EP1298195B1 - Méthode de dosage semi-automatique - Google Patents

Méthode de dosage semi-automatique Download PDF

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Publication number
EP1298195B1
EP1298195B1 EP02021944A EP02021944A EP1298195B1 EP 1298195 B1 EP1298195 B1 EP 1298195B1 EP 02021944 A EP02021944 A EP 02021944A EP 02021944 A EP02021944 A EP 02021944A EP 1298195 B1 EP1298195 B1 EP 1298195B1
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EP
European Patent Office
Prior art keywords
water
insoluble
process according
active substance
acid
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EP02021944A
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German (de)
English (en)
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EP1298195A1 (fr
Inventor
Christian Dr. Nitsch
Wolfgang Dr. Barthel
Rolf Dr. Bayersdörfer
Eiko Hasse
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
    • A47L15/00—Washing or rinsing machines for crockery or tableware
    • A47L15/42—Details
    • A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
    • A47L15/4445—Detachable devices
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/02—Devices for adding soap or other washing agents
    • D06F39/024—Devices for adding soap or other washing agents mounted on the agitator or the rotating drum; Free body dispensers

Definitions

  • Detergents and cleaning agents and processes for their preparation are well known and in the state the technology thus broadly described. Usually, they are the consumer in the form of spray-dried or granulated powder products or provided as a liquid product. the Following the consumer's request for simple dosing, in addition to these two classic variants products in pre-portioned form established in the market and are in the state of the art Technique also comprehensively described, wherein in particular compressed molded articles, ie tablets, Blocks, briquettes and the like, and sachets packed in sachets solid or liquid Washing and cleaning agents are mentioned.
  • EP 0 215 366 describes a detergent container with a melting closure, in which the melting closure melts at a certain operating temperature, whereby the cleaning agent is released.
  • the closure of the container is not reusable, also a multiple dosing with this system is not possible.
  • DE 39 02 356 discloses a Dosier aside, which can also be used only for a wash cycle, and its operating principle is also based on a temperature-dependent release of the detergent. By a resulting in increasing temperature overpressure in the dispenser a slide valve is moved to its open position and allows the exit of the detergent in the washing machine.
  • the process of the invention provided that the water-insoluble container not only two but three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, twenty-one, twenty-two, twenty-three, includes twenty-four or more receiving troughs and each of these receiving troughs is closed by a single water-insoluble protective film.
  • the aforementioned receiving troughs of the water-insoluble container not only allow the multiple portioning of active ingredients within a container, but allow it For example, to separate active ingredients and / or active substance preparations spatially from each other. This separation may be due, for example, to chemical incompatibility, but as in one the following paragraphs in detail, also with the purpose of controlled release of active substances or active substance preparations.
  • a method characterized is that the water-insoluble container three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty, twenty-one, twenty-two, twenty-three, twenty-four or more receptacles, and respectively two, three, four or more of these receptacles by a single water-insoluble Protective film are therefore excluded in the context of the present application prefers.
  • the dosing method described above is then particularly time-saving and consumer-friendly and thus in the context of the present application particularly preferred when the water-insoluble Before removing the protective film, the container is fixed inside the device, in which the subsequent contact with the water or the aqueous solution or the water-containing Solution should be done and after removing the protective film during the course of a manual and / or semiautomatic method and / or fully automatic method with water or aqueous Solutions or water-containing solutions is brought into contact.
  • Such an approach Reduces the necessary operations for dosing the active ingredient (s) on the removal of the water-insoluble protective film.
  • polymers in this application are referred to such high molecular weight compounds, whose construction is based on a chain growth mechanism.
  • Preferred polymers are in the context of the present application polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, Polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile and / or polystyrene.
  • Polyadducts are formed by polyaddition, ie polyreactions in which many times repeating and independent linking reactions of bis- or polyfunctional Educts (monomers) via reactive oligomers eventually polymers arise.
  • preferred Polyadducts are polyurethanes.
  • polycondensates are formed by repetitive and mutually repeating processes independent linking reactions of discrete oligomers and monomers, but in the Contrary to the polyaddition simultaneously a cleavage of low molecular weight compounds takes place.
  • Preferred polycondensates in the context of the present invention are polyamides, polycarbonates and polyester.
  • the watertight cover of the receiving trough of the dosing with one or more water-insoluble protective films is a basic requirement for the use of this container for repeated dosing of active substances.
  • water-insoluble polymers For the reasons mentioned above have become also proven for the production of these protective films water-insoluble polymers.
  • a preferred Embodiment of the method according to the invention consists of the aforementioned water-insoluble Film therefore of water-insoluble polymers and / or polymer blends.
  • Polymers and polymer mixtures are subject to the same explanations as already mentioned with regard to made the water-insoluble container forming preferred polymers and polymer blends were. To avoid repetition reference is made to these sections.
  • the water-insoluble protective film in the receiving cavity sealed volume is in addition to the by the water-insoluble protective film in the receiving cavity sealed volume and thereby defined amount of an active substance or an active ingredient preparation and the depth of the receiving trough significant.
