyclononane (TACN), 1, 5,9-tri-methyl-1, 5,9-t-azacyclododecane (Me-TACD), 2-methyl-1, 4,7-t-methyl-1, 4,7- Tr ⁇ azacyclononan (Me / Me- TACN) and / or 2-methyl-1,4,7-tr ⁇ azacyclononan (Me / TACN) contain Suitable manganese complexes are, for example, [Mn l " 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 ( TA
  • proteases amylases, lipases, hemicellulases, cellulases or oxidoreductases, as well as their mixtures, are preferred.
  • These enzymes are in principle of natural origin, starting from the natural molecules for the use in detergents or cleaning agents improved variants available, which are used accordingly preferred detergents or detergents contain enzymes preferably in total amounts of 1 x 10 6 to 5 wt - based on active protein
  • the protein concentration can be determined by known methods, for Example, the BCA method or the biuret method are determined
  • proteases of the Subt ⁇ l ⁇ s ⁇ n type are preferred examples thereof are the Subtihsine BPN 'and Carlsberg and their advanced forms, the protease PB92, Subtihsine 147 and 309, the alkaline protease from Bacillus lentus, Subtilism DY and the subtilases, not more however, the enzymes thermitase, proteinase K and the proteases TW3 and TW7, which can be classified as subtilisins in the narrower sense
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus lichenemisme, B amyloliquefaciens, S stearothermophilus, Aspergillus niger and A oryzae as well as the further developments of the abovementioned amylases which are improved for use in detergents and cleaners highlight the ⁇ -amylase from Bacillus sp A 7-7 (DSM 12368
  • lipases or cutinases in particular because of their T ⁇ glycerid-cleaving activities, but also to generate from suitable precursors in situ Persauren
  • lipases or cutinases include, for example, originally from Humicola lanugmosa (Thermomyces lanugmosus) available, or further developed lipases, especially those Furthermore, for example, the cutinases which were originally isolated from Fusa ⁇ um solani pisi and Humicola insolens can be used.
  • Lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusa ⁇ um solann can also be used
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can advantageously be used according to the invention to increase the bleaching effect additionally preferably organic, particularly preferably aromatic, interacting with the enzymes compounds added to enhance the activity of the respective oxidoreductases (enhancer) or to ensure at very different redox potentials between the oxidizing enzymes and the stains electron flow (mediators)
  • the enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers added
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, for example, by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core with a water, air and / or
  • other active substances for example stabilizers, emulsifiers, pigments, bleaches or dyes can be applied in deposited layers.
  • Capsules of this kind are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating
  • a protein and / or enzyme can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • damage for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • inhibition of proteolysis is particularly preferred. especially if the agents contain proteases washing or cleaning agents may contain stabilizers for this purpose, the provision of such agents constitutes a preferred embodiment of the present invention
  • enzymes and / or enzyme preparations preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4.5% by weight and in particular of 0.4 to 4% by weight, based in each case on the total enzyme-containing agent, that is to say on the entire portioned washing or cleaning composition
  • Disintegrating agents or disintegrants are understood as excipients which are used for the rapid disintegration of tablets in water or other media and for drained release of the active ingredients
  • Swelling disintegration aids are carbonate / citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers, such as polyvinylpyrrolidone. lidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein denvates
  • disintegration aids in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the total weight of the de-integration aid-containing agent
  • Preferred disintegrating agents are cellulosic disintegrating agents, so that preferred detergents or cleaners contain such disintegrants based on cellulose in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight
  • Cellulose has the formal gross composition (C 6 H 10 O 5 ) ,, and is formally a ß-1, 4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose
  • cellulose derivatives which are obtainable by polymer-analogous reactions of cellulose
  • Such chemically modified celluloses include, for example, products of esterification or etherification, in which hydroxy hydrogen atoms subst Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethyl cellulose (CMC), cellulose
  • CMC carboxymethyl cellulose
  • the content of these mixtures of cellulose derivatives is preferably less than 50% by weight, more preferably less than 20% by weight, based on the content of these mixtures of cellulosic derivatives cellulose-based disintegrant It is particularly preferred to use cellulose-based disintegrating agent as pure cellulose which is free of cellulose derivatives
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted before mixing into the premixes to be compressed.
  • the particle sizes of such disintegrating agents are generally above 200 .mu.m, preferably at least 90% by weight 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m
  • microcrystalline cellulose can be used as a further disintegrating agent based on cellulose or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses. the crystalline areas (about 70%) but leave unscathed a subsequent disaggregation by
  • the micro-crystalline cetluloses which form the hydrolysis yield the microcrystalline celluloses which have particle sizes of about 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m
  • Preferred disintegration aids preferably a Disintegrationstosmittel on Celluloseba- SiS, preferably in granular, cogranulated or compacted form, are in the desintegrati- onsstoffenden agents in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular of 4 to 6% by weight, based in each case on the total weight of the disintegrating agent-containing agent
  • the gas-evolving effervescent system may consist of a single substance which releases a gas on contact with water.
  • these compounds is in particular the magnesium peroxide, which releases oxygen upon contact with water
  • gas-releasing effervescent system in turn of at least two components that react with each other to form gas
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable from the Al kalimetallsalzen in wass ⁇ ger solution to release carbon dioxide
  • boric acid and alkali metal hydrogensulfates, alkali metal dihydrogen phosphates and other inorganic salts are preferably used.
  • organic acidifiers are preferably used, citric acid being a particularly preferred acidifier.
  • Acidifying agents in the effervescent system are preferably selected from the group of organic acids Di-, Tn- and Oligocarbonsauren or mixtures
  • perfume oils or perfumes may be selected from the group consisting of synthetic esters, ethers, aldehydes, ketones, alcohols and hydrocarbons.
  • mixtures of different fragrances are used which together produce an attractive fragrance.
  • Such par - Fumoils may also contain natural fragrance mixtures, such as those available from plant sources, such as pine, citrus, jasmine, patchouly, rose or ylang-ylang oil
  • a perfume In order to be perceptible, a perfume must be volatile, with molecular weight also important in addition to the nature of the functional groups and the structure of the chemical compound Thus, most fragrances have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception.
