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WO2005021381A1 - Procede de production d'agents de lavage ou de nettoyage - Google Patents

Procede de production d'agents de lavage ou de nettoyage Download PDF

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Publication number
WO2005021381A1
WO2005021381A1 PCT/EP2004/009022 EP2004009022W WO2005021381A1 WO 2005021381 A1 WO2005021381 A1 WO 2005021381A1 EP 2004009022 W EP2004009022 W EP 2004009022W WO 2005021381 A1 WO2005021381 A1 WO 2005021381A1
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WO
WIPO (PCT)
Prior art keywords
weight
acid
preferred
agents
receiving chamber
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/EP2004/009022
Other languages
German (de)
English (en)
Inventor
Wolfgang Barthel
Birgit Burg
Salvatore Fileccia
Arno DÜFFELS
Maren Jekel
Ulf Arno Timmann
Christian Nitsch
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
Publication of WO2005021381A1 publication Critical patent/WO2005021381A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • B65B47/00—Apparatus or devices for forming pockets or receptacles in or from sheets, blanks, or webs, comprising essentially a die into which the material is pressed or a folding die through which the material is moved
    • B65B47/08—Apparatus or devices for forming pockets or receptacles in or from sheets, blanks, or webs, comprising essentially a die into which the material is pressed or a folding die through which the material is moved by application of fluid pressure

Definitions

  • This application relates to a packaging process. In a preferred embodiment, this application relates to a method for packaging washing or cleaning agents.
  • Detergents or cleaning agents are now available to consumers in a wide variety of forms.
  • this offer also includes, for example, cleaning agent concentrates in the form of extruded or tableted compositions.
  • These solid, concentrated or compacted offer forms are characterized by a reduced volume per dosing unit and thus lower the costs for packaging and transport.
  • the detergent or cleaning agent tablets in particular also meet the consumer's desire for simple dosing.
  • the corresponding agents are described in detail in the prior art.
  • compacted detergents or cleaning agents also have a number of disadvantages.
  • tableted forms of offer are often characterized by a delayed disintegration and thus a delayed release of their ingredients due to their high compression.
  • solid or liquid detergents or cleaning agents which have water-soluble or water-dispersible packaging have been increasingly described in recent years. Like the tablets, these agents are characterized by a simplified dosage, since they are dosed together with the outer packaging into the washing machine or the dishwasher On the other hand, they also enable the assembly of liquid or powder detergents or cleaning agents, which are characterized by better resolution and faster effectiveness compared to the compact products.
  • EP 1 314 654 A2 (Unilever) discloses a dome-shaped pouch with a receiving chamber which contains a liquid.
  • WO 01/83657 A2 Procter & Gamble
  • bags which contain two particulate solids in a receiving chamber, each of which is present in fixed regions and does not mix with one another.
  • EP 1 256 623 A1 The subject of European application EP 1 256 623 A1 (Procter & Gamble) is a kit consisting of at least two bags with different compositions and different looks. The bags are separate from each other and not as a compact single product.
  • the object of the present application was to provide a method for packaging detergents or cleaning agents which enables the packaging of at least two detergent or cleaning agent compositions in separate receiving chambers of a compact metering unit.
  • the end product of the process should be characterized by an attractive appearance.
  • packaging films can be processed by repeated deformation to form packages with several receptacles.
  • a first subject of the present application is therefore a method for producing a packaged agent, comprising the steps: a) molding a packaging film into the trough of a deep-drawing die; b) filling the receiving chamber with one or more agent (s); c) sealing the filled receiving chamber; d) increasing the trough volume of the trough of the deep-drawing die; e) Forming the filled receiving chamber into the trough with increased volume to form a further receiving chamber f) filling the further receiving chamber with another agent.
  • a packaging film is molded into a trough to form a receiving chamber.
  • the volume of the receiving chamber formed in step a) is preferably between 1 and 100 ml, preferably between 2 and 80 ml, particularly preferably between 3 and 60 ml and in particular between 4 and 40 ml. Due to the high flexibility of the method according to the invention, the volume of the Receiving chamber can be easily adapted to the respective requirements. With the aid of the method according to the invention, both large-volume agents and agents with a small volume can be produced in this way.
