EP1776448B2 - Verfahren zur herstellung portionierter wasch- oder reinigungsmittel - Google Patents

Verfahren zur herstellung portionierter wasch- oder reinigungsmittel Download PDF

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Publication number
EP1776448B2
EP1776448B2 EP05776193.4A EP05776193A EP1776448B2 EP 1776448 B2 EP1776448 B2 EP 1776448B2 EP 05776193 A EP05776193 A EP 05776193A EP 1776448 B2 EP1776448 B2 EP 1776448B2
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EP
European Patent Office
Prior art keywords
container
acid
weight
preferred
agents
Prior art date
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EP05776193.4A
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German (de)
English (en)
French (fr)
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EP1776448B1 (de
EP1776448A1 (de
Inventor
Wolfgang Barthel
Birgit Burg
Salvatore Fileccia
Arno DÜFFELS
Maren Jekel
Ulf Arno Timmann
Christian Nitsch
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL05776193.4T priority Critical patent/PL1776448T5/pl
Publication of EP1776448A1 publication Critical patent/EP1776448A1/de
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B9/00—Enclosing successive articles, or quantities of material, e.g. liquids or semiliquids, in flat, folded, or tubular webs of flexible sheet material; Subdividing filled flexible tubes to form packages
    • B65B9/02—Enclosing successive articles, or quantities of material between opposed webs
    • B65B9/04—Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material
    • B65B9/042—Enclosing successive articles, or quantities of material between opposed webs one or both webs being formed with pockets for the reception of the articles, or of the quantities of material for fluent material
    • 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
    • C11D17/0052—Cast detergent compositions

Definitions

  • the present invention relates to stabilized portioned water-soluble detergents or cleaning agents and processes for producing them.
  • Detergents and cleaning products are now available to consumers in a variety of forms. In addition to washing powders and granules, this range also includes, for example, cleaning agent concentrates in the form of extruded or tableted compositions. These solid, concentrated or condensed forms of offering are characterized by a reduced volume per dosage unit and thus reduce the costs for packaging and transport. The detergent or cleaning agent tablets in particular also fulfill the consumer's wish for simple dosage.
  • solid or liquid detergents or cleaning agents which have a water-soluble or water-dispersible coating such as films have increasingly been described in recent years.
  • these agents are characterized by a simplified dosage, as they can be dosed together with the water-soluble coating in the washing machine or dishwasher, but at the same time they also enable the preparation of liquid or powdered detergents or cleaning agents, which are different from the Compacts are characterized by better resolution and faster effectiveness.
  • the cleaning agents packaged in this way into individual dosage units can be easily dispensed by inserting one or more bags directly into the washing machine or dishwasher or into its dispenser compartment, or by throwing them into a predetermined amount of water, for example in a bucket or in the handwasher or .Sink, dosed.
  • the packaged products produced using deep-drawing processes are characterized by an unattractive look and feel.
  • the bags are flabby and not dimensionally stable;
  • the packaging material shows wrinkles and distortions that are visible to the naked eye.
  • This instability of such packaged products causes further problems.
  • the instability can cause damage to the container more easily, particularly in containers filled with powder, where the powder can damage the casing due to friction if the container is deformed.
  • the handling of such floppy bags is more difficult compared to stable bodies.
  • One object of the present application is therefore to provide a method for producing dimensionally stable portioned detergents or cleaning agents.
  • Another task is to provide dimensionally stable portioned detergents or cleaning agents that fill as much as possible the volume of conventional dispenser compartments of washing machines or dishwashers.
  • a further object is to avoid the above-mentioned problem of mechanical damage to water-soluble or water-dispersible casings, especially if the washing or cleaning agent contains a powdery washing or cleaning-active substance.
  • a water-soluble or water-dispersible material is formed into a container which has at least one opening. At the opening, this container unavoidably has an edge or a rim surrounding the opening.
  • this container unavoidably has an edge or a rim surrounding the opening.
  • the shaping process produces a container which, in addition to the edge surrounding the opening, has at least one further corner and/or edge.
  • Spatial bodies according to the invention with a polygonal base, where the body represents a continuation of the polygonal base in space, are prism-shaped bodies in cuboid shape.
  • the shape of the container can also be adapted to any irregular shapes of dosing compartments/dispensing compartments of various washing machines and dishwashers.
  • the respective ideal spatial shape or the spatial shape predetermined by the deformation process can be disturbed in the finished portioned detergent or cleaning agent, for example the edges of a body can be curved outwards. This is based, among other things, on the shell material's tendency to return to its original shape after the deformation process. Compared to known methods, such a deviation from the ideal form or the predetermined form is reduced in the present invention.
  • cuboids are also to be understood as bodies in which small deviations from the ideal angularity occur, for example up to approximately ⁇ 5°, preferably up to approximately ⁇ 3°, more preferably up to approximately ⁇ 1°.
  • the container produced in step a) is a cuboid container.
  • An entire surface of the body is preferably provided as an opening. However, according to the invention, only part of a surface can be provided as an opening.
  • a cuboid shape is the best way to fill conventional cuboid dispenser compartments or dishwashers in terms of volume.
  • cuboid-shaped detergents or cleaning products can be stored very easily to save space.
  • the shell material made of a water-soluble or water-dispersible substance is preferably as thin as possible.
  • a too thick design of the covering material can disadvantageously delay the release of the detergent contained in the container.
  • Sufficiently thin shell thicknesses can be achieved, particularly through deep drawing.
  • the deformation after step a) is therefore preferably carried out by deep drawing.
  • at least one container wall or a closure part of the container has a wall thickness of less than 200 ⁇ m, preferably less than 120 ⁇ m, particularly preferably less than 90 ⁇ m and particularly preferably less than 70 ⁇ m.
  • both the water-soluble or water-dispersible container and the closure part each have a wall thickness of less than 200 ⁇ m, preferably less than 100 ⁇ m and particularly preferably less than 70 ⁇ m.
  • step a) to form the container and the deformation processes are described in more detail below.
  • the step in step a) the container formed is stabilized so that the shape of the body specified by the shaping process is largely retained even after the introduction of further detergents and / or cleaning agents and in the later packaging.
  • the solidified melt is also located in other areas of the container.
  • further stabilization of the container formed can be achieved, and the casing can also be better protected from further washing or cleaning-active substances that could possibly damage the casing or that are incompatible with the casing.
  • the solidified melt can be designed in such a way that a trough-shaped cavity is formed by the solidified melt, the lowest point of the trough in the direction of the opening of the container preferably being in the central region of the container.
  • the area of the edge surrounding the opening, where the closure is located in the finished portioned detergent or cleaning agent to be at least partially provided with the solidified melt.
  • partial filling of the further corner(s) and/or edge(s) is understood to mean at least such a proportion that the portioned detergent or cleaning agent is stabilized by the solidified melt.
  • the proportion of the further corner(s) and/or edge(s) which are filled with the solidified melt is preferably at least 50% of the further corner(s) and/or edge(s), more preferably at least 60%, more preferably at least 70%, more preferably at least 80%, more preferably 90% and most preferably 100%.
  • the percentages refer to the total length of the edges and corners in the container.
  • the solidified melt not only extends into the edges/corners, but also covers the area directly adjacent to the corners or edges.
  • the extent of this further area can be varied according to the invention, depending on the desired stabilization of the container.
  • the solidified melt can at least partially, but preferably completely, fill the corner(s) and/or edge(s) of a chamber, or this can be the case with several or all chambers.
  • the thickness of the melt can be largely varied by the person skilled in the art. Since the portioned detergents or cleaning agents are multi-phase agents, i.e. H. At least one further washing or cleaning agent is in the container, which can have a solid or liquid consistency, it is preferred that the layer thickness of the solidified melt is designed so that there is still a sufficiently large cavity for one or more washing or cleaning active Means remains, but the problem of the stability of the container is solved.
  • Cuboid-shaped packaged detergents or cleaning products can be produced, for example, by forming containers from water-soluble material which, after shaping, is filled with a melt of a detergent or detergent on the bottom, ie the lower surface of the container, including the lower corners and part of the side edges Cleaning agent is filled, which then solidifies. Then part of the remaining The cavity is filled with another powdered detergent or cleaning agent and a liquid or gel detergent or cleaning agent and the container is then closed.
  • one side wall, preferably two side walls, further preferably two opposite side walls, even more preferably all four side walls, of the cuboid container is/are filled by the solidified melt. Further embodiments are also possible, for example drawing the melt up on two adjacent side walls or on three side walls of the cuboid container. Furthermore, it is preferred that the bottom of the container, preferably a cuboid container, is covered with the solidified melt. Particularly preferred is a cuboid-shaped portioned detergent or cleaning agent in which all corners and edges of the cuboid are completely filled with the solidified melt and the bottom of the cuboid-shaped container is also filled with the solidified melt.
  • the problem can be solved in particular that powdery detergent or cleaning agent gets between the melt and the film or gets onto the film at all, so that the problem of damage to the film due to the penetration of powder between the film can be solved and melt can be dissolved and at the same time a stable body is formed.
  • the solidification of the melt in step b) can occur either passively by allowing it to stand or actively by cooling.
  • washing or cleaning-active melt mentioned in step b) of the process according to the invention is described in more detail below. According to the invention, this refers to a melt which at least partially contains a washing or cleaning-active substance.
  • Step b) is followed by filling with at least one additional detergent or cleaning agent.
  • Active ingredients or combinations of active ingredients are considered flowable if they do not have an inherent dimensional stability that enables them to assume a non-disintegrating spatial shape under normal conditions of production, storage, transport and handling by the consumer, whereby this spatial shape under the conditions mentioned not changed even over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, i.e. under the usual conditions of production, storage, transport and handling by the consumer in the spatial and spatial conditions caused by production. geometric shape remains, that is, does not flow.
  • the determination of the flowability refers in particular to the usual conditions for storage and transport, i.e. in particular to temperatures below 50 ° C, preferably below 40 ° C. Liquids are therefore in particular active ingredients or combinations of active ingredients with a melting point below 25°C, preferably below 20°C, particularly preferably below 15°C.