  • the depth of the receiving trough in particular however, the ratio of the opening area of the receiving trough to its depth, among others Factors the duration of the solution and / or dispersion process of the active ingredients in the receiving trough affected.
  • Particularly preferred methods according to the invention have now been found characterized in that the quotient of the dimensionless opening area of the receiving troughs and the dimensionless volume of the receiving wells at least 0.1, especially preferably at least 0.2 and in particular at least 0.4.
  • the active substances present in the receiving troughs of the water-insoluble container in principle no restrictions are imposed on the present process according to the invention, that is, in addition to solid and gel-like liquid, preferably liquid, non-aqueous active ingredients and / or active substance preparations are present in the receiving troughs.
  • the active substance preparations can be used as dispersions, that is, for example in the form of Suspensions or emulsions are present.
  • gel-like active ingredients and / or active-substance preparations are used in the context the present application viscous and highly viscous substances or mixtures of substances summarized to dimensionally stable gels, which understood as “dimensionally stable” such preparations which have an intrinsic dimensional stability which enables them, under usual conditions the manufacture, storage, transport and handling by the consumer to have a stable, non-disintegrating spatial form against breakage and / or pressure, which does not change even under the conditions mentioned for a long time, that is under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatio-geometric shape resulting from the production persists, or after the end of the action of an external under the conditions of manufacture, the storage, transport and handling usual force, in these spatial geometric Form returns.
  • Polymethacrylic Conn. Vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, Clay minerals such as montmorillonites, zeolites and silicas in the active ingredients and / or To incorporate active mixtures, wherein it has proved to be particularly advantageous if this Gels the thickener in amounts between 0.2 and 8 wt .-%, preferably between 0.3 and 6 Wt .-% and particularly preferably between 0.4 and 4 wt .-% based on the total weight of the active substance or the active substance preparation.
  • Naturally derived polymers used as thickening agents in the context of the present invention are preferably used, as described above, for example, agar-agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, Starch, dextrins, gelatin and casein.
  • Preferred modified natural products come from especially from the group of modified starches and celluloses, examples being carboxymethylcellulose and other cellulose ethers, hydroxyethyl and propyl cellulose, and yeast meal ethers called.
  • Thickeners from these classes of compounds are commercially available and are widely available for example under the trade names Acusol®-820 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral® GT-282-S (alkyl polyglycol ether, Akzo), Deuterol® polymer 11 (dicarboxylic acid copolymer, Schöner GmbH), Deuteron® XG (Anionic heteropolysaccharide based on ⁇ -D-glucose, D-mannose, D-glucuronic acid, more beautiful GmbH), Deuteron®-XN (nonionic polysaccharide, Schöner GmbH), Dicrylan®-thickener-O (Ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA®-81 and EMA®-91 (Ethylene-maleic anhydride copolymer, Mons
  • a method is preferred which is characterized in that the active substance (s) are in solid and / or gel and / or non-aqueous liquid form present in the receiving trough.
  • the film (s) contains one or more materials from the group of acrylic acid-containing polymers, polyacrylamides, Oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters and polyethers and their mixtures include / include.
  • the quality of the material as well as its quantity / strength take on these solubility properties direct influence. It is therefore within the scope of the present invention, such a method particularly preferred, which is characterized in that the thickness of the water-soluble Film between 1 .mu.m and 1000 .mu.m, preferably between 5 .mu.m and 500 .mu.m and in particular between 10 .mu.m and 200 .mu.m.
  • Different film thicknesses with the goal of a delayed Release of active substances and / or active substance preparations can also be advantageous, for example by the multiple sealing of one or more receiving wells by means of one or more realize several identical or different water-soluble films.
  • the thickness of the water-soluble Film in the sense of the present invention then results as the sum of the thicknesses the one receiving trough sealing, superimposed water-soluble individual sheets.
  • the latter can be different Quality of the material as well as by different amounts of material (thickness) or also different geometries of the water-insoluble container can be achieved. For example it is possible through the outer shape of the water-insoluble container to the water access complicate and thus delay the dissolution process.
  • the foils of different thicknesses too design and thus allow earlier dissolving at the thinner areas. Be such different thickness water-soluble films to cover different receiving troughs used, the active substances contained in these receiving wells to different Times released.
  • the films are made of materials of different water solubility, for example Polyvinalalkoholen (PVAL) with different residual acetate content.
  • inventive method for semiautomatic dosing in combination with a time controlled release of the active substances and / or active substance preparations consists in the use of Active substances and / or active substance preparations whose rate of release by dispersion and / or solution processes in water or aqueous solutions or water-containing Solutions are different.
  • Preferred is therefore a method which is characterized that the receiving trough contains at least two active substances and / or active substance preparations whose Release rate by dispersion and / or dissolution processes in the water or the aqueous solutions or water-containing solutions are different.
  • differences in the rate of release of active substances can be and / or active substance mixtures realize by their different melting temperatures, these different melting temperatures being at the melting temperatures relate to different matrices and / or different coatings.
