EP1543100B1 - Procede de production de doses de produit de lavage ou de nettoyage enveloppees - Google Patents

Procede de production de doses de produit de lavage ou de nettoyage enveloppees Download PDF

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Publication number
EP1543100B1
EP1543100B1 EP03798910A EP03798910A EP1543100B1 EP 1543100 B1 EP1543100 B1 EP 1543100B1 EP 03798910 A EP03798910 A EP 03798910A EP 03798910 A EP03798910 A EP 03798910A EP 1543100 B1 EP1543100 B1 EP 1543100B1
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EP
European Patent Office
Prior art keywords
acid
preferred
water
soluble
washing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP03798910A
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German (de)
English (en)
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EP1543100A1 (fr
Inventor
Alexander Lambotte
Matthias Reimann
Wolfgang Barthel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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
    • 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

Definitions

  • the present invention relates to a process for the preparation of detergent or cleaner portions having a coating of water-soluble materials which closely surrounds the compositions contained in the portion.
  • Portioned detergents and cleaners are widely described in the art and are becoming increasingly popular with consumers because of their ease of use.
  • the portioning can be achieved, for example, by conversion into a compact form or by separate packaging.
  • the tabletting has an outstanding role
  • portions are used in the field of washing or cleaning agents, which are surrounded by packages of water-soluble materials.
  • EP-A-700 989 discloses portion-packed detergents in a water-soluble film.
  • these portions have the disadvantage of not having the high degree of compactness which tablets have.
  • the Beyogllung of tubular bags on the one hand leads to a low degree of compaction, on the other hand to a technically related void volume, so that a measured for a washing or cleaning cycle amount of detergent or cleaning agent occupies a larger space than a corresponding amount in tableted form.
  • the void volume causes filled bags are unstable to mechanical influences and can burst.
  • a coating provides visually appealing tablets with a smooth, glossy surface and advantageous haptic properties.
  • the coating of tablets is technically complicated and expensive.
  • the use of water-soluble packaging is described in the form of bags of water-soluble film in the prior art.
  • WO-A-0055 415 and GB-A-2 361 685 disclose methods of making water-soluble packages.
  • these tablets have aesthetic disadvantages compared to conventional tablets.
  • the consumer acceptance is low in this form of supply because the outer packaging suggests to the consumer to have to be removed - a real advantage of the water-soluble "flow packs" is therefore not visible to the consumer.
  • the method should be so variable that both tablets and other ready-made detergent or cleaning compositions such as moldings, powders, granules, extrudates, dandruff, etc. pack aesthetically pleasing.
  • portions should be produced which combine the advantages of the compactness of tablets with those of the rapid solubility of portioned systems and, moreover, need not be provided with an outer packaging of water-insoluble film.
  • a water-soluble lower film is provided, which is placed on a transport chain or a mold (s) tool.
  • a combination of transport chain and mold (s) tool is used according to the invention.
  • a transport chain in the context of the present invention, conveyor belts etc. are understood. Transport chains or belts are preferred for reasons of process economy over fixed molds.
  • a combination of transport chain and mold (s) tool for example, a production line, which has recesses at regular intervals.
  • mold (s) tools are used, the molds may be designed as individual units, but it is also possible and preferred for reasons of process economy to use molds having a variety of shapes.
  • a water-soluble film is placed in step a) of the method according to the invention, to which in the next process step, one or more washing or cleaning agent portion (s) are applied.
  • Preferred processes according to the invention are characterized in that the lower film is preformed by the application of a vacuum and / or by heating. As a result, the film is provided with a cavity for receiving the particulate detergent composition.
  • the procedure described above is not on the Dosage of particulate compositions limited, but can also be used for the inventive packaging of tablets.
  • the water-soluble film prior to application to the mold (s) tool pre to temperatures above 50 ° C, preferably above 70 ° C and in particular above 90 ° C, heated. As a result, the subsequent deformation is facilitated.
  • the film can be further heated during the forming process.
  • process variants are preferred in which the deformation of the water-soluble film by heating the film to temperatures of 100 to 120 ° C is supported. A combination of the two process variants, i. Applying a heated film and further heating is possible and preferred.
  • the film may also be pressed into the mold by the dosage of the tablet or particulate composition.
  • particulate compositions for example, by placing an annular die on top of the film over the mold and metering the particulate composition through this tube into the mold.
  • the film can sink into the mold either because of the mass of the composition, but the metering process can also be assisted by pushing the composition into the mold, for example by means of a punch in the tubular metering device.
  • this dosing unit can also be used, but due to the compact shaped body structure, the tablet can also be placed without them.
  • a particulate composition it can also be easily precompressed to ensure the most complete possible filling of the mold. If multiphase portions are to be prepared, pressing the particulate composition first metered insures a plane interface between the two layers. Visually, such two-phase portions are closely related to the known two-layer tablets. However, the forces for pressing the particulate composition are chosen so that the range of elastic deformation is not left. The metering pressure thus does not lead to sintering together of the particles (as would be the case with tabletting), but only to the removal of bulk material cavities and to a flat surface.
  • methods according to the invention are preferred in which a particulate premix is slightly compacted by means of the punch, wherein compression forces below 1 kN are preferred.
  • Lightly precompacted particulate compositions can also be easily lifted out of the mold before sealing, without breaking immediately - this can be used to advantage for the position of the later seal, see below.
  • Preferred methods for coating particulate compositions according to the invention are characterized in that a further particulate washing or cleaning agent is metered onto the first precompressed particulate washing or cleaning agent. As a result, visually appealing portions can be produced.
  • step c) of the method according to the invention determines how high the composition protrudes from the film plane.
  • the sealed seam forms as a "brim" on an end face of the portion.
  • a simple plate however, has the disadvantage that the film that covers the top of the portion is exposed to the influence of heat.
  • the portion stands out of the mold and the portion of the portion protruding from the mold is covered with another film.
  • the seal can not be done now with a plate-like sealing tool, but takes place with an annular tool.
  • This method has the advantage that the lowering of the annular sealing tool additionally tightens the upper foil.
  • the heat on the portion compared to a "hot plate" is significantly reduced.