  • Filling the container with at least one further detergent and/or cleaning agent according to step c) includes filling with at least one powdered further detergent or cleaning agent.
  • additional detergent or cleaning agent components can be added to produce three- or higher-phase portioned detergents or cleaning agents. It is preferred, for example, that a powdered detergent or cleaning agent is first added after the melt has solidified and then a gel-like agent is added.
  • compositions of detergents and cleaning agents that can be used are described in detail below.
  • the term assembly includes closing and/or sealing the filled container and the formation of individual portions of the detergent or cleaning agent.
  • Closing and/or sealing is carried out using known methods, for example by heat sealing with a film.
  • the material of the closure/seal may preferably be made of the same material as the container. Portioning can be done using common methods such as cutting into individual portions or punching out.
  • the agents according to the invention in water-soluble or water-dispersible packaging can, for example, be manufactured as containers with one, two, three, four or more receiving chambers.
  • the assembly with more than one chamber is generally done by first filling the container formed in step a) only up to a certain height, so that a first filled area is obtained.
  • Methods are preferred in which the degree of filling of the container after filling is between 10 and 95% by volume, preferably between 20 and 90% by volume and in particular between 40 and 80% by volume.
  • This first area of the body can then be separated or closed or sealed by a separating layer, preferably a water-soluble or water-dispersible film, after which the remaining cavity of the container is filled. Closing and/or sealing can then take place. Of course, several chambers can also be formed in this way before the container is finally closed and sealed.
  • a separating layer preferably a water-soluble or water-dispersible film
  • the negative pressure generated in this preferred method variant is between -100 and -1013 mbar, preferably between -200 and -1013 mbar, particularly preferably between -400 and -1013 mbar and in particular between -800 and -1013 mbar . Also preferred are methods in which the negative pressure generated is between -50 and -1013 mbar, preferably between -100 and -800 mbar and in particular between -200 and -500 mbar.
  • the negative pressure in the filled container is generated after the water-soluble film web has been applied to the filled container in step c1) and before sealing in step c2).
  • the negative pressure is generated in the filled container after sealing in step c2) and before assembly in step d).
  • Methods according to the invention are particularly preferred in which the negative pressure is generated both in the filled containers, i.e. below the film web applied in step c1), and outside the filled container, above the film web applied in step c1).
  • Such a particularly advantageous process can be implemented, for example, in that the water-soluble material is deformed to form a container filled with an agent and this filling is then covered by applying a water-soluble film web. The filled and covered container is then placed in a vacuum chamber. Due to openings in the applied water-soluble film web, when a vacuum is applied to the vacuum chamber, both in the filled containers, i.e.
  • the film web applied in step c1) is sealed with the filled container in such a way that the container is closed on all sides and in particular no more air can get into the container through the openings of the film web applied in step c1). If the sealed container is then removed from the vacuum chamber, the atmospheric pressure acting on the container from outside causes the outer walls of the container, in particular the film web applied in step c1), to lie tightly against the filling material.
  • This particularly preferred process variant enables the production of compact and dimensionally stable portion packs with a small volume.
  • the container is preferably completely closed on all sides.
  • the sealing can be done in different ways. Heat sealing processes are particularly preferred.
  • sealing it is particularly preferred that the openings of the water-soluble film web applied in step c1) are closed by the sealing process, that is, welded, or separated from the interior of the container by the sealing seam. In the latter case, the openings are located outside the sealing seam after sealing and can be separated together with the surrounding film material, for example as part of the packaging process during separation.
  • the container formed in step a) and the container provided with melt in step b) are only partially filled.
  • Methods are preferred in which the degree of filling of the container after filling is between 10 and 95% by volume, preferably between 20 and 90% by volume and in particular between 40 and 80% by volume.
  • step a) it is furthermore particularly preferred to stabilize the spatial shape of the containers formed in step a) after they have been placed in the vacuum chamber in order to avoid collapse of the container due to the negative pressure generated between the filling material and the water-soluble film web.
  • these requirements apply, for example, to processes according to the invention in which the water-soluble material is deformed in step a) by deep-drawing a water-soluble film web.
  • the deep-drawing matrices used when deep-drawing the containers or matrices comparable to or identical to these matrices as a support form.
  • This second negative pressure is preferably between -100 and -1013 mbar, preferably between -200 and -1013 mbar, particularly preferably between -400 and -1013 mbar and in particular between -800 and -1013 mbar.
  • the negative pressure generated is between -50 and -1013 mbar, preferably between -100 and -800 mbar and in particular between -200 and -500 mbar. It is particularly preferred that this second negative pressure formed between the support mold and the container is higher in magnitude than the negative pressure formed in the negative pressure chamber.
  • the entire container formed in step a) can also be at least partially, preferably completely, filled with melt in the further corners and/or edges. Additional detergent or cleaning agent is then filled to a certain height, then a separating film is inserted to form the chambers.
  • the solidified melt can be viewed as part of the container, which is then filled with various detergents or cleaning agents that are present in different chambers.
  • a multi-chamber container can also be manufactured as follows. First, a first film is pulled out into a mold to form a first chamber. This chamber is filled according to the method of the present invention. A second film is then drawn into the mold to form a second chamber, which is subsequently filled with a detergent composition. Finally, sealing takes place. In this method, said first film is perforated and the second film is drawn into the mold by means of suction through the first film. Consequently, the first receiving chamber, into which the second film is drawn to form a further receiving chamber, can only be filled with solid agents, since liquid agents or gels would escape through the perforation due to the negative pressure.
  • Such a procedure is, for example, in WO 03/031266 (Procter & Gamble), to which reference is made here for further details on how to carry out the procedure.
  • the process is also suitable for producing containers with more than two chambers. However, for the reasons mentioned above, it is limited to the use of solid compositions in the receiving chambers through which the applied films were drawn into the mold.
  • one or more chambers of the entire container can be filled using the method according to the invention.
  • Liquids and gels can also be used as filling because the entire container is placed in a vacuum chamber.
  • the entire container formed in step a) can be at least partially, preferably completely, filled with melt in the further corners and/or edges. Additional detergent or cleaning agent is then filled to a certain height, then a separating film is inserted to form the chambers.
  • the solidified melt can be viewed as part of the container, which is then filled with various detergents or cleaning agents that are present in different chambers.
  • Suitable shaping processes for processing the shell materials are, for example, deep-drawing processes, injection molding processes or casting processes.
  • the method preferred according to the invention is deep drawing.
  • “deep-drawing processes” refer to those processes in which a first film-like wrapping material is deformed by the action of pressure and/or vacuum after being moved over a receiving trough located in a die forming the deep-drawing plane and the wrapping material is molded into this receiving trough .
  • the shell material can be pretreated before or during molding by the action of heat and/or solvents and/or conditioning by relative humidity and/or temperatures that are different from ambient conditions.
  • the pressure can be applied by two parts of a tool, which behave like positive and negative to each other and deform a film placed between these tools when pressed together.
  • the action of compressed air and/or the weight of the film and/or the weight of an active substance applied to the top of the film are also suitable as compressive forces.
  • the deep-drawn casing materials are preferably fixed by using a vacuum within the receiving troughs and in their spatial shape achieved by the deep-drawing process.
  • the vacuum is preferably applied continuously from deep drawing to filling, preferably to sealing and in particular to separating the receiving chambers.
  • a discontinuous vacuum is also possible with comparable success, for example for deep-drawing the receiving chambers and (after an interruption) before and during the filling of the receiving chambers.
  • the continuous or discontinuous vacuum can also vary in strength and, for example, assume higher values at the beginning of the process (when deep-drawing the film) than at the end (when filling or sealing or separating).
  • the covering material can be pretreated by the action of heat before or during molding into the receiving troughs of the matrices.
  • the shell material preferably a water-soluble one or water-dispersible polymer film, are heated for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds at temperatures above 60 ° C, preferably above 80 ° C, particularly preferably heated between 100 and 120 ° C and in particular to temperatures between 105 and 115 ° C.
  • the matrices used and the receiving troughs located in these matrices are particularly suitable for cooling.
  • the cooling is preferably carried out at temperatures below 20°C, preferably below 15°C, particularly preferably at temperatures between 2 and 14°C and in particular at temperatures between 4 and 12°C.
  • the cooling preferably takes place continuously from the start of the deep-drawing process until the receiving chambers are sealed and separated. Cooling liquids, preferably water, which are circulated in special cooling lines within the die, are particularly suitable for cooling.
  • This cooling like the previously described continuous or discontinuous application of a vacuum, has the advantage of preventing the deep-drawn containers from shrinking back after deep-drawing, which not only improves the appearance of the process product, but at the same time also prevents the agents filled into the receiving chambers from escaping the edge of the receiving chamber, for example in the sealing areas of the chamber, is avoided. This avoids problems with sealing the filled chambers.
  • the casing material is guided horizontally into a forming station and from there in a horizontal manner for filling and/or sealing and/or separating and processes in which the casing material is passed over a continuously rotating die-forming roller (possibly optionally with a counter-rotating male molding roller, which guides the forming upper punches to the cavities of the female molding roller).
  • the first-mentioned process variant of the flatbed process can be operated both continuously and discontinuously; the process variant using a forming roller is usually carried out continuously. All of the deep-drawing processes mentioned are suitable for producing the agents according to the invention.
  • the receiving troughs located in the matrices can be arranged “in a row” or offset.
  • injection molding refers to the reshaping of a molding compound in such a way that the mass contained in a compound cylinder for more than one injection molding process softens plastically under the influence of heat and flows under pressure through a nozzle into the cavity of a previously closed tool.
  • the process is mainly used for non-curable molding compounds that solidify in the mold when cooled.
  • Injection molding is a very economical, modern process for producing non-cutting shaped objects and is particularly suitable for automated mass production.