  • the odor of a perfume or fragrance composed of several fragrances changes during evaporation, with odor impressions in "top note", “middle note or body” as well as “base note” (end note or dry out) subdivided
  • the top note consists of a Perfume or fragrance not only from volatile compounds, while the base note for the most part consists of less volatile, ie adherent fragrances
  • the smell Substances in "light volatiles" or “adherent” fragrances is therefore nothing about the odor impression and whether the corresponding fragrance is perceived as the top or middle note
  • the fragrances can be processed directly, but it may also be advantageous to apply the fragrances on carriers, which provide a slower fragrance release for long-lasting fragrance As such Tragermate ⁇ alien, for example, cyclodextres have preserved, the Cyclodext ⁇ n-perfume complexes additionally with other excipients can be coated
  • the colorants When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light as well as not too high an affinity for textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be considered when choosing suitable colorants that colorants have different stabilities Generally speaking, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and hence the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners typically varies. In the case of readily water-soluble colorants, colorant concentrations are typically within the range selected from a few 10 "2 to 10 " 3 % by weight. In the case of the pigments, which are particularly preferred but less readily water-soluble because of their brilliance, the suitable concentration of F on the other hand, in detergents or cleaning agents, typically at some 10 3 to 10 4 % by weight.
  • Colorants are preferred which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants. For example, anionic nitrosoverses.
  • the detergents as well as the later-treated detergents may contain further ingredients which further improve the performance and / or esthetic properties of these compositions.
  • Preferred agents comprise one or more substances from the group of electrolytes, pH adjusters, fluorescers , Hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, polishing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers
  • the electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali metals and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the washing or cleaning agents prefers
  • pH adjusters In order to bring the pH of detergents or cleaners in the desired range, the use of pH adjusters may be displayed here are all known acids or alkalis, unless their use for technical application or environmental reasons or for reasons of consumer protection Usually, the amount of these adjusting agents does not exceed 1% by weight of the total formulation
  • Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone sols, which may optionally be applied to support materials.
  • Suitable support materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
  • Means contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably hnear-polymeric silicones, which are constructed according to the scheme (R 2 SiO) x and are also referred to as silicone oils. These siliconeols are usually clear, colorless, neutral , odorless, hydrophobic liquids having a molecular weight between 1000 and 150,000 and viscosities between 10 and 1,000,000 mPa s
  • Suitable antiredeposition 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 hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and 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 of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid.
  • Optical brighteners can be added to laundry detergents or cleaners to remove graying and yellowing of treated fabrics. These fabrics draw on the fiber and cause brightening and fake bleaching by converting invisible ultraviolet radiation into visible long wavelength light , wherein the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and with the yellow of the grayed or yellowed wash pure white yields
  • Suitable compounds are derived for example from the substance classes of 4,4 ' -D ⁇ am ⁇ no-2,2 ' - stilbendisulfonsauren (Flavesauren ), 4,4 '-D ⁇ styryl-b ⁇ phenylen, Methylumbelliferone, coumarins, Dihydrochmolinone, 1, 3-D ⁇ arylpyrazol ⁇ ne, Naphthalsaureimide, benzoxazole, benzisoxazole and benzimidazole systems, and the heterocyclic substituted Pyrendenvate
  • Graying inhibitors have the task to keep suspended from the fiber debris suspended in the fleet and so prevent the re-uptake of dirt
  • water-soluble colloids are mostly organic nature suitable, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic acid or acidic sulfuric acid esters.
  • water-soluble, acidic group-containing polyamides are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, eg degraded starch, aldehyde starch, etc.
  • graying inhibitors such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and their Ge mix
  • synthetic anti-crease agents can be used.
  • Phobizing and impregnation processes are used to furnish textiles with substances which prevent the deposition of dirt or facilitate its leaching ability.
  • Preferred lathering and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, perfluorinated polyacrylic acid esters Alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical Antistatic agents may also be present.
  • the antisoiling equipment with repellents and impregnating agents is often classified as an easy-care product.
  • hydrophobized materials do not feel greasy, yet pearl-like
  • silicone-impregnated textiles have a soft feel and are water and dirt repellent, stains of ink, wine, fruit juices and the like are easier to remove
  • Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercucacetate can be waived
  • the agents may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines as well as organic ones Sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates
  • Antistatics increase the surface conductivity and thus enable an improved outflow of formed charges.
  • Outer antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces
  • Surface-active antistatics can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatics.
  • Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistats for textiles or as an additive to detergents .
  • a softening effect is achieved
  • Sihkonderivate can be used to improve the water-absorbing capacity, the rewettability of the treated textiles and to facilitate the Bugeins of the treated textiles
  • Preferred Sihkonderivate are, for example, polydialkyl or alkylaryl siloxanes in which The alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes which may be de ⁇ vatflower if necessary and are then amino-functional or quaternized or Si-OH, Si-H and / or S ⁇ -Cl B'nditch Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes
  • UV absorbers which are absorbed onto the treated textiles and improve the light stability of the fibers.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone having substituents in 2 and 3 which are active by radiationless deactivation
  • substituted benzotnazoles in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic dialkyl complexes and natural substances such as umbelliferone and the endogenous urocanic acid are also suitable
  • Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents or cleaners
  • Protein hydrolyzates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins)
  • protein hydrolysates both plant and Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts.
  • protein hydrolysates of plant origin for example soya, almond, Rice, Pea, Potato and Wheat Protein Hydrolyzates
  • protein hydrolysates as such is preferred, otherwise obtained amino acid mixtures or individual amino acids such as, for example, arginine, lysine
  • derivatives of protein hydrolysates for example in the form of their fatty acid condensation products
  • agents according to the invention described above are used as automatic dishwashing detergents, they preferably contain, in addition to the already mentioned substances, further washing or cleaning substances, preferably from the group of the rust substances, surfactants, polymers, bleaching agents, bleach catalysts, bleach activators, enzymes, Glass corrosion inhibitors, corrosion inhibitors, disintegrants, perfumes and perfumers These preferred ingredients are described in more detail below.
  • bleaching agents, bleach catalysts and bleach activators and Klarspulsubsta ⁇ zen are also mentioned e-
  • nonionic surfactants which have a melting point above room temperature N ⁇ cht ⁇ on ⁇ sche (s) TEN s ⁇ d (e) having a melting point above 20 0 C, preferably above 25 ° C, particularly preferably between 25 and 6O 0 C and especially between 26.6 and 43.3 ° C, is / are particularly preferred
  • nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa Also, preferably nonionic surfactants which have wax-like consistency at room temperature are preferred depending on their intended use
  • Nonionic surfactants from the group of alkoxylated alcohols are also used with particular preference
  • the nonionic surfactant solid at room temperature preferably has propylene oxide units in the molecule.