  • washing or cleaning agent portion (s) in step b) does not terminate flush with the upper side of the mold after being placed on the lower film, but protrude from it, it being preferred that that a maximum of 50%, preferably a maximum of 40% and in particular a maximum of 30% of the greatest height of the washing or cleaning agent portion (s) are within the mold.
  • the portion can be metered i. the washing or cleaning agent composition or the washing or cleaning agent tablet is placed on a lower film, which in turn rests on a flat conveyor chain or a "conveyor belt".
  • Inventive methods in which the lower film during the steps b) to e) is completely flat, according to the invention are preferred because of the simpler apparatus design and the simplified procedure.
  • the washing or cleaning agent portion to be introduced onto or into the lower film may be particulate or may consist of a majority of moldings, as previously described.
  • Tablets and casting bodies have the advantage that they can be deposited exactly on the foil and do not slip even when the foil is transported on a flat conveyor belt or a conveyor chain. Particle clusters can change their shape in this approach.
  • Preferred methods according to the invention are therefore characterized in that the washing or cleaning agent portion (s) placed on the bottom foil in step b) is / are (a) washing or cleaning agent tablet (s).
  • inventive method for the packaging of washing or cleaning active casting bodies is used, wherein it is particularly preferred that the casting in the packaging with one or more particulate washing or cleaning agents, such as powders, extrudates or granules combined.
  • particulate washing or cleaning agents such as powders, extrudates or granules combined.
  • step c) of the process according to the invention an upper film is applied to the lower film coated with one or more washing or cleaning agent portions, which is fixed in step d) and sealed in step e).
  • the application of the top film preferably takes place with the aid of a dome-shaped tool, which carries the top film in itself and is slipped over the washing or cleaning agent portions located on the bottom film. It is preferred that the top film is not flat, so tense, but also formed like a dome. This can be achieved by applying the top film in the tool to its wall.
  • Preferred methods are characterized in that the top film is preformed before applying in step c) by applying a vacuum and / or by heating in a dome.
  • top film It may be advantageous to heat the top film to temperatures between 100 ° C and 200 ° C, with temperatures between 100 ° C and 120 ° C are preferred.
  • the dome-like shape with the top film is then slipped over the washing or cleaning agent portion (s) on the bottom film. This forms an already completely surrounded by water-soluble film washing or cleaning agent portion, which is partially separated by an air cushion of the film.
  • the air can be sucked through slots on the bottom surface of the upper tool.
  • the creation of a vacuum on these slots additionally causes the top film to detach from the dome as soon as the dome-shaped mold is ventilated from above.
  • step c) is introduced by pre-aeration from above.
  • the dome-like tool is fully ventilated from above.
  • a skin-tight enclosure is preferably achieved in that a vacuum is applied to the connecting surface between the upper and lower film.
  • the dome-like tool can be acted upon with an overpressure which presses the top film onto the washing or cleaning agent portion (s).
  • Inventive methods which are characterized in that the steps c) and / or d) by evacuating the Interspace between the upper and lower film and / or supported by applying pressure to the upper film are preferred according to the invention.
  • step d) the films are completely sealed around the washing or cleaning agent portion (s). Following sealing, the films can be stabilized by the differential pressure in the mold to prevent reforming. In addition, the mold can be cooled to keep the sealed product unchanged in shape and to shorten the residence times in the mold.
  • a further variant of the method envisages initially packaging the portions either in water-soluble films as disclosed above and then shrink-drying the film packaging onto the portions.
  • This shrink film is a film that has been stretched and is contracting again when heated. In this case, it is possible to produce envelopes lying very close to the surface of the portions.
  • Processes which are likewise preferred according to the invention are characterized in that pre-stretched films are used as the water-soluble film (s) in steps a) and c), which are shrunk onto the detergent or cleaning agent portion (s) in step e) or subsequently.
  • multi-layer film laminates can also be used according to the invention.
  • Such laminates have the advantage that the individual layers can be adapted to the respective environmental conditions.
  • an inner film can be used which is inert to the composition to be filled and does not undergo any undesired reactions with the filling.
  • An outer film which better resists environmental influences, can protect the composition from external influences in such a two-film laminate.
  • three-film laminates, four-film laminates, etc. can also be used according to the invention. Different functions (mechanical stabilization, vapor barrier, optics, incorporation of ingredients, etc.) can be assigned to the individual films.
  • water-soluble coating comprises one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and derivatives thereof, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof.
  • PVAL polyvinyl alcohol
  • PVAL polyvinylpyrrolidone
  • polyethylene oxide polyethylene glycol
  • gelatin cellulose and derivatives thereof, in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof.
  • the wraps may be mixed with plasticizers known to those skilled in the art in order to increase the flexibility of the material.
  • polyvinyl alcohols are particularly preferred as water-soluble polymers.
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of 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%. , so 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 highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically harmless and are biological at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Polyvinyl alcohol is largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.
  • the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis is 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 used, preference being given to processes according to the invention in which the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose molecular weight is in the range from 3,500 to 100,000 gmol -1 , preferably from 10,000 to 90,000 gmol -1 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.
  • the water-soluble coating comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MW (50%). ) to Mw (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.
  • polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant).
  • Polyvinyl alcohols which are particularly suitable for the purposes of the present invention 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).
  • ERKOL types from Wacker.
  • a further preferred group of water-soluble polymers which can serve as a coating according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskol® (BASF).
  • Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (I) which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators.
  • free-radical initiators peroxides, azo compounds
  • polyvinylpyrrolidones have molecular weights in the range from about 2500-750000 g / mol, which are characterized by the specification of the K values and, depending on the K value, have glass transition temperatures of 130-175 °. They are offered as white, hygroscopic powders or as aqueous solutions. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
  • copolymers of vinylpyrrolidone with other monomers in particular vinylpyrrolidone / vinyl ester copolymers, as are sold, for example, under the trademark Luviskol® (BASF).
  • Luviskol® VA 64 and Luviskol® VA 73, in each case vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
  • the vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II) as a characteristic building block of the macromolecules.
  • the vinyl acetate polymers (R CH 3 ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.
  • the polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization).
  • Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (I) and (II).