  • thermoplastic molding materials are heated until they liquefy (up to 180 ° C) and are then injected under high pressure (up to 140 MPa) into closed, two-part dies (formerly Die) and core (formerly male) existing, preferably water-cooled, hollow molds, where they cool and solidify.
  • Piston and screw injection molding machines can be used.
  • Water-soluble polymers such as the above-mentioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch are suitable as molding compounds (injection molding compounds).
  • the shell materials can also be cast into hollow shapes.
  • Water-soluble polymers in the context of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.
  • Preferred shell materials preferably comprise at least a portion of a substance from the group of (acetalized) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin.
  • Polyvinyl alcohols (abbreviation PVAL, sometimes also PVOH) is the name for polymers of the general structure which in small proportions (approx. 2%) are also structural units of the type contain.
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range of approx. 100 to 2500 (molar masses of approx. 4000 to 100,000 g/mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so they still contain a residual amount of acetyl groups.
  • the manufacturers characterize the polyvinyl alcohols by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly 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 at least partially biodegradable. The water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • an agent according to the invention has at least one packaging or wrapping material which at least partially comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the at least one shell material used consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight of a polyvinyl alcohol 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%.
  • the entire shell material used consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight of a polyvinyl alcohol 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 preferably used as the shell materials, it being preferred according to the invention that the shell material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , particularly preferably from 12,000 to 80,000 gmol -1 . 1 and in particular from 13,000 to 70,000 gmol -1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.
  • Detergents or cleaning agents preferred according to the invention with water-soluble or water-dispersible packaging are characterized in that the water-soluble or water-dispersible packaging material 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 MG (50%) to MG (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 that are particularly suitable in the context of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 as well as L648, L734, Mowiflex LPTC 221 ex KSE and the compounds from Texas Polymers such as Vinex 2034.
  • 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, MM11Q, KZ- 06 trademark of Nippon Gohsei KK.
  • ERKOL types from Wacker are also suitable.
  • the water content of preferred PVAL packaging materials is preferably less than 10% by weight, preferably less than 8% by weight, particularly preferably less than 6% by weight and in particular less than 4% by weight.
  • the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous due to their extremely good cold water solubility.
  • the reaction products from PVAL and starch are extremely advantageous to use.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
  • PVAL films are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen and carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available under the name “ SOLUBLON® ” from Syntana bottlesgesellschaft E. Harke GmbH & Co. Their solubility in water can be adjusted to the exact degree, and films from this product range are available that are soluble in the aqueous phase in all temperature ranges relevant to the application.
  • Preferred detergents or cleaning agents according to the invention with a water-soluble or water-dispersible packaging are characterized in that the water-soluble or water-dispersible packaging comprises hydroxypropylmethylcellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of 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) from 0.1 to 0.3, preferably from 0.15 to 0.25.
  • HPMC hydroxypropylmethylcellulose
  • PVP Polyvinylpyrrolidones
  • PVP are produced by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of approximately 2,500 to 750,000 g/mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides are polyalkylene glycols of the general formula H-[O-CH 2 -CH 2 ] n -OH are technically produced by basic catalyzed polyaddition of ethylene oxide (oxirane) in systems that usually contain small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range of approximately 200 to 5,000,000 g/mol, corresponding to degrees of polymerization n of approximately 5 to >100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxyl end groups and only show weak glycol properties.
  • Gelatin is a polypeptide (molar mass: approx. 15,000 to >250,000 g/mol) that 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 a water-soluble shell material is extremely widespread, particularly in pharmaceuticals in the form of hard or soft gelatin capsules. Gelatine is only rarely used in the form of films because of its high price compared to the polymers mentioned above.
  • coating materials which comprise a polymer from the group consisting of starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations.
  • amylose forms long, helical, intertwined chains with around 300 to 1,200 glucose molecules as a result of the bond in the 1,4 position
  • the chain in amylopectin branches after an average of 25 glucose building blocks through a 1,6 bond to form a branch-like structure with around 1,500 to 12,000 molecules of glucose.
  • starch derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for producing water-soluble coatings for the detergent, dishwashing liquid and cleaning agent portions in the context of the present invention.
  • Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • starches in which the hydroxy groups have been replaced by functional groups that are not bound via an oxygen atom can also be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkaline starches, carboxymethyl starch (CMS), starch esters and ethers as well as amino starches.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, from a formal point of view, represents a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose derivatives that can be used as cellulose-based disintegrants in the context of the present invention are also cellulose derivatives, which are obtainable from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxy groups have been replaced by functional groups that are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers as well as amino celluloses.
  • the washing or cleaning-active melt can be a melted pure substance or a mixture of several substances. It is of course possible to mix the individual substances of a multi-substance melt before melting or to produce separate melts that are then combined. Melts made from mixtures of substances can be advantageous, for example, if eutectic mixtures are formed that have a significantly lower melting point and thus reduce process costs.
  • the melt material at least partially comprises detergents or cleaning agents. It is preferred if the melt consists entirely of one or more washing or cleaning-active substances.
  • the melt consists of at least one material or mixture of materials whose melting point is in the range from 40 to 1000 ° C, preferably from 42.5 to 500 ° C, particularly preferably from 45 to 200 ° C and in particular from 50 to 160 °C.
  • the material of the melt preferably has a high water solubility, which is, for example, above 100 g/l, with solubilities above 200 g/l in distilled water at 20 ° C being particularly preferred.
  • melts which have proven to be particularly suitable are those which come from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and/or urea.
  • the material of the hollow mold contains one or more substances from the groups of carboxylic acids, carboxylic anhydrides, dicarboxylic acids, dicarboxylic anhydrides, hydrogen carbonates, hydrogen sulfates, polyethylene glycols, polypropylene glycols, sodium acetate trihydrate and / or urea in amounts of at least 40 wt .%, preferably at least 60% by weight and in particular at least 80% by weight, in each case based on the weight of the hollow mold.
  • carboxylic acids and their salts are also suitable as materials for producing the solidified melt. From this class of substances, citric acid and trisodium citrate as well as salicylic acid and glycolic acid have proven to be particularly suitable. Fatty acids, preferably with more than 10 carbon atoms, and their salts can also be used with particular advantage as material for the open hollow mold.
  • Carboxylic acids that can be used in the context of the present invention 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 is preferred in the context of the present compound 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), hexacosanoic acid (cerotinic acid), triacotanoic 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,12
  • coconut oil fatty acid (approx. 6 wt.% C 8 , 6 wt.% C 10 , 48 wt.% C 12 , 18 wt.% C 14 , 10 wt.% C 16 , 2 wt.% C 18 , 8 wt.% C 18' , 1 wt.% C 18"
  • palm kernel oil fatty acid (approx. 6 wt.% C 8 , 6 wt.% C 10 , 48 wt.% C 12 , 18 wt.% C 14 , 10 wt.% C 16 , 2 wt.% C 18 , 8 wt.% C 18' , 1 wt.% C 18" , palm kernel oil fatty acid (approx.
  • the above-mentioned carboxylic acids are technically obtained largely from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the last century led directly to alkali salts (soaps), today only water is used for splitting on an industrial scale, which splits the fats into glycerol and the free fatty acids. Processes used on an industrial scale include, for example, splitting in an autoclave or continuous high-pressure splitting.
  • the alkali metal lazes of the above-mentioned carboxylic acids or carboxylic acid mixtures can also be used - if necessary in a mixture with other materials - for the production of the open hollow mold.
  • Salicylic acid and/or acetylsalicylic acid or their salts, preferably their alkali metal salts, can also be used, for example.
  • Suitable materials that can be processed into open hollow molds via the state of the melt are hydrogen carbonates, in particular the alkali metal hydrogen carbonates, especially sodium and potassium hydrogen carbonate, and the hydrogen sulfates, in particular alkali metal hydrogen sulfates, especially potassium hydrogen sulfate and/or Sodium hydrogen sulfate.
  • the eutectic mixture of potassium hydrogen sulfate and sodium hydrogen sulfate which consists of 60% by weight of NaHSO 4 and 40% by weight of KHSO 4 , has also proven to be particularly suitable.
  • melt materials can be found in the table below: Melting point [°C] Solubility [g/l H2O ] Ammonium aluminum sulfate dodecahydrate 93 150 Potassium aluminum sulfate dodecahydrate 92 110 Aluminum sulfate monohydrate 90 600 Aluminum sulfate octadecahydrate 90 600 Sodium phosphinate monohydrate 90 1000 Sodium dihydrogen phosphate 100 1103 Sodium dihydrogen phosphate monohydrate 100 1103 Sodium ammonium hydrogen phosphate tetrahydrate 79 167 Disodium hydrogen phosphate heptahydrate 48 154 Trisodium phosphate dodecahydrate 75 258 Tripotassium phosphate heptahydrate 46 900 Ammonium iron(II) sulfate hexahydrate 100 269 Ferrous sulfate heptahydrate 64 400 glucose 83 820 Magnesium acetate tetrahydrate 80 1200 Manganese(II) chloride tetra
  • sugars are also suitable materials for melting.
  • agents which are characterized in that the material of the hollow mold contains one or more substances from the group of sugars and/or sugar acids and/or sugar alcohols, preferably from the group of sugars, particularly preferably from the group of Oligosaccharides, oligosaccharide derivatives, monosaccharides, disaccharides, monosaccharide derivatives and disaccharide derivatives and mixtures thereof, in particular from the group glucose and/or fructose and/or ribose and/or maltose and/or lactose and/or sucrose and/or maltodextrin and/or Isomalt® .
  • sugars, sugar acids and sugar alcohols have proven to be particularly suitable materials for the melt. These substances are generally not only sufficiently soluble but are also characterized by low costs and good processability.
  • Sugar and sugar derivatives, in particular the mono- and disaccharides and their derivatives can be processed, for example, in the form of their melts, these melts having good dissolving power both for dyes and for many washing and cleaning-active substances.
  • the solid bodies resulting from the solidification of the sugar melts are also characterized by a smooth surface and an advantageous appearance, such as a high surface brilliance or a transparent appearance.