  • these different melting temperatures being at the melting temperatures relate to different matrices and / or different coatings.
  • meltable or softenable Substances as matrix or coating material for the active substances or active substance preparations.
  • coating means in the context of the present invention in addition to the coating of one or more sides or surfaces of an object such as a solid particulate agent, the one complete coating, ie the wrapping of this particulate object.
  • fusible substances have a melting point above 30 ° C on. If active ingredient preparations by the inventive method to different Times, for example, during the various rinses of a cleaning process can be released, for example, through the use of various fusible Matrices or coatings are made, which differ in their melting point, wherein the melting points of these substances preferably to the temperature profile of this Cleaning process adapted and the difference of the melting points is sufficient to the separate Dissolve the individual matrices or coatings to ensure.
  • Dosing for example, for the dosage of cleaning agents for the machine dishwashing and continue to be two or more different Matrices or coatings as a carrier material or coating material of active substances and / or active substance preparations with the aim of the time-separated release in the different Matrices or coatings included active ingredients and / or active ingredient preparations used, such substances for the different matrices and / or Coatings preferred with respect to their melting point by at least 5 ° C, preferably differ by 10 ° C, more preferably by 15 ° C and especially by at least 20 ° C, it being further preferred that the melting point of at least one of the fusible Substances that form a matrix or coating below 30 ° C while the melting point of at least one further substance, which is another matrix or coating form, is above 30 ° C.
  • a softenable substance as a matrix for an active ingredient or an active ingredient preparation to be used, this can be made up under the action of heat softenable mass, by the desired further ingredients with this meltable or softenable Mixture mixed and the mixture heated to temperatures in the softening range of this substance and is processed molding at these temperatures.
  • the softening substances used as a coating agent such a coating, for example by dipping, spraying or tumbling in a drum coater or coating pan.
  • Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, Ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, Spermaceti, lanolin (wool wax), or raffia fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.
  • Synthetic waxes are generally polyalkylene waxes or polyalkylene glycol waxes Understood. As meltable or softenable substances for the hardening by cooling Compounds which can also be used are compounds from other substance classes which meet the stated requirements regarding the softening point. As suitable synthetic compounds have For example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, the commercial under the name Unimoll® 66 (Bayer AG). Also suitable are synthetic waxes prepared from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea). Conversely, synthetic ones too or partially synthetic esters of lower alcohols with fatty acids from natural sources.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms.
  • the wax alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes in front.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, Myristyl alcohol or melissyl alcohol.
  • meltable or softenable substances in the masses to be processed are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) Polyethylene glycols having molecular weights between 1500 and 36,000 are preferred, those with Molar masses of 2000 to 6000 are particularly preferred and those having molecular weights of 3000 to 5000 are particularly preferred. Also corresponding methods characterized that the plastically deformable mass (s) at least one substance from the group of Polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are / are preferred.
  • masses to be processed are particularly preferred, which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as sole meltable or softenable substances.
  • PPG propylene glycols
  • PEG polyethylene glycols
  • Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which have the following general formula satisfy, where n can take values between 10 and 2000.
  • Preferred PPG have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170.
  • Paraffin waxes have, compared to the other mentioned, natural waxes in the context of present invention has the advantage that in an alkaline detergent environment no hydrolysis the waxes take place (as is to be expected, for example, in the case of wax esters) Paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes.
  • the paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C, more preferably of more than 60 ° C on. shares refractory alkanes in paraffin can fall below this melting temperature in the Detergent liquor unwanted wax residue on the surfaces to be cleaned or leave the goods to be cleaned. Such wax residues usually lead to an unsightly Appearance of the cleaned surface and should therefore be avoided.
  • Preferred materials to be processed according to the invention are characterized in that they are used as meltable or softenable substances one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the mass.
  • Another preferred option for the delayed release of active substances or Active substance preparations is the staggered spatial arrangement of these substances in the receiving trough with the goal of a staggered release.
  • a spatially staggered Arrangement is, for example, the layer or phase arrangement of the active substances or active substance preparations, for example, the layered tabletting performed above or the layered pouring liquid active substances or mixtures of active substances and their subsequent solidification by solidification and / or crystallization are suitable.
  • Active substance preparations produced by the process according to the invention during the prewash cycle preferably include alkali sources or caustic alkali sources, such as Silicates, carbonates, sodium or potassium hydroxide and / or cobuilders (preferably citric acid) and / or enzymes (preferably lipases or amylases).
  • alkali sources or caustic alkali sources such as Silicates, carbonates, sodium or potassium hydroxide and / or cobuilders (preferably citric acid) and / or enzymes (preferably lipases or amylases).
  • Preferred active ingredients for the Rinse are, for example, nonionic surfactants.