  • PEG polyethylene glycols
  • PEG polyethylene oxides
  • n can take values between 5 and> 100,000.
  • PEGs are prepared industrially by anionic ring-opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on the reaction procedure, they have molar masses in the range of about 200-5,000,000 g / mol, corresponding to degrees of polymerization of about 5 to> 100,000.
  • PEG polyethylene glycols
  • PEOX polyethylene oxides
  • gelatine 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 largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
  • the water-soluble coating comprises hydroxypropylmethylcellulose (HPMC) having a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1.9 , and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) of from 0.1 to 0.3, preferably from 0.15 to 0.25.
  • HPMC hydroxypropylmethylcellulose
  • polymers which are suitable according to the invention are water-soluble amphopolymers.
  • Amphoteric polymers ie polymers which contain both free amino groups and free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule and -COO - or -SO 3 - groups, and those polymers comprising -COOH or SO 3 H groups and quaternary ammonium groups.
  • amphopolymer which can be used according to the invention is the acrylic resin obtainable under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • Amphomer® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and optionally further ionic or nonionic monomers, as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen.
  • unsaturated carboxylic acids for example acrylic and methacrylic acid
  • cationically derivatized unsaturated carboxylic acids for example acrylamidopropyltrimethylammonium chloride
  • optionally further ionic or nonionic monomers as described, for example, in German Offenlegungsschrift 39 29 973 and the one cited therein State of the art can be seen.
  • Terpolymers of acrylic acid, methyl acrylate and Methacrylamidopropyltrimoniumchlorid as they are commercially available under the name Merquat®2001 N, according to
  • amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).
  • cationic polymers preferably usable according to the invention as coating polymers are cationic polymers.
  • the cationic polymers the permanent cationic polymers are preferred.
  • "permanently cationic” refers to those polymers which have a cationic group independently of the pH. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.
  • Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers.
  • Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.
  • the coating or the film material can contain, in addition to the water-soluble polymer or the water-soluble polymers, further ingredients which in particular improve the processability of the starting materials for the coating.
  • plasticizers and release agents should be mentioned here.
  • colorants and / or fragrances as well as optical brighteners can be incorporated into the water-soluble sheath in order to achieve aesthetic effects there.
  • Hydrophilic, high-boiling liquids can be used according to the invention as plasticizers, it also being possible to use solids which are solid at room temperature as a solution, dispersion or melt.
  • plasticizers are selected from the group glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, dodecaethylene glycol, glycerol, neopentyl glycol, trimethylolpropane, pentaerythritol, mono -, di-, triglycerides, surfactants, in particular nonionic surfactants, and mixtures thereof.
  • Ethylene Glycol (1,2-Ethanediol, "Glycol”) is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113.
  • the solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C.
  • ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
  • Diethylene glycol (2,2'-oxydiethanol, digol), HO- (CH 2 ) 2 -O- (CH 2 ) 2 -OH, is a colorless, viscous, hygroscopic, sweet-tasting liquid of density 1.12 -6 ° C melts and boils at 245 ° C. With water, alcohols, glycol ethers, ketones, esters, chloroform, diglycol is miscible in any ratio, but not with hydrocarbons and oils.
  • the diethylene glycol which is usually abbreviated in practice to diglycol, is prepared from ethylene oxide and ethylene glycol (ethoxylation) and is therefore practically the starting element of the polyethylene glycols (see above).
  • Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C.
  • Glycerine was originally only one By-product of fat saponification, but today is technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO 3 contact via the step of the glycide.
  • Trimethylolpropane [TMP, etriol, etiol, 1,1,1-tris (hydroxymethyl) propane] is chemically exactly 2-ethyl-2-hydroxymethyl-1,3-propanediol and comes in the form of colorless, hygroscopic masses having a melting point of 57 -59 ° C and a boiling point of 160 ° C (7 hPa) in the trade. It is soluble in water, alcohol, acetone, but insoluble in aliphatic and aromatic hydrocarbons. The preparation is carried out by reaction of formaldehyde with butyraldehyde in the presence of alkalis.
  • Pentaerythritol [2,2-bis (hydroxymethyl) -1,3-propanediol, penta, PE] is a white, crystalline powder with a sweetish taste that is non-hygroscopic and combustible and has a density of 1.399, a melting point of 262 ° C and has a boiling point of 276 ° C (40 hPa). Pentaerythritol is readily soluble in boiling water, poorly soluble in alcohol and insoluble in benzene, carbon tetrachloride, ether, petroleum ether.
  • pentaerythritol is prepared by reacting formaldehyde with acetaldehyde in aqueous solution of Ca (OH) 2 or NaOH at 15-45 ° C.
  • a mixed aldol reaction takes place in which reacting formaldehyde as a carbonyl component, acetaldehyde as a methylene component. Due to the high carbonyl activity of formaldehyde, the reaction of acetaldehyde with itself hardly occurs at all.
  • the thus formed tris (hydroxymethyl) acetaldehyde is converted with formaldehyde in a crossed Cannizzaro reaction into pentaerythritol and formate.
  • Mono-, di-, triglycerides are esters of fatty acids, preferably longer-chain fatty acids with glycerol, wherein depending on the type of glyceride, one, two or three OH-groups of glycerol are esterified.
  • the acid component with which the glycerol can be esterified in mono-, di- or triglycerides which can be used according to the invention there are, for example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), Undecanoic acid, etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid) are preferred. .
  • Hexacosanoic acid (cerotic acid), triacotinic acid (melissic acid) and the unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic acid), 9c, 12c octadecadienoic acid (linoleic acid), 9t, 12t octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c octadecranic acid (linolenic acid).
  • the native fatty substances triglycerides
  • the modified native fatty substances partially hydrolyzed fats and oils
  • fatty acid mixtures can also be prepared by cleavage of native fats and oils and subsequently separated, with the purified fractions subsequently being converted again to mono-, di- or triglycerides.
