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WO2004058592A1 - Agent de lavage ou de nettoyage en portion - Google Patents

Agent de lavage ou de nettoyage en portion Download PDF

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Publication number
WO2004058592A1
WO2004058592A1 PCT/EP2003/013568 EP0313568W WO2004058592A1 WO 2004058592 A1 WO2004058592 A1 WO 2004058592A1 EP 0313568 W EP0313568 W EP 0313568W WO 2004058592 A1 WO2004058592 A1 WO 2004058592A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
receiving chambers
weight
particularly preferably
preferred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2003/013568
Other languages
German (de)
English (en)
Inventor
Matthias Reimann
Arno DÜFFELS
Christian Nitsch
Ulrich Pegelow
Hans-Georg MÜHLHAUSEN
Wolfgang Barthel
Maren Jekel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AU2003298161A priority Critical patent/AU2003298161A1/en
Publication of WO2004058592A1 publication Critical patent/WO2004058592A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B65B3/00—Packaging plastic material, semiliquids, liquids or mixed solids and liquids, in individual containers or receptacles, e.g. bags, sacks, boxes, cartons, cans, or jars
    • B65B3/02—Machines characterised by the incorporation of means for making the containers or receptacles
    • B65B3/022—Making containers by moulding of a thermoplastic material
    • 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
    • B65B61/00—Auxiliary devices, not otherwise provided for, for operating on sheets, blanks, webs, binding material, containers or packages
    • B65B61/20—Auxiliary devices, not otherwise provided for, for operating on sheets, blanks, webs, binding material, containers or packages for adding cards, coupons or other inserts to package contents
    • B65B61/202—Auxiliary devices, not otherwise provided for, for operating on sheets, blanks, webs, binding material, containers or packages for adding cards, coupons or other inserts to package contents for attaching articles to the outside of a container
    • 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
    • C11D17/04—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