  • the group of sugars preferred as material for the melt in the context of the present application include from the group of mono- and disaccharides and derivatives of mono- and disaccharides in particular glucose, fructose, ribose, maltose, lactose, sucrose, maltodextrin and Isomalt ® as well as mixtures of two, three, four or more mono- and / or disaccharides and /or the derivatives of mono- and/or disaccharides.
  • Isomalt® and glucose, Isomalt® and lactose, Isomalt® and fructose, Isomalt® and ribose, Isomalt® and maltose, glucose and sucrose, Isomalt® and maltodextrin or Isomalt® and sucrose are particularly preferred as materials for the melt.
  • the proportion by weight of Isomalt® in the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.
  • maltodextrin and glucose are also particularly preferred as material for the melt.
  • the proportion by weight of the maltodextrin in the total weight of the aforementioned mixtures is preferably at least 20% by weight, particularly preferably at least 40% by weight, and in particular at least 80% by weight.
  • maltodextrin refers to water-soluble carbohydrates (dextrose equivalents, DE 3-20) obtained by enzymatic degradation of starch with a chain length of 5-10 anhydroglucose units and a high proportion of maltose.
  • Maltodextrin is added to foods to improve the rheological and caloric properties, tastes only slightly sweet and does not tend to retrograde.
  • Commercial products for example from Cerestar, are usually offered as spray-dried, free-flowing powders and have a water content of 3 to 5% by weight.
  • Isomalt® is a mixture of 6-O- ⁇ -D-glucopyrano-syl-D-sorbitol (1,6-GPS) and 1-O- ⁇ -D-glucopyranosyl-D-mannitol (1 ,1-GPM).
  • the proportion by weight of the 1,6-GPS in the total weight of the mixture is less than 57% by weight.
  • Such mixtures can be produced technically, for example, by enzymatic rearrangement of sucrose into isomaltose and subsequent catalytic hydrogenation of the resulting isomaltose to form an odorless, colorless and crystalline solid.
  • the solidified melt can form a hollow shape.
  • Hollow molds that comprise at least one further solid body are preferred, with the at least one further solid body being at least partially cast into the wall of the hollow mold.
  • the term “hollow shape” denotes a shape that encloses at least one space, wherein the enclosed space can be or can be filled. In addition to the at least one enclosed space, the hollow shape can have further enclosed spaces and/or not completely enclosed spaces. In the context of the present invention, the hollow shape does not have to consist of a uniform wall material, but can also be composed of several different materials.
  • the inclusion of at least one solid body in the wall of the hollow mold is possible, for example, if the solidified melt at least partially encloses at least one solid body.
  • This hollow mold can then be filled and closed - for example with a differently composed melt.
  • the agents according to the invention described above or the agents produced by the method according to the invention described above contain washing or cleaning-active substances, preferably washing and cleaning-active substances from the group of builders, surfactants, polymers, bleaching agents, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids , fragrances and perfume carriers. These preferred ingredients are described in more detail below.
  • the builders include in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also phosphates.
  • the finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and/or P.
  • Zeolite MAP® commercial product from Crosfield
  • zeolite X and mixtures of A, ) distributed by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula n Na 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 both as a builder in a granular compound and as a kind of "powdering" of a granular mixture, preferably a mixture to be pressed, with both ways of incorporating the zeolite into the premix usually being used.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • 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.
  • Preferred crystalline layered silicates of the formula given are those in which M stands for sodium and x has the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O5 ⁇ y H 2 O are preferred.
  • crystalline layered silicates of the general formula NaMSi .9 to 4 and y is a number from 0 to 33.
  • the crystalline layered silicates of the formula NaMSi x O 2 O 2x+1 ⁇ y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 ⁇ x H 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ⁇ x H 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 ⁇ x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ x H 2 O, Makatite).
  • Na-SKS-5 ⁇ -Na 2 Si 2 O 5
  • Na-SKS-7 ß-Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaHSi 2 O 5
  • Na-SKS-10 NaH-Si 2 O 5 ⁇ 3 H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 ⁇ -Na 2 Si 2 O 5
  • these detergents preferably contain a proportion by weight of the crystalline layered silicate of the formula NaMSi x O 2x+1 ⁇ y H 2 O of 0.1 to 20% by weight of 0.2 to 15 wt. -% and in particular from 0.4 to 10% by weight, each based on the total weight of these agents. It is particularly preferred if such automatic dishwashing detergents have a total silicate content below 7% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably below 4% by weight, very particularly preferably below 3% by weight.
  • this silicate based on the total weight of the silicate contained, preferably being at least 70% by weight, preferably at least 80% by weight and in particular at least 90% by weight .-% is silicate of the general formula NaMSi- x O 2x+1 ⁇ y H 2 O.
  • Amorphous sodium silicates with a modulus Na 2 O:SiO 2 of 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 can also be used are delayed in dissolution and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be 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 produce sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-radiation, which have a width of several degree units of the diffraction angle.
  • Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses.
  • Particularly preferred are densified/compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • phosphates As builder substances, it is also possible to use the generally known phosphates as builder substances, provided such use should not be avoided for ecological reasons. This applies in particular to the use of agents according to the invention or produced by methods according to the invention as automatic dishwashing agents, which is particularly preferred in the context of the present application.
  • alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general name for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can differentiate between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 alongside higher molecular weight representatives.
  • the phosphates combine several Advantages in themselves: They act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to cleaning performance.
  • Suitable phosphates are, for example, sodium dihydrogen phosphate, NaH 2 PO 4 , in the form of the dihydrate (density 1.91 gcm -3 , melting point 60°) or in the form of the monohydrate (density 2.04 gcm -3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na 2 HPO 4 , which is anhydrous or with 2 mol (density 2.066 gcm -3 , loss of water at 95°), 7 mol (density 1.68 gcm -3 , melting point 48° with loss of 5 H 2 O) and 12 mol Water (density 1.52 gcm -3 , melting point 35° with loss of 5 H 2 O) can be used, but in particular the trisodium phosphate (tertiary sodium phosphate) Na 3 PO 4 , which is used as dodecahydrate, as decahydrate (corresponding to 19-20% P 2 O 5 ) and in anhydrous form (corresponding
  • Another preferred phosphate is tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 .
  • tetrasodium diphosphate sodium pyrophosphate
  • Na 4 P 2 O 7 tetrasodium diphosphate
  • decahydrate decahydrate
  • potassium salt potassium diphosphate potassium 4 P 2 O 7 .
  • the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate) is commercially available, for example, in the form of a 50% by weight solution (> 23% P 2 O 5 , 25% K 2 O). Potassium polyphosphates are widely used in the detergent and cleaning agent industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • phosphates are used as detergent or cleaning active substances in detergents or cleaning agents
  • preferred agents contain these phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or . Potassium tripolyphosphate), in amounts of 5 to 80% by weight, preferably from 15 to 75% by weight and in particular from 20 to 70% by weight, in each case based on the weight of the detergent or cleaning agent.
  • potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1:1, preferably more than 2:1, preferably more than 5:1, particularly preferably more than 10:1 and in particular more than 20:1. It is particularly preferred to use only potassium tripolyphosphate without admixtures of other phosphates.
  • Alkaline carriers include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal silicates, and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4% by weight and in particular below 2% by weight, based on the total weight of the detergent or cleaning agent. Particular preference is given to agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • Particular organic cobuilders include polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These substance classes are described below.
  • Useful organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, with polycarboxylic acids being those carboxylic acids that carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and are therefore also used to adjust a lower and milder pH value of detergents or cleaning agents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned.
  • Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the respective acid form, which were basically determined using gel permeation chromatography (GPC), using a UV detector.
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural similarity to the polymers examined. This information differs significantly from the molecular weight information in which polystyrene sulfonic acids are used as the standard.
  • the molar masses measured against polystyrene sulfonic acids are generally significantly higher than the molar masses given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2000 to 20,000 g/mol. Due to their superior solubility, the short-chain polyacrylates, which have molecular weights of 2000 to 10,000 g/mol, and particularly preferably of 3000 to 5000 g/mol, can be preferred from this group.
  • Copolymeric polycarboxylates are also suitable, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular mass, based on free acids, is generally 2000 to 70,000 g/mol, preferably 20,000 to 50,000 g/mol and in particular 30,000 to 40,000 g/mol.
  • the (co-)polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co)polymeric polycarboxylates in detergents or cleaning agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
  • biodegradable polymers made from 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 which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers .
  • copolymers are those which preferably have acrolein and acrylic acid/acrylic acid salts or acrolein and vinyl acetate as monomers.
  • Polymeric aminodicarboxylic acids, their salts or their precursor substances should also be mentioned as further preferred builder substances.
  • Polyaspartic acids or their salts are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon 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 using conventional processes, for example acid- or enzyme-catalyzed processes. These are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000 g/mol.
  • DE dextrose equivalent
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents, which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Ethylenediamine N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerin disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in zeolite-containing and/or silicate-containing formulations are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which can optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups.
  • the group of surfactants includes non-ionic, anionic, cationic and amphoteric surfactants.
  • nonionic surfactants known to those skilled in the art can be used as nonionic surfactants.
  • Low-foaming nonionic surfactants are used as preferred surfactants.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with 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 residue is linear or preferably methyl-branched in the 2-position can be or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of 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 alcohol 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 ethoxylation levels reported represent statistical averages, which may correspond to a whole or a fractional number for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO( G ) G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula, in which R represents an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 represents hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances that are usually produced 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 can be obtained.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula in which R represents a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, where C 1-4 alkyl or phenyl radicals are preferred and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryl-oxy-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 a catalyst.
  • Surfactants which contain one or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer are also particularly preferably used.
  • Nonionic surfactants from the group of alkoxylated alcohols particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are also used with particular preference.
  • Nonionic surfactants that have a melting point above room temperature are particularly preferred.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that they have a viscosity above 20 Pa s, preferably above 35 Pa s and in particular above 40 Pa s. Niotensides, which have a waxy consistency at room temperature, are also preferred.