  • Acids which are here esterified with the glycerol, in particular coconut oil fatty acid (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt % C 16 , 2% by weight C 18 , 8% by weight C 18 ' , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50 wt .-% C 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 ' , 1 wt .-% C 18 " ), tallow fatty acid (about 3% by weight C 14 , 26% by weight C 16 , 2% by weight C 16 ' , 2% by weight C 17 , 17% by
  • soybean oil fatty acid (approx. 2 wt .-% C 14 , 15 wt .-% C 16 , 5 wt .-% C 18 , 25 wt .-% C 18 ' , 45 wt .-% C 18 " , 7 wt .-% C 18''' ).
  • nonionic surfactants are also suitable as further plasticizers.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • 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 stated degrees of ethoxylation represent statistical averages, which for a particular product a whole 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 fat ohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants having a melting point above room temperature.
  • preferred wraps are characterized in that nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43, are used as the plasticizer , 3 ° C, are used.
  • Suitable 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 high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the 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) surfactants.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles 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.
  • ethoxylated nonionic surfactant which are selected from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes 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 nonionic surfactants.
  • 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. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • 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.
  • plasticizers substances may be glycerol carbonate, Prpylenglycol and propylene carbonate.
  • Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO 2 to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm -3 , which boils at 125-130 ° C (0.15 mbar).
  • 1,3-Propanediol trimethylene glycol
  • 1,0597 a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C.
  • the preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.
  • 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C.
  • 1,2-Propanediol is prepared from propylene oxide by water addition.
  • Propylene carbonate is a water-bright, easily mobile liquid, with a density of 1.21 gcm -3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO 2 at 200 ° C and 80 bar.
  • additional additives which are preferably in solid form at room temperature.
  • Fumed silicas such as the commercially available Aerosil® or precipitated silicas are suitable here.
  • Particularly preferred processes according to the invention are characterized in that as further additives one or more materials from the group (preferably highly dispersed) silica, dispersion powder, high molecular weight polyglycols, stearic acid and / or stearic acid salts, and / or from the group of inorganic salts such as sodium sulfate, calcium chloride and / or from the group of Inclusiontruckner such as urea, cyclodextrin and / or from the group of super adsorbers such as (preferably crosslinked) polyacrylic acid and / or their salts such as Cabloc 5066 / CTF and mixtures thereof, is / are used.
  • casting bodies are used in the process according to the invention as a washing or cleaning agent portion, with particular preference.
  • starting materials for the o.g. Casting bodies have been found to be washing or cleaning agent dispersions.
  • the processing of these dispersions into casting bodies and the subsequent packaging by means of the process according to the invention has a number of advantages. First of all, spatial shapes can be realized by the casting technology, which are not accessible by the tabletting. Furthermore, the castings, as described below against the tablets characterized by improved solubility.
  • foundry bodies unlike tablets, are generally ductile, and can be plastically deformed to some degree in the course of the packaging process according to the invention by the action of pressure, for example when applying the top film or during the subsequent fixing of the top film on the bottom film.
  • irregularities in the production of the casting bodies for example height, thickness, etc.
  • optically enhancing features can be embossed into the casting body.
  • dispersions are characterized in that the dispersion has a density above 1.040 g / cm 3 .
  • dispersions according to the invention having a density of 1040-1670 g / cm 3, preferably 1.120 to 1.610 g / cm 3, particularly preferably 1.210 to 1.570 g / cm 3, most preferably 1.290 to 1.510 g / cm 3 , and in particular between 1.340 and 1.480 g / cm 3 .
  • the density data refer to the densities of the dispersions at 20 ° C.
  • dispersion in this application a system of several phases is referred to, one of which is dispersed continuously (dispersion medium) and at least one further (dispersed substances).
  • Particularly preferred detergents or cleaners according to the invention are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, more preferably above 15% by weight, most preferably above 17% by weight. and in particular above 19 wt .-%, each based on the total weight of the dispersion.
  • agents according to the invention which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion.
  • the maximum content of preferred dispersions of dispersants according to the invention is preferably less than 63% by weight, preferably less than 57% by weight, more preferably less than 52% by weight, very particularly preferably less than 47 Wt .-% and in particular less than 37 wt .-%.
  • the dispersants used are preferably water-soluble or water-dispersible.
  • the solubility of these dispersants at 25 ° C. is preferably more than 200 g / l, preferably more than 300 g / l, more preferably more than 400 g / l, very preferably between 430 and 620 g / l and especially between 470 and 580 g / l.
  • Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers.
  • the dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers.
  • Polyvinylpyrrolidones are preferred dispersants in the invention.
  • Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (I) which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators.
  • free-radical initiators peroxides, azo compounds
  • polyvinylpyrrolidones have molecular weights in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - K value-dependent - glass transition temperatures of 130-175 ° have. They are called white, hygroscopic powder or aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
  • Viliylpyrrolidone / vinyl ester copolymers such as those sold under the trademark Luviskol® (BASF).
  • Luviskol® VA 64 and Luviskol® VA 73, in each case vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
  • the vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II) as a characteristic building block of the macromolecules.
  • the vinyl acetate polymers (R CH 3 ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.
  • Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (I) and (II)
  • Cellulose ethers such as hydroxypropyl cellulose, hydroxyethyl cellulose and methyl hydroxypropyl cellulose, such as those sold under the trademarks Culminal® and Benecel® (AQUALON).
  • Cellulose ethers can be described by the following general formula R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula is -CH 2 CH 2 CH 2 -OH or -CH 2 CH 2 -OH.
  • Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit.
  • Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and - propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their watery Solutions are relatively insensitive to changes in pH or electrolyte addition.
  • Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n in small proportions also structural units of the type [-CH 2 -CH (OH) -CH (OH) -CH 2 ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but in particular technically by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. By these technical methods also PVAL are accessible, which contain a predeterminable residual portion of acetate groups.
  • PVAL polyvinyl acetates with a residual content of acetyl groups of about 1-2 or 11-13 mol%.
  • Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols.
  • Polymers of ethylene glycol, those of general formula III H- (O-CH 2 -CH 2 ) n -OH (III) satisfy, where n can assume values between 1 (ethylene glycol) and several thousand.
  • n can assume values between 1 (ethylene glycol) and several thousand.
  • polyethylene glycols there are various nomenclatures that can lead to confusion.
  • Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210.