  • the volume of the receiving chamber formed in step a) is between 30 and 100 ml, preferably between 40 and 90 ml and particularly preferably between 50 and 80 ml. Also preferred is an embodiment in which the volume of the in Step a) formed receiving chamber is between 1 and 40 ml, preferably between 2 and 30 ml, particularly preferably between 3 and 25 ml and in particular between 6 and 20 ml.
  • packaging films for carrying out the process according to the invention.
  • a process variant is particularly preferred in which the packaging film is a water-soluble or water-dispersible film.
  • Particularly suitable packaging materials for the film are (acetalized) polyvinyl alcohols, polyvinyl pyrrolidones, polyethylene oxides, (modified) cellulose or gelatin. These substances are described in more detail below.
  • Polyvinyl alcohols (abbreviation PVAL, sometimes 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 approximately 100 to 2500 (molar masses from approximately 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturers by specifying the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, 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.
  • packaging or wrapping material which at least partially comprise 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 Is mol%.
  • the film material used consists of at least 20% by weight, particularly preferably at least 40% by weight, very particularly preferably at least 60% by weight and in particular at least 80% by weight, of a polyvinyl alcohol, the 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 film 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 88 mol%.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as film materials, it being preferred according to the invention that the film 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.
  • film materials are preferably used which are polyvinyl alcohols and / or PVAL -Copolymers comprise whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or whose molecular weight ratio MG (50%) to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and L648, L734, Mowiflex LPTC KSE 221 as well as the ex Compounds of Texas polymer such as Vinex 2034.
  • polyvinyl alcohols ® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of the Du Pont )
  • ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol ® NK-05, A-300, AH- 22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11 Q, KZ-06 (trademark the Nippon Gohsei KK).
  • ERKOL types from Wacker are also suitable.
  • the water content of preferred PVAL packaging materials is preferably less than 10% by weight, preferably less than 8% by weight, particularly preferably less than 6% by weight and in particular less than 4% by weight.
  • the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • 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.
  • Further preferred film materials are characterized in that they comprise hydroxypropylmethyl cellulose (HPMC), which have a degree of substitution (average number of methoxy groups per anhydroglucose unit of cellulose) from 1.0 to 2.0, preferably from 1.4 to 1.9, and has a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) from 0.1 to 0.3, preferably from 0.15 to 0.25.
  • HPMC hydroxypropylmethyl cellulose
  • 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
  • Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily produced by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline Conditions is won.
  • 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 film material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules.
  • film materials which comprise a polymer from the group consisting of starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. 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, from a formal point of view, 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 amino celluloses.
  • the packaging film used is conditioned prior to molding. Methods according to the invention are particularly preferred in which the packaging film is pretreated by heating and / or solvent application before the molding in step a).
  • the packaging film is pretreated by the action of heat before or during molding into the recesses of the matrices, this is preferably done for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0 , 4 to 2 seconds to temperatures above 60 ° C, preferably above 80 ° C, particularly preferably between 100 and 120 ° C and in particular to temperatures between 105 and 115 ° C.
  • the receiving trough formed is filled with one or more agents.
  • agents can be both solids and liquids. All stationary or movable metering devices for solids or liquids known to the person skilled in the art are suitable for filling the receiving chamber.
  • a further packaging film preferably a water-soluble or water-dispersible film, is preferably used for sealing.
  • This further packaging film can be identical to the film used in step a), but can also differ from it, for example, in composition and / or thickness.
  • the film used in step c) is a film which is identical in its composition to the film from step a), but has a comparatively smaller thickness. Sealing is preferably carried out by heat sealing (for example by means of heated tools or a laser beam), by the action of solvents and / or adhesives or by pressure or squeezing forces.
  • the receiving chamber in step c) can also simply be covered with another film without permanently connecting this film to the packaging film forming the receiving chamber.