Definitions

  • the present invention is in the field of portion packaging for active substances or combinations of active substances.
  • this invention relates to subdivided or compartmentalized packaging, that is to say packaging with a plurality of receiving chambers, for the common dosing of active substances or combinations of active substances which are incompatible with one another, and to processes for producing these packaging.
  • a preferred field of application of the claimed agents and processes is in the field of detergents or cleaning agents, such as those used for cleaning textiles, dishes or hard surfaces.
  • the portioned packaging of active ingredients or combinations of active ingredients plays an important role in many areas of applied chemistry, for example in pharmacy, crop protection, but also in the area of washing or cleaning agents.
  • the portioning avoids a possibly time-consuming and labor-intensive dosage by the user, as well as the direct contact of the user with the corresponding active ingredients.
  • WO 93/08095 A1 discloses a bag made of water-soluble or water-dispersible material which has two receiving chambers and is suitable, for example, for packaging toxic substances.
  • the bags can be produced by the thermoforming process.
  • WO 02/42401 A1 (Procter & Gamble) claims a method for the automatic cleaning of dishes, which is carried out using a container with a plurality of receiving chambers.
  • the corresponding containers have a horizontal arrangement of the individual receiving chambers and are produced by sequential adhesive bonding of individual foils to form the receiving chambers, it also being possible to use individual foils which have been shaped by deep drawing.
  • WO 02/85738 A1 (Reckitt Benckiser) relates to water-soluble containers with at least two receiving troughs. These containers are manufactured by gradually sealing individual foils or prefabricated individual compartments to the final container.
  • WO 02/85736 A1 (Reckitt Benckiser) describes water-soluble containers with at least two receiving chambers.
  • the receiving chambers can be produced by injection molding or deep drawing, and are designed so that the closed chambers can be folded up in a mirror-image arrangement by folding. Due to the manufacturing process, each of the multi-chamber containers disclosed in the cited documents is necessarily characterized by a horizontal arrangement of the receiving chambers, the containers for realizing these receiving chambers, due to their design, having a high packaging proportion in relation to the number of receiving chambers.
  • the object of the present invention was to avoid the disadvantages described above.
  • the proportion of packaging per metering unit should be reduced and the containers obtained should be made more mechanically stable despite the reduced use of materials.
  • the present application now discloses a method for packaging active substances or combinations of active substances, which differs from the methods disclosed in the prior art by a reduced consumption of packaging materials, an increased flexibility in the arrangement of the individual receiving chambers, an optimized space utilization of the packaging body and an increased rigidity and the transport and storage stability of the resulting containers.
  • a first subject of this application is therefore a method for producing a filled container with at least two receiving chambers separated by a web and at least one intermediate space between these receiving chambers below the web, comprising the steps: a) shaping processing of a first wrapping material to form the at least two receiving chambers separated by a web and at least one intermediate space located between these receiving chambers below the web; b) filling the receiving chambers; c) filling the or at least one of the interstices / interstices located between the receiving chambers below the web;
  • suitable methods for shaping processing are deep-drawing, injection molding and casting of solidifying dispersions, solidifying solutions or melts.
  • “deep-drawing” or “deep-drawing methods” are methods for processing packaging materials in which, after optional pretreatment by means of heat and / or solvent, they are brought into shape by means of a suitably shaped die.
  • the packaging material can be introduced, for example, as a plate or film between the two parts of the tool, the positive and the negative, and deformed by compressing these parts, but the deformation can also be used without use a negative tool by the action of a vacuum and / or compressed air and / or the dead weight of the enclosed active substances or combinations of active substances.
  • the first wrapping material is provided in the form of a film over a die provided with depressions and is particularly preferred by the action of compressed air from the top of the films or by the action of a vacuum from the underside of the films is introduced into the recesses of the die under the simultaneous action of compressed air and vacuum and is shaped according to the shape of the recess.
  • Particularly advantageous processes are characterized in that the film is pretreated by the action of heat and / or solvents before it is deformed.
  • a film is pressed after the optional pretreatment (solvent, heat) by the action of a stamp and / or by the action of the weight of the filling material into the recess of a die.
  • the action of heat and / or solvents on the casing material serves to facilitate its plastic deformation.
  • the casing material can be heated, for example, by heat radiation, hot air or, particularly preferably, by direct contact with a heating plate.
  • the duration of the heat treatment and the temperature of the heat radiation, hot air or hotplate surface used naturally depend on the type of the covering material used.
  • a temperature between 90 and 130 ° C., in particular between 105 and 115 ° C. is preferred.
  • the duration of the heat treatment, in particular the contact time when using a heating plate is preferably between 0.1 and 7 seconds, particularly preferably between 0.2 and 6 seconds and in particular between 0.3 and 4 seconds.
  • the wrapping material can be guided between two mutually opposite plates, at least one of which serves as a heating plate, and brought into direct contact with the surfaces thereof by lowering and / or lifting one of these plates.
  • the wrapping material can also be guided under or over a heated surface and a contact can subsequently be made by blowing the material onto the surface by means of compressed air.
  • the preferably film-shaped casing material can be heated uniformly over the entire surface of the film or unevenly by a so-called target heating.
  • the heating takes place in a targeted manner by means of heating yards located in the heating plate.
  • the heating yards located in the heating plates can be planar, concave or convex. If the heating zones are convex or concave, the ratio of the maximum diameter of the heating zone to its maximum height is preferably greater than 2, particularly preferably greater than 4 and in particular greater than 8.
  • the target heating described above creates a grid or mesh of unheated and not very elastic film material on the film to be processed, which undesirable deformation and stretching of the film material, for example due to the weight of the film or the tensile forces acting during film transport, in the area between the heated film pieces avoids.
  • the spatial orientation of the receiving troughs to one another and the spatial orientation of the receiving troughs within the film are stabilized in this way, so that the receiving troughs are in the intended positions during further transport for filling, sealing and separating and incorrect filling, sealing or separating is avoided.
  • a preferred subject of this application is a method for producing a filled container with at least two separate receiving chambers, comprising the steps: a) providing a film of a first wrapping material; b) heating the film, preferably by target heating; c) deep-drawing this film by the action of compressed air and / or a vacuum, with the formation of at least two separate receiving chambers; d) filling the receiving chambers; e) filling the or at least one of the interstices / interstices located between the receiving chambers;
  • Preferred continuous deep-drawing processes that is to say processes on a continuous endless die, in which the receiving chambers produced by deformation remain in the depressions of the die until they are filled or sealed or even cut out, are characterized in that the Recesses formed receptacles by a vacuum, which is applied during the forming process and until the completion of the filling process, preferably until the completion of sealing, particularly preferably until the container is cut out of the film grid, is kept in its deformed state.
  • the preformed containers in the filling station are in the same way with the die recesses identical or spatially similar loading forms are placed, in which a vacuum is applied before and / or during and / or after filling in order to keep the preformed receiving chambers in their shape and, for example, to prevent shrinkage and / or wrinkling.
  • the vacuum should be selected in such a way that the receiving chambers are kept in their shape, the corresponding covering material is not damaged by the action of the vacuum and spillage of the active ingredient (s) after filling in the receiving chambers by shrinking back of the receiving chamber becomes.
  • the exact value for the vacuum depends, among other things, on the type of envelope material used or its wall thickness. Typically, however, a vacuum is in the range from 0.01 to 1 bar, preferably between 0.1 and 0.8 bar, particularly preferably between 0.2 and 0.6 bar.
  • the filled receiving chambers and / or the filled space (s) can optionally be sealed with another covering material.
  • the sealing is preferably carried out by the action of pressure and / or heat and / or solvent.
  • the further wrapping material used for sealing can be identical to the wrapping material used in step a) of the method according to the invention, but can also differ from it both in its composition or in its thickness.
  • the surface of the wrapping material is first dissolved by solvent before sealing (in the case of water-soluble films, water is particularly suitable here) and then sealed by the action of pressure and heat.
  • Suitable sealing temperatures for water-soluble casing materials are, for example, 120 to 200 ° C., preferably temperatures in the range from 130 to 170 ° C., in particular in the range from 140 to 150 ° C.
  • Pressures in the range from 250 to 800 kPa, preferably 272 to 554 kPa, particularly preferably from 341 to 481 kPa have proven to be advantageous as the sealing pressure.
  • the sealing times are preferably at least 0.3 seconds, preferably between 0.4 and 4 seconds.
  • the sealing seams have a width of between 0.5 and 7 mm, preferably between 1.0 and 6 mm and in particular between 1.5 and 5 mm.
  • Sealing seams with a width above 2 mm, preferably above 2.5 mm, particularly preferably above 3 mm and in particular above 3.5 mm have proven to be sufficiently durable. Since the width of the sealed seam can vary depending on the production, even for a single package, the above-mentioned information about the width of the sealed seam relates to the minimum seam width measured for an individual package.
  • the receiving chambers and / or the intermediate space (s) are / are sealed after filling with a further covering material. Sealing takes place in particular when the contents are liquid or flowable. Examples of such filling goods are liquids, gels or particulate solids such as powder.
  • the first envelope material is processed in a shaping manner (for example by deep drawing or injection molding) in such a way that the intermediate space (s) only have an opening on the bottom side of the container.
  • the sealing of the receiving chambers and / or the gaps not only prevents contact of the filled-in active substances or active substance mixtures with the surrounding atmosphere (e.g. atmospheric oxygen, air humidity) or skin contact with the consumer, the sealing rather enables the choice of suitable sealing materials at the same time also controls the release of the active ingredients located within the sealed cavity.
  • An example of such a control is the use of water-soluble or water-dispersible sealing and / or wrapping materials with different solubilities with the aim of releasing the contents of individual receiving chambers or spaces into the surrounding aqueous medium in a chronologically defined order.
  • methods can be implemented in which the envelope materials used to seal the receiving chambers or intermediate spaces are the same or different materials.
  • the same wrapping materials are used for sealing the receiving chambers and the spaces. This embodiment enables the contents to be released under the sealing surfaces at the same time.
  • the materials used for sealing the receiving chambers differ from the materials used for sealing the interspaces.
  • the envelope materials used for sealing the receiving chambers preferably have a higher solubility than the materials used for sealing the interspaces.
  • the envelope material used to seal the interspaces has a higher solubility than the envelope material used to seal the receiving chambers.
  • the receiving chambers formed by the shaping processing can have any technically feasible shape. Spherical-dome-shaped, cylindrical or cubic chambers are particularly preferred.
  • Preferred receiving chambers have at least one edge and one corner, receiving chambers with two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more edges or two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are also feasible and preferred according to the invention. Further feasible and preferred in alternative embodiments of the inventive method receiving chambers have a dome-shaped structure.
  • the side walls of the receiving chambers are preferably planar. Spatially opposite side walls can be arranged both parallel and not parallel to one another.
  • the base area of the receiving chambers can be convex, concave or planar, with planar base areas being preferred in view of the subsequent filling of the intermediate space (s) located between the receiving chambers.
  • the base area itself can be designed as a circle, but can also have corners.
  • Base areas with a corner (teardrop shape), two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are in Preferred within the scope of the present application.
  • the transition from the base area to the side wall (s) or the transition of the side walls into one another is designed in a rounded form.
  • the receiving chambers therefore have no pointed or sharp, but rather rounded edges.
  • a preferred method according to the invention is therefore characterized in that the base areas of the receiving chambers are planar.
  • the receiving chambers become a total volume between 0.1 and 1000 ml, preferably between 0.2 and 100 ml, particularly preferably between 0.4 and 50 ml, very particularly preferably between 0.6 and 20 ml and especially deep drawn between 0.8 and 10 mL.
  • the at least two receiving chambers have the same spatial shape and an identical volume.
  • the at least two receiving chambers present in the container have different volumes, the ratio of these volumes preferably being between 25: 1 and 1.05: 1, preferably between 20: 1 and 2: 1 and is in particular between 15: 1 and 4: 1.
  • the container has two receiving chambers of different volumes, the volume of the smaller receiving chamber being at least 2%, preferably at least 5%, particularly preferably at least 10% and in particular at least 20%, 30%, 40%, 50%, 60% , 65%, 70%, 75% or 80% of the volume of the larger receiving chamber.
  • the volume of the individual chambers is preferably between 0.05 and 900 ml, particularly preferably between 0.1 and 90 ml, very particularly preferably between 0.5 and 40 ml and in particular between 1.0 and 25 ml.
  • the containers have receiving chambers with different depths.
  • the receiving chamber with the smaller chamber depth can certainly have the larger chamber volume, while the receiving chamber with the greater chamber depth has a smaller volume.
  • the two or more chambers can also have the same volume despite different chamber depths.
  • a method is preferred in which the receiving chamber with the smaller chamber depth also has a smaller volume in comparison with the other receiving chamber (s), with reference to the above in terms of the absolute volumes and the volume ratios Information is referenced.
  • Containers produced according to a preferred method according to the invention have receiving chambers with vertically sloping side walls.
  • containers in which at least one receiving chamber has an inclined side wall are particularly preferred.
  • the angle between the side wall and an imaginary seal closing the receiving chamber is therefore less than 90 °.
  • this angle can vary for the different side walls of a single receiving chamber. If the receiving chamber has only a single side wall (cylinder-like receiving chambers), even a single side wall can have different angles with the corresponding shaping of the deep-drawing troughs used in deep-drawing.
  • Preference is given to receiving chambers in which the said angle is 30 and 90 °, preferably between 35 and 89 °, particularly preferably between 40 and 88 ° and in particular between 45 and 87 °.
  • the receiving chambers produced by the shaping processing can also have gradations.
  • the corresponding receiving chambers produced in a preferred method variant accordingly have no flat side walls, but rather have side walls which are characterized by steps or curvatures.
  • the number of Curvatures can vary, methods being preferred in which the number of steps and / or curvatures in one or more receiving chamber (s) per chamber is at most 10, preferably between 1 and 9, particularly preferably between 1 and 8, very particularly preferably between 2 and 7 and in particular between 2 and 6.
  • the steps or curvatures can be circumferential in the respective receiving troughs or only on individual side walls.
  • the course of the steps or curvatures is preferably horizontal. Steps and / or curvatures with an upward or downward course similar to a screw thread can, however, also be realized and are preferred for certain fields of application.
  • the “volume” of the receiving chambers or the interstices is the filling volume which can be achieved by filling the chambers or interstices with a liquid without overflowing this liquid onto the preferably planar sealing edges.
  • the total volume of the space or spaces located between the receiving chambers is not greater than the total volume of the receiving chambers.
  • the total volume of the interstices is preferably between 0.1 and 1000 L, preferably between 0.2 and 100 mL, particularly preferably between 0.4 and 50 mL, very particularly preferably between 0.6 and 20 mL and in particular between 0, 8 and 10 mL.
  • Spaces with a volume below 7 ml, preferably below 6 ml, particularly preferably below 5 ml, in particular below 4 ml are particularly preferred, the volume of a single gap between 0.05 and 2.0 ml, preferably between 0, in particularly advantageous process variants, 1 and 1, 5 mL, particularly preferably between 0.2 and 0.9 mL and in particular between 0.3 and 0.7 mL.
  • the ratio of the sum of the volumes of the receiving chambers to the sum of the volumes of the spaces is between 50: 1 and 1: 5, preferably between 40: 1 and 1: 4, particularly preferably between 30: 1 and 1: 3, very particularly preferably between 20: 1 and 1: 2 and in particular between 10: 1 and 1: 1.
  • the width of the webs located between the individual receiving chambers can vary.
  • Preferred method variants according to the invention are characterized in that the web (s) located between the receiving chambers has a width between 0.5 and 40 mm, preferably between 0.6 and 30 mm, particularly preferably between 0.7 and 20 mm , all particularly preferably have between 0.8 and 10 mm and in particular between 1.0 and 5.0 mm.
  • the width of the webs depends, among other parameters, on the choice of the deep-drawing process used to manufacture the corresponding containers.
  • these processes i.a. distinguish two variants, all of which are particularly preferred for carrying out the method according to the invention. These are processes in which the wrapping material is fed horizontally into a molding station and from there in a horizontal manner for filling and / or sealing and / or singling, again differentiating between continuous and discontinuous processes, and processes in which the Wrapping material is guided over a continuously rotating forming roller.
  • envelope materials that can be processed by injection molding or deep-drawing methods can be used in the method according to the invention, although the use of water-soluble or water-dispersible packaging materials is preferred.
  • Preferred methods according to the invention are accordingly characterized in that at least one of the coating materials used is water-soluble or water-dispersible.
  • water-soluble or water-dispersible coating materials which are suitable both for producing the receiving chambers and for sealing them are listed below.
  • the polymers mentioned can be used as a sealing material or shell material either alone or in combination with one another or in combination with other substances, for example plasticizers or solubilizers.
  • Water-soluble polymers in the sense of the invention are those polymers which are more than 2.5% by weight soluble in water at room temperature.
  • the wrapping material used in the process according to the invention is preferably at least partially a substance from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin.
  • the container comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof.
  • PVAL polyvinyl alcohol
  • PVP polyvinyl pyrrolidone
  • polyethylene oxide polyethylene oxide
  • gelatin gelatin
  • cellulose and their derivatives and mixtures thereof.
  • Polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 9 ⁇ -99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups.
  • the manufacturers characterize the polyvinyl alcohols by stating 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 safe and are at least partially biodegradable.
  • the water solubility can be reduced by post-treatment with aldehydes (acetaiization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the shell material used in the process according to the invention 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 Is 62 to ⁇ mol%.
  • the first covering material used in the process according to the invention 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 ⁇ O% by weight from a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably ⁇ O to 90 mol%, particularly preferably 61 to 89 mol% and in particular 82 to ⁇ mol%.
  • Polyvinyl alcohols of a specific molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the shell material comprises a polyvinyl alcohol, the molecular weight of which ranges from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly preferably from 12,000 up to 80,000 gmol "1 and in particular from 13,000 to 70,000 gmol " 1 .
  • the degree of polymerization of such preferred polyvinyl alcohols is between 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.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-8 ⁇ , Mowiol ® 5-8 ⁇ and Mowiol ® 8-88.
  • ELVANOL ® 51-05, 52-22, 50-42, 85- ⁇ 2, 75-15, T-25, T-66, 90-50 (trademark of DuPont)
  • ALCOTEX ® 72.5, 7 ⁇ , B72, F ⁇ 0 / 40, F ⁇ / 4, F ⁇ / 26, F ⁇ 8 / 40, F ⁇ / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol ® NK-05, A-300, AH-22, C-500, GH -20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK).
  • the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which have been found to be particularly preferred and particularly advantageous on account of their extremely good solubility in cold water have been those which contain the aldehyde or keto groups of saccharides or Polysaccharides or mixtures thereof can be acetalized or ketalized.
  • the reaction products made of PVAL and starch are extremely advantageous to use.
  • solubility in water 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.
  • Films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be adjusted to the degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.
  • PVP Polyvinylpyrrolidones
  • PVPs are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • ethylene oxide oxirane
  • ethylene glycol ethylene glycol
  • Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of the 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 coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules.
  • gelatin In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
  • enveloping materials which comprise a polymer from the group 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. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions.
  • Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products Esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which 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 and aminoceiluloses.
  • Preferred methods according to the invention are characterized in that at least one of the envelope materials used is transparent or translucent.
  • the wrapping material used for example for injection molding and / or deep drawing and / or sealing is preferably transparent.
  • transparency is understood to mean that the transmittance within the visible spectrum of light (410 to ⁇ OO nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%.
  • a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.
  • Containers produced according to the invention for the manufacture of which transparent envelope material was used, can contain a stabilizing agent.
  • Stabilizing agents in the sense of the invention are materials which protect the ingredients in the receiving chambers and / or the ingredients located in an intermediate space against decomposition or deactivation by light radiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • Particularly suitable stabilizers in the sense of the invention are the antioxidants.
  • the formulations can contain antioxidants.
  • Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants.
  • Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
  • Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with Ci-i ⁇ -alkanols, in particular C 10 - 18 alkanols, metal ion deactivators that are capable of catalyzing the auto-oxidation of metal ions such as copper, to complex how Nitrilotriacetic acid and its derivatives and their mixtures.
  • Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in
  • UV absorbers can improve the lightfastness of the recipe components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ® H), are also phenyl-substituted acrylates ( 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 urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ® FD or Tinosorb ® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 4-