  • polyethylene glycols for example under the trade names Carbowax® PEG 200 (Union Carbide), Einkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone -Poulenc), Lutrol® E300 (BASF) and the corresponding trade name with higher numbers.
  • the average relative molecular weight of at least one of the dispersants used in the detergents or cleaners according to the invention, in particular at least one of the poly (alkylene) glycols used, is preferably between 200 and 36,000, preferably between 200 and 6000 and more preferably between 300 and 5000.
  • washing or cleaning agents contain as dispersing agent a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, wherein the weight fraction of the poly (ethylene) glycol on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight.
  • a nonionic polymer preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, wherein the weight fraction of the poly (ethylene) glycol on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight.
  • Detergents or cleaning compositions according to the invention in which the dispersion medium is more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very particularly preferably more than 98, are particularly preferred Wt .-% and in particular to 100 wt .-% of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular Poly (ethylene) glycol.
  • Dispersing agents which also contain poly (propylene) glycol in addition to poly (ethylene) glycol preferably have a ratio of the weight proportions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1 and in particular between 7: 1 and 2: 1 on.
  • Further preferred dispersants are the nonionic surfactants, which are used alone, but particularly preferably in combination with a nonionic polymer.
  • nonionic surfactants are preferably used alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 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 is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G 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 oligoglycosides, is any number between 1 and 10; preferably x is 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-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (V) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic Alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the machine dishwashing detergents according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
  • compositions according to the invention which comprise a nonionic surfactant which has a melting point above room temperature.
  • preferred dishwashing detergents are characterized in that they contain nonionic surfactant (s) having a melting point above 20 ° C., preferably above 25 ° C., more preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C, included.
  • Suitable 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 highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the 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) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also distinguished by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles 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.
  • particularly preferred dishwashing agents 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 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (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 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes 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 nonionic surfactants.
  • Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain 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 Surfactants are included.
  • 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. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants which may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.
  • a further preferred dishwashing detergent according to the invention contains nonionic surfactants of the formula (VI) R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ], (VI) 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 prefers.
  • 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.
  • dishwashing agents according to the invention are preferred, 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 represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • 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 agents which contain surfactants of the general formula VII as nonionic surfactant (s) are preferred here 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.
  • the preferred nonionic surfactants of formula VII can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in formula VII above 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 which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals.
  • R 1 in formula VII 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 have a C 9-15 -alkyl radical with 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 are particularly preferred for use in the agents according to the invention.
  • These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula (VIII) R 1 O [CH 2 CH (R 3 ) O] x R 2 (VIII) in which R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical, x for values between 1 and 40.
  • R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 2 represents linear or branched,
  • R 3 is H.
  • R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms
  • R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.
  • those end-capped poly (oxyalkylated) nonionic surfactants are preferred, which according to the formula (X) R 1 O [CH 2 CH 2 O] x CH 2 CH (OH) R 2 (X) in addition to a radical R 1 , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical with 1 have up to 30 carbon atoms R 2 , which is a monohydroxylated intermediate group -CH 2 CH (OH) - adjacent.
  • x stands for values between 1 and 40.
  • Such end-capped poly (oxyalkylated) nonionic surfactants can be prepared, for example, by reacting a terminal epoxide of the formula R 2 CH (O) CH 2 with an ethoxylated alcohol of the formula R 1 O [CH 2 CH 2 O] x-1 CH 2 CH 2 OH.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned nonionic surfactants represent statistical mean values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned are usually not made of an individual representative, but of mixtures, which may result in mean values for the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation and subsequently broken numbers.
  • Particularly preferred detergents or cleaners according to the invention contain as dispersing agent at least one nonionic surfactant, preferably at least one end-capped polyoxyalkylenated nonionic surfactant, the proportion by weight of the nonionic surfactant in the total weight of all dispersants preferably between 1 and 60 wt .-%, more preferably between 2 and 50 wt .-% and in particular between 3 and 40 wt.%.
  • washing or cleaning agents according to the invention in which the total weight of the nonionic surfactant (s) in the total weight of the composition according to the invention is between 0.5 and 40% by weight, preferably between 1 and 30% by weight, especially preferably between 2 and 25 and in particular between 2.5 and 23 wt .-% is.
  • Preferred washing or cleaning agents according to the invention are characterized in that at least one dispersing agent has a melting point above 25 ° C., preferably above 35 ° C. and in particular above 40 ° C.
  • Particularly preferred is the use of dispersants having a melting point or melting range between 30 and 80 ° C, preferably between 35 and 75 ° C, more preferably between 40 and 70 ° C and in particular between 45 and 65 ° C, these dispersants, based on the total weight of the dispersants used, a weight fraction above 10 wt .-%, preferably above 40 wt .-%, more preferably above 70 wt.% And in particular between 80 and 100 wt .-%.
  • Preferred agents according to the invention are dimensionally stable at 20 ° C.
  • dimensionally stable means according to the invention which have an intrinsic dimensional stability, which enables them to assume a non-disintegrating spatial form under normal conditions of manufacture, storage, transport and handling by the consumer, said space form under the conditions mentioned over longer Time, preferably 4 weeks, more preferably, 8 weeks and especially 32 weeks, not changed, that is, under the usual conditions of manufacture, storage, transport and handling by the consumer remains in the caused by the production spatial-geometric shape that is, does not melt away.
  • the water content of the abovementioned dispersions is preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 15% by weight and in particular less than 12% by weight.
  • preferred detergents or cleaners are low in water or anhydrous.
  • Particularly preferred washing or cleaning agents according to the invention are characterized in that the dispersion, based on their total weight, a content of free Water below 10 wt .-%, preferably below 7 wt .-%, more preferably below 3 wt .-% and in particular below 1 wt .-%.
  • the density of the dispersants used at 20 ° C. is preferably between 0.8 and 1.4 g / cm 3 .
  • dispersants water-soluble or water-dispersible polymers having a density (20 ° C) above 1.040 g / cm 3, preferably 1040-1670 g / cm 3, preferably 1.120 to 1.610 g / cm 3, particularly preferably 1.210 to 1.570 g / cm 3 , very particularly preferably between 1.290 and 1.510 g / cm 3 , and in particular between 1.340 and 1.480 g / cm 3 used.