  • Surfactants that are preferably used and are solid at room temperature come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants).
  • Such (PO/EO/PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant, which is obtained from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol were produced.
  • a particularly preferred nonionic surfactant which is solid at room temperature, is obtained from a straight-chain fatty alcohol with 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide.
  • C 16-20 alcohol a straight-chain fatty alcohol with 16 to 20 carbon atoms
  • C 18 alcohol preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide.
  • the so-called “narrow range ethoxylates” are particularly preferred.
  • ethoxylated nonionic surfactants which consist of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole Alcohol was obtained, used.
  • the nonionic surfactant which is solid at room temperature, preferably also has propylene oxide units in the molecule.
  • Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule account for 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 identify surfactants.
  • Nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend, which contains 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.
  • Non-ionic surfactants which can be used with particular preference, are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.
  • Surfactants of the formula R 1 O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2 in which R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x represents values between 0.5 and 1.5 as well y represents a value of at least 15, are further particularly preferred nonionic surfactants.
  • nonionic surfactants that can preferably be used 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 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x represents values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 6 to 22 carbon atoms, with radicals with 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 can be different if x ⁇ 2.
  • the value 3 for x was chosen as an example and can certainly be larger, with the range of variation increasing with increasing x values and, for example, including a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R 1 , R 2 and R 3 are as defined above and x represents numbers 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 carbon atoms, R 3 is H and x has values of 6 to 15.
  • end-capped poly(oxyalky-lated) nonionic surfactants are 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 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x represents values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5, preferably, 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.
  • Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants in the context of the present invention.
  • surfactants with EO-AO-EO-AO blocks are preferred, with one to ten EO or AO groups attached to each other are bound before a block follows from the other groups.
  • Nichionic surfactants of the general formula preferred in which R 1 represents 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 stand for integers from 1 to 6.
  • the preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is usually unbranched, with the linear radicals coming from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or Oleyl alcohol, are preferred.
  • Alcohols available from synthetic sources include, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched residues in the 2-position in a mixture, as are usually present in oxo alcohol residues.
  • nonionic surfactants in which R 1 in the above formula represents an alkyl radical with 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 addition to propylene oxide, butylene oxide in particular comes into consideration.
  • R 2 and R 3 are independently selected from -CH 2 CH 2 -CH 3 or CH(CH 3 ) 2 are also suitable.
  • nonionic surfactants are particularly preferred 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.
  • These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.
  • nonionic surfactants that can preferably be used are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH(R 3 )O] x R 2 , in which R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, which is 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 and x stands for values between 1 and 40.
  • R 3 in the aforementioned general formula represents H.
  • R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, preferably with 4 to 20 carbon atoms
  • R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxy groups and x stands for values between 1 and 40.
  • those end-capped poly(oxyalkylated) nonionic surfactants are preferred which are according to the formula R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2 in addition to a radical R 1 which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, preferably with 4 to 20 carbon atoms, further have a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 with 1 to 30 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH 2 CH(OH)-.
  • x stands for values between 1 and 90.
  • Nonionic surfactants of the general formula are particularly preferred R 1 O[CH 2 CH 2 O] x CH 2 CH(OH)R 2 , which, in addition to a radical R 1 which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals with 1 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R 2 with 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH 2 CH(OH)- and in which x stands for values between 40 and 80, preferably for values between 40 and 60.
  • the corresponding end-capped poly(oxyalkylated) nonionic surfactants of the above formula 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 obtained.
  • R 1 O[CH 2 CH 2 O] x [CH 2 CH(CH 3 )O] y CH 2 CH(OH)R 2 in which R 1 and R 2 independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical with 2 to 26 carbon atoms, R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH(CH 3 ) 2 , but preferably -CH 3 , and x and y independently represent values between 1 and 32, where nonionic surfactants with values for x from 15 to 32 and y from 0, 5 and 1.5 are particularly preferred.
  • R 1 and R 2 independently represent a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical with 2 to 26 carbon atoms
  • R 3 is independently selected from -CH 3 -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH(CH 3 ) 2 , but preferably -CH 3
  • x and y independently of one another represent values between 1 and 32, are preferred according to the invention, with nonionic surfactants with values for x from 15 to 32 and y of 0.5 and 1.5 are particularly preferred.
  • the specified C chain lengths and degrees of ethoxylation or alkoxylation of the aforementioned nonionic surfactants represent statistical average values, which can be a whole or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but rather of mixtures, which means that average values and the resulting fractional numbers can result for both the C chain lengths and the degrees of ethoxylation or alkoxylation.
  • nonionic surfactants can be used not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants.
  • surfactant mixtures does not refer to mixtures of nonionic surfactants which, in their entirety, fall under one of the general formulas mentioned above, but rather to mixtures which contain two, three, four or more nonionic surfactants which can be described by different ones of the general formulas mentioned above .
  • the anionic surfactants used are, for example, those of the sulfonate and sulfate types.
  • Sulfonate-type surfactants are preferably C 9-13 alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is taken into consideration.
  • Alkane sulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfated fatty acid glycerol esters include the mono-, di- and triesters as well as their mixtures, as they are produced by esterification of one Monoglycerol can be obtained 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 sulfation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk(en)yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid monoesters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk(en)yl sulfates of the chain length mentioned, which contain a synthetic straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on fatty chemical 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 which can be obtained as commercial products from the Shell Oil Company under the name DAN® , are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming properties, they are only used in cleaning agents in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters and which represent 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 which is derived from ethoxylated fatty alcohols, which in themselves represent nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk(en)yl succinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or its salts.
  • Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, are suitable.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • anionic surfactants are part of automatic dishwashing detergents, their content, based on the total weight of the detergents, is preferably less than 4% by weight, preferably less than 2% by weight and most preferably less than 1% by weight. Machine dishwashing detergents that do not contain anionic surfactants are particularly preferred.
  • Cationic and/or amphoteric surfactants can also be used instead of the surfactants mentioned or in conjunction with them.
  • the content of cationic and/or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %.
  • Machine dishwashing detergents that do not contain cationic or amphoteric surfactants are particularly preferred.
  • the group of polymers includes in particular the washing or cleaning-active polymers, for example the rinse aid polymers and/or polymers that act as softeners.
  • the rinse aid polymers and/or polymers that act as softeners In general, in addition to nonionic polymers, cationic, anionic and amphoteric polymers can also be used in detergents or cleaning agents.
  • “Cationic polymers” in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, and copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • Amphoric polymers in the sense of the present invention have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • Cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a compound of the general formula as the monomer unit in which R 1 and R 4 independently represent H or a linear or branched hydrocarbon radical with 1 to 6 carbon atoms; R 2 and R 3 independently represent an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, which is preferably a methyl group; x and y independently represent integers between 1 and 3.
  • R 1 and R 4 independently represent H or a linear or branched hydrocarbon radical with 1 to 6 carbon atoms
  • R 2 and R 3 independently represent an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, which is preferably a methyl group
  • x and y independently represent integers between 1 and 3.
  • Preferred radicals R 1 and R 4 in the above formula are selected from -CH 3 , -CH 2 -CH 3 , - CH 2 -CH 2 -CH 3 , -CH(CH 3 )-CH 3 , -CH 2 -OH , -CH 2 -CH 2 -OH, -CH(OH)-CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH(OH)-CH 3 , -CH(OH)-CH 2 -CH 3 , and -(CH 2 CH 2 -O) n H.
  • Polymers which have a cationic monomer unit of the above general formula in which R 1 and R 4 are H, R 2 and R 3 are methyl and x and y are each 1 are very particularly preferred.
  • polymers which have a cationic monomer unit of the above general formula, in which R 1 is H and R 2 , R 3 , R 4 and R 5 are methyl and x is 3.
  • amphoteric polymers mentioned above have not only cationic groups, but also anionic groups or monomer units.
  • anionic monomer units come, for example, from the group of linear or branched, saturated or unsaturated carboxylates, linear or branched, saturated or unsaturated phosphonates, linear or branched, saturated or unsaturated sulfates or linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth)acrylic acid, (dimethyl)acrylic acid, (ethyl)acrylic acid, cyanoacrylic acid, vinylacetic acid, allylacetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their derivatives, the allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid or the allylphosphonic acids.
  • Preferred amphoteric polymers that can be used come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkyl-aminoalkyl (meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid / Alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.
  • Zwitterionic polymers that can preferably be used come from the group of acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali and ammonium salts and methacroylethyl betaine/methacrylate copolymers.
  • amphoteric polymers which, in addition to one or more anionic monomers, comprise methacrylamidoalkyl-trialkyl ammonium chloride and dimethyl (diallyl) ammonium chloride as cationic monomers.
  • amphoteric polymers come from the group of methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/methacrylic acid copolymers and methacrylamidoalkyltrialkylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth) acrylic acid copolymers and their alkali and ammonium salts.
  • amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers, methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/acrylic acid copolymers and methacrylamidopropyltrimethylammonium chloride/dimethyl(diallyl)ammonium chloride/alkyl(meth )-acrylic acid copolymers and their alkali and ammonium salts.
  • Detergents or cleaning agents contain the aforementioned cationic and/or amphoteric polymers preferably in amounts between 0.01 and 10% by weight, based on the total weight of the detergent or cleaning agent.
  • Polymers that are effective as softeners include, for example, the polymers containing sulfonic acid groups, which are used with particular preference.
  • Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferred as polymers containing sulfonic acid groups.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-meth-acrylamido-2-methyl-1- propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-S ulfopropyl acrylate , 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethyl methacrylamide and water-soluble salts of the
  • ionic or non-ionic monomers include, in particular, ethylenically unsaturated compounds into consideration.
  • the content of these additional ionic or non-ionic monomers in the polymers used is preferably less than 20% by weight, based on the polymer.
  • the copolymers can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, with all representatives from group i) being able 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.
  • These polymers are produced by copolymerizing acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which is also preferred.