  • the inventive method relates on the dosage of washing and cleaning active substances and therefore in particular a method characterized in that it is at the / Active substance (s) and / or the active substance preparation (s) (one) washing and cleaning substance (s) which is selected from the group of builders, cobuilders, surfactants, bleaches, Bleach activators, enzymes, dyes, fragrances, electrolytes, pH adjusters, perfume carriers, fluorescers, Hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, Grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, Ironing aids, repellents and impregnating agents, swelling and anti-slip agents and / or UV absorbers.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • both the monoalkali metal salts and the dialkali metal salts of Carbonic acid and sesquicarbonates may be included in the compositions.
  • Preferred alkali metal ions represent sodium and / or potassium ions.
  • the carbonate and / or bicarbonate at least partially separately as another component or to be added later.
  • compounds from, for example, carbonate, silicate and optionally further adjuvants such as anionic surfactants or others, In particular, organic builders, as a separate component in the finished Agents are present.
  • the alkali metal phosphates have particular preference of pentasodium or Pentakaliumtriphosphat (sodium or Potassium tripolyphosphate) in the detergents and cleaning agents industry the greatest importance.
  • 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 acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
  • KH 2 PO 4 is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • sodium tripolyphosphate potassium tripolyphosphate or Mixtures of these two can be used; also mixtures of sodium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and Potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
  • preferred active ingredients or active substance preparations may also contain sodium and / or potassium hydroxide.
  • sodium and / or potassium hydroxide as the alkali source has proved to be advantageous when used as zinc salts Zinc gluconate, zinc formate and zinc acetate are used.
  • organic cobuilders can in the receiving wells in the context of the present invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates used become. These classes of substances are described below.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, understood by polycarboxylic acids such carboxylic acids which carry more than one acidity function.
  • these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use of ecological reasons, as well as mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, methylglycine diacetic acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids are next to theirs Builder action typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of washing or Detergents.
  • polymeric polycarboxylates are suitable, these are for example the Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • compositions are both polyacrylates and Copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally further ionic or nonionic monomers used.
  • Sulfonic acid-containing copolymers will be described in detail below.
  • the invention is characterized by an improved "cleanability" of the treated substrates later cleaning operations and by a significant reduction in the drying time compared to comparable agents without the use of sulfonic acid-containing polymers.
  • Drying time in the context of the teaching according to the invention is generally understood to mean the meaning of the word, ie the time that elapses until a dish surface treated in a dishwasher has dried, but in particular the time that elapses, up to 90% with a cleaning or Rinse aid is dried in concentrated or diluted form treated surface.
  • copolymers according to the invention in the compositions can be selected from the monomers of the Groups i) and ii) and optionally iii) in varying amounts, all Representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined.
  • Particularly preferred polymers have certain Structural units, which are described below.
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • machine dishwashing detergents which comprise one or more copolymers as ingredient b), the structural units of the formulas IV and / or V and / or VI and / or VII and / or VIII and / or IX - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C
  • the monomer distribution of the copolymers used in the agents according to the invention is in copolymers containing only monomers from groups i) and ii), preferably in each case 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from Group i) and 10 to 50 wt .-% monomer from group ii), each based on the polymer.
  • terpolymers particular preference is given to those which contain from 20 to 85% by weight of monomer Group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer Group iii).
  • the molecular weight of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred automatic dishwashing agents are characterized in that the copolymers have molar masses of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the content of one or more copolymers in the compositions of the invention may vary depending on Purpose and desired product performance vary, with preferred inventive automatic dishwashing detergents are characterized in that they contain the copolymer (s) in amounts of from 0.25 to 50% by weight, preferably from 0.5 to 35% by weight, especially preferably from 0.75 to 20 wt .-% and in particular from 1 to 15 wt .-%.
  • preferred automatic dishwashing detergents therefore comprise one or more zinc salts, preferably from the group of zinc stearate, zinc oleate, zinc citrate, zinc gluconate, zinc lactate and / or zinc acetate, as well as one or more sulfonic acid groups.
  • the preferred weight ratio of zinc salt (calculated on Zn 2+ ) to sulfonic acid group-containing copolymer in such a preferred automatic dishwashing detergent is between 20: 1 and 1: 500, in particular between 1: 1 and 1: 400 and particularly preferably between 1:10 and 1: 250th
  • copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • acrylic acid with maleic acid the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
  • Their molecular weight relative to free Acids is generally 2000 to 100000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.
  • biodegradable polymers of more than two various monomer units for example those containing as monomers salts of acrylic acid and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or salts as monomers of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers have as monomers preferably acrolein and Acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polyacetals which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained.
  • Preferred polyacetals are selected from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such Gluconic acid and / or glucoheptonic acid.
  • oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders.
  • This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts.
  • EDDS ethylenediamine-N, N'-disuccinate
  • Glycerol disuccinates and glycerol trisuccinates are also linked to this context. Suitable quantities are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two Contain acid groups.
  • phosphonates these are in particular hydroxyalkane or aminoalkanephosphonates.
  • Hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular Meaning as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • aminoalkanephosphonates preferably, ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, e.g. B.