  • the trough volume in step d) is increased by 1 and 70% by volume, preferably by 1 to 50% by volume, particularly preferably by 1 to 40% by volume and in particular 1 to 30% by volume. -%, each based on the original trough volume, increased.
  • the increase in the trough volume in step d) of the method according to the invention is achieved by increasing the volume of the trough used in step a).
  • Methods according to the invention are particularly preferred in which the increase in the trough volume in step d) of the method according to the invention is achieved by lowering the trough bottom.
  • the trough floor can be lowered over its entire surface or over part of its surface.
  • Methods are particularly preferred in which at least 10%, preferably at least 20%, preferably at least 40%, particularly preferably at least 80% and in particular 100% of the area of the trough bottom are lowered.
  • the use of trough floors made of elastic materials is particularly preferred.
  • the increase in the trough volume in step d) of the method according to the invention is achieved by shifting the outer walls of the trough.
  • the trough volume is increased in step d) of the process according to the invention by transferring the filled receiving chambers to a second deep-drawing die.
  • the troughs of this second deep-drawing die have a larger volume than the troughs used in step a) of the method according to the invention.
  • the increased trough volume can be achieved, for example, by a greater depth of the die troughs with the same shape and area of the trough openings in steps a) and d).
  • the volume of this second receiving chamber is between 0.4 and 15 ml, preferably between 0.8 and 13 ml, particularly preferably between 1.2 and 11 ml and in particular between 1.6 and 9 ml.
  • the ratio of the volume of the receiving chamber formed in step a) to the volume of the receiving chamber formed in step e) is preferably between 20: 1 and 1: 2, preferably between 15: 1 and 1: 1 and in particular between 10: 1 and 2: 1.
  • the resulting receiving chamber is filled.
  • these agents can be both solids and liquids. All stationary or movable metering devices for solids or liquids known to the person skilled in the art are in turn suitable for filling the receiving chamber.
  • the resulting filled receiving chamber is resealed in a further step g).
  • Methods are therefore characterized in that after step f) in step g) the filled receiving chamber is sealed.
  • a further packaging film preferably a water-soluble or water-dispersible film, is preferably used for sealing.
  • the sealing in step c) and / or in step g) is accordingly carried out by means of a packaging film, preferably a water-soluble or water-dispersible film.
  • sealing in steps c) and / or g) according to methods which are particularly preferred according to the invention can also be carried out, for example, by means of solidifying liquids, preferably solidifying melts, or prefabricated pouches, that is to say filled and sealed sachets.
  • a particularly preferred method variant, in which prefabricated bags are used for sealing, is the folding together of two pouches along a common (folding) fold.
  • a first preferred method variant for example, in a first step a) two rows are formed from a packaging film in pairs of opposing receiving chambers.
  • the two receiving chambers belonging to a pair can be identical to one another in terms of their volume, their shape and their spatial orientation, or they can differ from one another in terms of their spatial arrangement (for example, mirror-image arrangement of the two receiving chambers belonging to a pair in variant 1).
  • pairs of receiving chambers can also be used, which differ from one another both in size and in shape. After the filling of one or both receiving chambers and the sealing of one or both receiving chambers along a common fold, the two receiving chambers belonging to a pair are folded onto one another and adhesively connected to one another. Methods according to the invention according to variant 1 are particularly preferred, in which only one of the two receiving chambers is sealed before folding.
  • the packaging foils can be molded into the mold cavity in different ways. Methods in which the molding in step a) and / or in step e) is carried out by the action of a negative pressure are preferred.
  • a preferred subject of the present application is therefore a method for producing a packaged agent, comprising the steps of: a) forming a packaging film into the depression of a deep-drawing die with a vacuum, forming a receiving chamber; b) filling the receiving chamber with one or more agent (s); c) sealing the filled receiving chamber; d) increasing the trough volume; e) molding the filled receiving chamber into the trough with increased volume to form a further receiving chamber f) filling the further receiving chamber with a further agent; g) Optionally seal the further filled receiving chamber.
  • All the pumps known to the person skilled in the art for these purposes are suitable for generating the required negative pressure, in particular the water jet, liquid vapor jet, water ring and the like which can be used above for a rough vacuum.