  • such PO monomers make up to 25% by weight, more preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant
  • particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units
  • the alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such Preferred nonionic surfactants are characterized by containing ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the Molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant
  • surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) -Tens ⁇ de) Such (PO / EO / PO) -N ⁇ otens ⁇ de are also characterized by good foam control
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight.
  • nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • 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 J 2 and the indices w, x, y, z independently of one another are integers from 1 to 6
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene oxide or alkylene oxide.
  • the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, the linear radicals are selected from alcohols of natural origin having 12 to 18 carbon atoms, such as coconut, palm, Taigfett- or oleyl alcohol, are preferably accessible from synthetic sources alcohols
  • the Guerbet alcohols or methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture as they usually in Oxoalkoholresten Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions, preference is given to nonionic surfactants 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
  • butylene oxide is also suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 or R 3 are selected independently of one another from -CH 2 CH 2 -CH 3 or -CH ( CH 3 J 2 are suitable
  • R 2 or R 3 is a radical -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another for values of 1 or 2 stand
  • nonionic surfactants which have a C 9-15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • These surfactants have in an aqueous solution the required low viscosity and are inventively used with particular preference
  • R 1 and R 2 independently of one another represent a straight-chain or branched, saturated or mono- or polyunsaturated C 2 .
  • radical R 1 which is linear or branched, saturated or unsaturated, ahphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 having 1 to 30 carbon atoms, wherein x stands for values between 1 and 90, preferably for values between 40 and 80 and in particular for values between 40 and 60 Particularly preferred are surfactants of the formula
  • R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15
  • R 1 and R 2 independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 J 2 , but preferably is -CH 3
  • nonionic surfactants are the end-capped poly (oxyalkyl ⁇ erten) nonionic surfactants of the formula
  • 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
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket may be varied.
  • the value 3 for x has been selected here by way of example and can certainly may be larger, with the variation width increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number (PO) groups or vice versa
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18 Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15
  • the indicated C chain lengths and degrees of ethoxylation or degree of alkoxylation of the aforementioned nonionic surfactants represent statistical averages which may be a whole or a fractional number for a particular product. Because of the preparation processes, commercial products of the formulas mentioned are usually not made of an individual member but of mixtures Both for the C chain lengths and for the degrees of ethoxylation or degrees of alkoxylation, mean values and, consequently, fractional numbers may result
  • nonionic surfactants can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.
  • Surfactant mixtures are not mixtures of nonionic surfactants which fall in their entirety under one of the abovementioned general formulas but rather such mixtures containing two, three, four or more nonionic surfactants, which can be described by different of the aforementioned general formulas
  • anionic surfactants are part of automatic dishwashing agents, their content, based on the total weight of the compositions, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight of automatic dishwashing agents which do not contain any anionic surfactants are particularly preferred It is also possible to use cationic and / or amphoteric surfactants in place of the surfactants mentioned or in conjunction with them. These classes of substances have already been described in the preferred ingredients of detergents according to the invention
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very preferably less than 2% by weight and in particular less than 1% by weight of machine dishwashing detergent.
  • Spulsch which contain no cationic or amphoteric surfactants, are particularly preferred
  • the group of polymers in particular pay the washing or cleaning-active polymers, such as the clear-spooled and / or effective as Entharter polymer
  • cationic, anionic and amphoteric polymers are used in detergents or cleaning agents in addition to nonionic polymers.
  • Some cationic and amphoteric polymers were already in the preferred ingredients erfmdungsgeschreiber detergent described
  • particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula
  • R 1 and R 4 independently of one another are H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms
  • R 2 and R 3 independently of one another are an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched is and having from 1 to 6 carbon atoms, preferably being a methyl group
  • x and y independently of one another are integers between 1 and 3.
  • X " represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate , Methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3, -CH 2 -CH 3, - CH 2 -CH 2 -CH 3, -CH (CH 3) -CH 3, -CH 2 -OH , -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n H
  • cationic or amphoteric polymers comprise a monomer unit of the general formula
  • Ri HC C Rs-C (O) -NH- (CH 2 ) -N + R 3 R 4 R 5
  • X " in the R 1 , R 2 , R 3 , R 4 and R 5 are independently of one another a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , - CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , - CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -O) n is H and x is an integer between 1 and 6
  • amphoteric polymers have not only cationic groups but also anionic groups or monomer units.
  • anionic monomer units are derived, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched , saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates
  • Preferred monomer units are the acrylic acid, the (meth) acrylic acid, the (dimethyl) acrylic acid, the (ethyl) acrylic acid, the cyanoacrylic acid, the vinyllowing acid, the Allyl acetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and its derivatives, the allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids
  • Preferred amphoteric polymers which can be used are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkylmethacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkylmethacrylic acid copolymers, the alkylacrylamide / alkylmethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and also the copolymers of unsaturated carboxylic acids, cationically de ⁇ vated unsaturated carboxylic acids and optionally further ionic or nonionic
  • Preferred zwitterionic polymers are from the group of acrylamidoalkylt ⁇ - alkylammoniumchlo ⁇ d / acrylic acid copolymers and their alkali metal and Ammomumsalze, the Acry- lamidoalkylt ⁇ alkylammoniumchlo ⁇ d / methacrylic acid copolymers and their alkali metal and Ammomumsalze and Methacroylethylbetain / methacrylate copolymers Also preferred are amphoteric polymers which, in addition to one or more anionic monomers, comprise, as cationic monomers, methacrylamidoalkyl-tn-alkylammonium chloride and dimethyl (diallyl) -ammonium chloride
  • amphoteric polymers are from the group of methacrylamidoalkyl trialkylammon ⁇ umchlor ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlor ⁇ d / acrylic acid copolymers, the Methacryl- am ⁇ doalkyltr ⁇ alkylammon ⁇ umchlor ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlo ⁇ d / methacrylic acid copolymers and the Methacrylamidoalkylt ⁇ alkylammoniumchlorid / DimethyKdiallyOammoniumchlo ⁇ d / alkyl (meth) acrylic acid Copolymers and their alkali metal and ammonium salts
  • amphoteric polymers from the group of Methacrylamidopro- pyltr ⁇ methylammon ⁇ umchlor ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlor ⁇ d / acrylic acid copolymers, the Meth- thacrylam ⁇ dopropyltr ⁇ methylammon ⁇ umchlo ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ um-chlor ⁇ d / acrylic acid copolymers and the Methacrylamidopropyltrimethylammonium chlo ⁇ d / D ⁇ methyl (d ⁇ allyl) ammon ⁇ umchlo ⁇ d / Al-kyl (meth) acrylic acid copolymers and their alkali metal and ammonium salts
  • the polymers are present in prefabricated form.