  • EDTMP EDTMP
  • DTPMP DTPMP
  • HEDP HEDP
  • the aminoalkane phosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may, especially if the Agents also contain bleach, preferably, aminoalkanephosphonates, in particular DTPMP, to use or mixtures of the phosphonates mentioned.
  • Preferred active ingredients and / or active substance preparations are within the scope of the present invention Notification characterized in that it builders, preferably from the group of Silicates, carbonates, organic cobuilders and / or phosphates in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95 wt .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80% by weight, based in each case on the composition.
  • Preferred active ingredients or active substance preparations contain in the context of a preferred Embodiment of the method according to the invention one or more surfactant (s) from the Groups of anionic, nonionic, cationic and / or amphoteric surfactants.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • fatty acid glycerine esters are the mono-, di- and triesters and their mixtures to understand how they in the Preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated Fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 Carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable are saturated Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants used either alone nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable Alkypolyglycoside meet the general formula RO (G) z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.
  • nonionic surfactants used either alone nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 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-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide be suitable.
  • the amount of these nonionic surfactants is preferably not more than the ethoxylated fatty alcohols, especially not more than half of them.
  • polyhydroxy fatty acid amides of the formula (X) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (XI) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • 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
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted compounds can then be converted by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
  • surfactants are generally suitable as surfactants.
  • the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose.
  • Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols.
  • the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols preferably in the context of the present invention, the longer-chain alcohols (C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, C 11 - C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 -alcohols).
  • the longer-chain alcohols C 10 to C 18 , preferably between C 12 and C 16 , such as, for example, C 11 - C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 -alcohols.
  • nonionic surfactants have been low foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units.
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • machine dishwashing detergents according to the invention are preferred which contain surfactants of the general formula XII as nonionic surfactant (s) in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.
  • surfactants of the general formula XII as nonionic surfactant (s) in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 alkyl or alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and
  • the preferred nonionic surfactants of formula XII can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula XII may 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 undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals.
  • R 1 in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide.
  • R 2 or R 3 are independently selected from -CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are suitable.
  • Preferred automatic dishwashing agents are characterized in that R 2 and R 3 are each a residue -CH 3 , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.
  • nonionic surfactants which contain 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 exhibit.
  • Low-foaming nonionic surfactants are used as preferred additional surfactants.
  • the automatic dishwashing compositions of the invention are particularly preferred nonionic surfactant having a melting point above room temperature.
  • preferred agents are characterized by containing nonionic surfactant (s) with a Melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, included.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures thereof
  • Surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are outstanding out by good foam control.
  • the nonionic surfactant is with a melting point above room temperature, an ethoxylated nonionic surfactant resulting from the reaction from a monohydroxyalkanol or alkylphenol having 6 to 20 C atoms, preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 mol of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • active ingredients or active compound formulations contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally comprise polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol- or alkylphenol part 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 Molar mass of such nonionic surfactants.
  • Preferred active ingredients or active substance preparations are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the Propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 wt .-% and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant, contain.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, 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 wt% of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 Mole of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants which can be used with particular preference are, for example available under the name Poly Tergent® SLF-18 from Olin Chemicals.
  • a further preferred active substance / active substance preparation according to the invention contains nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ], in which 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.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (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.
  • active compounds / active substance preparations are preferred in the process according to the invention, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from
  • anionic, cationic and / or amphoteric Surfactants are used, these being because of their foaming behavior in machine Dishwashing have only minor importance and mostly only in quantities below from 10% by weight, in most cases even below 5% by weight, for example from 0.01 to 2.5% by weight, in each case based on the agent used.
  • the active ingredients / active substance preparations can thus, as a surfactant component and anionic, cationic and / or amphoteric surfactants.
  • Bleaching agents and bleach activators are important constituents of detergents and cleaning agents, and an active substance or an active substance preparation may in the context of the present invention contain one or more substances from the groups mentioned.
  • sodium percarbonate has particular significance.
  • Further useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process).
  • aqueous solutions of sodium carbonate and hydrogen peroxide, Kristallisieryskar (for example, polyphosphates, polyacrylates) and stabilizers are combined and the sodium percarbonate by salting-out agent (mainly sodium chloride) (for example, Mg 2+ ions) like.
  • the precipitated salt which still contains 5 to 12 wt .-% mother liquor, is then removed by centrifugation and dried in a fluidized bed dryer at 90 ° C.
  • the bulk density of the finished product may vary between 800 and 1200 g / l, depending on the manufacturing process.
  • the percarbonate is stabilized by an additional coating. Coating methods and materials used for coating are widely described in the patent literature. In principle, all commercially available percarbonate types can be used according to the invention, as offered for example by the companies Solvay Interox, Degussa, Kemira or Akzo.
  • the active substances or active substance preparations can also bleaches from the group of organic Contain bleach.
  • Typical organic bleaches as ingredients in the frame of the present invention the diacyl peroxides, e.g. Dibenzoyl.
  • Other typical organic bleaches are the peroxyacids, as examples especially the alkyl peroxyacids and the arylperoxy acids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic ones or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-de
  • chlorine or bromine releasing substances be used as a bleaching agent according to the present invention.