  • Piston pumps can also be used.
  • Rotary vane pumps, diffusion pumps, roots blowers, displacement pumps, turbomolecular pumps, sorption pumps and ion getter pumps (getters) are particularly suitable for setting a fine vacuum.
  • the thickness and quality of the packaging films used, the process temperature and humidity, and in particular the vacuum used, must be coordinated.
  • the negative pressure is between -700 and -1013 mbar, preferably between -800 and -1013 mbar and in particular between -900 and -1013 mbar.
  • essentially constant pressures are those vacuum pressures which in the course of the process are less than ⁇ 150 mbar, preferably less than ⁇ 120 mbar, particularly preferably less than ⁇ 90 mbar, in particular less than ⁇ 60 mbar and particularly preferred fluctuate by less than ⁇ 10 mbar.
  • the molding in step a) and / or in step e) is carried out by the action of pressure, preferably by the action of a stamp or by the action of compressed air.
  • a preferred subject of the present application is therefore a method for producing a packaged agent, comprising the steps of: a) forming a packaging film into the trough of a deep-drawing die by the action of pressure, preferably by the action of a stamp or by the action of compressed air with the formation of a receiving chamber; b) filling the receiving chamber with one or more agent (s); c) sealing the filled receiving chamber; d) increasing the trough volume; e) shaping the filled receiving chamber into the trough with increased volume by the action of pressure, preferably by the action of a stamp or by the action of compressed air to form a receiving chamber, f) filling the further receiving chamber with another agent; g) Optionally seal the further filled receiving chamber.
  • Process variants are particularly preferred in the context of the present application, in which an indentation by the action of pressure is combined with an indentation by means of negative pressure.
  • the molding in one of steps a) or e) can take place through the combined action of pressure forces and vacuum, pressure forces and vacuum being able to act simultaneously or at different times.
  • one of the two indentations in steps a) or e) can also take place by compressive forces, while the other indentation is achieved by negative pressure.
  • a process variant for producing a packaged agent comprising the steps: a) forming a packaging film into the trough of a deep-drawing die by the action of pressure, preferably by the action of a stamp or by the action of compressed air with the formation of a receiving chamber, which are not fills the entire trough volume, and hold the formed receiving chamber by means of a negative pressure applied to the trough of the die; b) filling the receiving chamber with one or more agent (s); c) sealing the filled receiving chamber; d) increasing the trough volume; e) molding of the filled receiving chamber into the trough with increased volume with a negative pressure with formation of a further receiving chamber; f) filling the further receiving chamber with a further agent; g) Optionally seal the further filled receiving chamber.
  • the method according to the invention can be used for packaging solid and / or liquid agents.
  • the method according to the invention serves to package liquid agents, with particular preference being given to those methods in which the agent (s) filled in step f) is a liquid.
  • the method according to the invention offers particular advantages with regard to the production of solid / liquid combination products.
  • solids are introduced in step b), liquids in step f), or conversely liquids in step b) and solids in step f).
  • processes for producing a packaged composition comprising the steps: a) molding a packaging film into the trough of a deep-drawing die to form a receiving chamber; b) filling the receiving chamber with one or more solid (s); c) sealing the filled receiving chamber; d) increasing the trough volume; e) molding the filled receiving chamber into the trough with increased volume to form a further receiving chamber; f) filling the further receiving chamber with (a) liquid agent (s); g) Optionally seal the further filled receiving chamber.
  • Also preferred are methods for producing a packaged agent comprising the steps of: a) forming a packaging film into the trough of a deep-drawing die to form a receiving chamber; b) filling the receiving chamber with one or more liquid agents; c) sealing the filled receiving chamber; d) increasing the trough volume; e) molding the filled receiving chamber into the trough with increased volume to form a further receiving chamber; f) filling the further receiving chamber with (one) or more solid (s); g) Optionally seal the further filled receiving chamber.