  • the encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers, encapsulation of the polymers is suitable by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 0 C, the cogranulation of the polymers with inert Tragermate ⁇ alien, preferably with support materials from the group of washing or cleaning-active substances, particularly preferred from the group of builders (scaffolds) or cobuilders
  • Machine dishwashing agents contain the abovementioned cationic and / or amphoteric polymers, preferably in amounts of between 0.01 and 10% by weight, based in each case on the total weight of the dishwashing agent.
  • automatic dishwashing agents in which the weight fraction of the cationic and or amphoteric polymers between 0.01 and 8% by weight, preferably between 0.01 and 6% by weight, preferably between 0.01 and 4% by weight, more preferably between 0.01 and 2% by weight and in particular between 0.01 and 1% by weight, based in each case on the total weight of the automatic dishwashing agent
  • polymers effective as a softener are the sulfonic acid group-containing polymers which are used with particular preference
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers
  • R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-Methacrylam ⁇ do-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , 3-Sulfo ⁇ ropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of
  • ethylenically unsaturated compounds are suitable as further ionic or nonionogenic monomers.
  • the content of the polymers used in these other ionic or nonionic monomers is less than 20% by weight, based on the polymer.
  • the copolymers may contain the monomers from the groups I) and n) and, if appropriate, in varying amounts, it being possible to combine all representatives from the group I) with all representatives from the group I) and all representatives from the group I) Preferred polymers have certain structural units which are described below
  • copolymers which are structural units of the formula are preferred.
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, whereby the structural units in the molecule are changed.
  • the sulfonic acid groups may be completely or partially present in neutralized form, ie that the acidic hydrogen atom of the sulfonic acid group may be exchanged in some or all of the sulfonic acid groups for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • pen-containing copolymers is inventively preferred
  • the monomer distribution of the copolymers preferably used according to the invention is in the case of copolymers which contain only monomers from groups (I) and (I), preferably in each case from 5 to 95% by weight (I) or n), particularly preferably from 50 to 90% by weight, monomer from the group ⁇ ) and 10 to 50% by weight of monomer from the group ⁇ ), each based on the polymer
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from the group I), from 10 to 60% by weight of monomer from the group I) and from 5 to 30% by weight of monomer from the group III)
  • the molecular weight of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred detergents or cleaners are characterized in that the copolymers have molar masses of 2,000 to 200,000 gmol -1 , preferably 4000 to 25,000 gmol "1 and in particular from 5000 to 15,000 gmol " 1 have
  • Automatic dishwashing agents contain, in addition to or in addition to the bleaching agents, bleach activators and bleach catalysts already mentioned, (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxybenzoic acids, but also peroxy-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylic acid, peroxystearic acid, ⁇ -phthalimido peroxyhexanoic acid (PAP),
  • PAP ⁇ -phthalimido peroxyhexanoic acid
  • Nonenylamidopersuccinate and (c) aliphatic and aphiphatic peroxydicarboxylic acids, such as 1, 12-D ⁇ peroxycarbonsaure, 1, 9-D ⁇ peroxyazela ⁇ nsaure, Diperocysebacinsaure, Diperoxybrassylsauer, the Diperoxyphthalsauren, 2-Decyld ⁇ peroxybutan-1, 4-diacid, N, N-terephthaloyl -d ⁇ (6- ammopercapronsaue)
  • automatic dishwashing agents which contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleaching agent, preferably sodium carbonate
  • Particularly preferred bleach activator is a cationic nitrile of the formula
  • Glass corrosion inhibitors prevent the occurrence of turbidity, streaks and scratches, but also iridescence of the glass surface of mechanically cleaned glasses.
  • Preferred glass corrosion inhibitors originate from the group of magnesium and zinc salts as well as magnesium and zinc complexes
  • the spectrum of the preferred zinc salts according to the invention ranges from salts which are difficult or insoluble in water, ie a solubility below 100 mg / l, preferably below 10 mg / l, in particular below 0.01 to salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and in particular above 5 g / l (all properties in the case of 20 mg / l) ° C. water temperature)
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate
  • the glass corrosion inhibitor used is at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.
  • Zinccinoleate, zinc abietate and zinc oxalate are also preferred
  • the content of zinc salt in machine dishwashing agents is preferably between 0.1 and 5% by weight, preferably between 0.2 and 4% by weight and in particular between 0.4 and 3% by weight
  • Content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1% by weight, preferably between 0.02 to 0.5% by weight and in particular between 0.04 to 0.2% by weight, in each case based on the total weight of the glass corrosion inhibitor-containing agent, ie the total weight of the automatic dishwashing agent
  • Corrosion inhibitors are used to protect the Spulgutes or the machine, wherein in the field of automatic dishwashing, especially silver protectants are of particular importance can be used
  • the known substances of the prior art can generally silver protectants selected in particular from the group of T ⁇ azole, the Benzotnazole, the Bisbenzotnazo- Ie
  • Particular preference is given to using benzotnazole and / or alkylaminotetazole
  • preference is given to using 3-amino-5-alkyl-1,2,4-triazoles or their physiologically tolerated salts where: C these substances with particular preference in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulphurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acids.