  • acrylic acid and/or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, whereby the structural units in the molecule are changed.
  • the sulfonic acid groups can be present entirely or partially in neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the 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.
  • partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention for copolymers which only contain monomers from groups i) and ii) is preferably 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight of monomer from group ii), each based on the polymer.
  • terpolymers those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred .
  • the molecular weight of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred detergents or cleaning agents 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 .
  • Bleaching agents are a particularly preferred washing or cleaning substance.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents include, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -providing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminooperic acid or diperdodecanedioic acid.
  • Bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxyacids, with alkylperoxyacids and arylperoxyacids being particularly mentioned as examples.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphtoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-di-peroxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-dec
  • Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium.
  • heterocyclic N-bromo- and N-chloramides for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • washing or cleaning agents in particular automatic dishwashing agents, are preferred which contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight and in particular 5 to 15% by weight .-% bleach, preferably sodium percarbonate.
  • the active oxygen content of the detergents or cleaning agents, in particular the automatic dishwashing agents is, based on the total weight of the agent, preferably between 0.4 and 10% by weight, particularly preferably between 0.5 and 8% by weight and in particular between 0.6 and 5% by weight.
  • Particularly preferred agents have an active oxygen content above 0.3% by weight, preferably above 0.7% by weight, particularly preferably above 0.8% by weight and in particular above 1.0% by weight.
  • Bleach activators are used in detergents or cleaning agents, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 °C and below.
  • Compounds which can be used as bleach activators are aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms under perhydrolysis conditions. in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid can be used.
  • Substances which carry O- and/or N-acyl groups of the stated number of carbon atoms and/or optionally substituted benzoyl groups are suitable.
  • TAED
  • bleach activators preferably used in the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula in which R 1 represents -H, -CH 3 , a C 2-24 -alkyl or -alkenyl radical, a substituted C 2-24 -alkyl or -alkenyl radical with at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical with a C 1-24 alkyl group, or represents a substituted alkyl or alkenylaryl radical with a C 1-24 alkyl group and at least one further substituent on the a-romatic 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 , -
  • a cationic nitrile of the formula is particularly preferred in which R 4 , R 5 and R 6 are independently selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH(CH 3 )-CH 3 , where R 4 additionally can also be -H and _ _ _ _ _ CH 2 -CN X - , ( CH 3 CH 2 ) 3 N (+ ) CH 2 -CN CH 3 )) 3 N (+) CH 2 -CN X - , or (HO-CH 2 -CH 2 ) 3 N (i) CH 2 -CN Nitrile of the formula (CH 3 ) 3 N (+) CH 2 -CN is selected, is particularly preferred.
  • Compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid can also be used as bleach activators.
  • Substances which carry O- and/or N-acyl groups of the stated number of carbon atoms and/or optionally substituted benzoyl groups are suitable.
  • acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexa-hydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acyl-imides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nona-noyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-Diacetoxy-2,5-dihydrofuran, n
  • bleach activators preference is given to bleach activators from the group of multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl or Isononanoyloxybenzenesulfonate (n-or iso-NOBS), n-methyl-morpholinium acetonitrile methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, in each case based on the total weight of the bleach activator-containing agents, used.
  • TAED tetraacetylethylenediamine
  • NOSI N-nonanoylsuccinimide
  • bleach catalysts can also be used. These substances are bleach-intensifying transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru ammine complexes can also be used as bleaching catalysts.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, preferably selected from the group of manganese and/or cobalt salts and/or complexes, particularly preferably cobalt (ammine) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, and manganese sulfate, are used in usual amounts, preferably in an amount of up to 5% by weight, in particular 0.0025 % by weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total weight of the bleach activator-containing agents. But in special cases, more bleach activator can be used.
  • Enzymes can be used to increase the washing or cleaning performance of detergents or cleaning agents. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents and are therefore preferred.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 x 10 -6 to 5% by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN' and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilisins, which can no longer be assigned to the subtilisins in the narrower sense Proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ® from Novozymes A/S, Bagsvaerd, Denmark.
  • Subtilisins 147 and 309 are sold by Novozymes under the trade names Esperase ® and Savinase ® , respectively.
  • the variants known as BLAP ® are derived from the protease from Bacillus lentus DSM 5483.
  • proteases are, for example, those under the trade names Durazym ® , Relase ® , Everlase ® , Nafizym, Natalase ® , Kannase ® and Oyozymes ® from the company Novozymes, which under the trade names Purafect ® , Purafect ® OxP and Properase ® from the company Genencor, which is sold under the trade name Protosol ® by the company Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ® by the company Wuxi Snyder Bioproducts Ltd., China, which is sold under the trade names Proleather ® and Protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and their further developments, which have been improved for use in detergents and cleaning agents.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar ® ST.
  • this ⁇ -amylase is available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ® .
  • the ⁇ -amylase from B. amyloliquefaciens is sold by the Novozymes company under the name BAN ® , and derived variants of the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ® , also by the Novozymes company.
  • Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • these include, for example, the lipases originally available or further developed from Humicola lanuginosa ( Thermomyces lanuginosus ), especially those with the amino acid exchange D96L. They are sold, for example, by the company Novozymes under the trade names Lipolase ® , Lipolase ® Ultra, LipoPrime ® , Lipozyme ® and Lipex ® .
  • the cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used.
  • Lipase CE® Lipase P® , Lipase B® , or Lipase CES® , Lipase AKG® , Bacillis sp.
  • Lipase ® Lipase AP ® , Lipase M-AP ® and Lipase AML ® available.
  • the lipases or cutinases from the company Genencor can be used, the starting enzymes of which were originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • Lipase ® and Lipomax ® originally sold by the company Gist-Brocades and the enzymes sold by the company Meito Sangyo KK, Japan, under the names Lipase MY-30 ® , Lipase OF ® and Lipase PL ® also worth mentioning is the product Lumafast ® from Genencor.
  • mannanases include, for example, under the names Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec® B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
  • the ⁇ -glucanase obtained from B. subtilis is available under the name Cereflo ® from Novozymes.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin-, glucose- or manganese-peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention.
  • Suitable commercial products include Denilite® 1 and 2 from Novozymes.
  • organic, particularly preferably aromatic, compounds that interact with the enzymes are added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of very different redox potentials between the oxidizing enzymes and the soils (mediators).
  • the enzymes for example, either originally come from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and/or are produced by suitable microorganisms using known biotechnological processes, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the enzymes in question are preferably purified using established processes, for example precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • the enzymes can be used in any form established in the state of the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or containing stabilizers.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is covered with a water-, air- and/or chemical-impermeable protective layer.
  • Additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.
  • a protein and/or enzyme can be protected, particularly during storage, against damage such as inactivation, denaturation or decay caused by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or decay caused by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents or cleaning agents can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
  • One group of stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are often used, including especially derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
  • the peptidic protease inhibitors that should be mentioned include ovomucoid and leupeptin; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can also stabilize an enzyme contained therein.
  • Lower aliphatic alcohols but especially polyols such as glycerin, ethylene glycol, propylene glycol or sorbitol, are other frequently used enzyme stabilizers.
  • Calcium salts are also used, such as calcium acetate or calcium formate, and magnesium salts.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and/or polyamides stabilize the enzyme preparation against, among other things, physical influences or pH fluctuations.
  • Polyamine N-oxide containing polymers act as enzyme stabilizers.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkyl polyglycosides can stabilize the enzymatic components and even increase their performance.
  • Cross-linked N-containing compounds also act as enzyme stabilizers.
  • a sulfur-containing reducing agent is, for example, sodium sulfite.
  • Combinations of stabilizers are preferably used, for example from polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and/or boric acid derivatives and polyols and further enhanced by the additional use of divalent cations, such as calcium ions.
  • One or more enzymes and/or enzyme preparations are preferred in amounts of 0.1 to 5% by weight, preferably 0.2 to 4.5% by weight and in particular from 0.4 to 4% by weight, based on the total enzyme-containing agent.
  • Glass corrosion inhibitors prevent the appearance of clouding, streaks and scratches as well as iridescence on the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and/or zinc salts and/or magnesium and/or zinc complexes.
  • a preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.
  • Insoluble zinc salts in the sense of this preferred embodiment are zinc salts that have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C.
  • Examples of insoluble zinc salts that are particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 CO 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (PO 4 ) 2 ) and zinc pyrophosphate (Zn 2 (P 2 O 7 )).
  • the zinc compounds mentioned are preferably used in amounts which have a zinc ion content of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 % by weight, based on the total glass corrosion inhibitor-containing agent.
  • the exact amount of zinc salt or zinc salts in the agent naturally depends on the type of zinc salt - the less soluble the zinc salt used is, the higher its concentration should be in the agent.
  • the particle size of the salts is a criterion to consider so that the salts do not stick to glassware or machine parts. Agents are preferred here in which the insoluble zinc salts have a particle size of less than 1.7 millimeters.
  • the insoluble zinc salt preferably has an average particle size that is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 ⁇ m. This applies all the more the less soluble the zinc salt is.
  • the glass corrosion-inhibiting effectiveness increases as the particle size decreases.
  • the average particle size is preferably below 100 ⁇ m. For even less soluble salts it can be even lower; For example, for the very poorly soluble zinc oxide, average particle sizes below 60 ⁇ m are preferred.
  • a further preferred class of compounds are magnesium and/or zinc salt(s) of at least one monomeric and/or polymeric organic acid. These ensure that the surfaces of glass dishes are not corrosively changed even after repeated use, in particular that no clouding, streaks or scratches or iridescence are caused on the glass surfaces.
  • magnesium and/or zinc salt(s) of monomeric and/or polymeric organic acids can be used, the magnesium and/or zinc salts of monomeric and/or polymeric organic acids 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, oxoacids, amino acids and / or polymeric carboxylic acids.
  • the spectrum of zinc salts of organic acids preferred according to the invention ranges from salts that are sparingly or insoluble in water, i.e. a solubility below 100 mg/l, preferably below 10 mg/l, in particular below 0.01 mg/l have, up to those salts that are in water have a solubility above 100 mg/l, preferably above 500 mg/l, particularly 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.