  • esters of cinnamic acid preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);
  • Esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-benzylidene camphor such as 4- (2-oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
  • UV-A filters -4'-methoxy-dibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds.
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs in some other way from the spherical shape.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobicized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 605 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.
  • UV absorbers can be used in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight, in each case based on the total weight of a contained in a receiving chamber or a space mixture of substances.
  • Another class of stabilizers to be used with preference are the fluorescent dyes.
  • the fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1, 3-diarylpyrazolines, naphthalic imides, benzoxazole and benzisoxazole and Benzimidazole systems and the pyrene derivatives substituted by heterocycles.
  • the sulfonic acid salts of the diaminostilbene derivatives and polymeric fluorescent substances are of particular importance.
  • Fluorescent substances based on the total weight of a substance mixture located in a receiving chamber or in a space, in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 up to 0.1% by weight.
  • the aforementioned stabilizing agents are used in any mixtures.
  • the stabilizing agents are, based on the total weight of a substance mixture located in a receiving chamber or an intermediate space, in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5 wt .-% used.
  • the shell material (s) used in the process (s) according to the invention is preferably a water-soluble or water-dispersible polymer. If the shaping processing of the water-soluble or water-dispersible polymer is carried out by deep drawing, a film is preferably used for this process.
  • Preferred process variants are characterized in that the film used in step a) of the process according to the invention has a thickness of 5 to 2000 ⁇ m, preferably from 10 to 1000 ⁇ m, particularly preferably from 15 to 500 ⁇ m, very particularly preferably from 20 to 200 ⁇ m and in particular from 25 to 100 microns.
  • the foils used can be single or multi-layer foils (laminate foils).
  • the water content of the films is preferably below 10% by weight, particularly preferably below 7% by weight, very particularly preferably below 5% by weight and in particular below 4% by weight.
  • a particularly preferred method according to the invention is characterized in that the at least two receiving chambers in step b) are filled with different agents in each case.
  • the agents can differ in their composition, as well as in their composition and state of matter.
  • active substances and active substance combinations are summarized which have a solid, that is to say dimensionally stable, non-flowable consistency.
  • This category includes, for example, substances in the solid state, but also dimensionally stable substances such as dimensionally stable gels and combinations of these substances.
  • Filled bodies with a solid outer shell are also referred to as solids, regardless of the physical state of the fillers contained in these filled bodies.
  • solids are preferably powders and / or granules and / or extrudates and / or compactates and / or castings, regardless of whether they are pure substances or mixtures of substances.
  • the solids mentioned can be in amorphous and / or crystalline and / or partially crystalline form.
  • loading Preferred solids in the context of the present invention have a water content (for example, determinable as a loss on drying or according to Karl Fischer) below 7% by weight, preferably below 4.5% by weight, and particularly preferably below 2% by weight.
  • Powder is a general term for a form of separation of solid substances and / or mixtures of substances which is obtained by comminution, i.e. grinding or crushing in the grinding bowl (pulverization), grinding in mills or as a result of atomization or freeze drying.
  • a particularly fine division is often called atomization or micronization; the corresponding powders are called micro powders.
  • Preferred powders have a uniform (homogeneous) mixture of the solid, finely divided constituents and, in the case of substance, tend not to separate into individual constituents of these mixtures.
  • Powders which are particularly preferred in the context of the present application therefore have a particle size distribution in which at least ⁇ O% by weight, preferably at least 60% by weight, particularly preferably at least 95% by weight and in particular at least 99% by weight of the powder, in each case based on its total weight, deviate from the mean particle size of this powder by a maximum of 60%, preferably a maximum of 60% and in particular a maximum of 40%.
  • the powders are roughly divided into coarse, fine and. Very fine powder common; A more precise classification of powdered bulk goods is based on their bulk density and by sieve analysis.
  • powders of any particle size can be used, but preferred powders have average particle sizes of 40 to 500 ⁇ m, preferably from 60 to 400 ⁇ m and in particular from 100 to 300 ⁇ m. Methods for determining the average particle size are usually based on the aforementioned sieve analysis and are described in detail in the prior art.
  • the unwanted caking of the powders can be countered by using pouring aids or powdering agents.
  • the powders produced in the process according to the invention therefore contain free-flowing aids or powdering agents, preferably in parts by weight of 0.1 to 4% by weight, particularly preferably of 0.2 to 3% by weight and in particular of 0 , 3 to 2 wt .-%, each based on the total weight of the powder.
  • Preferred trickles or powdering agents are, preferably in finely ground form, silicates and / or silicon oxide and / or urea.
  • powders can be agglomerated using a number of techniques. Any method known in the prior art for agglomeration of particulate mixtures is in principle suitable for converting the solids enclosed in the containers produced according to the invention into larger aggregates. Preferred in the context of the present invention agglomerates used as solid (s) are, in addition to the granules, the compactates and extrudates.
  • Granules Accumulations of granules are referred to as granules.
  • a granulate is an asymmetrical aggregate of powder particles.
  • Granulation processes are widely described in the prior art.
  • Granules can be produced by wet granulation, by dry granulation or compacting and by melt solidification granulation.
  • the most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and is the safest way to produce granules with favorable properties.
  • Moist granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably carried out in mixers, fluidized beds or spray towers, it being possible for said mixers to be equipped, for example, with stirring and kneading tools.
  • combinations of fluidized bed (s) and mixer (s) or combinations of different mixers can also be used for the granulation.
  • the granulation takes place depending on the starting material and the desired product properties under the influence of low to high shear forces.
  • the starting materials used can be, for example, melts (melt solidification) or, preferably aqueous, slurries (spray drying) solid substances which are sprayed at the top of a tower in a defined droplet size, freeze or dry in free fall, and on Bottom of the tower accumulate as granules.
  • melt solidification is generally particularly suitable for shaping low-melting substances that are stable in the melting temperature range (e.g. urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals, etc.), the corresponding granules are also referred to as prills.
  • Spray drying is used particularly for the production of detergents or detergent components.
  • extruder or perforated roller granulation in which powder mixtures optionally mixed with granulating liquid are plastically deformed when pressed by perforated disks (extrusion) or on perforated rollers.
  • the products of extruder granulation are also called extrudates.
  • Compactates can be produced, for example, using dry granulation techniques such as tableting or roller compaction. Compacting into tablets enables single or multi-phase tablets or briquettes to be produced. To the multi-phase tablets In addition to the multi-layer or sandwich tablets, the coated tablets and the point tablets (bull-eye tablets) also count. Following the compaction, the briquettes, like the slugs produced in compacting rollers, can be comminuted by opposing spiked rollers or beaten by sieves.
  • dry granulation techniques such as tableting or roller compaction.
  • casting bodies are solid substance particles which are produced by solidification and / or crystallization from melts or solutions.
  • the solidification and / or crystallization preferably takes place in prefabricated matrices.
  • the casting bodies released from the dies after solidification can subsequently be used in their original size or, if appropriate, after comminution, as solids in the water-soluble containers according to the invention.
  • Suitable matrix material for the abovementioned solids are in particular meltable substances from the group of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or paraffins.
  • Fat (s) or triglyceride (s) is the name for compounds of glycerol in which the three hydroxyl groups of the glycerol are esterified by carboxylic acids.
  • the naturally occurring fats are triglycerides, which usually contain different fatty acids in the same glycerin molecule.
  • synthetic triglycerides in which only one fatty acid is bound are also accessible (e.g. tripalmitin, triolein or tristearin).
  • Natural and / or synthetic fats and / or mixtures of the two are preferred as matrix material or matrix component for castings or one of the other solids mentioned in the context of the present invention.
  • fatty acids Aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain are referred to as fatty acids in the present application.
  • Fatty acids have proven to be particularly advantageous, some Have a melting point above 25 ° C.
  • Preferred matrix materials and / or constituents are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or erucic acid and / or elaeosteraric acid.
  • fatty acids with a melting point below 25 ° C can be used as a component of the matrix for castings or other solids mentioned above.
  • Fatty alcohol is a collective name for the linear, saturated or unsaturated primary alcohols with 6 to 22 carbon atoms that can be obtained by reducing the triglycerides, fatty acids or fatty acid esters.
  • the fatty alcohols can be saturated or unsaturated depending on the manufacturing process.
  • the solids enclosed in the containers produced according to the invention contain waxes as matrix material.
  • Preferred waxes have a melting range that is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are on the one hand dimensionally stable at room temperature, but melt at temperatures of 30 ° C. to 90 ° C. which are typical for machine dishwashing and are therefore more readily water-dispersible at these temperatures.
  • 'Waxing' is understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C without decomposition and which are relatively low-viscosity and non-stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.
  • the waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.
  • Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, whale, lanolin (wool wax), or pretzel fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
  • vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, Shellac wax, whale, lanolin (wool wax), or pretzel fat, mineral waxes such as ceres
  • the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea).
  • esters from lower alcohols with fatty acids from native sources can also be used.
  • Tegin ® 90 Goldschmidt
  • Shellac for example Shellac-KPS-Dreiring-SP (KalkhofF GmbH)
  • wax alcohols are also included in the waxes in the context of the present invention, for example.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms.
  • the wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • one or more of the solids enclosed in the containers produced according to the invention predominantly contains paraffin wax (paraffins) as the matrix material.
  • paraffin wax paraffins
  • Paraffin wax contents based on the total weight of the matrix materials
  • Paraffin wax contents of approximately 60% by weight, approximately 70% by weight or approximately ⁇ O% by weight are particularly suitable, with even higher proportions of, for example, more than 90 % By weight are particularly preferred.
  • the entire matrix material of one or more of the solids filled into the containers produced according to the invention consists of paraffin wax.
  • Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that when the containers produced according to the invention are used as dosing units for detergents and cleaning agents in an alkaline cleaning agent environment, there is no hydrolysis of the waxes (as is the case, for example, with the wax esters is to be expected) since paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes.
  • the paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C.
  • Preferred solids in particular castings, contain at least one paraffin wax with a melting range of 40 ° C. to 60 ° C. as matrix material and / or matrix constituent.
  • the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature is as high as possible.
  • wax alcohols i.e. fatty alcohols with approx. 24-36 carbon atoms, which are the main constituent of many natural waxes in the form of wax esters of higher molecular weight fatty acids (wax acids).
  • fatty alcohols i.e. fatty alcohols with approx. 24-36 carbon atoms
  • wax esters of higher molecular weight fatty acids (wax acids).
  • preferred wax alcohols are lignoceryl alcohol, ceryl alcohol, myricyl alcohol or melissyl alcohol.
  • Dispersions are particularly suitable for processing as castings, dispersions with washing or cleaning-active substances or mixtures of active substances being used with particular preference.
  • the washing- or cleaning-active preparation used to produce the casting is a dispersion of solid particles in a dispersing agent, dispersions which, based on their total weight i), comprise 10 to 85% by weight of dispersing agent and ii) contain 15 to 90% by weight of dispersed substances, are particularly preferred.
  • dispersion is a system consisting of several phases, one of which is continuous (dispersant) and at least one other is finely divided (dispersed substances).
  • Particularly preferred dispersions are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight, very particularly preferably above 17% by weight and in particular above 19 % By weight, based in each case on the total weight of the dispersion.
  • Dispersions which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion can furthermore preferably be used.
  • the maximum dispersant content of preferred dispersions is preferably less than 63% by weight, preferably less than 57% by weight, particularly preferably less than 52% by weight, very particularly preferably less than 47% by weight .-% and in particular less than 37 wt .-%.
  • those active washing or cleaning preparations which, based on their total weight, contain dispersing agents in amounts of 12 to 62% by weight, preferably 14 to 49% by weight and in particular 16 to 38% by weight. % contain.
  • the dispersants used are preferably water-soluble or water-dispersible.
  • the solubility of these dispersants at 25 ° C. is preferably more than 200 g / l, preferably more than 300 g / l, particularly preferably more than 400 g / l, very particularly preferably between 430 and 620 g / l and in particular between 470 and 580 g / l.
  • Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers.
  • the dispersant can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers.
  • the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone-vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.
  • Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols. Polymers of ethylene glycol which have the general formula III
  • n can take values between 1 (ethylene glycol) and several thousand.
  • polyethylene glycols There are various nomenclatures for polyethylene glycols that can lead to confusion.
  • the specification of the average relative molecular weight following the specification "PEG” is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210.
  • a different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula VII mentioned above.
  • polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone - Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
  • the average relative molecular weight of at least one of the dispersants used in the washing or cleaning agents according to the invention, in particular at least one of the poly (alkylene) glycols used is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and 5000.
  • Polypropylene glycols are polymers of propylene glycol that have the general formula IV
  • n can take values between 1 (propylene glycol) and several thousand.
  • Dispersions are particularly preferably used which contain a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the weight fraction of the poly (ethylene) glycol being used the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Dispersions in which the dispersant is more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% by weight are particularly preferred.
  • a nonionic polymer preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol
  • the weight fraction of the poly (ethylene) glycol being used the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by
  • a poly (alkylene) glycol preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol!
  • Dispersing agents which, in addition to poly (ethylene) glycol, also contain poly (propylene) glycol, preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol of between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1, 5: 1 and in particular between 7: 1 and 2: 1.
  • nonionic surfactants which are used both alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the nonionic surfactants that can be used can be found below in the description of detergent or cleaning substances.
  • Dispersions which are preferably used are characterized in that at least one dispersant has a melting point above 25 ° C., preferably above 35 ° C. and in particular above 40 ° C.
  • the use of dispersants with a melting point or melting range between 30 and 80 ° C., preferably between 35 and 75 ° C., particularly preferably between 40 and 70 ° C. and in particular between 45 and 65 ° C. is particularly preferred, these dispersants based on the total weight of the dispersants used, a weight fraction above 10% by weight, preferably above 40% by weight, particularly preferably above 70% by weight and in particular between 80 and 100% by weight.
  • Suitable dispersed substances in the context of the present application are all substances which are active in washing or cleaning at room temperature, but in particular substances which are active in washing or cleaning from the group of builders (builders and cobuilders), active polymers for washing or cleaning, bleaching agents and bleach activators , the glass corrosion protection agent, the silver protection agent and / or the enzymes. A more detailed description of these ingredients can be found below in the text.
  • the water content of the dispersions preferably used in the process according to the invention is, based on their total weight, preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 15% by weight .-% and in particular less than 12 wt .-%.
  • Preferred according to the invention Dispersions used are low in water or anhydrous. Dispersions used with particular preference are characterized in that, based on their total weight, their free water content is below 10% by weight, preferably below 7% by weight, particularly preferably below 3% by weight and in particular below 1% by weight. -% exhibit.
  • the dispersions which are preferably used as washing or cleaning active preparations, are distinguished by a high density. Dispersions with a density above 1.040 g / cm 3 are particularly preferably used. Processes which are preferred according to the invention are characterized in that the washing and cleaning active preparation has a density above 1.040 g / cm 3 , preferably above 1.15 g / cm 3 , particularly preferably above 1.30 g / cm 3 and in particular above 1.40 g / cm 3 . This high density not only reduces the total volume of a dosing unit cast body but also improves its mechanical stability.
  • the dispersion has a density between 1,050 and 1,670 g / cm 3 , preferably between 1,120 and 1,610 g / cm 3 , particularly preferably between 1,210 and 1,570 g / cm 3 , very particularly preferably between 1,290 and 1, 510 g / cm 3 , and in particular between 1.340 and 1, 480 g / cm 3.
  • the information on density relates in each case to the densities of the compositions at 20 ° C.
  • dispersing agents and dispersed substances preferably have densities which are less than 0.6 g / cm 3 , preferably less than 0.4 g / cm 3 and differ in particular by less than 0.3 g / cm 3 .
  • Dispersions preferably used according to the invention as a detergent or cleaning preparation are distinguished in that they disperse in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably in less than 6 minutes, particularly preferably in less than 5 Minutes, especially in less than 4 minutes.
  • 20 g of the dispersion are introduced into the interior of a dishwasher (Miele G 646 PLUS).
  • the main wash cycle of a standard wash program (45 ° C) is started.
  • the solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor.
  • the dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau.
  • the conductivity measurement begins with the insertion of the circulation pump in the main wash cycle.
  • the amount of water used is 5 liters.
  • Dimensionally stable gels are another solid which is particularly preferred in the context of the present invention.
  • the term “dimensionally stable” here designates gels which have an inherent dimensional stability which enables them, under the usual conditions of manufacture, storage, transport and handling by the consumer, to prevent breakage, non-disintegration
  • This spatial form does not change under the conditions mentioned even over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, that is to say under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatial-geometric shape caused by the production, i.e., not, for example, not deliquescent, or in the action of an external force customary in the conditions of production, storage, transport and handling, in this spatial-geometric shape returns.
  • the gels with good product properties it is preferred in the context of the present invention to use one or more substances from the group agar-agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, core flour ether, polyacrylic and.
  • the gels Contain polymethacrylic, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas, it having proven to be particularly advantageous if the gels contain these or one of the following thickeners in amounts between 0.2 and 10 % By weight, preferably between 0.3 and 7% by weight and particularly preferably between 0.4 and 4% by weight, based on the total weight of the shaped body.
  • Polymers derived from nature which are used as thickeners in the context of the present invention, are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, as described above and casein.
  • Modified natural products mainly come from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
  • thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • Thickening agents from these classes of compounds are widely available commercially and are sold for example under the trade name Acusol ® - ⁇ 20 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ®-GT-282 -S (alkyl polyglycol ether, Akzo), Deuterol ® polymer 11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH) , Deuteron ® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan thickener-0 (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ® -81 and EMA ® -91 (ethylene
  • preferred gels contain various solvents, gels having proven particularly advantageous in terms of their product properties, the water and / or one or more water-miscible solvents in amounts of 5 to 70% by weight, preferably of Contain 10 to 65 wt .-% and particularly preferably from 15 to 60 wt .-%.
  • the water-miscible solvents contain one or more substances from the group consisting of ethanol, n- or i-propanol, n- or sec- or tert-butanol, glycol, propane or butanediol, glycerol, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl or ethyl propylene glycol, dipropylene ether Di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl
  • capsules are further preferred solids enclosed in containers produced according to the invention.
  • Capsule is a term for a frequently used form of packaging that contains solid, semi-solid or liquid substances in differently sized, possibly colored, layers of gelatin, wax or wafer material. The most common are the gelatin capsules (made of hard or soft Gelatin) is used.
  • one or more or all of the solids filled into the containers produced according to the invention ie for example one, several or all of the powders and / or granules and / or extrudate (s) filled into these containers. and / or compact (s) and / or cast body and / or dimensionally stable gel (s) and / or capsule (s), a coating (coating).
  • a coating can serve different purposes.
  • coating can, for example, result in undesired contact of active substances, which are sensitive to hydrolysis or oxidation, contained in the solids, with the outside air or other in the enclosed solids according to the invention can be avoided.
  • an advantageous visual effect can also be achieved by a coating.
  • Liquids and solids are suitable as ingredients for the receiving chambers or spaces.
  • solids a distinction is made between powders, granules, extrudates, compactates, castings and dimensionally stable gels.
  • liquids are not only low-viscosity, flowable liquids or flowable gels, but also flowable dispersions, for example emulsions or suspensions.
  • Active substances or combinations of active substances are considered to be flowable if they have no inherent dimensional stability which enables them to assume a non-disintegrating spatial form under the usual conditions of manufacture, storage, transport and handling by the consumer, this spatial form under the conditions mentioned also not changed over a longer period of time, preferably 4 weeks, particularly preferably ⁇ weeks and in particular 32 weeks, that is to say under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatially geometric shape persists, that is, does not melt away.