  • Chlorine-free detergents also contain oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, Phloroglucin, pyrogallol or derivatives of these compounds are also used salt and complex inorganic compounds, such as salts of metals Mn 1 Ti, Zr, Hf, V, Co and Ce are often used
  • the preferred transition metal salts which are selected from the group the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of the cobalt or manganese and the Manganese Sulphate Zinc compounds can also be used to prevent corrosion on the product
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group consisting of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium. Salts and / or complexes, wherein the metals are preferably present in one of the oxidation states II, III, IV, V or VI
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation comprise all conventional mono-, di-, or tri-negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) -citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate], V 2 O 5, V 2 O 4, VO 2, TiOSO 4, K 2 TiF 6, K 2 ZrF 6, CoSO 4, Co (N0 3) 2, Ce (NO 3) 3) and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) -citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [I -hydroxyethane-1, 1 - diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2
  • the inorganic redox-active substances are preferably coated, ie completely with a water-tight, at the cleaning temperature.
  • preferred coating materials applied by known processes include paraffins, microwaxes, natural waxes such as carnauba wax, candellila wax, beeswax , higher melting alcohols such as hexadecanol, soaps or fatty acids
  • the metal salts and / or metal complexes mentioned are contained in cleaning agents and especially in automatic dishwashing agents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, in each case based on the total agent
  • Portioned detergent or cleaning compositions according to the invention comprise a water-soluble or water-dispersible container
  • this container is transparent or translucent and allows the consumer to recognize the individual phases through the container wall.
  • This embodiment makes it possible to visualize the consumer's multifunction properties of the product.
  • Corresponding products are characterized by an attractive appearance, which is taken into account by the consumer in the purchase decision
  • transparency is understood to mean that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%
  • a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention
  • At least one side / flat of the container is transparent or translucent and the first phase is visible through at least one Behalterwand
  • detergents or cleaning the container is transparent or translucent and the first phase is at least one, preferably only one Behalterwand visible
  • the first phase is adhesively bonded to the container wall.
  • the first phase In the case of a container which has transparent or translucent and non-transparent or non-translucent container walls, it is possible for the first phase to be adhesively bonded to a non-transparent or non-translucent container wall and is visible through another container wall, which is transparent or translucent. Preferably, however, the first phase is visible through the container wall to which it is adhesively bonded.
  • the first phase is visible through two opposing container walls. Such an embodiment is associated with a very high degree of attractiveness of the central portion
  • the first phase does not completely cover the wall of the container, but only 10 to 90 area%, preferably only 15 to 75 area% and particularly preferably only 20 to 50 area%.
  • the first phase does not cover the wall of the container in the area of the corners and edges, but only in the area of the surfaces (mm)
  • the melt is translucent to clear and is preferably located between two opposite container walls, so that the consumer can look through the melt
  • agents according to the invention may also contain two, three, four or more "first phases” which are in the form of solidified melts. These may have the same composition, color, elasticity , Have large and / or shape or differ in one, several or all of these properties.
  • the inventive composition contains at least two, at least three, at least four, at least five, preferably 2 to 50 solid adhering to the Be Daveermate ⁇ al connected phases , preferably different shape and / or color
  • these optional optically divergent "first phases" possibly have the same compositions except for the dye
  • the container has only one compartment.
  • This embodiment is particularly preferred in the context of the present invention due to the saving of time and costs.
  • the present invention makes it possible to combine incompatible active substances within a compartment to formulate an attractive appearance such that the active ingredients do not decompose each other
  • incompatible active substances can be present even within one and the same phase, in the sugar melt, without decomposing. It has surprisingly been found that in melts according to the invention which have two incompatible active substances. Substances such as enzyme and bleach / bleach activator / bleach catalyst contain, even over a period of several weeks or even months, almost no decomposition of the active substances takes place So far, only the strict separation of incompatible active ingredients within different container or container compartments was a possibility for stabilization with each other incompatible ingredients of detergents or cleaners known
  • the present invention allows access to highly active agents, which can be assembled in a one-compartment container at low cost.
  • the use of multicompartment containers is also possible, with multi-compartment containers containing only one composition per compartment There is an advantage since the number of compartments required in the containers according to the invention is given due to the filling of a compartment with two or more phases
  • containers can be filled with two, three, four or more, but preferably with two compartments with at least a first phase and at least one second phase and other phases
  • the first phase is adhesively bonded to the container material.
  • This adhesive bond between container material and first phase can be achieved by the use of an adhesive bond
  • the adhesive bond can be achieved, for example, by moistening the point of the water-soluble packaging in which the core is used.
  • the water-soluble coating is hereby partially annealed, as a result of which a highly concentrated polymer solution is generated virtually "in situ", which can serve as adhesion promoter but also other adhesion promoters can be used
  • adhesion promoters Preferred materials for the adhesive bond are adhesives or so-called adhesion promoters.
  • adhesives, dispersions, emulsions or melts which have a viscosity of less than 3000 mPas are preferred as adhesion promoters
  • the viscosity values relate to viscosity measurements at a sample temperature which corresponds to the processing temperature of the adhesive (s) (see below) with a Carpi-plate-plate rheometer, with a shear force of 50 N per Square meters, a plate diameter of 5 cm and a measuring system gap of 250 microns, the value was read after 10 seconds measurement time
  • Preferred adhesion promoters have a viscosity below 2500 mPas, preferably below 2000 mPas and in particular below 1000 mPas during processing
  • the processing temperature of / the Haftverm ⁇ ttler (s) depends on the material nature of the adhesion promoter used and the desired time within which the adhesion promoter is intended to exert its adhesive property
  • temperatures from room temperature which may be part of 10 to 15 0 C in winter months
  • preferred embodiments of adhesive compounds, the adhesion promoters at a temperature between 10 and 130 ° C, preferably between 20 and 110 ° C and in particular between 20 and 9O 0 C. the container material and / or dosed to the first phase
  • the adhesion promoter (s) can be metered in as a melt, which usually may necessitate temperatures above 30 ° C., preferably above 40 ° C. and in particular above 50 ° C.
  • meltable adhesion promoters are substances from the group of polyethylene and polypropylene glycols. Also substance mixtures containing these substances are preferably adhesion promoters from the groups of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are therefore preferred embodiments of the present invention
  • Polyethylene glycols (abbreviated to PEG) which can be used according to the invention are polymers of ethylene glycol corresponding to the general formula
  • the viscosity of the PEG at the processing temperature Da in preferred processes is above 2O 0 C and below 9O 0 C is the polyethylene glycols of the above formula are particularly suitable in which n values between about 15 to about 150 takes
  • the polyethylene glycols having higher molecular weights are polymolecular, ie they consist of groups of macromolecules with different molecular weights.
  • For polyethylene glycols exist various nomenclatures The indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molar mass of about 190 to about 210 is technically customary.