  • suitable chlorine or bromine releasing materials come for example heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach catalysts in the detergents become.
  • These substances are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
  • active substances or active substance preparations which contain one or more Substances from the group of bleach activators, in particular from groups of multiple acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), of N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), in amounts of 0.1 to 20 wt .-%, preferably from 0.5 to 15 wt .-% and in particular from 1 to 10% by weight, in each case based on the total active / active-substance preparation (s), contain.
  • TAED tetraacetylethylenediamine
  • NOSI N-nonanoylsuccinimi
  • the bleach activators preferred in the context of the present invention furthermore include the "nitrile quats", cationic nitriles of the formula (XIII), in which 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 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -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 ,
  • preferred active substances or active substance preparations are characterized in that it contains the cationic nitrile of the formula (XIII) in amounts of from 0.1 to 20 Wt .-%, preferably from 0.25 to 15 wt .-% and in particular from 0.5 to 10 wt .-%, respectively based on the total active / active substance preparation.
  • hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glykosylhydrolasen and mixtures of the enzymes mentioned in question. All of these hydrolases carry in the laundry to remove stains such as proteinaceous, fatty or starchy stains and graying at. Cellulases and other glycosyl hydrolases may be over it In addition, by removing pilling and microfibrils for color retention and increasing the Softness of the textile contribute. For bleaching or for inhibiting the color transfer can Oxidoreductases are also used.
  • subtilisin-type proteases and in particular proteases used from Bacillus lentus.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting Enzymes or protease and cellulase or cellulase and lipase or lipolytic Enzymes or protease, amylase and lipase or lipolytic enzymes or Protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of special interest. Examples of such lipolytic enzymes are known Cutinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulating substances to them to protect against premature decomposition.
  • Preferred agents according to the invention contain enzymes preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10 Wt .-%, preferably from 0.5 to 8 wt .-% and in particular from 1 to 5 wt .-%, respectively based on the total active / active substance preparation (s).
  • Dyes the selection of which does not cause any difficulty for the skilled person, have a high level of Shelf life and insensitivity to the other ingredients of the product.
  • Preferred for use in the process according to the invention are all colorants which are used in the Washing process can be oxidatively destroyed as well as mixtures thereof with suitable blue Dyes, so-called blue toners. It has proved to be advantageous to use dyes which are in Water or at room temperature in liquid organic substances are soluble.
  • anionic colorants e.g. anionic nitrosofarads.
  • a possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1, Part 2: 10020), which is referred to as Commercial product, for example, as Basacid® Green 970 from BASF, Ludwigshafen, available is, as well as mixtures of these with suitable blue dyes.
  • Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (Cl 45100), Basacid® Yellow 094 (Cl 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acid Blue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).
  • the colorant When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid® Green or the abovementioned Sandolan® Blue, colorant concentrations in the range from a few 10 -2 to 10 -3 % by weight are typically selected.
  • the suitable concentration of the colorant in detergents or cleaners is typically between 10 -3 and 10 -4 % by weight.
  • Fragrances are added to the compositions in the context of the present invention in order to enhance the aesthetic Impression of the products to improve and the consumer in addition to the performance of the product a visually and sensory "typical and unmistakable" product available too put.
  • the ethers include Benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms Citral, Citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethylionone and methyl cedryl ketone, to the alcohols Anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the Hydrocarbons mainly include the terpenes such as limonene and pinene.
  • perfume oils can also be natural fragrance mixtures as available from plant sources, e.g. Pine, Citrus, Jasmine, Patchouly, Rose or Ylang-Ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, Melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • Active ingredients or active-product formulations for automatic dishwashing may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes [Me-TACN) Mn IV (m-0) 3 Mn IV (Me-TACN)] 2+ (PF 6 - ) 2 , [Me-MeTACN) Mn IV (m-0) 3 Mn IV (Me-MeTACN)] 2+ (PF 6 - ) 2 , [Me-TACN) Mn III (m-0) (m-0Ac) 2 Mn III (Me-TACN)] 2+ (PF 6 - ) 2 and [Me-MeTACN) Mn III (m-0) (m-0) (m-
  • active substances or active substance preparations are preferred, in addition at least one silver protecting agent selected from the group of triazoles, the Benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, preferably Benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1 wt .-%, preferably from 0.01 to 0.5 wt .-% and in particular from 0.05 to 0.25 wt .-%, each based on the / total active / active substance preparation.
  • corrosion inhibitors which is a glass corrosion prevent or reduce it during machine dishwashing.
  • particularly preferred means are the magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids, in particular the zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate.
  • water-insoluble Containers comprising at least two receiving wells and at least one in this Receiving trough active and at least one of these receiving troughs occlusive water-insoluble protective film and at least one between this / these water-insoluble Foil (s) and the water-insoluble container water-soluble film for Dosing of active substances, as well as a water-insoluble container, comprising at least two Receiving troughs and at least one active substance located in these receiving troughs, at least one of these receiving wells completely occlusive water-insoluble film and at least one between this water-insoluble film (s) and the water-insoluble one Container located water-soluble film.