  • the determination of the flowability relates in particular to the conditions customary for storage and transport, that is to say in particular to temperatures below 50 ° C., preferably below 40 ° C. Liquids are therefore in particular active substances or combinations of active substances with a melting point below 25 ° C., preferably below 20 ° C., particularly preferably below 15 ° C.
  • the following tables list the containers which can be produced by preferred methods according to the invention with two filled receiving troughs and one filled intermediate space.
  • the receiving troughs or interstices filled with liquid, powder or granules preferably have a seal.
  • the sealing is optional, but is preferred.
  • Processes according to the invention which are particularly preferred in the context of the present application are characterized in that at least one receiving chamber and / or at least one intermediate space is filled with a liquid, at least one further receiving chamber and / or at least one intermediate space is filled with a solid. Methods according to the invention are particularly preferred in which the intermediate space located between the receiving chambers is filled with a melt.
  • Liquid and solid active substances or active substance mixtures are suitable for filling the intermediate space (s) located between the receiving chambers.
  • the intermediate space is filled with a liquid or a solid, preferably in a prefabricated form, particularly preferably in the form of a filled capsule of a compact or a melting body.
  • the solids introduced into the intermediate space can be fixed by gluing.
  • the prefabricated shaped body can preferably be fixed by plugging, particularly preferably in combination with a snap mechanism,
  • Suitable adhesives are all substances known to the person skilled in the art for the adhesive connection of two bodies made from the shell materials mentioned. These adhesives can be used either alone or in combination with a further active substance, for example a coloring substance or a fragrance. If water-soluble or water-dispersible substances or substance mixtures are used as the covering material for the receiving chambers, water or water-containing solutions or dispersions are particularly suitable as adhesives. After the adhesive has been introduced into the intermediate space, it is preferred according to the invention
  • the method according to the invention is suitable for portioning, packaging and metering active substances or active substance mixtures.
  • the substances filled in step b) and / or step c) are active substances or mixtures of active substances from the fields of pharmaceuticals, cosmetics, animal feed, crop protection agents or fertilizers, adhesives, foods and / or personal care products, but preferably from the area of washing and cleaning-active substances.
  • Preferred active substances or active substance mixtures from the field of cosmetics are, in particular, hair setting agents, hair shaping agents and hair coloring agents.
  • the preferred personal care products also include pre-treatment agents, hairdressing aids and course rinses. Active substances from the area of bath additives, such as bath salts or bath tablets, but also shower, foam or cream baths, are also preferred.
  • a particularly preferred method according to the invention is characterized in that the agent (s) filled in step b) and / or step c) of the method are washing or cleaning agents. Washing and cleaning-active substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, disintegration aids, electrolytes, pH regulators, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, are particularly preferred.
  • Anti-shrink agents anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobing and impregnating agents, swelling and anti-slip agents, non-aqueous solvents, fabric softeners, protein hydrolyzate and UV absorbers. More detailed information on the washing and cleaning-active substances mentioned can be found below in the text.
  • the gap (s) located between the receiving chambers can be filled by cutting knives or punches before or after the separation of the containers. Regardless of whether the filling takes place before or after the separation, filling of the intermediate space (s) from the top and the bottom of the container is possible. Filling from the bottom is particularly advantageous when the agent to be filled is in a pre-assembled form, preferably in the form of a single molded body, and is fixed, for example, by gluing or plugging in the space (s). However, the containers can also be turned over before filling the gap (s) in step c). In this case, the gaps are accessible from the top and, in addition to the pre-assembled solids mentioned, liquids or free-flowing solids such as powders or granules can now also be filled in.
  • the present application also relates to means comprising at least two filled receiving chambers, which are separated from one another by at least one web and which consist of a first covering material, and at least one filled intermediate space located between these receiving chambers below the web.
  • the means according to the invention are designed in such a way that the side walls or part of the side walls of the receiving chambers together with one or more web (s) located between the receiving chambers or part of this web / these webs form an intermediate space which has at least one opening.
  • the agents according to the invention can be produced, for example, by injection molding and / or deep drawing and / or pouring solidifying dispersions, solutions or melts.
  • Further preferred objects of the present application are therefore means comprising at least two filled or at least one deep-drawn or injection-molded receiving chamber, separated from one another by at least one web, and at least one filled intermediate space located between the receiving chambers below the web.
  • the filled receiving chambers and / or the filled space (s) can optionally be sealed with a further covering material. Part of the receiving chambers as well as all of the receiving chambers can be sealed with a further covering material.
  • the sealing is preferably carried out by the action of pressure and / or heat and / or solvent.
  • the further wrapping material used for sealing can be identical to the wrapping material used in step a) of the method according to the invention, but can also differ from it both in its composition or in its thickness.
  • the wrapping materials used to seal the receiving chambers and the intermediate spaces can be the same or different wrapping materials.
  • the sealing of the receiving chambers and the intervening materials used are identical. This embodiment enables the contents to be released under the sealing surfaces at the same time.
  • the materials used for sealing the receiving chambers differ from the materials used for sealing the interspaces.
  • the envelope materials used for sealing the receiving chambers preferably have a higher solubility than the materials used for sealing the interspaces.
  • Preferred coating materials are water-soluble or water-dispersible.
  • agents are preferably produced which have at least one water-soluble or water-dispersible coating material.
  • the manufacture such agents according to the invention are particularly preferred in which the shell materials used comprise a water-soluble or water-dispersible polymer.
  • Particularly preferred agents are distinguished by the fact that they comprise at least two different shell materials with different dissolution behavior, these preferably differing in their chemical composition.
  • the dissolving behavior of the receiving chambers or the container and the closure part, which is used to seal the receiving chambers can be influenced, for example, by the thickness of the container walls or the closure parts in addition to the chemical composition of the casing materials used.
  • preferred containers are characterized in that the side walls of the receiving chambers, which are made of the first covering material, have a thickness of 5 to 2000 ⁇ m, preferably 10 to 1000 ⁇ m, particularly preferably 15 to 500 ⁇ m, very particularly preferably 20 to 200 ⁇ m and in particular from 25 to 100 ⁇ m.
  • the second covering material used for sealing preferably has a thickness of 5 to 100 ⁇ m, particularly preferably 6 to ⁇ O ⁇ m and in particular 7 to 50 ⁇ m. It is particularly preferred that the container and the sealing material have different thicknesses, whereby those containers whose sealing material have a smaller wall thickness than the associated containers are advantageous.
  • the agents according to the invention are particularly suitable for the controlled release of the active substances contained, in particular the active substances from the group of washing or cleaning agents.
  • the container as a whole is water-soluble, ie. H. dissolves completely when used as intended for washing or machine cleaning, if the conditions for loosening have been reached.
  • a major advantage of this embodiment is that the container can be at least partially detached in the cleaning liquor within a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions, and thus, according to the requirements, the encapsulated content, ie. H. the active cleaning material or several materials into the fleet. This release can only be controlled or controlled in different ways.
  • the water-soluble container comprises areas which are less or not water-soluble at all or areas which are water-soluble only at higher temperatures and areas which are water-soluble or water-soluble at low temperatures.
  • the container is not one uniform material with the same water solubility in all areas, but from materials with different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only at a changed electrolyte concentration the desired value achieved, on the other hand.
  • a container with pores or holes is formed, into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can be discharged from the container.
  • Systems in the form of multi-chamber containers or in the form of containers arranged one inside the other (“onion system”) can also be provided in the same way. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.
  • containers can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material.
  • incorporated compounds for example salts
  • polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble.
  • water-soluble areas of the containers are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or a content of a water-insoluble polymer.
  • portioned detergent or cleaning agent compositions according to the invention can be provided which have advantageous properties in the release of active substances, in particular of active substances from the group of detergents or cleaning agents, into the respective Have fleet.
  • active substances in particular of active substances from the group of detergents or cleaning agents
  • the person skilled in the art has other methods available.
  • An alternative procedure, which is suitable for the controlled release of active substances or active substance mixtures alone or in combination with the above-mentioned control by selecting certain coating materials is the integration of one or more "switches" in the above-mentioned active substances, active substance mixtures or active substance preparations.
  • Possible “switches” which influence the dissolution rate of the active substances enclosed in the containers according to the invention are, in particularly preferred embodiments, physicochemical parameters. Examples include, but should not be construed as a limitation
  • the mechanical stability for example of a capsule, a coating or a compacted shaped body such as a tablet, which - depending on the time of the
  • Temperature or other parameters - can be a factor determining disintegration; the solubility of optionally used capsules or coatings or matrices in
  • the agent produced according to the invention comprises at least one active substance or active substance preparation, the release of which is delayed.
  • the delayed release is preferably delayed by the use of at least one of the agents described above, but in particular by the use of different packaging materials and / or the use of selected coating materials, it being particularly preferred that this delayed release occurs when active substances or mixtures of active substances are used the group of detergents or cleaning agents is carried out at the earliest 5 minutes, preferably at the earliest 7 minutes, particularly preferably at the earliest 10 minutes, very particularly preferably at the earliest 15 minutes and in particular at the earliest 20 minutes after the start of the cleaning or washing process.
  • the use of meltable coating materials from the group of waxes or paraffins is particularly preferred.
  • Agents according to the invention will in particular have a seal if the filling material located in the receiving chambers or spaces is liquid or flowable. Examples of such filling goods are liquids, gels or particulate solids such as powder.
  • the receiving chambers can have any technically feasible shape. Spherical-dome-shaped, cylindrical or cubic chambers are particularly preferred. Preferred receiving chambers have at least one edge and one corner, receiving chambers with two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more edges or two, three, four, five, six, seven, eight nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are also realizable and preferred according to the invention. Further receptacle chambers which can be realized and which are preferred in alternative embodiments of the means according to the invention have a dome-shaped structure.
  • the side walls of the receiving chambers are preferably planar. Spatially opposite side walls can be arranged both parallel and not parallel to one another.
  • the base area of the receiving chambers can be convex, concave or planar, planar base areas being preferred with regard to the subsequent filling of the intermediate space (s) located between the receiving chambers.
  • the base area itself can be designed as a circle, but can also have corners. Base areas with a corner (teardrop shape), two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen, twenty or more corners are in Preferred within the scope of the present application.
  • the transition from the base area to the side wall (s) or the transition of the side walls into one another is designed in a rounded form.
  • the receiving chambers therefore have no pointed or sharp, but rather rounded edges.
  • a preferred agent according to the invention is characterized in that the base areas of the receiving chambers are planar.
  • Containers preferred according to the invention have a total volume of the receiving chambers between 0.1 and 1000 ml, preferably between 0.2 and 100 ml, particularly preferably between 0.4 and 50 ml, very particularly preferably between 0.6 and 20 ml and in particular between 0, 8 and 10 L.
  • Agents preferred according to the invention have at least two receiving chambers with the same spatial shape and an identical volume. In another preferred embodiment, the at least two receiving chambers in the container have different volumes The ratio of these volumes is preferably between 25: 1 and 1.05: 1, preferably between 20: 1 and 2: 1 and in particular between 15: 1 and 4: 1.
  • the container has two receiving chambers of different volumes, the volume of the smaller receiving chamber being at least 2%, preferably at least 5%, particularly preferably at least 10% and in particular at least 20%, 30%, 40%, 50%, 60%, 65%, 70%, 75% or 30% of the volume of the larger receiving chamber is.
  • the volume of the individual chambers is preferably between 0.05 and 900 ml, particularly preferably between 0.1 and 90 ml, very particularly preferably between 0.5 and 40 ml and in particular between 1.0 and 25 ml.
  • the containers according to the invention have receiving chambers with different depths.
  • the receiving chamber with the smaller chamber depth can certainly have the larger chamber volume, while the receiving chamber with the greater chamber depth has a smaller volume.
  • the two or more chambers can also have the same volume despite different chamber depths.
  • a method is preferred in which the receiving chamber with the smaller chamber depth also has a smaller volume in comparison with the other receiving chamber (s), with reference to the above in terms of the absolute volumes and the volume ratios Information is referenced.
  • Means preferred according to the invention comprise receiving chambers with vertically sloping side walls.
  • means in which at least one receiving chamber has an inclined side wall are particularly preferred.
  • the angle between the side wall and an imaginary seal closing the receiving chamber is therefore less than 90 °.
  • this angle can vary for the different side walls of a single receiving chamber. If the receiving chamber has only a single side wall (cylinder-like receiving chambers), even a single side wall can have different angles with the corresponding shaping of the deep-drawing troughs used in deep-drawing.
  • the receiving chambers can also have gradations.
  • the corresponding preferred means have receiving chambers without flat side walls, but rather have side walls which are characterized by steps or curvatures.
  • the number of curvatures can vary, means according to the invention are preferred in which the number of steps and / or curvatures in one or more receiving chamber (s) per chamber is a maximum of 10, preferably between 1 and 9, particularly preferably between 1 and 8, very particularly preferably between 2 and 7 and in particular between 2 and 6.
  • the steps or curvatures can be circumferential in the respective receiving troughs or only on individual side walls.
  • the course of the steps or curvatures is preferably horizontal. Steps and / or curvatures with an upward or downward course similar to a screw thread can, however, also be realized and are preferred for certain fields of application.
  • the “volume” of the receiving chambers or the interstices is the filling volume which can be achieved by filling the chambers or interstices with a liquid without overflowing this liquid onto the preferably planar sealing edges.
  • the total volume of the space or spaces located between the receiving chambers is not greater than the total volume of the receiving chambers.
  • the total volume of the interstices is preferably between 0.1 and 1000 ml, preferably between 0.2 and 100 ml, particularly preferably between 0.4 and 50 ml, very particularly preferably between 0.6 and 20 ml and in particular between 0, 8 and 10 mL.
  • Spaces with a volume below 7 ml, preferably below 6 ml, particularly preferably below 5 ml, in particular below 4 ml are particularly preferred, the volume of a single gap between 0.05 and 2.0 ml, preferably between 0, in particularly advantageous process variants, 1 and 1.5 mL, particularly preferably between 0.2 and 0.9 mL and in particular between 0.3 and 0.7 mL.
  • the ratio of the sum of the volumes of the receiving chambers to the sum of the spaces between spaces is between 50: 1 and 1: 5, preferably between 40: 1 and 1: 4, particularly preferably between 30: 1 and 1: 3, very particularly preferably between 20: 1 and 1: 2 and in particular between 10: 1 and 1: 1.
  • the width of the webs located between the individual receiving chambers can vary.
  • Preferred agents according to the invention are characterized in that the web (s) located between the receiving chambers has a width between 0.5 and 40 mm, preferably between 0.6 and 30 mm, particularly preferably between 0.7 and 20 mm , very particularly preferably between 0.8 and 10 mm and in particular between 1.0 and 5.0 mm.
  • Preferred agents according to the invention are characterized in that the intermediate space (s) only have an opening on the bottom side of the container. In particularly preferred embodiments, however, the intermediate space (s) can also have more than one opening, for example two, three or four openings, or have an opening which is open to more than one side of the container.
  • a corresponding intermediate space can be opened, for example, on the bottom side and one side surface or on the bottom side and two side surfaces, preferably opposite side surfaces.
  • Preferred agents according to the invention are characterized in that at least one of the shell materials used for deep drawing or sealing is water-soluble or water-dispersible.
  • Polyquaternium 1 ⁇ and Polyquaternium 27 indicated polymers.
  • water-soluble polymers are those polymers which are more than 2.7% by weight soluble in water at room temperature.
  • the wrapping material used in the process according to the invention is preferably at least partially a substance from the group (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin.
  • the container comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and mixtures thereof.
  • PVAL polyvinyl alcohol
  • PVP polyvinyl pyrrolidone
  • polyethylene oxide polyethylene oxide
  • gelatin gelatin
  • cellulose and their derivatives and mixtures thereof.
  • Polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure
  • polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 67-89 mol%. , so contain another Residual content of acetyl groups.
  • the manufacturers characterize the polyvinyl alcohols by stating 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 safe 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.
  • the 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 shell 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 is in particular 82 to 8 ⁇ 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 60% 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 envelope material used preferably 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 is up to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 8 ⁇ mol%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as the coating materials, it being preferred according to the invention that the coating 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 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.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
  • Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72.5, 78 , B72, F80 / 40, F ⁇ / 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, NM11 Q, KZ-06 (trademark of Nippon Gohsei KK).
  • the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • aldehydes acetalization
  • ketones ketalization
  • Polyvinyl alcohols which have been 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 because of their extremely good solubility in cold water.
  • the reaction products made of 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 in a targeted manner to desired values to adjust.
  • Films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVAL films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be adjusted to the degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.
  • PVP Polyvinylpyrrolidones
  • PVPs are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2,500 to 760,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of the 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 coating material is extremely widespread, particularly in pharmacy in the form of hard or soft gelatin capsules. In Gelatine is used only to a limited extent in the form of foils because of its high price compared to the abovementioned polymers.
  • wrapping materials which comprise a polymer from the group 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. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions.
  • Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approx. 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained 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 hydroxyl groups have been replaced by functional groups which 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 and aminocelluloses.
  • Preferred agents according to the invention are characterized in that at least one of the envelope materials is transparent or translucent.
  • the envelope material used is preferably transparent.
  • transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%.
  • a wavelength of the visible spectrum of light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.
  • Stabilizing agents in the sense of the invention are materials which protect the ingredients in the receiving chambers and / or the ingredients located in an intermediate space against decomposition or deactivation by light radiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • Particularly suitable stabilizers in the sense of the invention are the antioxidants.
  • the formulations can contain antioxidants.
  • Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants.
  • Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
  • aromatic amines preferably secondary aromatic amines and substituted p-phenylenediamines
  • phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites
  • citric acids and citric acid derivatives such as isopropyl citrate
  • compounds containing endiol groups so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate
  • organosulfur compounds such as the esters of 3,3'-thiodipropionic acid with C ⁇ s-alkanols, in particular C 10 - 18 alkanols
  • metal ion deactivators that are capable of catalyzing the auto-oxidation of metal ions such as copper, to complex, such as nitrilotriacetic acid and its derivatives and their mixtures.
  • Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20
  • UV absorbers can improve the lightfastness of the recipe components.
  • organic substances light protection filters
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles such as, for example, the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast ® H), are also phenyl-substituted acrylates ( 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 urocanoic acid. Of particular importance are biphenyl and especially stilbene derivatives, which are commercially available as Tinosorb ® FD or Tinosorb ® FR ex Ciba. 3-Benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 4-
  • esters of cinnamic acid preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene);
  • Esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester;
  • benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-benzylidene camphor e.g. 4- (2-oxo-3-bornylidenemethyl) benzene-sulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and their salts.
  • UV-A filters -4'-methoxy-dibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds.
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and in addition oxides of iron, zirconium, silicon, manganese, aluminum and cerium as well as their mixtures.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoid or in some other way deviate from the spherical shape.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobicized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.