  • polyethylene glycols are 540 (Union Carbide), Emkapol ® 2000 (ICI Americas), Lipoxol ® 2000 MED (Huls America), polyglycol ® E-1550 (Dow Chemical), Lutrol ® E2000 example, under the trade names carbo wax ® PEG ( BASF) and the corresponding trade name with higher numbers
  • Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which are of the general formula
  • the viscosity of the PPG at the processing temperature is within the scope of the present invention the technically common polypropylene glycols PPG 1550, PPG 3000, PPG 4000 and PPG 6000 preferably used
  • solutions or dispersions of solid at room temperature adhesion promoters or emulsions of liquid at room temperature adhesion promoters are the emulsions because of possibly occurring later problems in the adhesion of the melt to the Be bachelorermate ⁇ al only a minor importance. Also the dispersions are because of Absetzproblematik less suitable for processing compared to the more preferred solutions
  • adhesion promoters are solutions of certain nonionic substances.
  • Preferred adhesion promoters are solutions of polyhydric alcohols and / or sugars which are solid at room temperature, preference being given to solutions which, based on the solution, have at least 30% by weight, preferably at least 40% by weight and in particular at least 50% by weight solids)
  • Polyhydric alcohols in the context of the present invention are compounds which have at least two hydroxyl groups. The state of aggregation of these compounds at room temperature (2O 0 C) is fixed.
  • Particularly suitable polyhydric alcohols are, for example, methylolpropane, pentaerythnt and the "sugar alcohols", ie Monosaccharides by reduction of the carbonyl group resulting polyhydroxy compounds One distinguishes among these according to the number of hydroxyl groups contained in the molecule Tet ⁇ te, Pentite, Hexite, etc.
  • sugar alcohols are eg Threit u Erythnt, adonite (ribitol) , Arabitol (formerly lyxite) and xylitol, dulcitol (galactitol), mannitol and sorbitol (glucitol), the latter also being referred to as sorbitol
  • Em preferred sorbitol which can be used in the form of a solution is sorbitol
  • Preferred embodiments are those in which solutions of sorbitol are used as adhesion promoters which, based on the solution, contain at least 50% by weight, preferably at least 60% by weight and in particular at least 70% by weight. Sorbitol included
  • diols are at least partially selected from polyethylene glycols (a) and / or polypropylene glycols (b)
  • the first phase is adhesively bonded to the container material by means of an adhesive such as a melt or wet solution, preferably a melt and in particular a sugar-containing melt
  • the adhesive connection between container material and first phase can be achieved by using a first phase adhering to the container material.
  • the first phase is self-adhesive
  • Self-adhesive is the first phase in the meaning of the application, when the container material and the first phase adhere to each other without adhesive.
  • adhesive also includes water here because water can be used to solubilize a water-soluble container material such as polyvinyl alcohol and the highly concentrated product thus produced PVAL solution to use as the actual adhesive
  • the first phase has good properties in the area of "self-adhesion" and the portioned detergent or cleaner composition provides an improved washing or cleaning performance if the first phase contains 20 to 90% by weight, preferably 30 to 80% by weight. and in particular 35 to 70% by weight of glucose, fructose and / or maltose, in particular glucose or maltose and 10 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 60% by weight of active substances, preferably bleach, bleach catalyst containing and / or bleach activator
  • An object of the present invention is a portioned washing or cleaning composition comprising
  • a container of a water-soluble or water-dispersible material preferably of PVA and in particular of PVA film
  • a further subject of the present invention is a portioned washing or cleaning composition
  • a portioned washing or cleaning composition comprising
  • At least one fixed, preferably self-adhering first phase adhering to the container material comprising, in each case based on the respective first phase
  • glucose, fructose or maltose Preferably 20 to 90% by weight, preferably 30 to 80% by weight, of glucose, fructose or maltose, in particular glucose or maltose,
  • At least one further, preferably particulate phase comprising cleaning or washing-active substances
  • a container of a water-soluble or water-dispersible material preferably of PVA and in particular of PVA film
  • the detergents according to the invention are highly active even after storage and transport and have a very attractive appearance.
  • the first phase does not undergo infiltration through the second phase.
  • the solidified melt imparts strength to the medium, while the second phase is capable of binding in that a mechanical stress on the means does not result in unsightly deformation of the entire container, as in the case of tablets for breaking or crumbling of corners and edges or as in the case of liquid and gel-form agents.
  • Means according to the invention are thus distinguished not only by the improved appearance and favorable production method increased mechanical and chemical (stability of the active ingredients) stability
  • a preferred container in the context of the present invention completely envelopes the detergent or pronounced portion.
  • Suitable packaging materials are known from the prior art and originate, for example, from the group (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, Polyethylene oxide, gelatin and mixtures thereof
  • Particularly preferred portioned detergents or repellent compositions according to the invention are characterized in that the water-soluble or water-dispersible container one or more iganlosl ⁇ che (s) polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), Polyvinylpyrrohdon, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof
  • s a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), Polyvinylpyrrohdon, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with polymerization degrees in the range from about 100 to 2500 (molar masses of about 4000 to 100 000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , thus still contain a residual content of acetyl groups
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity
  • polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethylsulfoxide); they are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically harmless and are at least partially biodegradable Waterlessness can be reduced by aftertreatment with aldehydes (acetahilation), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, however allow water vapor to pass through
  • the water-soluble or water-dispersible container comprises a polyvinyl alcohol whose degree of hydrolysis is from 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%
  • polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the water-soluble or water-dispersible container comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol '1 , more preferably from 12,000 to 80,000 gmol "1 and in particular from 13,000 to 70,000 gmol " 1
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500
  • polyvinyl alcohols described above are commercially widely translated, for example, under the trademark Mowiol ® (Clanant) are particularly suitable in the context of the present invention, polyvinyl alcohols are for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8- 88
  • ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72 5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co)
  • Gohsenol ® NK 05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK )
  • the waterlessness of PVAL can be modified by aftertreatment with aldehydes (acetalization) or ketones (ketalization).