  • the preferred retaining device is not is necessarily integrative part of the water-insoluble container is one Kit of parts for the dosing of active ingredients, comprising an above-described, water-insoluble container and a holding device possible.

Claims (24)

  1. Procédé pour le dosage de substances actives et/ou de préparations de substances actives choisies parmi le groupe des agents de lavage ou des agents de nettoyage, caractérisé en ce qu'à partir d'un récipient insoluble dans l'eau, comprenant au moins deux cavités de réception et au moins une substance active et/ou une préparation de substance active disposées dans ces cavités de réception, chacune de ces cavités de réception étant fermée par une feuille de protection séparée insoluble dans l'eau, on enlève au moins une de ces feuilles de protection insolubles dans l'eau et on amène le récipient en contact avec de l'eau ou avec des solutions aqueuses ou avec des solutions contenant de l'eau de telle sorte que la ou les substances actives et/ou la ou les préparations de substances actives se libère(nt) dans l'eau ou dans les solutions aqueuses ou dans des solutions contenant de l'eau via des processus de dispersion et/ou de dissolution.
  2. Procédé selon la revendication 1, caractérisé en ce que le récipient insoluble dans l'eau comprend trois, quatre, cinq, six, sept, huit, neuf, dix, onze, douze, treize, quatorze, quinze, seize, dix-sept, dix-huit, dix-neuf, vingt, vingt et un, vingt-deux, vingt-trois, vingt-quatre cavités de réception ou plus, chacune de ces cavités de réception étant fermée par une feuille de protection séparée insoluble dans l'eau.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le récipient insoluble dans l'eau comprend trois, quatre, cinq, six, sept, huit, neuf, dix, onze, douze, treize, quatorze, quinze, seize, dix-sept, dix-huit, dix-neuf, vingt, vingt et un, vingt-deux, vingt-trois, vingt-quatre cavités de réception ou plus, respectivement deux, trois, quatre de ces cavités de réception ou plus étant fermées par une même feuille de protection insoluble dans l'eau.
  4. Procédé selon la revendication 3, caractérisé en ce que le récipient insoluble dans l'eau, avant d'enlever la feuille de protection, est fixé à l'intérieur d'un lave-vaisselle et est mis en contact avec de l'eau ou avec des solutions aqueuses ou avec des solutions contenant de l'eau après l'élimination de la feuille de protection lors du déroulement d'un programme de lavage.
  5. Procédé selon la revendication 4, caractérisé en ce que la fixation a lieu via un dispositif de retenue à l'intérieur du dispositif ou via un dispositif de retenue placé contre le récipient insoluble dans l'eau.
  6. Procédé selon la revendication 5, caractérisé en ce que le récipient insoluble dans l'eau est placé dans le dispositif de retenue de façon à pouvoir se déplacer par rapport à ce dispositif de retenue ou par rapport à une partie de ce dispositif de retenue.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le récipient insoluble dans l'eau est constitué par des polymères et/ou des mélanges de polymères insolubles dans l'eau.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le récipient insoluble dans l'eau est une pièce moulée par emboutissage.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que l'épaisseur de paroi du récipient insoluble dans l'eau s'élève entre 5 µm et 2000 µm, de préférence entre 10 µm et 1000 µm, et en particulier entre 50 µm et 500 µm.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que la feuille de protection insoluble dans l'eau est constituée par des polymères et/ou par des mélanges de polymères insolubles dans l'eau.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que l'épaisseur de la feuille de protection insoluble dans l'eau s'élève entre 1 µm et 1000 µm, de préférence entre 5 µm et 500 µm, et en particulier entre 10 µm et 200 µm.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que les cavités de réception fermées avec la feuille de protection insoluble dans l'eau présentent un volume de 1 ml à 1000 ml, de préférence de 1 ml à 100 ml, et en particulier de 1 ml à 50 ml.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce que le quotient de la surface d'ouverture adimensionnelle des cavités de réception et du volume adimensionnel des cavités de réception s'élève à au moins 0,1, de manière particulièrement préférée à au moins 0,2, et en particulier à au moins 0,4.
  14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce que la ou les substances actives/préparations de substances actives sont présentes sous forme solide et/ou sous forme de gel et/ou sous forme d'un liquide non aqueux dans la cavité de réception.
  15. Procédé selon l'une quelconque des revendications 1 à 14, caractérisé en ce qu'une feuille soluble dans l'eau est disposée entre la feuille insoluble dans l'eau et le récipient insoluble dans l'eau, qui ferme complètement la ou les cavités de réception après l'élimination de la feuille de protection insoluble dans l'eau, mais qui se dissout au contact avec de l'eau ou avec des solutions aqueuses ou avec des solutions contenant de l'eau.