  • At least one zinc salt of an organic carboxylic acid as the glass corrosion inhibitor, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and/or zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the zinc salt content of cleaning agents is preferably between 0.1 to 5% by weight, preferably between 0.2 to 4% by weight and in particular between 0.4 to 3% by weight, or the Content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight, each based on the total weight of the agent containing glass corrosion inhibitor.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, with silver protection agents being particularly important in the area of automatic dishwashing.
  • the known substances from the prior art can be used.
  • silver protective agents selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used. Benzotriazole and/or alkylaminotriazole are particularly preferred.
  • 3-amino-5-alkyl-1,2,4-triazoles to be used preferably according to the invention include: propyl-, -butyl-, -pentyl-, -heptyl-, -octyl-, -nonyl-, -decyl -, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acidalkyl-, -Phenyl-, -p-Tolyl-, -(4-tert.
  • alkyl-amino-1,2,4-triazoles or their physiologically tolerated salts are used in dishwashing detergents in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0. 04% by weight used.
  • Preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric and succinic acid.
  • 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-acid alkyl-3-amino-1,2,4-triazoles and mixtures are particularly effective of these substances.
  • Cleaning formulations often contain agents containing active chlorine, which can significantly reduce the corrosion of the silver surface.
  • organic redox-active compounds containing oxygen and nitrogen such as divalent and trivalent phenols, e.g. hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these compound classes, are used in particular.
  • Set-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also often used.
  • transition metal salts which are selected from the group of manganese and/or cobalt salts and/or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) Complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the items to be washed.
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, the metals preferably being in one of the oxidation states II, III, IV, V or VI are present.
  • the metal salts or metal complexes used should be at least partially soluble in water.
  • the counterions suitable for salt formation include all usual one-, two- or three-fold negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate.
  • Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and, if appropriate, additionally one or more of the above-mentioned anions.
  • the central atom is one of the metals mentioned above in one of the oxidation states mentioned above.
  • the ligands are neutral molecules or anions that are monodentate or polydentate; the term “ligands” in the sense of the invention is, for example, in “ Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9th edition, 1990, page 2507 " explained in more detail.
  • Suitable complexing agents are, for example, citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
  • metal salts and/or metal complexes are selected from the group MnSO 4 , Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II)-[1-hydroxyethane-1,1- diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co(NO 3 ) 2 , Ce(NO 3 ) 3 , and mixtures thereof, so that the metal salts and/or metal complexes are selected from the group MnSO 4 , Mn(II) -citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II)-[1-hydroxyethane-1,1-diphosphonate], V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4
  • metal salts or metal complexes are generally commercially available substances that can be used in detergents or cleaning agents for the purpose of protecting silver from corrosion without prior cleaning.
  • the mixture of pentavalent and tetravalent vanadium (V 2 O 5 , VO 2 , V 2 O 4 ) known from SO 3 production (contact process) is suitable, as is that obtained by diluting a Ti(SO 4 ) 2 - Titanyl sulfate, TiOSO 4 , formed in the solution.
  • the inorganic redox-active substances are preferably coated, i.e. completely covered with a waterproof material that is easily soluble at the cleaning temperatures, in order to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials that are applied using known processes, such as Sandwik melt coating processes from the food industry, are paraffins, microwaxes, waxes of natural origin such as carnauba wax, candellila wax, beeswax, higher melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature, is applied in a molten state to the material to be coated, for example by spinning finely divided material to be coated in a continuous stream through a spray mist zone of the molten coating material, which is also continuously generated.
  • the melting point must be chosen so that the coating material dissolves easily or melts quickly during the silver treatment.
  • the melting point should ideally be in the range between 45°C and 65°C and preferably in the range 50°C to 60°C.
  • the metal salts and/or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, based on the total corrosion inhibitor-containing agent.
  • disintegration aids so-called tablet disintegrating agents
  • Tablet disintegrants or disintegration accelerators are according to: Römpp (9th edition, vol. 6, p. 4440 ) and Voigt "Textbook of Pharmaceutical Technology” (6th edition, 1987, pp. 182-184 ) Excipients are understood to ensure the rapid disintegration of tablets in water or gastric juice and the release of the pharmaceuticals in an absorbable form.
  • disintegration aids include, for example, carbonate/citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • Disintegration aids are preferably used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based on the total weight of the agent containing disintegration aids.
  • the preferred disintegrating agents used are cellulose-based disintegrating agents, so that preferred detergents and cleaning agents contain such a cellulose-based disintegrating agent in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight. % contain.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, from a formal point of view, represents a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose derivatives that can be used as cellulose-based disintegrants in the context of the present invention are also cellulose derivatives, which are obtainable from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But celluloses in which the hydroxy groups have been replaced by functional groups that are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers as well as amino celluloses.
  • the cellulose derivatives mentioned are preferably not used alone as cellulose-based disintegrating agents, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. Particular preference is given to using pure cellulose, which is free of cellulose derivatives, as the cellulose-based disintegrating agent.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being mixed into the premixes to be pressed.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the coarser, cellulose-based disintegration aids mentioned above and described in more detail in the documents cited are preferably used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the Rettenmaier company.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrating agent or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that attack and completely dissolve only the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis produces the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • Preferred disintegration aids preferably a cellulose-based disintegration aid, preferably in granular, co-granulated or compacted form, are in the disintegration agent-containing agents in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 % by weight, based on the total weight of the disintegrating agent-containing agent.
  • gas-evolving effervescent systems can also preferably be used as tablet disintegration aids.
  • the gas-evolving shower system can consist of a single substance that releases a gas when it comes into contact with water. Particularly noteworthy among these compounds is magnesium peroxide, which releases oxygen when it comes into contact with water.
  • the gas-releasing bubble system usually consists of at least two components that react with each other to form gas. While a variety of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the bubble system used in the detergents and cleaning agents can be selected based on both economic and ecological aspects.
  • Preferred effervescent systems consist of alkali metal carbonate and/or bicarbonate and an acidification agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
  • alkali metal carbonates or hydrogen carbonates the sodium and potassium salts are clearly preferred over the other salts for cost reasons.
  • the pure alkali metal carbonates or bicarbonates in question do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred.
  • the preferred effervescent system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12% by weight and in particular 3 to 10% by weight 10% by weight of an acidification agent, based on the total weight of the agent, was used.
  • alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used as acidification agents which release carbon dioxide from the alkali metal salts in aqueous solution.
  • organic acidification agents are preferably used, with citric acid being a particularly preferred acidification agent.
  • the other solid mono-, oligo- and polycarboxylic acids can also be used. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • Sokalan ® DCS commercially available and also preferably used as an acidification agent in the context of the present invention is Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid ( max. 33% by weight.
  • Acidifying agents in the effervescent system are preferred from the group of organic di-, tri- and oligocarboxylic acids or mixtures.
  • fragrance compounds for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the ionones, ⁇ -isomethyl ionone and methyl cedryl ketone , to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • perfume oils can also contain natural fragrance mixtures such as those available from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • natural fragrance mixtures such as those available from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • fragrances In order to be perceptible, a fragrance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role plays. Most fragrances have molecular weights of up to around 200 Daltons, while molecular weights of 300 Daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, with the odor impressions being divided into “top note” and “middle note” or “body”. ) and “base note” (end note or dry out).
  • the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists largely of less volatile, i.e. more adhesive, odorants.
  • more volatile fragrances can, for example, be bound to certain fixatives, which prevents them from evaporating too quickly.
  • the following classification of fragrances into "more volatile” or “firm” fragrances says nothing about the olfactory impression and whether the corresponding fragrance is perceived as a top or middle note.
  • Adherent fragrances that can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champaca flower oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, Gurjun balsam oil, Helichrysum oil, Ho oil, Ginger oil, Iris oil, Kajeput oil, Calamus oil, Chamomile oil, Camphor oil, Kanaga oil, Cardamom oil, Cassia oil, Pine needle oil, Copa ⁇ va balsam oil, Coriander oil, Spearmint oil, Caraway oil, Cumin oil, Lavender oil, Lemongrass oil, Lime oil, Tangerine oil, Melissa oil, Musk seed oil, myrrh oil, clove oil, neroli oil, niaoul
  • fragrances can also be used within the scope of the present invention as adhesive fragrances or fragrance mixtures, i.e. fragrances.
  • These compounds include the following compounds and mixtures of these: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol , Bornlaceta, ⁇ -bromstyren, n-decylalhyde, n-dodecylalhyde, eugenol, eugenolmethy ether,
  • the more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers, which ensure a long-lasting scent through a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can also be coated with other auxiliary substances.
  • Preferred dyes the selection of which poses no difficulty for the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the agents and to light as well as none pronounced substantivity compared to the substrates to be treated with the dye-containing agents, such as textiles, glass, ceramics or plastic tableware, in order not to stain them.
  • the colorants When choosing the colorant, it must be taken into account that in the case of textile detergents, the colorants do not have a strong affinity for textile surfaces and in particular for synthetic fibers, while in the case of cleaning products, a too strong affinity for glass, ceramics or plastic tableware must be avoided. At the same time, when choosing suitable colorants, it must be taken into account that colorants have different levels of stability against oxidation. In general, water-insoluble dyes are more stable to oxidation than water-soluble dyes. Depending on the solubility and therefore also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaning agents varies.
  • dye concentrations in the range of a few 10 -2 to 10 -3 % by weight are typically selected.
  • the suitable concentration of the dye in detergents or cleaning agents is typically a few 10 -3 to 10 -4 % by weight. .
  • Colorants that can be destroyed oxidatively in the washing process are preferred, as well as mixtures of these with suitable blue dyes, so-called blue tinters. It has proven to be advantageous to use colorants that are soluble in water or in liquid organic substances at room temperature.
  • anionic dyes for example anionic nitroso dyes, are suitable.