  • polyvinyl alcohols have been found to acetalize with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof
  • the reaction products of PVAL and starch are extremely advantageous
  • PVP Polyvinyl pyrrolidone
  • PVPs are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVPs have molecular weights in the range from about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • Gelatin is a polypeptide (molecular weight about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions
  • the amino acid composition of gelatin corresponds
  • the use of gelatin as a water-soluble Hullmate ⁇ al is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules in the form of films gelatin because of their comparison to the above-mentioned polymers of high price only minor use
  • agents whose packaging consists of at least partially water-soluble film of at least one polymer selected from the group consisting of starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose, and mixtures thereof
  • starches in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can be prepared as starches Use of derivatives
  • the group of starch derivatives includes, for example, alkali metal starches, carboxymethyl starch (CMS), starch esters and ethers and amino tokens
  • Pure cellulose has the formal empirical composition (C 6 H 10 O) n and, formally, is a beta-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose Suitable celluloses consist of ca 500-5000 glucose
  • cellulose derivatives which are obtainable by polymer-analogous reactions from cellulose.
  • Such chemically modified celluloses comprise, for example, products of esterifications or etherifications,
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. They fall into the group of cellulose derivatives for example, alkali celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers and aminocelluloses
  • the water-soluble or water-soluble material of the invention preferably comprises at least partially polyvinyl alcohol
  • foil pouches so-called pouches
  • containers produced by injection molding, casting or by thermoforming, preferably by deep-drawing, are preferably used
  • the water-soluble film forming the container have a thickness of 1 to 150 .mu.m, preferably 2 to 100 .mu.m, more preferably 5 to 75 .mu.m, and in particular from 10 to 50 microns,
  • the film is preferably prepared by casting or blown extrusion process and then deep-drawn to a container
  • the term "deep-drawing process” refers to such processes in which a first film-like Hullmate ⁇ al is deformed by applying pressure and / or vacuum after passing through a receiving trough located in a die forming the deep-drawing mold and forming the Hullmate ⁇ als into this receiving trough
  • the Hullmate- ⁇ al can before before or during the forming by the action of heat and / or solvent and / or conditioning pretreated by ambient relative humidity and / or temperatures changed
  • the pressure can be effected by two parts of a tool, which is like Positively and negatively behave to each other and deformation of a film placed between these tools during compression As pressure forces, however, are also the effect of compressed air and / or the weight of the film and / or the weight of a self on the top of the film v provided active substance
  • the deep-drawn Hullmate ⁇ alien be after deep drawing preferably by using a vacuum within the receiving wells and achieved in their thermoforming space fixed the vacuum is preferably continuously applied from deep drawing to Befullen until sealing and in particular until the separation of the receiving chambers created with comparable success
  • a discontinuous vacuum for example, for deep drawing of the receiving chambers and (after an interruption) before and during the filling of the receiving chambers, also possible the continuous or discrete vary in its strength and, for example, take higher values at the beginning of the process (during deep drawing of the film) than at its end (when filling or sealing or separating)
  • the Hullmatenal can be pretreated by the action of heat before or during the molding into the receiving troughs of the matrices.
  • the Hullmatenal preferably a water-soluble or water-dispersible polymer film, is held for up to 5 seconds, preferably for 0 to 4 seconds.
  • the cooling is preferably carried out at temperatures below 20 0 C, preferably below 15 ° C, particularly preferred t to temperatures between 2 and 14 ° C and in particular to temperatures between 4 and 12 ° C.
  • the cooling is carried out continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers for cooling are in particular Kuhlmanntechniken, preferably water, which in special Kuhltechnischen within the template are circulated
  • This cooling has the advantage of preventing shrinkage of the deep-drawn containers after deep-drawing, which not only improves the appearance of the process product, but also simultaneously discharges the means filled into the receiving chambers the edge of the receiving chamber, for example in the Siegei Kunststoffe the chamber is avoided problems in the sealing of the filled chambers are thus avoided
  • the deep-drawing process can be between methods in which the Hullmatenal horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating is performed and methods in which the Hullmatenal via a continuously rotating Matrizenformwalze (optionally optionally with The first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is generally continuous All the mentioned deep drawing methods are suitable for the production of the inventively preferred means
  • the receiving troughs located in the matrices can be arranged "in series" or staggered
  • the containers according to the invention are preferably produced by means of a deep-drawing process.
  • the film used in the thermoforming process is preferably produced by means of blown, calendering and casting processes.
  • the films are blown from a melt with air through a blow mandrel to a hose in the case of the calendering process.
  • ren which is also one of the preferred production methods used, the plasticized by suitable additives raw materials for forming the films verdust
  • the casting process which is also one of the preferred production, is a wass ⁇ ge polymer preparation is placed on a heatable drying roller, after evaporation of the water is optionally cooled and the film is peeled off as a film If necessary, this film is additionally powdered before or during the removal
  • injection molding refers to the molding of a molding compound in such a way that the mass contained in a mass cylinder for more than one injection molding plastically softens under the action of heat and under pressure through a nozzle into the mold
  • the process is mainly used for non-curable molding compositions which solidify in the mold by cooling.
  • the Sp ⁇ tzguss is a very economical modern process for the production of non-cutting shaped objects and is particularly suitable for automated mass production thermoplastic molding compounds (powder, grains, cubes, pastes, etc.) to liquefaction (up to 180 0 C) and injected then under high pressure (up to 140 MPa) in a closed, two-piece, that is from Gesenk (earlier Mold and (formerly patrix) existing, preferably water-cooled molds where they cool and solidify are used Piston and Schneckens ⁇ tzgussmaschinen
  • molding materials injection molding compounds
  • injection molding compounds are water-soluble polymers such as the above cellulose ethers, pectins, polyethylenglycols, polyvinyl alcohols, polyvinylpyrrolidones , Alginates, gelatin or starch
  • the Hullmate ⁇ alien can also be cast into molds
  • the container as a whole is water-soluble or water-dispersible, ie dissolves completely when used properly during washing or machine cleaning, when the conditions provided for dissolving are achieved.
  • the essential advantage of this embodiment is that the container Within a practically relevant short time - as a non-limiting example can be a few seconds to 5 mm - under exactly defined conditions in the cleaning liquor at least partially loose and thus according to the requirements of the wrapped content, ie the cleaning active material or multiple materials, brings into the fleet
  • the water-soluble container comprises regions which are less soluble or not water-soluble or water-soluble at relatively high temperatures and regions which are readily soluble in water or soluble in water at low temperature.