  • solids refers in particular to powders, granules, extrudates, compactates or castings. Castings are preferably obtained by the solidification of cast substances or substance mixtures, the solidification, for example, by changing the physical state (falling below the melting point of some or all of the constituents of the starting substance), by crystallization from supersaturated solutions, by solvent storage (e.g. formation of hydrates or gels) or by chemical reaction (eg polymerization) takes place.
  • the solidification can take place both before filling the receiving chambers and after filling the receiving chambers.
  • the term “solid” in the context of the present application also includes those substances or substance mixtures which only solidify after being filled into one of the receiving chambers.
  • the one or more in step b) and / or f) filled agent around a solidifying liquid, preferably a solidifying melt are each filled with a substance or a mixture of substances.
  • the receiving chambers can each be filled with several different substances or substance mixtures.
  • Methods are particularly preferred in which the receiving chamber formed in step a) and / or in step e) in step b) and / or f) with a solidifying liquid, preferably a solidifying melt and with a further solid, preferably a powder or Granules that are filled.
  • the agent (s) filled in step b) comprises at least one solid and at least one solidifying liquid, preferably a solidifying melt.
  • Another preferred subject of the present application is therefore a method for producing a packaged agent, comprising the steps of: a) shaping a packaging film into the trough of a deep-drawing die to form a receiving chamber; b) filling the receiving chamber with a solidifying liquid, preferably a solidifying melt, and a further solid, preferably a powder or a granulate; c) sealing the filled receiving chamber; d) increasing the trough volume; e) molding the filled receiving chamber into the trough with increased volume to form a further receiving chamber; f) filling the further receiving chamber with (a) liquid agent (s).
  • the melt and the solid in step b) and / or step f) can be filled into the receiving chamber simultaneously or in succession.
  • Processes according to the invention are particularly preferred in which the melt in step b) is filled into the receiving chamber before the further solid, preferably a powder or granulate.
  • Also preferred are processes in which the powder, preferably a powder or granulate, is filled into the receiving chamber in step b) before the melt.
  • solidifying liquids are filled with particular preference into the receiving chamber formed in the course of the method according to the invention.
  • the solidifying liquid is a dispersion of solid particles in a dispersant, with dispersions which, based on their total weight, i) 10 to 85% by weight of dispersant and ii) 15 to 90% by weight. -% dispersed substances contain, 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 washing or cleaning agents according to the invention are characterized in that they contain the dispersing agent 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 with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, based in each case on the total weight of the dispersion can also be implemented and are also preferred.
  • 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 .-%.
  • dispersions which, based on their total weight, contain dispersants in amounts of from 12 to 62% by weight, preferably from 17 to 49% by weight and in particular from 23 to 38% by weight.
  • 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.
  • Particularly preferred dispersions 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 in the total weight of all dispersants preferably being between 10 and 90% by weight, particularly preferably between 30 and 80% by weight and in particular between 50 and 70% by weight.
  • a nonionic polymer preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol
  • the weight fraction of the poly (ethylene) glycol in the total weight of all dispersants preferably being 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 and in particular also 100 wt .-% consists of 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 explanations of the nonionic surfactants that can be used can be found in the description of detergent or cleaning substances below in the description.
  • Dispersions which are preferably used as the first wash- or cleaning-active preparation 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 having a washing or cleaning activity which are solid at room temperature, but in particular washing or cleaning substances from the group of builders (builders and cobuilders), washing or cleaning polymers, 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, based on their total weight, is preferably less than 30% by weight, preferably less than 23% by weight, preferably less than 19% by weight, particularly preferably less than 15% by weight and in particular less than 12% by weight.
  • Dispersions preferred according to the invention are low in water or anhydrous. Particularly preferred dispersions 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 used with preference are characterized by a high density. Dispersions with a density above 1.040 g / cm 3 are particularly preferred.
  • Dispersions preferred according to the invention are characterized in that they have 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 exhibit. This high density not only reduces the total volume of a metering unit produced by the method according to the invention, but at the same time improves the mechanical stability of this metering unit.
  • dispersions are therefore characterized in that 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.
  • Dispersions which are preferably used according to the invention are notable for the fact 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 and in particular in less than Dissolve for 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.