  • Detergents or cleaning compositions which are preferred according to the invention are characterized in that they are dissolved in water (40 ° C.) in less than 12 minutes, preferably less than 10 minutes, preferably less than 9 minutes, more preferably less than 8 minutes, and in particular dissolve in less than 7 minutes.
  • 20 g of the dispersion are introduced into the interior of a dishwashing machine (Miele G 646 PLUS).
  • the main rinse of a standard rinse program (45 ° C) is started.
  • the determination of the solubility is carried out by the measurement of the conductivity, which is recorded via a conductivity sensor.
  • the dissolution process is completed when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau.
  • the conductivity measurement starts with the replacement of the circulation pump in the main wash cycle.
  • the amount of water used is 5 liters.
  • washing or cleaning agent portions coated with the aid of the method according to the invention may contain all customary constituents of detergents or cleaners, which will be briefly described below.
  • the washing or cleaning agent portions coated with the process according to the invention preferably comprise surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants can be used.
  • surfactant s
  • anionic, nonionic, cationic and / or amphoteric surfactants can be used.
  • the Total surfactant content of the washing or cleaning agent portions is preferably below 30% by weight, based on the total agent.
  • Nonionic surfactants have already been described above as optional plasticizers for the coating. The same substances can also be used as detergents in the compositions.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G 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 oligoglycosides, is any number between 1 and 10; preferably x is 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, especially fatty acid methyl esters.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the following formula VIII, 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 are customary can 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 following formula IX, 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 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 radical
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the content of detergent or cleaning agent portions of nonionic surfactants which is suitable for textile washing and which is produced by the process according to the invention is from 5 to 20% by weight, preferably from 7 to 15% by weight and in particular from 9 to 14% by weight, based in each case on the entire remedy.
  • low-foaming nonionic surfactants are preferably used.
  • anionic, cationic and / or amphoteric surfactants can be used, which, because of their foaming behavior in automatic dishwashing detergents have only minor importance and mostly only in amounts below 10 wt .-%, usually even below 5 wt .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent used become. In detergents, however, these surfactants have a significantly higher importance.
  • the washing or cleaning agent portions prepared according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • 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 to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they 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.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated and unsaturated 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, olive oil or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the content of preferred textile detergents according to the invention on anionic surfactants is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the total agent.
  • preferred agents additionally comprise one or more substances from the group of builders, bleaches, bleach activators, enzymes, Electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • Builders which may be present in the compositions according to the invention are in particular phosphates, silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • 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 lime deposits on machine parts or lime incrustations in fabrics 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.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also 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
  • 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 Phyllosilicates of the formula given are those in which M is sodium and x takes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • alkali carriers may be present.
  • Suitable alkali carriers are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metal silicates, and mixtures of the abovementioned substances, preference being given for the purposes of this invention to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • washing, rinsing or cleaning agents according to the invention which additionally contain one or more substances from the group of acidifying agents, chelating agents or coating-inhibiting polymers.
  • Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid.
  • the anhydrides of these acids can also be used as acidifying agents in particular maleic anhydride and succinic anhydride are commercially available.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • Sokalan® DCS commercially available and likewise preferably usable as acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid ( at most 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
  • Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • complex-forming polymers ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms generally with the formation of chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA are preferred.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • Scale-inhibiting polymers can likewise be present in the agents according to the invention. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.
  • Scale-inhibiting polymers may also have co-builder properties.
  • organic cobuilders it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of washing or Detergents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can 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 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.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 500 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 1000 to 10 000 g / mol, and particularly preferably from 1000 to 4000 g / mol, may again be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention.
  • the sulfonic acid group-containing copolymers are described in detail below.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, 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 (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • 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 as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives .
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • 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 obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • 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.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts 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 contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • compositions according to the invention may contain further customary ingredients of detergents, dishwashing detergents or cleaners, wherein especially bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances are of importance. These substances will be described below.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the detergent tablets.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach activators are cationic nitrile of the formula below in the 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 Alkenylarylrest with a C 1-24 alkyl group, or 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 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH
  • compositions according to the invention contain cationic nitriles in which R 1 is methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n Hexadecyl or n-octadecyl radical.
  • R 2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.
  • preferred cationic nitriles of the formula (I) according to the invention are characterized by their radicals R 1 , R 2 and R 3 : R 1 R 2 R 3 -H -CH 3 -CH 3 -H -CH 2 -CH 3 -CH 3 -H -CH 2 -CH 2 -CH 3 -CH 3 -H -CH (CH 3 ) -CH 3 -CH 3 -H -CH 2 -OH -CH 3 -H -CH 2 -CH 2 -OH -CH 3 -H -CH (OH) -CH 3 -CH 3 -H -CH 2 -CH 2 -OH -CH 3 -H -CH 2 -CH (OH) -CH 3 -CH 3
  • radicals R 1 to R 3 are identical, for example (CH 3 ) 3 N (+) CH 2 -CN X - , (CH 3 CH 2 ) 3 N (+) CH 2 -CN X -, (CH 3 CH 2 CH 2) 3 N (+) CH 2 -CN X -, (CH 3 CH (CH 3)) 3 N (+) CH 2 -CN X -, or (HO -CH 2 -CH 2 ) 3 N (+) CH 2 -CN X - .
  • Preferred anions X (-) are selected from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate), cumene sulfonate or xylene sulfonate.
  • bleach catalysts can be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%.
  • Detergent tablets for machine dishwashing according to the invention 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 the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the 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.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
  • the proportion of electrolytes in the inventive compositions is usually 0.5 to 5 wt .-%.
  • pH adjusting agents may be indicated.
  • Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited.
  • the amount of these adjusting agents does not exceed 5% by weight of the total formulation.
  • the agents according to the invention can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.
  • Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and the polymers known from the prior art Phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these.
  • Especially preferred of these are the sulfonated derivatives of the phthalic and terephthalic acid polymers.