  • UV absorbers can be used in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight, in each case based on the total weight of a contained in a receiving chamber or a space mixture of substances.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1, 3-diarylpyrazoilines, naphthalic acid imides, benzoxazole and benzisoxazole and Benzimidazole systems and the pyrene derivatives substituted by heterocycles.
  • the sulfonic acid salts of the diaminostilbene derivatives and polymeric fluorescent substances are of particular importance.
  • Fluorescent substances based on the total weight of a substance mixture located in a receiving chamber or in a space, in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0, ⁇ and in particular from 0.03 up to 0.1% by weight.
  • the aforementioned stabilizing agents are used in any mixtures.
  • the stabilizing agents are, based on the total weight of a substance mixture located in a receiving chamber or an intermediate space, in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to ⁇ wt .-% used.
  • Preferred coating materials are water-soluble or water-dispersible. Agents within the scope of the present application are therefore preferred which have at least one water-soluble or water-dispersible coating material. Agents according to the invention are particularly preferred in which the coating materials used comprise a water-soluble or water-dispersible polymer.
  • Particularly preferred agents are distinguished by the fact that they comprise at least two different shell materials with different dissolution behavior, these preferably differing in their chemical composition.
  • the water-soluble envelope material of the receiving chambers or the container can differ from the envelope material of the seal or the closure part.
  • the dissolving behavior of the container and the closure part, which is used to seal the receiving chambers can be influenced not only by the chemical composition of the casing materials used, but also, for example, by the thickness of the container walls or the closure parts.
  • preferred containers are characterized in that the side walls of the receiving chambers, which are made of the first covering material, have a thickness of 5 to 2000 ⁇ m, preferably 10 to 1000 ⁇ m, particularly preferably 15 to 500 ⁇ m, very particularly preferably 20 to 200 ⁇ m and in particular from 25 to 100 ⁇ m.
  • the second wrapping material used for sealing preferably has a thickness of 5 to 100 ⁇ m, particularly preferably 6 to 80 ⁇ m and in particular 7 to 50 ⁇ m. It is particularly preferred that the container and the sealing material have different thicknesses, whereby those containers whose sealing material have a smaller wall thickness than the associated containers are advantageous.
  • the agents according to the invention are particularly suitable for the controlled release of the active substances contained, in particular the active substances from the group of washing or cleaning agents.
  • the container as a whole is water-soluble, that is to say it dissolves completely when used as intended for washing or machine cleaning when the conditions provided for the dissolution have been reached.
  • a major advantage of this embodiment is that the container can be at least partially detached in a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions in the cleaning liquor and thus the encapsulated content, that is, according to the requirements cleaning-active material or several materials into the fleet. This release can only be controlled or controlled in different ways.
  • the water-soluble container comprises areas which are less or not water-soluble at all or areas which are water-soluble only at a higher temperature and areas which are water-soluble or water-soluble at a low temperature.
  • the container does not consist of a uniform material that has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only at a changed electrolyte concentration the desired value achieved, on the other hand.
  • a container with pores or holes is formed, into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can be discharged from the container.
  • Systems in the form of multi-chamber containers or in the form of containers arranged one inside the other (“onion system”) can also be provided in the same way. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be manufactured.
  • containers can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material.
  • incorporated compounds for example salts
  • polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble.
  • water-soluble areas of the containers are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer.
  • PVAL for example with saccharides, polysaccharides, such as starch
  • portioned detergent or cleaning agent compositions according to the invention can be provided which have advantageous properties in the release of active substances, in particular of active substances from the group of detergents or cleaning agents, into the respective Have fleet.
  • Possible “switches” which influence the dissolution rate of the active substances enclosed in the containers according to the invention are, in particularly preferred embodiments, physicochemical parameters. Examples include, but should not be construed as a limitation
  • the mechanical stability for example of a capsule, a coating or a compacted shaped body such as a tablet, which - depending on the time of the
  • Temperature or other parameters - can be a factor determining disintegration; the solubility of optionally used capsules or coatings or matrices in
  • the agent according to the invention comprises at least one active substance or active substance preparation, the release of which is delayed.
  • the delayed release is preferably delayed by the use of at least one of the agents described above, but in particular by the use of different packaging materials and / or the use of selected coating materials, it being particularly preferred that this delayed release occurs when active substances or mixtures of active substances are used the group of washing or cleaning agents at the earliest 5 minutes, preferably at the earliest 7 minutes, particularly preferably at the earliest 10 minutes, very particularly preferably at the earliest 15 minutes and in particular at the earliest 20 minutes after the start of the cleaning or washing process.
  • the use of meltable coating materials from the group of waxes or paraffins is particularly preferred.
  • Preferred agents are characterized in that the receptacles have a wall thickness of 5 to 2000 ⁇ m, preferably from 10 to 1000 ⁇ m, particularly preferably from 15 to 500 ⁇ m, very particularly preferably from 20 to 200 ⁇ m and in particular from 25 to 100 ⁇ m.
  • the foils used can be single or multi-layer foils (laminate foils).
  • the water content of the films is preferably below 10% by weight, particularly preferably below 7% by weight, very particularly preferably below 5% by weight and in particular below 4% by weight.
  • a particularly preferred agent according to the invention is characterized in that two different active substances are present separately from one another in different receiving chambers.
  • the active substances can differ in their composition as well as in their composition and state of matter.
  • solid substances within the scope of the present application active substances and active substance combinations are summarized which have a solid, that is to say dimensionally stable, non-flowable consistency.
  • This category includes, for example, substances in the solid state, but also dimensionally stable substances such as dimensionally stable gels and combinations of these substances.
  • Filled bodies with a solid outer shell are also referred to as solids, regardless of the physical state of the fillers contained in these filled bodies.
  • solids are preferably powders and / or granules and / or extrudates and / or compactates and / or castings, regardless of whether they are pure substances or mixtures of substances.
  • the solids mentioned can be in amorphous and / or crystalline and / or partially crystalline form.
  • preferred solids have a water content (for example determinable as a loss on drying or according to Karl Fischer) below 7% by weight, preferably below 4.5% by weight, and particularly preferably below 2% by weight.
  • Powder is a general term for a form of division of solid substances and / or mixtures of substances, which can be achieved by crushing, i.e. grinding or crushing, in the grinding bowl (Pulverizing), grinding in mills or as a result of atomization or freeze drying.
  • a particularly fine division is often called atomization or micronization; the corresponding powders are called micro powders.
  • Preferred powders have a uniform (homogeneous) mixture of the solid, finely divided constituents and, in the case of substance mixtures, in particular do not tend to be separated into individual constituents of these mixtures.
  • Powders which are particularly preferred in the context of the present application therefore have a particle size distribution in which at least 80% by weight, preferably at least 60% by weight, particularly preferably at least 95% by weight and in particular at least 99% by weight of the powder, in each case based on its total weight, deviate from the mean particle size of this powder by a maximum of 80%, preferably a maximum of 60% and in particular a maximum of 40%.
  • the powders are roughly divided into coarse, fine and. Very fine powder common; A more precise classification of powdered bulk goods is based on their bulk density and by sieve analysis.
  • powders of any particle size can be used, but preferred powders have average particle sizes of 40 to 500 ⁇ m, preferably from 60 to 400 ⁇ m and in particular from 100 to 300 ⁇ m. Methods for determining the average particle size are usually based on the aforementioned sieve analysis and are described in detail in the prior art.
  • the unwanted caking of the powders can be countered by using pouring aids or powdering agents.
  • the powders therefore contain pouring aids or powdering agents, preferably in proportions by weight of 0.1 to 4% by weight, particularly preferably 0.2 to 3% by weight and in particular 0.3 to 2% by weight. %, each based on the total weight of the powder.
  • Preferred pouring aids or powdering agents are, preferably in finely ground form, silicates and / or silicon oxide and / or urea.
  • powders can be agglomerated using a number of techniques. Any method known in the prior art for agglomeration of particulate mixtures is in principle suitable for converting the solids enclosed in the containers produced according to the invention into larger aggregates.
  • agglomerates which are preferably used as solids are, in addition to the granules, the compactates and extrudates.
  • Granules Accumulations of granules are referred to as granules.
  • a granulate is an asymmetrical aggregate of powder particles.
  • Granulation processes are widely described in the prior art. Granules can be obtained by wet granulation Dry granulation or compacting and be produced by melt solidification granulation.
  • the most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and is the safest way to produce granules with favorable properties.
  • Moist granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably carried out in mixers, fluidized beds or spray towers, it being possible for said mixers to be equipped, for example, with stirring and kneading tools.
  • combinations of fluidized bed (s) and mixer (s) or combinations of different mixers can also be used for the granulation.
  • the granulation takes place depending on the starting material and the desired product properties under the influence of low to high shear forces.
  • the starting materials used can be, for example, melts (melt solidification) or, preferably aqueous, slurries (spray drying) solid substances which are sprayed at the top of a tower in a defined droplet size, freeze or dry in free fall, and on Bottom of the tower accumulate as granules.
  • Melt solidification is generally particularly suitable for shaping low-melting substances that are stable in the melting temperature range (e.g. urea, ammonium nitrate and various formulations such as enzyme concentrates, medicines, etc.), the corresponding granules are also referred to as prills.
  • Spray drying is used particularly for the production of detergents or detergent components.
  • extruder or perforated roller granulation in which powder mixtures optionally mixed with granulating liquid are plastically deformed when pressed by perforated disks (extrusion) or on perforated rollers.
  • the products of extruder granulation are also called extrudates.
  • Compactates can be produced, for example, using dry granulation techniques such as tableting or roller compaction.
  • Compacting in tablet presses enables single-phase or multi-phase tablets or briquettes to be produced.
  • the multi-phase tablets also include, for example, the coated tablets and the point tablets (bull-eye tablets).
  • the briquettes like the slugs produced in compacting rollers, can be comminuted by opposing spiked rollers or beaten by sieves.
  • casting bodies are solid substance particles which are produced by solidification and / or crystallization from melts or solutions. The solidification and / or crystallization preferably takes place in prefabricated matrices.
  • the casting bodies released from the dies after solidification can subsequently be used in their original size or, if appropriate, after comminution, as solids in the water-soluble containers according to the invention.
  • Suitable matrix material for the abovementioned solids are in particular meltable substances from the group of fats and / or triglycerides and / or fatty acids and / or fatty alcohols and / or waxes and / or paraffins.
  • Fat (s) or triglyceride (s) is the name for compounds of glycerol in which the three hydroxyl groups of the glycerol are esterified by carboxylic acids.
  • the naturally occurring fats are triglycerides, which usually contain different fatty acids in the same glycerin molecule.
  • synthetic triglycerides in which only one fatty acid is bound are also accessible (e.g. tripalmitin, triolein or tristearin).
  • Natural and / or synthetic fats and / or mixtures of the two are preferred as matrix material or matrix component for castings or one of the other solids mentioned in the context of the present invention.
  • fatty acids Aliphatic saturated or unsaturated, carboxylic acids with branched or unbranched carbon chain are referred to as fatty acids in the present application.
  • Fatty acids which have a melting point above 25 ° C. have proven particularly advantageous.
  • Preferred matrix materials and / or constituents are therefore capric acid and / or undecanoic acid and / or lauric acid and / or tridecanoic acid and / or myristic acid and / or pentadecanoic acid and / or palmitic acid and / or margaric acid and / or stearic acid and / or nonadecanoic acid and / or arachic acid and / or erucic acid and / or elaeosteraric acid.
  • fatty acids with a melting point below 25 ° C components of the matrix can be used for castings or other solids mentioned above.
  • Fatty alcohol is a collective name for the linear, saturated or unsaturated primary alcohols with 6 to 22 carbon atoms that can be obtained by reducing the triglycerides, fatty acids or fatty acid esters.
  • the fatty alcohols can be saturated or unsaturated depending on the manufacturing process.
  • the solids enclosed in the containers produced according to the invention contain waxes as matrix material.
  • Preferred waxes have a melting range that is between approximately 45 ° C. and approximately 7 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range. Waxes with such a melting range are on the one hand dimensionally stable at room temperature, but melt at temperatures of 30 ° C. to 90 ° C. which are typical for machine dishwashing and are therefore more readily water-dispersible at these temperatures.
  • “Waxing” is understood to mean a number of natural or artificially obtained substances which, as a rule, melt above 40 ° C. without decomposition and are relatively low-viscosity and not stringy just above the melting point. They have a strongly temperature-dependent consistency and solubility.
  • the waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.
  • the natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
  • vegetable waxes such as candelilla wax, carnauba wax, Japanese wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or
  • the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ® (Bayer AG), proved.
  • Synthetic waxes of lower carboxylic acids and fatty alcohols such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea).
  • synthetic or semi-synthetic esters from lower alcohols with fatty acids from native sources can also be used.
  • Tegin ® 90 Goldschmidt
  • a glycerol monostearate palmitate falls into this class of substances.
  • Shellac for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used according to the invention as a matrix material in solids, preferably in castings.
  • wax alcohols are also included in the waxes in the context of the present invention, for example.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms.
  • the wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the coating of the present invention the solid particles coated can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin understood, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
  • one or more of the solids enclosed in the containers produced according to the invention predominantly contains paraffin wax (paraffins) as the matrix material.
  • paraffin wax paraffins
  • Paraffin wax contents based on the total weight of the matrix materials of approximately 60% by weight, approximately 70% by weight or approximately 80% by weight are particularly suitable, with even higher proportions of, for example, more than 90% by weight being particularly preferred .
  • the entire matrix material of one or more of the solids filled into the containers produced according to the invention consists of paraffin wax.
  • Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that when the inventive preparations are used Container as a dosing unit for detergents and cleaning agents in an alkaline cleaning agent environment there is no hydrolysis of the waxes (as is to be expected, for example, in the wax esters), since paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes.
  • the paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C.
  • Preferred solids in particular castings, contain at least one paraffin wax with a melting range of 40 ° C. to 60 ° C. as matrix material and / or matrix constituent.
  • the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature is as high as possible.
  • wax alcohols i.e. fatty alcohols with approx. 24-36 carbon atoms, which are the main constituent of many natural waxes in the form of wax esters of higher molecular weight fatty acids (wax acids).
  • wax alcohols i.e. fatty alcohols with approx. 24-36 carbon atoms
  • Lignoceryla alcohol, ceryl alcohol, myricyl alcohol or melissyl alcohol may be mentioned here as examples of preferred wax alcohols.
  • Dispersions are particularly suitable for processing as castings, dispersions with washing or cleaning-active substances or mixtures of active substances being used with particular preference.
  • the washing or cleaning-active preparation used to produce the casting is a dispersion of solid particles in a dispersing agent, dispersions which, based on their total weight i), 10 to 8 ⁇ % by weight of dispersing agent and ii) contain 1 ⁇ to 90% by weight of dispersed substances, are particularly preferred.
  • dispersion is referred to as a system consisting of several phases, one of which is continuous (dispersant) and at least one further is finely divided (dispersed
  • Particularly preferred dispersions are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, particularly preferably above 15% by weight, very particularly preferably above 17% by weight and in particular above 19 wt .-%, each based on the total weight of the dispersion.
  • Dispersions which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion can furthermore preferably be used.
  • the maximum content of dispersions in preferred dispersions, based on the total weight of the dispersion, is preferably less than 63% by weight, preferably less than 57% by weight, particularly preferably less than ⁇ 2% by weight, very particularly preferably less than 47% by weight .-% and in particular less than 37 wt .-%.
  • those washing or cleaning-active preparations which, based on their total weight, contain dispersing agents in amounts of 12 to 62% by weight, preferably 14 to 49% by weight and in particular 16 to 3 ⁇ % by weight. % contain.
  • Dispersions with a dispersant content of between 16 and 30% by weight, preferably between 16 and 26% by weight and in particular between 16 and 22% by weight, in each case based on the total weight of the dispersion, are particularly preferred.
  • the dispersants used are preferably water-soluble or water-dispersible.
  • the solubility of these dispersants at 2 ⁇ ° C. is preferably more than 200 g / l, preferably more than 300 g / l, particularly preferably more than 400 g / l, very particularly preferably between 430 and 620 g / l and in particular between 470 and ⁇ 80 g / l.
  • Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers.
  • the dispersant can be either a single polymer or a mixture of different water-soluble or water-dispersible polymers.
  • the dispersant or at least ⁇ O% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, vinylpyrrolidone-vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.
  • Polyalkylene glycols in particular include polyethylene glycols and polypropylene glycols.
  • Polymers of ethylene glycol which have the general formula III
  • n can take values between 1 (ethylene glycol) and several thousand.
  • polyethylene glycols There are various nomenclatures for polyethylene glycols that can lead to confusion.
  • the specification of the average relative molecular weight following the specification "PEG” is customary in technical terms, so that "PEG 200" characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210.
  • a different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula VII mentioned above.
  • polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone - Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
  • the average relative molecular weight of at least one of the dispersants used in the washing or cleaning agents according to the invention, in particular at least one of the poly (alkylene) glycols used is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and 5000.
  • Polypropylene glycols are polymers of propylene glycol that have the general formula IV
  • n can take values between 1 (propylene glycol) and several thousand.
  • Dispersions are particularly preferably used which contain a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the proportion by weight of the poly (ethylene) glycol in the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by weight. Dispersions in which the dispersant is more than 92% by weight, preferably more than 94% by weight, particularly preferably more than 96% by weight, very particularly preferably more than 98% by weight are particularly preferred.
  • a nonionic polymer preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol
  • the proportion by weight of the poly (ethylene) glycol in the total weight of all dispersants is preferably between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by
  • a poly (alkylene) glycol preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular poly (ethylene) glycol.
  • Dispersants, which besides Poly (ethylene) glycol also contain poly (propylene) glycol preferably have a ratio by weight of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, particularly preferably between 10: 1 and 1.5: 1 and in particular between 7: 1 and 2: 1.
  • nonionic surfactants which are used both alone, but particularly preferably in combination with a nonionic polymer. Detailed information on the nonionic surfactants that can be used can be found below in the description of detergent or cleaning substances.
  • Dispersions which are preferably used are characterized in that at least one dispersant has a melting point above 25 ° C., preferably above 35 ° C. and in particular above 40 ° C. Particularly preferred is the use of dispersants with a melting point or melting range between 30 and 80 ° C, preferably between 3 ⁇ and 7 ⁇ ° C, particularly preferably between 40 and 70 ° C and in particular between 4 ⁇ and 6 ⁇ ° C, these dispersants based on the total weight of the dispersants used, a weight fraction above 10% by weight, preferably above 40% by weight, particularly preferably above 70% by weight and in particular between 80 and 100% by weight.
  • Suitable dispersed substances in the context of the present application are all substances which are active in washing or cleaning at room temperature, but in particular substances which are active in washing or cleaning from the group of builders (builders and cobuilders), active polymers for washing or cleaning, bleaching agents and bleach activators , the glass corrosion protection agent, the silver protection agent and / or the enzymes. A more detailed description of these ingredients can be found below in the text.
  • the water content of the dispersions preferably used in the process according to the invention is, based on their total weight, preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 1 ⁇ % by weight .-% and in particular less than 12 wt .-%.
  • Dispersions preferably used according to the invention are low in water or anhydrous. Dispersions used with particular preference are characterized in that, based on their total weight, their free water content is below 10% by weight, preferably below 7% by weight, particularly preferably below 3% by weight and in particular below 1% by weight. -% exhibit.
  • the dispersions which are preferably used as washing or cleaning active preparations, are distinguished by a high density. Dispersions with a density are particularly preferred used above 1.040 g / cm 3 . Preferred methods according to the invention are characterized in that the washing and cleaning active preparation has a density above 1.040 g / cm 3 , preferably above 1.15 g / cm 3 , particularly preferably above 1.30 g / cm 3 and in particular above 1.40 g / cm 3 . This high density not only reduces the total volume of a dosing unit cast body but also improves its mechanical stability.
  • the dispersion has a density between 1,050 and 1,670 g / cm 3 , preferably between 1,120 and 1,610 g / cm 3 , particularly preferably between 1,210 and 1,570 g / cm 3 , very particularly preferably between 1,290 and 1.510 g / cm 3 , and in particular between 1.340 and 1.480 g / cm 3.
  • the information on the density relates in each case to the densities of the compositions at 20 ° C.