  • a possible colorant is, for example, naphthol green (Colour Index (CI) Part 1: Acid Green 1; Part 2: 10020), which is available as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen, as well as mixtures of these with suitable ones blue dyes.
  • Pigmosol ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan ® Rhodamine EB400 (CI 45100), Basacid ® Yellow 094 (CI 47005), Sicovit ® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 ( CAS 12217-22-0 , CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol ® Blue GLW ( CAS 12219-32-8 , CI Acidblue 221)), Nylosan ® Yellow N-7GL SGR ( CAS 61814-57-1 , CI Acidyellow 218) and/or Sandolan ® Blue (CI Acid Blue 182, CAS 12219-26-0 ) for use.
  • Pigmosol ® Blue 6900 (CI 74160), Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red
  • the detergents and cleaning agents can contain further ingredients which further improve the application-related and/or aesthetic properties of these agents.
  • Preferred agents contain one or more substances from the group of electrolytes, pH adjusters, fluorescent agents, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, shrink preventers, anti-crease agents, color transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, antistatic agents, ironing aids , phobic and impregnating agents, swelling and anti-slip agents as well as UV absorbers.
  • a wide range of different salts can be used as electrolytes from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing perspective, the use of NaCl or MgCl 2 in the detergents or cleaning agents is preferred.
  • pH adjusters may be advisable. All known acids or alkalis can be used here, provided their use is not prohibited for application-related or ecological reasons or for consumer protection reasons.
  • the amount of these adjusting agents usually does not exceed 1% by weight of the total formulation.
  • Possible foam inhibitors include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable carrier materials include, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials.
  • Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and/or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R 2 SiO)x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000 and 150,000, and viscosities between 10 and 1,000,000 mPa ⁇ s.
  • Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether as well as the polymers of phthalic acid and/or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and/or polyethylene glycol terephthalates or anionically and/or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of the phthalic acid and terephthalic acid polymers.
  • Optical brighteners can be added to detergents or cleaning agents to eliminate graying and yellowing of the treated textiles. These substances absorb onto the fiber and produce a whitening and simulated bleaching effect by converting invisible ultraviolet radiation into visible convert longer wavelength light, whereby the ultraviolet light absorbed from sunlight is emitted as a weak bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry.
  • Suitable compounds come, for example, from the substance classes of 4,4'-diamino-2,2'-stilbendisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalamides, benzoxazole. , benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.
  • the task of graying inhibitors is to keep the dirt that has been detached from the fiber suspended in the liquor and thus prevent the dirt from being absorbed again.
  • Water-soluble colloids usually of an organic nature, are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • soluble starch preparations and starch products other than those mentioned above can be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxy-methylcellulose and mixtures thereof can also be used as graying inhibitors.
  • synthetic anti-crease agents can be used. 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 esters.
  • Phobia and impregnation processes are used to equip textiles with substances that prevent dirt from depositing or make it easier to wash out.
  • Preferred repelling and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol components or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radicals.
  • Antistatic agents may also be included.
  • the dirt-repellent finish with repellents and waterproofing agents is often classified as easy-care finish. The penetration of the impregnating agents in the form of solutions or emulsions of the active ingredients in question can be facilitated by adding wetting agents that reduce the surface tension.
  • hydrophobic agents used for hydrophobicization cover textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable hydrophobic agents include paraffins, waxes, metal soaps, etc.
  • silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juice and the like are easier to remove.
  • Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups include benzalkonium chlorides, alkylarlylsulfonates, halogenphenols and phenol mercuriacetate, although these compounds can also be dispensed with entirely.
  • the agents can 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 surface conductivity and thus enable improved discharge of charges that have formed.
  • External antistatic agents are usually substances with at least one hydrophilic molecular ligand and produce a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided 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) dimethytbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, whereby an additional finishing effect is achieved.
  • Fabric softeners can be used to care for the textiles and to improve the textile properties such as a softer “handle” (avivage) and reduced electrostatic charge (increased wearing comfort).
  • the active ingredients In fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride, which, however, is increasingly being replaced by quaternary ammonium compounds due to its insufficient biodegradability, which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
  • esters with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and/or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents.
  • Dimethylolethylene urea is also suitable as a finish.
  • Silicone derivatives can be used to improve the water absorption capacity, the rewettability of the treated textiles and to make ironing of the treated textiles easier. These also improve the rinsing behavior of detergents or cleaning agents thanks to their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are wholly or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and/or Si-Cl bonds.
  • Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, i.e. polysiloxanes which have, for example, polyethylene glycols, and the polyalkylene oxide-modified dimethylpolysiloxanes.
  • UV absorbers can also be used which absorb onto the treated textiles and improve the light resistance of the fibers.
  • Compounds that have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in the 2- and/or 4-position that are effective through radiationless deactivation.
  • Substituted benzotriazoles, acrylates substituted with phenyl in the 3-position (cinnamic acid derivatives), 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 are also suitable.
  • protein hydrolysates are further active substances from the field of detergents and cleaning agents that are preferred in the context of the present invention.
  • Protein hydrolysates are product mixtures that are obtained through acidic, basic or enzymatically catalyzed degradation of proteins.
  • protein hydrolysates of both plant and animal origin can be used.
  • Animal protein hydrolysates include, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which can also be in the form of salts.
  • preference is given to using protein hydrolysates of plant origin, for example soy, almond, rice, pea, potato and wheat protein hydrolysates.
  • protein hydrolysates as such is preferred, amino acid mixtures obtained elsewhere or individual amino acids such as, for example, arginine, lysine, histidine or pyroglutamic acid can also be used instead. It is also possible to use derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.
  • the non-aqueous solvents that can be used according to the invention include, in particular, the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, diethylene glycol), ether and glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, glycol esters), amides and other nitrogen compounds ( Dimethylformamide, pyridine, N-methylpyrrolidone, acetonitrile), sulfur compounds (carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (nitrobenzene), halohydrocarbons (d
  • a solvent mixture which is particularly preferred in the context of the present application, is, for example, mineral spirits, a mixture of various hydrocarbons suitable for chemical cleaning, preferably with a content of C12 to C14 hydrocarbons above 60% by weight, particularly preferably above 80% by weight and in particular above 90% by weight, based on the total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.
  • Fig. 1 shows an embodiment of the present invention, in which a cuboid container was formed by deep drawing from PVA with a wall thickness of 180 ⁇ m, with the bottom, the edges in the lower area of the container as well as the corners in the lower area of the container and partially the edges in the side Area of the cuboid container are filled with detergent melt.
  • a powdered detergent was poured in, followed by the introduction of a gel-like component.
  • the container filled in this way was then covered with a closure part in the form of a film made of the same material as the container and the same wall thickness closed by heat sealing. An air bubble can still be seen in the upper area of photo 1.
  • a stabilized, essentially cuboid container can be obtained which largely retains its cuboid shape and which is stabilized, particularly in the lower region, by the solidified melt.
  • Photo 2 shows an improved embodiment of the present invention with the same filling goods and shell materials as in photo 1, but in which, compared to photo 1, the melt is in all corners and edge areas of the cuboid container, with the exception of the edge surrounding the opening. Furthermore, the side wall of the cuboid on the left in the photo is also completely filled with melt, as is the opposite side.
  • This embodiment has the advantage over embodiment 1 that further stabilization is achieved.
  • the cuboid shape is also better preserved than in photo 1.
  • the powder component of the packaged detergent or cleaning agent is still visible through the front side wall in photo 2.
  • the powdered detergent ingredient is also visible through the bubble at the top.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Detergent Compositions (AREA)
  • Wrappers (AREA)
  • Packages (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
EP05776193.4A 2004-08-14 2005-07-28 Verfahren zur herstellung portionierter wasch- oder reinigungsmittel Active EP1776448B2 (de)

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DE102005045440A1 (de) * 2005-09-22 2007-04-05 Henkel Kgaa Portionierte Wasch- oder Reinigungsmittelzusammensetzung
US8557100B2 (en) * 2008-10-16 2013-10-15 Atotech Deutschland Gmbh Metal plating additive, and method for plating substrates and products therefrom
EP2350249B1 (de) * 2008-10-31 2014-04-16 Henkel AG & Co. KGaA Maschinelles geschirrspülmittel
DK2681247T3 (en) * 2011-02-28 2018-06-25 Cadena Bio Inc Polymers containing an acid group and their use as catalyst
US9238845B2 (en) 2012-08-24 2016-01-19 Midori Usa, Inc. Methods of producing sugars from biomass feedstocks
ES2725612T3 (es) 2013-03-14 2019-09-25 Ecolab Usa Inc Composición de detergente y prelavado que contiene enzima y métodos de uso
DE102014222602A1 (de) 2014-11-05 2016-05-12 Henkel Ag & Co. Kgaa Wasserlöslicher Behälter und Verfahren zur Herstellung
US20160200501A1 (en) 2015-01-14 2016-07-14 Monosol, Llc Web of cleaning products having a modified internal atmosphere and method of manufacture
DE102017210141A1 (de) 2017-06-16 2018-12-20 Henkel Ag & Co. Kgaa Portion zur Bereitstellung tensidhaltiger Flotten
ES2913658T3 (es) 2017-03-01 2022-06-03 Ecolab Usa Inc Mecanismo de interacción urea/ácido sólido bajo condiciones de almacenamiento y composiciones sólidas estables en almacenamiento que comprenden urea y ácido
DE102022208665A1 (de) 2022-08-22 2024-02-22 Henkel Ag & Co. Kgaa Reinigungsmittelportion umfassend Gelphase(n), Pulver und Formkörper

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JP2008510023A (ja) 2008-04-03
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US20070244024A1 (en) 2007-10-18
EP1776448B1 (de) 2013-12-11
WO2006018108A1 (de) 2006-02-23
PL1776448T5 (pl) 2024-01-15
EP1776448A1 (de) 2007-04-25
ES2441729T5 (es) 2024-03-27
DE102004039472A1 (de) 2006-03-02

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