  • Optical brighteners can be added to the compositions according to the invention in order to eliminate graying and yellowing of the treated textiles. These fabrics impinge on the fiber and cause whitening and bleaching by transforming invisible ultraviolet radiation into visible longer wavelength light, emitting ultraviolet light absorbed from the sunlight as faint bluish fluorescence, and pure yellow with the yellowed or yellowed wash White results.
  • Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as heterocyclic substituted pyrene derivatives.
  • the optical brighteners are usually used in amounts between 0.05 and 0.3 wt .-%, based on the finished composition.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions
  • compositions according to the invention can also be provided with further added benefits.
  • color transfer inhibiting compositions for example, color transfer inhibiting compositions, anti-gray formula agents, ironing facilitators, fragrance release agents, soil repellency improvers, antibacterial agents Agents, UV protectants, color-enhancing agents, etc. can be formulated.
  • compositions of the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, - alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • compositions of the invention may contain antimicrobial agents.
  • antimicrobial agents 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, alkylarylsulfonates, halophenols and phenolmercuric acetate, and the compounds according to the invention can be completely dispensed with.
  • the agents may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect being achieved.
  • silicone derivatives can be used in the compositions according to the invention. These additionally improve the rinsing out of the compositions according to the invention by their foam-inhibiting properties.
  • Preferred silicone derivatives 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 optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 centistokes at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the agents according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2 and / or 4 position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • automatic dishwasher detergents are prepared by means of the process according to the invention, they preferably contain further substances which improve the cleaning result and / or perform further functions.
  • a particularly preferred ingredient for automatic dishwasher detergents is a polymer which contains sulfonic acid groups.
  • Preferred compositions according to the invention are therefore characterized in that they comprise at least one copolymer of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers
  • Suitable further ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the content of the monomers used according to the invention to monomers of group iii) is preferably less than 20% by weight, based on the polymer.
  • Particularly preferred polymers to be used consist only of monomers of groups i) and ii).
  • the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • compositions according to the invention which contain one or more copolymers which contain structural units of the formulas III and / or IV and / or V and / or VI and / or VII and / or VIII - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (XV), - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - (XVI), - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XVII), [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - (XVIII) - [HOOCCH-CHCOOH] m - [CH 2 -CH
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. in that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged 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.
  • Corresponding compositions which are characterized in that the sulfonic acid groups are partially or fully neutralized in the copolymer are preferred according to the invention.
  • the monomer distribution of the copolymers used in the compositions according to the invention in the case of copolymers containing only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight. % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molecular weight of the above-described sulfo-copolymers used in the compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired use.
  • Preferred compositions are characterized in that the copolymers have molecular weights 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 .
  • compositions for machine dishwashing detergents prepared according to the invention are agents which are capable of providing corrosion protection for glassware during cleaning and / or rinsing operations of a dishwashing machine. They preferably come from the group of the compounds of zinc, aluminum, silicon, tin, magnesium, calcium, strontium, titanium, zirconium, manganese and / or lanthanum. Of the compounds mentioned, the oxides are particularly preferred.
  • a preferred agent for providing anticorrosive protection to glassware during dishwashing and / or rinsing operations of a dishwashing machine is zinc in oxidized form, i. Zinc compounds in which zinc is cationic.
  • magnesium salts are also preferred.
  • both soluble and poorly soluble or insoluble zinc or magnesium compounds can be used.
  • Preferred compositions according to the invention comprise one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.
  • the acids in question preferably come from the group of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the Amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acids having at least 8 carbon atoms and / or resin acids.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids may be contained according to the invention, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids are selected from the groups of unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or polymeric carboxylic acids. Within these groups, the acids mentioned below are again preferred in the context of the present invention:
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionklare).
  • sugar acids galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.
  • hydroxy acids From the group of hydroxy acids: hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), malic acid (malic acid), 2,3-dihydroxybutanedioic acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2 Hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
  • oxo acids 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
  • amino acids From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.
  • polymeric carboxylic acids polyacrylic acid, polymethacrylic acid, alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers.
  • the spectrum of the inventively preferred zinc salts of organic acids ranging from salts which are difficult or insoluble in water, ie a solubility below 100 mg / L, preferably below 10 mg / L, in particular have no solubility, to such salts having 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 solubilities at 20 ° 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:
  • compositions according to the invention contain at least one zinc salt but no magnesium salt of an organic acid, which is preferably at least one zinc salt of an organic carboxylic acid, more preferably a zinc salt selected from zinc stearate, zinc oleate, zinc gluconate, zinc acetate , Zinc lactate and / or zinc citrate.
  • zinc ricinoleate, zinc abietate and zinc oxalate are also preferably used.

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Claims (8)

  1. Procédé pour la préparation de doses d'agent de lavage ou de nettoyage enrobées de manière serrée par des enrobages solubles dans l'eau, caractérisé par les étapes de
    a) dépôt d'une feuille sous-jacente soluble dans l'eau sur une chaîne de transport ou un outil à moule(s)
    b) dépôt d'une ou de plusieurs doses d'agent de lavage ou de nettoyage sur la feuille sous-jacente, où, dans le cas où un outil à moule(s) est utilisé dans l'étape a), la ou les portions d'agent de lavage ou de nettoyage ne ferment pas de manière affleurante la face supérieure de l'outil à moule(s), après avoir été déposés sur la feuille sous-jacente, mais ressortent de celle-ci de telle manière qu'au maximum 50%, de préférence au maximum 40% et en particulier au maximum 30% de la plus grande hauteur de la ou des doses d'agent de lavage et de nettoyage se trouvent dans le moule
    c) dépôt d'une feuille supérieure soluble dans l'eau sur la ou les portions d'agent de lavage ou de nettoyage se trouvant sur la feuille sous-jacente
    d) fixation de la feuille supérieure sur la feuille sous-jacente en enfermant la ou les portions d'agent de lavage ou de nettoyage
    e) scellage et éventuellement découpe des feuilles.
  2. Procédé selon la revendication 1, caractérisé en ce que la feuille sous-jacente est préfaçonnée par l'application d'un vide et/ou par chauffage.
  3. Procédé selon la revendication 1,caractérisé en ce que la feuille sous-jacente est complètement plane pendant les étapes b) à e).