  • dispersing agents and dispersed substances preferably have densities which are less than 0.6 g / cm 3 , preferably less than 0.4 g / cm 3 and differ in particular by less than 0.3 g / cm 3 .
  • Dispersions preferably used according to the invention as a detergent or cleaning preparation are distinguished in that they disperse in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably in less than 6 minutes, particularly preferably in less than 5 Minutes, especially in less than 4 minutes.
  • 20 g of the dispersion are introduced into the interior of a dishwasher (Miele G 646 PLUS).
  • the main wash cycle of a standard wash program (45 ° C) is started.
  • the solubility is determined by measuring the conductivity, which is recorded by a conductivity sensor.
  • the dissolving process ends when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau.
  • the conductivity measurement begins with the insertion of the circulation pump in the main wash cycle.
  • the amount of water used is ⁇ liters.
  • Dimensionally stable gels are another solid which is particularly preferred in the context of the present invention.
  • the term "dimensionally stable” here means gels which have an inherent dimensional stability which enables them to assume a non-disintegrating spatial form which is stable against breakage and which under normal conditions of manufacture, storage, transport and handling by the consumer Spatial shape under the conditions mentioned, even over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, has not changed, that is to say under the usual conditions of manufacture, storage, transport and handling by the consumer in the course of the production-related spatial-geometric form remains, that is, for example, does not melt, or when exposed to an external under the conditions of production, the Storage, transport and handling usual force, returns to this spatial-geometric form.
  • the gels with good product properties it is preferred within the scope of the present invention to use one or more substances from the group agar-agar, carrageenan, Tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose, seed flour ether, polyacrylic and.
  • the gels Contain polymethacrylic, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, zeolites and silicas, it having proven to be particularly advantageous if the gels contain these or one of the following thickeners in amounts between 0.2 and 10 % By weight, preferably between 0.3 and 7% by weight and particularly preferably between 0.4 and 4% by weight, based on the total weight of the shaped body.
  • Polymers derived from nature which are used as thickeners in the context of the present invention, are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, as described above and casein.
  • Modified natural products mainly come from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
  • thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • Thickeners from these classes of substances are widely available commercially and are sold, for example, under the trade names Acusol ® -620 (methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer, 30% strength in water, Rohm & Haas), Dapral ® -GT-282 -S (alkyl polyglycol ether, Akzo), Deutero -Polymer-11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron ® -XG (anionic heteropolysaccharide based on ß-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron ® -XN (non-ionic polysaccharide, Schönes GmbH), Dicryian ® -thickener-0 (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ® - ⁇ 1 and EMA
  • preferred gels contain various solvents, gels having proven particularly advantageous in terms of their product properties, which contain water and / or one or more water-miscible solvents in amounts of ⁇ to 70% by weight, preferably of Contain 10 to 6 ⁇ wt .-% and particularly preferably from 15 to 60 wt .-%.
  • the water-miscible solvents contain one or more substances from the group consisting of ethanol, n- or i-propanol, n- or sec- or tert-butanol, glycol, propane or butanediol, glycerol, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl methyl, ethyl or propylene glycol, diphenyl ether, dipropylene ether Di-isopropyl glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl
  • capsules are further preferred solids used in agents according to the invention.
  • Capsule is a term for a frequently used form of packaging that contains solid, semi-solid or liquid substances in differently sized, possibly colored, layers of gelatin, wax or wafer material. The most common are the gelatin capsules (made of hard or Soft gelatin) is used.
  • one or more or all of the solids filled into the containers produced according to the invention ie for example one, several or all of the powders and / or granules and / or extrudate (s) filled into these containers. and / or compact (s) and / or cast body and / or dimensionally stable gel (s) and / or capsule (s), a coating (coating).
  • a coating can serve different purposes.
  • coating can, for example, prevent undesired contact of active substances which are sensitive to hydrolysis or oxidation in the solids, with the outside air or other solids enclosed in the water-soluble container according to the invention.
  • an advantageous visual effect can also be achieved by a coating.
  • Liquids and solids are suitable as ingredients for the receiving chambers or spaces.
  • solids a distinction is made between powders, granules, extrudates, compactates, castings and dimensionally stable gels.
  • As Liquids apply in the context of this application in addition to low-viscosity, flowable liquids or flowable gels and also flowable dispersions, for example emulsions or suspensions.
  • Active substances or combinations of active substances are considered to be flowable if they have no inherent dimensional stability which enables them to assume a non-disintegrating spatial form under the usual conditions of manufacture, storage, transport and handling by the consumer, this spatial form under the conditions mentioned also not changed over a longer period of time, preferably 4 weeks, particularly preferably 8 weeks and in particular 32 weeks, that is under the usual conditions of manufacture, storage, transport and handling by the consumer in the spatial conditions caused by the manufacture. geometric shape persists, that is, does not melt away.
  • the determination of the flowability relates in particular to the conditions customary for storage and transport, that is to say in particular to temperatures below 50 ° C., preferably below 40 ° C. Liquids are therefore in particular active substances or combinations of active substances with a melting point below 25 ° C., preferably below 20 ° C., particularly preferably below 15 ° C.
  • the preferred agents according to the invention are listed with two filled receiving troughs and one filled intermediate space.
  • the receiving troughs or interstices filled with liquid, powder or granules preferably have a seal.
  • the sealing is optional, but is preferred.
  • Agents which are particularly preferred in the context of the present application are characterized in that at least one receiving chamber and / or at least one intermediate space is filled with a liquid, at least one further receiving chamber and / or at least one intermediate space is filled with a solid. Agents according to the invention in which at least one intermediate space is filled with a melt are particularly preferred.
  • Liquid and solid active substances or active substance mixtures are suitable for filling the intermediate space (s) located between the receiving chambers.
  • the intermediate space of agents according to the invention is filled with a liquid or a solid, preferably in a prefabricated form, particularly preferably in the form of a filled capsule of a compact or a melting body.
  • the solids introduced into the intermediate space can be fixed by gluing.
  • the prefabricated shaped body can preferably be fixed by plugging, particularly preferably in combination with a snap mechanism,
  • Particularly preferred agents are characterized in that at least one space is filled with an adhesive. Filling the intermediate space with adhesive and then gluing the side walls surrounding the intermediate space gives the entire container increased rigidity and in this way prevents, for example, the container from buckling along the web separating the receiving chambers. Such kinking not only leads to a disadvantageous appearance of the agent but also weakens the sealing seams located in the area of the web. These disadvantages are eliminated by subsequently filling an intermediate space with substances that are active in washing or cleaning and / or with adhesives.
  • Suitable adhesives are all substances known to the person skilled in the art for the adhesive connection of two bodies made from the shell materials mentioned. These adhesives can be used either alone or in combination with a further active substance, for example a coloring substance or a fragrance. If water-soluble or water-dispersible substances or substance mixtures are used as the covering material for the receiving chambers, water or water-containing solutions or dispersions are particularly suitable as adhesives. After the adhesive has been introduced into the intermediate space, it is preferred according to the invention
  • agents according to the invention are suitable for portioning, packaging and metering active substances or active substance mixtures.
  • Preferred agents include active substances or mixtures of active substances from the fields of pharmaceuticals, cosmetics, feed and crop protection or fertilizers, adhesives, food and / or personal care products, but preferably washing and cleaning substances.
  • Preferred active substances or active substance mixtures from the field of cosmetics are, in particular, hair setting agents, hair shaping agents and hair coloring agents.
  • the preferred personal care products also include pre-treatment agents, hairdressing aids and course rinses.
  • Active substances from the area of bath additives such as bath salts or bath tablets, but also shower, foam or cream baths, are also preferred.
  • a particularly preferred agent according to the invention is characterized in that it comprises detergents or cleaning agents. Washing and cleaning-active substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, disintegration aids, electrolytes, pH regulators, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, are particularly preferred. Anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobing and impregnating agents, swelling and anti-slip agents, non-aqueous solvents, fabric softeners, protein hydrolyzate and UV absorbers. More detailed information on the washing and cleaning-active substances mentioned can be found below in the text.
  • the gap (s) located between the receiving chambers can be filled by cutting knives or punches before or after the containers are separated. Regardless of whether the filling takes place before or after the separation, filling of the intermediate space (s) from the top and the bottom of the container is possible. Filling from the bottom is particularly advantageous when the agent to be filled is in a pre-assembled form, preferably in the form of a single molded body, and is fixed, for example, by gluing or plugging in the space (s). However, the containers can also be turned over before filling the gap (s) in step c). In this case, the gaps are accessible from the top and, in addition to the pre-assembled solids mentioned, liquids or free-flowing solids such as powders or granules can now also be filled in.
  • the agents according to the invention comprise active substances or active substance mixtures from the fields of pharmaceuticals, cosmetics, feed, crop protection or Fertilizers, adhesives, food and / or personal care products, but preferably from the area of washing and cleaning-active substances.
  • Preferred active substances or active substance mixtures from the field of cosmetics are, in particular, hair setting agents, hair shaping agents and hair coloring agents.
  • the preferred personal care products also include pre-treatment agents, hairdressing aids and course rinses.
  • Active substances from the area of bath additives such as bath salts or bath tablets, but also shower, foam or cream baths, are also preferred.
  • Particularly preferred agents according to the invention are characterized in that at least one receiving chamber and / or at least one intermediate space is filled with a washing or cleaning agent. Washing and cleaning-active substances from the group of bleaching agents, bleach activators, polymers, builders, surfactants, enzymes, disintegration aids, electrolytes, pH regulators, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, anti-redeposition agents, optical brighteners, graying inhibitors, are particularly preferred.
  • Anti-shrink agents anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, phobing and impregnating agents, swelling and anti-slip agents, non-aqueous solvents, fabric softeners, protein hydrolyzate and UV absorbers.
  • Bleaching agents and bleach activators can be contained in the agents according to the invention as important components of detergents and cleaning agents.
  • the compounds which serve as bleaching agents and supply H 2 0 2 in water sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Detergent tablets for automatic dishwashing can also contain bleaches from the group of organic bleaches.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxyaloacidoperoxycaproic acid (P ⁇ ) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,
  • Diperoxybrassylic acid the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di ( ⁇ -aminopercaproic acid) can be used.
  • the agents according to the invention are used as automatic dishwashing agents, they can contain bleach activators in order to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C. and below.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3, ⁇ -triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate diacetate and ethylene glycol, 2,5-dihydrofuran.
  • TAED tetraacetylethylene diamine
  • DADHT acy
  • bleach activators which are preferably used in the context of the present application are compounds from the group of the cationic nitriles, in particular cationic nitrile of the formula
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH3, -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
  • a particularly preferred agent according to the invention is a cationic nitrile of the formula R 4
  • bleach catalysts can also be incorporated into the agents.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt 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 amine complexes can also be used as bleaching catalysts.
  • the surfactants include in particular the anionic surfactants in acid form, aqueous solutions or pastes of the neutralized anionic surfactant acids, nonionic surfactants and / or cationic surfactants or amphoteric surfactants.
  • surfactant-containing agents according to the invention can be used, for example, in the removal of grease or oil contamination, their field of use ranging from textile cleaning to the removal of oil contamination in nature.
  • granules are preferred which have a surfactant content of 1 to 70% by weight, particularly preferably 2 to 60% by weight, particularly preferably 4 to ⁇ O% by weight, in each case based on the total weight of the compositions , exhibit.
  • builders are other important ingredients of detergents.
  • Preferred agents according to the invention can contain all builders commonly used in cleaning agents, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where none There are ecological prejudices against their use - including phosphates.
  • the builders mentioned can of course also be used in surfactant-free compressed products.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x 0 2x + ⁇ 'H 2 0, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 -yH 2 0 are preferred.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. ⁇ O nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • 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.
  • phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.
  • Sodium and potassium phosphates in which one can differentiate between cyclic representatives, the sodium and potassium metaphosphates and chain-like types, the sodium and potassium polyphosphates, as well as the pentasodium triphosphate, Na 5 P 3 O 10 (sodium tripolyphosphate) are further within the scope of the present Registration with advantage used builders.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their alkali and in particular sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and also mixtures from 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.
  • Alkali carriers can be present as further constituents.
  • Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the above-mentioned substances are considered to be alkali carriers, with the meaning of these Invention preferably uses the alkali carbonates, especially sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate.
  • water-soluble builders are preferred, since they generally have less tendency to form insoluble residues on dishes and hard surfaces.
  • Common builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates.
  • Trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicate and / or metasilicate are preferably used for the production of tablets for machine dishwashing.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system which contains a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic 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 thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • 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 weight of ⁇ OO to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated.
  • This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • the copolymers containing sulfonic acid groups are described in detail below.
  • agents according to the invention which combine the conventional cleaners, rinse aid and a salt replacement function as so-called “3in1” products, can also be provided.
  • automatic dishwashing detergents according to the invention are preferred, which additionally 0.1 to 70
  • copolymers have the effect that the items of tableware treated with such agents become significantly cleaner in subsequent cleaning operations than items of tableware that have been washed with conventional agents.
  • Drying time is generally understood in the context of the teaching according to the invention in the literal sense, that is to say the time which elapses until a dish surface treated in a dishwasher is dried, but in particular the time which elapses, up to 90% of one with a detergent or rinse aid surface dried in a concentrated or diluted form.
  • R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • H 2 C C (CH 3 ) -X-S0 3 H (llb),
  • ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the group iii) monomer content of the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).
  • R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, single or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH 2 , -OH or - COOH as defined above or represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical with 1 to 12 carbon atoms,
  • Particularly preferred copolymers consist of
  • H 2 C CH-X-S0 3 H (Ila),
  • H 2 C C (CH 3 ) -X-S0 3 H (llb),
  • the copolymers contained in the compositions can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined.
  • Particularly preferred polymers have certain structural units, which are described below.
  • agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula III
  • These polymers are produced by copolymerization of 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 in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula IV
  • acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are modified. be changed.
  • Agents according to the invention which contain one or more copolymers which have structural units of the formula V
  • maleic acid can also be used as a particularly preferred monomer from group i).
  • preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula VII
  • automatic dishwashing agents which contain, as ingredient b), one or more copolymers which have structural units of the formein III and / or IV and / or V and / or VI and / or VII and / or VIII
  • All or part of the sulfonic acid groups in the polymers can be in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.
  • the monomer distribution of the copolymers used in the agents according to the invention is preferably in each case ⁇ to 9 ⁇ % by weight i) or ii), particularly preferably 60 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % Monomer from group i) and 10 to ⁇ O% by weight monomer from group ii), in each case based on the polymer.
  • terpolymers those which contain 20 to 8% 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 molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the intended use.
  • Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 16,000 gmol "1 .
  • the content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of from 0.2 ⁇ to ⁇ O% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 1 ⁇ % by weight.
  • polyacrylates As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention.
  • the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred.
  • Such polyacrylates are commercially available under the trade names Sokalan ® PA1 ⁇ or Sokalan ® PA2 ⁇ (BASF).
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain ⁇ O to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.6 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid
  • Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • Anionic surfactants in acid form are preferably one or more substances from the group of carboxylic acids, sulfuric acid half-esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, that is to say they should have at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.
  • Carboxylic acids which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage.
  • Carboxylic acids which can be used as anionic surfactants in acid form 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 dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), hexotanoic acid (hexotonic acid) (hexotonic 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), 9cadienoi
  • Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C 8, 6 wt .-% C 10 48 wt .-% C 12, 18% by weight of C, 4, 0 wt .-% C 16, 2% by weight C 18 , 8% by weight C 18 -, 1% by weight C 8 -), palm core oil fatty acid (approx. 4% by weight C 8 , ⁇ % by weight C 10 , ⁇ O% by weight) -% C 12 , 1 ⁇ % by weight C-,, 7% by weight C 16 , 2% by weight C 18 , 1 ⁇ % by weight Ci 8 -, 1% by weight C 18 -) > tallow fatty acid (approx.
  • Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention.
  • Their alkali metal, in particular sodium salts, the fatty alcohol sulfates are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized.
  • the fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters.
  • the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SOs / air mixtures in special cascade, falling film or tube bundle reactors.
  • alkyl ether sulfuric acids the salts of which, the alkyl ether sulfates, are distinguished by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
  • alkyl ether sulfuric acids are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question.
  • ethylene oxide propylene oxide can also be used.
  • the subsequent sulfonation with gaseous sulfur trioxide in short-term sulfation reactors yields over 98% of the alkyl ether sulfuric acids concerned.
  • Alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention.
  • Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the carbon chain (secondary alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which, when hydrolysed with alkalis, provide the alkanesulfonates directly, and when reacted with water, the alkanesulfonic acids.
  • di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.
  • alkanesulfonic acids Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under irradiation with UV light.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals.
  • the reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical.
  • the reaction of the two radicals with unreacted paraffin gives the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to give sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then stopped.
  • Olefin sulfonates are produced industrially by the reaction of ⁇ -olefins with sulfur trioxide. Intermediate hermaphrodites are formed, which cyclize to form so-called sultans. Under suitable conditions (alkaline or acidic hydrolysis), these sultans react to give hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids.
  • alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • propylene was tetramerized to give branched ⁇ -dodecylene and the product was converted to tetrapropylenebenzene via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride, which was subsequently sulfonated and neutralized.
  • TPS tetrapropylene benzene sulfonates
  • Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and into the n-olefins dehydrated, resulting in both ⁇ - and i-olefins.
  • anionic surfactants in acid form are C 8 - ⁇ 6 -, preferably C 9 - ⁇ 3 -alkylbenzenesulfonic acids.
  • C 8 . 16 - preferably use C 9 - ⁇ 3 alkylbenzene sulfonic acids derived from alkylbenzenes which have a tetralin content below ⁇ % by weight, based on the alkylbenzene.
  • alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C 8-0 6 , preferably C 9 used .
  • 13- Alkylbenzenesulfonic acids have a content of 2-phenyl isomer below 22% by weight, based on the alkylbenzenesulfonic acid.
  • anionic surfactants in their acid form can be used alone or in a mixture with one another.
  • the anionic surfactant in acid form, before addition to the carrier material (s) contains further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably of 1 to 1 ⁇ % by weight and in particular from 2 to 10% by weight, based in each case on the weight of the mixture to be reacted.
  • Suitable acidic reactants in the context of the present invention are, in addition to the “surfactant acids”, also the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids as well as “builder acids” and “complex builder acids” (details later in the text) alone and in any mixtures.
  • surfactant acids also the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids as well as “builder acids” and “complex builder acids” (details later in the text) alone and in any mixtures.
  • builder acids and “complex builder acids” (details later in the text) alone and in any mixtures.
  • phosphonic acids which in neutralized form (phosphonates) are components of many detergents and cleaning agents as incrustation inhibitors.
  • anionic surfactants partially or fully neutralized. These salts can then be present as a solution, suspension or emulsion in the granulating liquid, but can also be part of the solid bed as a solid.
  • ammonium and mono-, di- or triethanolalkonium ions are suitable cations for such anionic surfactants.
  • the analog representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation.