  • the container does not consist of a uniform, non-aqueous container
  • areas of good water-repellency are to be distinguished from areas with less good water-repellency, with poor or even lacking water-immunity, or areas in which the water-permeability only at higher temperatures or first At a different pH or only at a changed electrolyte concentration reaches the desired value, on the other hand, this can lead to that under normal use under adjustable Conditions loosen certain areas of the container, while other areas remain intact.
  • containers can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example, salts) which are more rapidly soluble in water than the polymer material different water dissimilarity (polymer blend), so that the faster soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the slower soluble
  • the less readily water-soluble areas or water-insoluble areas or only at higher temperature water-soluble areas of the container areas are made of a material chemically substantially that of the water-soluble areas or at lower temperature water-soluble areas but has a higher layer thickness and / or has a modified degree of polymerization of the same polymer and / or has a higher degree of crosslinking the same polymer structure and / or a higher Acetahs mecanicsgrad (PVAL, for example, with Saccha ⁇ den, polysaccharides, such as starch) and / or a content Having water-insoluble salt components and / or has a content of a water-insoluble polymer
  • PVAL Acetahs effetsgrad
  • Another object of the present invention is a process for preparing a portioned detergent or detergent composition in a water-soluble or water-dispersible container comprising the steps of a) producing a container of water-soluble or water-dispersible material, b) partially filling the container with a melt, which after solidification adheres to the Behaltermate ⁇ al and contains sugar, c) after solidification of the melt further Befullen the container with at least one other solid or liquid phase, d) optionally closing the container
  • the solidified melt adheres to the Behaltermate ⁇ al after solidification due to their adhesive properties
  • a solidified melt can also be glued to the container material with the aid of an adhesive or by partial softening of the solidified melt
  • a further subject of the invention is a process for producing a portioned detergent or cleaner composition in a water-soluble or water-dispersible container comprising the steps of a) producing a container of water-soluble or water-dispersible material, b) preparing one or more solidified melts, which sugars c) adhering the solidified melt (s) to the Be fiscalermate ⁇ al by ⁇ ) partial softening of the solidified melt and placing the partially softened phase on the Behaltermate ⁇ al or ⁇ ) use of an adhesive, preferably a melt and in particular a sugar-containing melt, d ) further filling of the container with at least one further solid or liquid phase, e) optionally closing the container
  • the filled compartment is closed, preferably another film on the completely or partially filled compartment applied and sealed by means of heat or solvent Compositions according to the invention which comprise closed containers are characterized by an improved loose behavior which results in an increased cleaning performance.
  • a fixable powder or granules is used as the second phase and the container is closed after the filling has been completed
  • Container at least 75% by volume, preferably at least 80% by volume, more preferably at least 85% by volume, more preferably at least 90% by volume and in particular at least 95% by volume, and thus the void volume of the container dimensioned as low as possible
  • the container can be shrunk by the action of heat and / or vacuum following the filling and closing process
  • the containers are preferably produced by injection molding, thermoforming, preferably thermoforming. It is particularly preferred if the container is produced by deep-drawing a water-soluble or water-dispersible film produced by casting or blown-extrusion processes
  • the first phase can be cast in the inventive method in any shape
  • pyramids, truncated pyramids, cones, truncated cones, (half) spheres, cylinders, prisms, or even animals, clouds, leaves, flowers or stars in advance of To pour filling of the container and then stick to the Behaltermate ⁇ al, or even corresponding objects with the aid of suitable forms directly to the Behaltermate ⁇ al pour
  • objects preferably have a volume between 2 and 50 ml, preferably between 5 and 40 ml, preferably between 10 and 30 ml up
  • the agents according to the invention are used with particular preference in a textile cleaning process.
  • Another use of the agents according to the invention is the use in a cleaning process, preferably in a dishwasher machine

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

L'invention concerne des compositions de lessive ou de détergent en portions, comportant a) un contenant soluble ou dispersible dans l'eau, b) au moins une première fonte solidifiée, connectée par adhérence au matériau du contenant, contenant du sucre, et c) au moins une autre phase. Les compositions selon l'invention sont caractérisées par un meilleur pouvoir lavant et un aspect plus flatteur.
PCT/EP2006/008273 2005-09-22 2006-08-23 Composition de lessive ou de detergent en portions WO2007033743A1 (fr)

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DE200510045440 DE102005045440A1 (de) 2005-09-22 2005-09-22 Portionierte Wasch- oder Reinigungsmittelzusammensetzung

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WO2018138119A1 (fr) * 2017-01-24 2018-08-02 Henkel Ag & Co. Kgaa Dose de détergent comprenant au moins deux phases
WO2018229038A1 (fr) * 2017-06-16 2018-12-20 Henkel Ag & Co. Kgaa Partie permettant d'obtenir des bains contenant un tensioactif

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US9249380B2 (en) 2009-08-07 2016-02-02 Robert McBride Ltd. Dosage form detergent products
WO2018138119A1 (fr) * 2017-01-24 2018-08-02 Henkel Ag & Co. Kgaa Dose de détergent comprenant au moins deux phases
WO2018138124A1 (fr) * 2017-01-24 2018-08-02 Henkel Ag & Co. Kgaa Dose de détergent comprenant au moins deux phases
CN110225965A (zh) * 2017-01-24 2019-09-10 汉高股份有限及两合公司 具有至少两个相的洗涤剂或清洁剂部分
US11268051B2 (en) 2017-01-24 2022-03-08 Henkel Ag & Co. Kgaa Detergent or cleaning agent portion having at least two phases
US11268050B2 (en) 2017-01-24 2022-03-08 Henkel Ag & Co. Kgaa Detergent or cleaning agent portion having at least two phases
WO2018229038A1 (fr) * 2017-06-16 2018-12-20 Henkel Ag & Co. Kgaa Partie permettant d'obtenir des bains contenant un tensioactif
KR20200019705A (ko) * 2017-06-16 2020-02-24 헨켈 아게 운트 코. 카게아아 계면활성제-함유액을 제공하기 위한 분배물
US11414627B2 (en) 2017-06-16 2022-08-16 Henkel Ag & Co. Kgaa Unit-dose detergent portion comprising a granular solid and a viscoelastic solid
KR102605849B1 (ko) * 2017-06-16 2023-11-24 헨켈 아게 운트 코. 카게아아 계면활성제-함유액을 제공하기 위한 분배물

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