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la ou les doses d'agent de lavage ou de nettoyage qui sont déposées pendant l'étape b) sur la feuille sous-jacente sont des comprimés d'agent de lavage ou de nettoyage.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la feuille supérieure est préfaçonnée dans un mandrin avant le dépôt dans l'étape c) par l'application d'un vide et/ou par chauffage.
  6. Procédé selon la revendication 5, caractérisé en ce que l'étape c) est démarrée par une préaération à partir du dessus.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que les étapes de travail c) et/ou d) sont soutenues par la mise sous vide de l'espace intermédiaire entre la feuille supérieure et inférieure et/ou par l'application de pression sur la feuille supérieure.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'on utilise comme feuille(s) soluble(s) dans l'eau dans les étapes a) et c) des feuilles pré-étirées qui sont thermorétractées dans l'étape e) ou après celle-ci sur la ou les doses d'agent de lavage ou de nettoyage.
EP03798910A 2002-09-27 2003-09-18 Procede de production de doses de produit de lavage ou de nettoyage enveloppees Revoked EP1543100B1 (fr)

Applications Claiming Priority (3)

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DE10245260A DE10245260A1 (de) 2002-09-27 2002-09-27 Verfahren zur Herstellung umhüllter Wasch- oder Reinigungsmittel-Portionen
DE10245260 2002-09-27
PCT/EP2003/010370 WO2004031338A1 (fr) 2002-09-27 2003-09-18 Procede de production de doses de produit de lavage ou de nettoyage enveloppees

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EP1543100A1 EP1543100A1 (fr) 2005-06-22
EP1543100B1 true EP1543100B1 (fr) 2006-04-26

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AT (1) ATE324432T1 (fr)
AU (1) AU2003262514A1 (fr)
DE (2) DE10245260A1 (fr)
ES (1) ES2263065T3 (fr)
WO (1) WO2004031338A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2006221791B2 (en) 2005-03-10 2012-03-22 Reckitt Benckiser Finish B.V. Process for the preparation of a package containing compacted composition and the package obtained with this process
GB0714811D0 (en) 2007-07-31 2007-09-12 Reckitt Benckiser Nv Improvements in or relating to compositions
DE102015213943A1 (de) 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel umfassend wenigstens zwei Phasen
DE102015213939A1 (de) 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Mehrphasiges Geschirrspülmittel umfassend einen Tensid-Kern
DE102015213942A1 (de) 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel enthaltend Bleichmittel und Polymere
DE102015213938A1 (de) 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Einsatz einer Kombination aus Komplexbildner und Tensid zur Verbesserung der Klarspülleistung
DE102015213940A1 (de) 2015-07-23 2017-01-26 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel enthaltend Bleichmittel, Builder und Enzyme
DE102016210628A1 (de) 2016-06-15 2017-12-21 Henkel Ag & Co. Kgaa Bacillus gibsonii Protease und Varianten davon
DE102017201095A1 (de) 2017-01-24 2018-07-26 Henkel Ag & Co. Kgaa Tenside in Kapseln mit optimiertem Trübungspunkt
DE102017201096A1 (de) 2017-01-24 2018-07-26 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Formkörpers
DE102017201097A1 (de) 2017-01-24 2018-07-26 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittel umfassend wenigstens zwei Phasen
DE102017212348A1 (de) 2017-07-19 2019-01-24 Henkel Ag & Co. Kgaa Verwendung eines Reinigungsmittels enthaltend Aminocarbonsäuren und Sulfopolymere zur Belagsinhibierung
EP3770240A1 (fr) 2019-07-22 2021-01-27 Henkel AG & Co. KGaA Lave-vaisselle pourvu de catalyseur de blanchiment et protéase de bacillus gibsonii
EP3770237A1 (fr) 2019-07-22 2021-01-27 Henkel AG & Co. KGaA Agent de lavage et de nettoyage à stabilité de l'enzyme améliorée
EP3770238A1 (fr) 2019-07-22 2021-01-27 Henkel AG & Co. KGaA Agent de lavage et de nettoyage comprenant de la protéase et de l'amylase
FR3109392B1 (fr) 2020-04-20 2023-06-30 Eurotab Operations Ensemble de tablette détergente
DE102020131794A1 (de) 2020-12-01 2022-06-02 Henkel Ag & Co. Kgaa Verbesserte Reinigung durch Hydrogencarbonat im maschinellen Geschirrspülmittel
EP4314225A1 (fr) * 2021-03-23 2024-02-07 Henkel AG & Co. KGaA Pastille d'agent de lavage
EP4393828A1 (fr) * 2023-01-02 2024-07-03 Henkel AG & Co. KGaA Procédé de fabrication d'unités de dose de détergent ou de détergent

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DE3929973A1 (de) * 1989-09-08 1991-03-14 Henkel Kgaa Haarpflegemittel
DE69427696T2 (de) * 1994-09-12 2002-05-08 Procter & Gamble Portionsverpacktes Waschmittel
DE19713545A1 (de) * 1997-04-02 1998-10-08 Lemo Maschb Gmbh Packung für agrikulturchemisch eingesetzte Materialien, wie z. B. Herbicide, Fungicide, Düngemittel oder dergleichen sowie Verfahren und Vorrichtung zum Herstellen einer solchen Packung
GB9906172D0 (en) * 1999-03-17 1999-05-12 Unilever Plc A process for producing a water soluble package
GB2361685A (en) * 2000-04-28 2001-10-31 Procter & Gamble Water-soluble pouch containing composition
DE10050958A1 (de) * 2000-10-13 2002-04-18 Basf Ag Verwendung von wasserlöslichen oder wasserdispergierbaren Polyetherblöcken enthaltenden Pfropfpolymerisaten als Beschichtungs- und Verpackungsmittel für Wasch-, Reinigungs- und Wäschebehandlungsmitte

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ATE324432T1 (de) 2006-05-15
AU2003262514A1 (en) 2004-04-23
DE10245260A1 (de) 2004-04-15
DE50303130D1 (de) 2006-06-01
ES2263065T3 (es) 2006-12-01
EP1543100A1 (fr) 2005-06-22

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