  • Cationic surfactants can also be used with advantage as active substances.
  • the delivery form of the cationic surfactant can be added directly to the mixer, or it can be sprayed onto the solid carrier in the form of a liquid to pasty form of cationic surfactant.
  • Such cationic surfactant preparation forms can be prepared, for example, by mixing commercially available cationic surfactants with auxiliaries such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol can also be used, the amount of such lower alcohols in the liquid cationic surfactant preparation form being below 10% by weight for the reasons mentioned above.
  • the agents according to the invention can contain one or more cationic, fabric softening agents of the formulas X, XI or XII as cationic active substances with fabric softening effect: R 1
  • the solid (s) additionally contain nonionic surfactant (s) as active substance.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 2 -alcohols with 3 EO or 4 EO, Cg-n alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, ⁇ 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 - ⁇ 4 alcohol with 3 EO and C 12 . 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction 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, 26 EO, 30 EO or 40 EO.
  • nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants.
  • surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
  • Agents according to the invention which contain surfactants of the general formula XIV as nonionic surfactant (s) are preferred here
  • 24 is alkyl or alkenyl; 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 represent integers from 1 to 6.
  • the preferred nonionic surfactants of the formula XIV 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 XIV 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 generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred.
  • Alcohols accessible from synthetic sources are, for example, Guerbet alcohols or residues which are methyl-branched in the 2-position or linear and methyl-branched residues in a mixture, as are usually present in oxo alcohol residues.
  • agents according to the invention are preferred in which R 1 in formula XIV for an alkyl radical having 6 to 24, preferably ⁇ to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • R 1 in formula XIV for an alkyl radical having 6 to 24, preferably ⁇ to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 or R 3 are selected independently of one another from - CH 2 CH 2 -CH 3 or CH (CH 3 ) 2 are also suitable.
  • Preferred agents are characterized in that R 2 or R 3 for a radical -CH 3 , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.
  • nonionic surfactants which have a C 9 . 15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • the specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation represent statistical mean values which can be an integer 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 of mixtures, which can result in mean values and fractional numbers both for the C chain lengths and for the degrees of ethoxylation or alkoxylation.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 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, in particular fatty acid methyl esters.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can 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 them.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula XV,
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for 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 which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula XVI,
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to ⁇ carbon atoms, C 1 -C 8 -alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical ,
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7, ⁇ : 1 and 1: 6 and in particular between ⁇ : 1 and 1: 2.
  • surfactants in cleaning agents for automatic dishwashing is preferably limited to the use of nonionic surfactants in small amounts. If the containers according to the invention are intended to enclose such agents, these agents preferably contain only certain nonionic surfactants, which are described below. Usually only weakly foaming nonionic surfactants are used as surfactants in automatic dishwashing detergents. By contrast, representatives from the groups of anionic, cationic or amphoteric surfactants are of lesser importance.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may 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 of 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 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 . 14 alcohols with 3 EO or 4 EO, Cg-n alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, ⁇ EO, 7 EO or 8 EO, C 12 . 18 alcohols with 3 EO, ⁇ EO or 7 EO and mixtures thereof, such as mixtures of C 12 . 14 alcohol with 3 EO and C 12 . 18 alcohol with ⁇ EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction 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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactant which has a melting point above room temperature, preferably a nonionic surfactant with a melting point above 20 ° C.
  • Nonionic surfactants to be used preferably have melting points above 25 ° C, particularly preferred nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.
  • 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.
  • nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 3 ⁇ Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature originate from the groups of the 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 results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 1 ⁇ mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
  • a particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms, (C ⁇ . 6 2 --Alkohol), a C preferably 18 alcohol and at least 12 mole, preferably at least 1 ⁇ mol and in particular at least 20 moles of ethylene oxide won.
  • a straight chain fatty alcohol having 16 to 20 carbon atoms (C ⁇ . 6 2 --Alkohol)
  • a C preferably 18 alcohol and at least 12 mole preferably at least 1 ⁇ mol and in particular at least 20 moles of ethylene oxide won.
  • the so-called “narrow ranks ethoxylates" are particularly preferred.
  • the nonionic surfactant which is solid at room temperature, preferably has additional propylene oxide units in the molecule.
  • Such PO units preferably make up up to 26% by weight, particularly preferably up to 20% by weight and in particular up to 1 ⁇ % 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 molar mass of such nonionic 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 an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight of a block copoly - Ho ⁇
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • Another preferred surfactant can be represented by the formula
  • R 1 represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof
  • x denotes values between 0.5 and 1
  • ⁇ and y stands for a value of at least 16.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
  • R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
  • x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and ⁇ . If the value x ⁇ 2, each R 3 in the above formula can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 16 carbon atoms being particularly preferred.
  • H, -CH 3 or - CH 2 CH 3 are particularly preferred for the radical R 3 .
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 1 ⁇ .
  • each R 3 in the above formula can be different if x ⁇ 2.
  • the value 3 for x has been chosen here as an example and may well be larger, the range of variation increasing with increasing x values and for example, includes 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 stands for 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 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 1 ⁇ .
  • Preferred agents according to the invention which are used as automatic dishwashing detergents, also contain amphoteric or cationic polymers in addition to the surfactants mentioned to improve the rinse aid result.
  • Agents according to the invention can contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all the enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 "6 to ⁇ weight percent based on active protein. The protein concentration can be determined using known methods, for example the BCA process (bicinchoninic acid; 2,2'-bichinolyl-4,4 '-dicarboxylic acid) or the biuret method can be determined.
  • BCA process bicinchoninic acid; 2,2'-bichinolyl-4,4 '-dicarboxylic acid
  • biuret method can be determined.
  • 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 that 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 under the trade names Esperase ®, or Savinase ® from Novozymes.
  • the variants listed under the name BLAP ® are derived from the protease from Bacillus lentus DSM 6483.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, which is sold under the trade name Protosol ® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name Proleather ® and Protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from ⁇ . amyloliquefaciens or from ß. stearothermophilus and its further developments for use in detergents and cleaning agents.
  • the enzyme from ß. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar ® ST. Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • the ⁇ -amylase from ß. Amyloliquefaciens is sold by Novozymes under the name BAN ® , and derived variants from the ⁇ -amylase from ⁇ . stearothermophilus under the names BSG ® and Novamyl ® , also from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 1236 ⁇ ) and the cyclodextrin glucanotransferase (CGTase) from ß. highlight agaradherens (DSM 9948); fusion products of the molecules mentioned can also be used.
  • Agents according to the invention can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ® , Lipolase ® Ultra, LipoPrime ® , Lipozyme ® and Lipex ® .
  • the cutinases that were originally used can be used from Fusarium solani pisi and Humicola insolens.
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase ® , Lipase AP ® , Lipase M-AP ® and Lipase AML ® available.
  • the Genencor company can use the lipases or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Agents according to the invention can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a “stone washed” effect.
  • EG endoglucanase
  • Novozymes A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ® .
  • Other possible commercial products from this company are Cellusoft ® and Renozyme ® .
  • the 20 kD EG cellulase from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ® and Biotouch ® can also be used.
  • Suitable mannanases include, for example, under the names Gamanase ® and Pektinex AR ® from Novozymes under the name ® Rohapec B1L by AB Enzymes and under the name ® Pyrolase® from Diversa Corp., San Diego, CA, USA available. The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ® from Novozymes.
  • washing or cleaning agents can use oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) contain.
  • Suitable commercial products are Denilite ® 1 and 2 from Novozymes.
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.
  • the enzymes used in agents according to the invention either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological processes known per se by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • Agents according to the invention can be added to the enzymes in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.
  • the enzymes can be encapsulated both for the solid and for the liquid administration form, 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 enzyme is enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers.
  • Such capsules are made according to methods known per se, applied, for example, by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • a protein and / or enzyme contained in an agent according to the invention can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • Agents according to the invention can contain stabilizers for this purpose; the provision of such agents is a preferred embodiment of the present invention.
  • a group of stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho-.meta- or para-substituted phenylboronic acids, or their salts or esters.
  • Peptide aldehydes, ie oligopeptides with a reduced C-terminus are also suitable. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End group-capped fatty acid amide alkoxylates can also be used as stabilizers.
  • Di-glycerol phosphate also protects against denaturation by physical influences.
  • 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, such as cellulose ethers, acrylic polymers and / or polyamides, stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polymers containing polyamine N-oxide act both as enzyme stabilizers and as Dye transfer inhibitors.
  • Other polymeric stabilizers are the linear C 8 -C 8 polyoxyalkylenes.
  • Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and even increase their performance.
  • Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.
  • Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of the enzymes against oxidative breakdown.
  • Combinations of stabilizers are preferably used, for example made of 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 action of peptide-aldehyde stabilizers can be increased by the combination with boric acid and / or boric acid derivatives and polyols and can be further enhanced by the additional use of divalent cations, such as calcium ions.
  • Agents according to the invention are preferred here which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to ⁇ % by weight, preferably of 1.5 to 4 , 5 and in particular from 2 to 4 wt .-%, each based on the total agent.
  • these compresses can contain disintegration aids, so-called tablet disintegrants.
  • tablet disintegrants According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 19 ⁇ 7, p. 182-164), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form.
  • preferred disintegration aids are cellulose-based disintegration aids, preferably in granular, cogranulated or compacted form.
  • Pure cellulose has the formal gross composition (C 6 H ⁇ 0 O 5 ) n and, formally speaking, is a ß-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 consequently have average molecular weights of 60,000 to 600,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained 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 hydroxyl groups have been replaced by functional groups which 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 and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the cellulose derivative content of these mixtures is preferably below 60% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant.
  • Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve 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 produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately ⁇ ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • the agents according to the invention can contain a gas-releasing system composed of organic acids and carbonates / hydrogen carbonates.
  • the solid mono-, oligo- and polycarboxylic acids can be used as organic acids which release carbon dioxide from the carbonates / bicarbonates in aqueous solution. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • a commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. ⁇ O wt .-%) and adipic acid ( max. 33% by weight).
  • a detergent and cleaning agent compact preferred in the context of the present invention additionally contains a shower system.
  • the gas-developing shower system consists of carbonates and / or bicarbonates in addition to the organic acids mentioned.
  • the alkali metal salts are clearly preferred among representatives of this class of substances.
  • the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
  • the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.
  • a wide number 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 production point of view, the use of NaCl or MgCl 2 in the granules according to the invention is preferred.
  • pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not derived from for technical or ecological reasons or for reasons of consumer protection. The amount of these steeping agents usually does not exceed 1% by weight of the total formulation.
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate and styrallyl propylate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • fragrance substances In order to be perceptible, a fragrance substance 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 odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, the odor impressions being described as "top note”, “heart or middle note” (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 largely consists of less volatile, ie sticky odorants.
  • more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly.
  • fixatives for example, which prevents them from evaporating too quickly.
  • the smell of the water-soluble containers according to the invention or the solids contained in them (product fragrance) and, after the cleaning and care process has ended, the laundry fragrance can also be influenced by a suitable selection of the fragrances or perfume oils mentioned. Due to their design, in particular due to the openings in the outer wall, water-soluble containers according to the invention are particularly suitable in comparison to completely closed containers to ensure an unmistakable product fragrance even when using smaller amounts of fragrance, whereby in particular also more volatile fragrances can be used, while To achieve a sufficient scent of laundry, the use of stronger odoriferous substances is advantageous.
  • Adhesive odoriferous substances which 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, champagne flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, geranium oil, spruce oil, spruce oil, spruce oil, oil spruce oil, spruce oil, oil spruce oil, spruce oil, spruce oil, spruce oil, spruce 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, Kopa ⁇ vabalsam oil, coriander oil, spearmint
  • the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances.
  • These compounds include the compounds mentioned below and mixtures of these: ambrettolide, ⁇ -amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, boryl formate benzyl, benzyl benzyl benzate, boryl formate benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl benzate, benzyl formate benzyl benz
  • 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 alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the compositions and to light. If the containers according to the invention contain detergents and cleaning agents for textile cleaning, the dyes used should furthermore have no pronounced substantivity towards textile fibers in order not to stain them.
  • Hydrotropes or solubilizers are substances that, through their presence, make other compounds that are practically insoluble in a certain solvent soluble or emulsifiable in this solvent (solubilization). There are solubilizers that form a molecular compound with the poorly soluble substance and those that work through micell formation. It can also be said that solubilizers only give a so-called latent solvent its solvency. When water is used as a (latent) solvent, one speaks mostly of hydrotropes instead of solubilizers, in some cases better of emulsifiers.
  • Foam inhibitors which can be used in the agents according to the invention include soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable carrier materials are, 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 structured according to the scheme (R 2 SiO) x and are also referred to as silicone oils.
  • 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 from 15 to 30% by weight and of hydroxypropyl groups from -1 to 1 ⁇ % by weight, based in each case on the nonionic Cellulose ethers and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.
  • Optical brighteners can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly 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'-stilbene disulfonic acids ( Flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well as pyrene derivatives substituted by heterocycles.
  • Flavonic acids 4,4'-diamino-2,2'-stilbene disulfonic acids
  • 4'-distyryl-biphenyls 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly 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 acidic 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 also be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • graying inhibitors are cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as
  • Methylhydroxyethyl cellulose methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.
  • the invention Agents contain synthetic anti-crease. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • a substance that is particularly suitable for textile finishing and care is cottonseed oil, which can be produced, for example, by pressing out the brown, cleaned cottonseed and refining it with about 10% sodium hydroxide or by extraction with hexane at 60-70 ° C.
  • cotton oils contain 40 to ⁇ % by weight of linoleic acid, 16 to 26% by weight of oleic acid and 20 to 26% by weight of palmitic acid.
  • Further agents which are particularly preferred for fiber smoothing and fiber care are the glycerides, in particular the monoglycerides of fatty acids such as, for example, glycerol monooleate or glycerol monostearate.
  • the agents according to the invention can contain antimicrobial agents.
  • antimicrobial agents 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 are, for example, benzalkonium chlorides, alkylarlyl sulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the inventive agents.
  • the agents according to the invention can contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
  • External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give 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) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect. Phobing and impregnation processes are used to finish textiles with substances that prevent dirt from accumulating or make it easier to wash out.
  • Preferred waterproofing 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 component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents can also be included.
  • the dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care finish.
  • the penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension.
  • Another area of application of waterproofing and impregnating agents is the water-repellent finishing of textile goods, tents, tarpaulins, leather etc., which, in contrast to waterproofing, does not close the fabric pores, which means that the fabric remains breathable (hydrophobic).
  • the hydrophobizing agents used for hydrophobizing coat textiles, leather, paper, wood etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups.
  • Suitable hydrophobizing agents are, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organic tin Compounds and glutardialdehyde and perfluorinated compounds.
  • the hydrophobized materials do not feel greasy; nevertheless - similar to greased substances - water drops roll off them without wetting them.
  • silicone-impregnated textiles have a soft feel and are water u. stain-resistant; Stains from ink, wine, fruit juices and the like are easier to remove.
  • the non-aqueous solvents which can be used in the agents 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 the like Glycol ethers (diethyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ether), 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),
  • a solvent mixture which is particularly preferred in the context of the present application, is, for example, mineral spirits, a mixture of different substances suitable for chemical cleaning Hydrocarbons, 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, in each case based on the total weight of the mixture, preferably with a boiling range from 81 to 110 ° C.
  • the agents according to the invention can contain fabric softeners.
  • the active ingredients in fabric softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as, for example, disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds 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 with alkylating agents in a manner known per se.
  • Dimethylolethylene urea is also suitable as a finish.
  • silicone derivatives can be used in the agents according to the invention. These additionally improve the rinsing behavior of the agents according to the invention due 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 completely 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, ie polysiloxanes which have, for example, polyethylene glycols and the polyalkylene oxide-modified dimethyl polysiloxanes.
  • protein hydrolyzates are further active substances preferred in the field of detergents and cleaning agents in the context of the present invention.
  • Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins).
  • protein hydrolyzates of both vegetable and animal origin can be used.
  • Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts.
  • the use of protein hydrolysates of plant origin e.g. B. soy, almond, rice, pea, potato and wheat protein hydrolyzates.
  • protein hydrolyzates as such is preferred, amino acid mixtures obtained in some other way or individual amino acids such as, for example, arginine, lysine, histidine or pyrroglutamic acid may also be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products.
  • the agents according to the invention can also contain UV absorbers, which absorb onto the treated textiles and improve the light resistance of the fibers.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles, phenyl-substituted acrylates (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 urocanoic acid are also suitable.
  • Detergents for automatic dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents and glass corrosion inhibitors in particular being particularly important in the field of automatic dishwashing.
  • the known substances of the prior art can be used.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface.
  • oxygen and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes
  • At least one silver protective agent from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1% by weight, preferably from 0.01 to 0, ⁇ % by weight and in particular from 0.0 ⁇ to 0.25% by weight, in each case based on the total weight of the solids enclosed in the water-soluble containers according to the invention.
  • agents according to the invention can also contain one or more substances for reducing glass corrosion.
  • additives of zinc and / or inorganic and / or organic zinc salts and / or silicates for example the layered crystalline sodium disilicate SKS 6 from Clariant GmbH, and / or water-soluble glasses, for example glasses which have a mass loss of have at least 0.1 mg under the conditions specified in DIN ISO 719, preferred for reducing glass corrosion.
  • Particularly preferred agents contain at least one zinc salt of an organic acid, preferably selected from the group zinc oleate, zinc stearate, zinc gluconate, zinc acetate, zinc lactate and zinc citrate.