  16. Procédé selon l'une quelconque des revendications 1 à 15, caractérisé en ce que deux, trois, quatre feuilles solubles dans l'eau ou plus identiques et/ou différentes sont disposées entre la feuille insoluble dans l'eau et le récipient insoluble dans l'eau, qui ferment complètement respectivement une, deux, trois cavités de réception ou plus après l'élimination de la feuille de protection insoluble dans l'eau, mais qui se dissolvent au contact avec de l'eau ou avec des solutions aqueuses ou avec des solutions contenant de l'eau.
  17. Procédé selon l'une quelconque des revendications 15 ou 16, caractérisé en ce que les feuilles solubles dans l'eau se distinguent par leur épaisseur et/ou par leur composition.
  18. Procédé selon l'une quelconque des revendications 15 à 17, caractérisé en ce que l'épaisseur de la feuille soluble dans l'eau s'élève entre 1 µm et 1000 µm, de préférence entre 5 µm et 500 µm, et en particulier entre 10 µm et 200 µm.
  19. Procédé selon l'une quelconque des revendications 15 à 18, caractérisé en ce que la feuille soluble dans l'eau est constituée d'alcool polyvinylique (acétalisé), de polyvinylpyrrolidone, d'oxyde de polyéthylène, de gélatine, d'amidon et de dérivé(s) de l'amidon, de cellulose et de dérivé(s) de la cellulose, en particulier de méthylcellulose et/ou par de mélanges de ces substances.
  20. Procédé selon l'une quelconque des revendications 1 à 15, caractérisé en ce que la cavité de réception contient au moins deux substances actives et/ou préparations de substances actives dont la vitesse de libération, via des processus de dispersions et/ou de dissolution dans l'eau ou dans des solutions aqueuses ou dans des solutions contenant de l'eau, diffère.
  21. Procédé selon la revendication 20, caractérisé en ce que la vitesse de libération des substances actives et/ou des préparations de substances actives diffère sur base d'une solubilité différente, d'une température de fusion différente, d'une enduction différente et/ou d'un agencement spatial différent de ces substances actives dans la cavité de réception.
  22. Procédé selon la revendication 1, caractérisé en ce que la ou les substances actives et/ou la ou les préparations de substances actives contiennent une ou plusieurs substances actives de lavage et de nettoyage qui sont choisies parmi le groupe comprenant des builder, des cobuilder, des agents tensioactifs, des agents de blanchiment, des activateurs du blanchiment, des enzymes, des colorants, des arômes, des électrolytes, des agents de réglage du pH, des porteurs de parfums, des agents de fluorescence, des hydrotropes, des inhibiteurs de mousse, des huiles de silicone, des agents s'opposant à la redéposition, des agents d'azurage optique, des inhibiteurs du grisonnement, des agents s'opposant au rétrécissement, des agents de protection contre le froissement, des inhibiteurs du transfert des couleurs, des substances actives antimicrobiennes, des germicides, des fongicides, des antioxydants, des inhibiteurs de la corrosion, des antistatiques, des agents facilitant le repassage, des répulsifs et des agents d'imprégnation, des agents s'opposant au gonflement et au glissement et/ou des absorbants de l'ultraviolet.
  23. Récipient insoluble dans l'eau, comprenant au moins deux cavités de réception et au moins une substance active et/ou une préparation de substance active disposées dans ces cavités de réception, choisies parmi le groupe des agents de lavage ou des agents de nettoyage, chacune de ces cavités de réception étant fermée par une feuille de protection séparée insoluble dans l'eau.
  24. Récipient insoluble dans l'eau selon la revendication 23, caractérisé en ce que le récipient présente un dispositif de retenue placé contre le récipient soluble dans l'eau.
EP02021944A 2001-10-01 2002-09-30 Méthode de dosage semi-automatique Expired - Lifetime EP1298195B1 (fr)

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DE10148571A DE10148571B4 (de) 2001-10-01 2001-10-01 Semiautomatische Dosierung

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FR2940101B1 (fr) 2008-12-19 2011-02-18 Oreal Composition de teinture d'oxydation de fibres keratiniques comprenant un corps gras et un derive 4,5-diaminopyrazole
FR2940102B1 (fr) 2008-12-19 2016-03-11 Oreal Composition de teinture d'oxydation des fibres keratiniques comprenant un corps gras, un epaississant et un precurseur de colorant d'oxydation
FR2940105B1 (fr) 2008-12-19 2011-04-08 Oreal Composition comprenant un corps gras et un tensioactif oxyethylene particulier, procede de coloration la mettant en oeuvre et dispositifs
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FR2940077B1 (fr) 2008-12-19 2012-07-20 Oreal Procede de coloration eclaircissante de matieres keratiniques mettant en oeuvre une composition anhydre colorante comprenant un agent alcalin et une composition oxydante.
FR2940078B1 (fr) 2008-12-19 2011-05-13 Oreal Composition comprenant un corps gras et un polymere cationique, procede de coloration la mettant en oeuvre et dispositifs
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ATE309324T1 (de) 2005-11-15
DE50204840D1 (de) 2005-12-15
ES2253482T3 (es) 2006-06-01

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