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Abstract

L'invention concerne des contenants composés d'au moins deux chambres de réception séparées, obtenues par formage d'un premier matériau d'enveloppe sous forme desdites chambres de réception séparées, remplissage des chambres de réception, et remplissage du ou des espaces intermédiaires situés entre les chambres de réception. Les contenants selon l'invention se caractérisent par une proportion d'emballage réduite et une stabilité mécanique élevée.
PCT/EP2003/013568 2002-12-20 2003-12-02 Agent de lavage ou de nettoyage en portion Ceased WO2004058592A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003298161A AU2003298161A1 (en) 2002-12-20 2003-12-02 Portioned detergent or cleaning agent

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2002159848 DE10259848A1 (de) 2002-12-20 2002-12-20 Portioniertes Wasch- oder Reinigungsmittel
DE10259848.7 2002-12-20

Publications (1)

Publication Number Publication Date
WO2004058592A1 true WO2004058592A1 (fr) 2004-07-15

Family

ID=32477848

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/013568 Ceased WO2004058592A1 (fr) 2002-12-20 2003-12-02 Agent de lavage ou de nettoyage en portion

Country Status (3)

Country Link
AU (1) AU2003298161A1 (fr)
DE (1) DE10259848A1 (fr)
WO (1) WO2004058592A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004062328A1 (de) * 2004-12-20 2006-06-29 Henkel Kgaa Dosiereinheit für Wasch- oder Reinigungsmittel
DE102005038070A1 (de) * 2005-08-10 2007-03-15 Henkel Kgaa Wasch- und Reinigungsmittel mit gut löslichen Kapseln
DE102021209934A1 (de) * 2021-09-08 2023-03-09 Henkel Ag & Co. Kgaa Verfahren zur Herstellung von Waschmitteldosiereinheiten mit verbesserten Eigenschaften
WO2023036488A1 (fr) * 2021-09-08 2023-03-16 Henkel Ag & Co. Kgaa Procédé de production d'unités de dosage de détergent présentant des propriétés améliorées

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3218776A (en) * 1961-09-11 1965-11-23 Cloud Machine Corp Packaging method and apparatus
DE10056115A1 (de) * 2000-11-13 2002-05-23 J W Geyssel Entwicklungs Und K Vorrichtung und Verfahren zum Anbringen von Gegenständen an Packungen, Bechern oder anderen Objekten
GB2370552A (en) * 1999-11-17 2002-07-03 Aquasol Ltd Rigid water-soluble container
WO2003072694A1 (fr) * 2002-02-26 2003-09-04 Reckitt Benckiser N.V. Composition detergente conditionnee

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2374580B (en) * 2001-04-20 2003-07-16 Reckitt Benckiser Water-soluble containers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3218776A (en) * 1961-09-11 1965-11-23 Cloud Machine Corp Packaging method and apparatus
GB2370552A (en) * 1999-11-17 2002-07-03 Aquasol Ltd Rigid water-soluble container
DE10056115A1 (de) * 2000-11-13 2002-05-23 J W Geyssel Entwicklungs Und K Vorrichtung und Verfahren zum Anbringen von Gegenständen an Packungen, Bechern oder anderen Objekten
WO2003072694A1 (fr) * 2002-02-26 2003-09-04 Reckitt Benckiser N.V. Composition detergente conditionnee

Also Published As

Publication number Publication date
DE10259848A1 (de) 2004-07-08
AU2003298161A1 (en) 2004-07-22

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