  • the agents packaged by the method according to the invention are preferably washing or cleaning agents, in particular washing agents, dishwashing agents or surface cleaning agents.
  • the group of detergents includes in particular universal detergents, color detergents, mild detergents, fabric softeners or ironing aids.
  • the group of dishwashing detergents includes machine dishwashing detergents and machine rinse aids as well as manual dishwashing detergents.
  • Surface cleaning agents include decalcifying agents, agents for disinfecting or sterilizing surfaces or objects, and agents for cleaning metal or glass surfaces.
  • These agents preferably contain one or more other usual constituents of detergents and cleaning agents, preferably from the group of builders, surfactants, polymers, bleaching agents, bleach activators, enzymes, dyes, fragrances, electrolytes, pH regulators, perfume carriers, fluorescent agents, hydrotopes, foam inhibitors , Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, anti-phobic and impregnating agents and anti-slip agents, swelling and anti-abrasion agents, swelling and anti-retarding agents, swelling and anti-retarding agents, swelling and anti-spattering agents, swelling and anti-retarding agents, swelling and anti-retardants, These substances will be described in more detail below. builders, surfactants, polymers, bleaching agents, bleach activators, enzymes, dyes, fragrances,
  • the builders in particular include the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates
  • Suitable crystalline, layered sodium silicates have the general formula NaMS ⁇ x 0 2x + 1 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 sheet silicates of the formula given are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 yH 2 0 are preferred
  • Amorphous sodium silicates with a module Na 2 0 S ⁇ 0 2 from 1 2 to 1 3.3, preferably from 1 2 to 1 2.8 and in particular from 1 2 to 1 2.6, which are loosely delayed and have secondary washing properties, can also be used Compared to conventional amorphous sodium silicates, this can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying. In the context of this invention, 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.However, it can very well lead to particularly good builder properties if the silicate particles in electron diffraction phenomena This results in blurred or even sharp diffraction maxima.This is to be interpreted as meaning that the products have microcrystalline regions of the size 10 to a few hundred nm, with values up to max. 50 nm and in particular up to max. 20 nm being preferred Compared to the conventional water glasses, particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates
  • these detergents preferably contain at least one crystalline layered silicate of the general formula NaMS ⁇ x 0 2x + 1 y H 2 0, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, is preferably from 1.9 to 4 and y is a number from 0 to 33.
  • the crystalline layered silicates of the formula NaMSi x O ⁇ - ⁇ y H 2 0 are for example from Clanant GmbH (Germany) under the trade name Na- SKS sold, e.g. Na-SKS-1 (Na 2 Si22 ⁇ 45 xH 2 0, Kenyait), Na-
  • crystalline sheet silicates of the formula (I) in which x is 2 are particularly suitable.
  • Na-SKS-5 ⁇ -Na 2 Si 2 20 5
  • Na-SKS- are particularly suitable.
  • these detergents contain, in the context of the present application, a proportion by weight of the crystalline layered silicate of the formula NaMS ⁇ x 0 2x + 1 y H 2 0 of 0.1 to 20% by weight, preferably of 2 to 15% by weight and in particular from 0.4 to 10% by weight, in each case based on the total weight of these agents. It is particularly preferred if such automatic dishwashing agents have a total silicate content below 7% by weight, preferably below 6% by weight.
  • this silicate preferably being based on the total weight of the silicate contained at least 70% by weight, preferably at least 80% by weight and in particular at least 90% by weight, is silicate of the general formula NaMS ⁇ x 0 2x + 1 y H 2 0
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • Zeolite MAP® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are also commercial obtainable and preferably used in the context of the present invention is, for example, a co-installation of zeolite X and zeolite A (approx.
  • zeolite X 80% by weight zeolite X, which is sold by CONDEA Augusta S p A under the brand name VEGOBOND AX ® and by the formula nNa 2 0 (1-n) K 2 0 Al 2 0 3 (2 - 2.5) S ⁇ 0 2 (3.5 - 5.5) H 2 0
  • the zeolite can be used both as a builder in a granular compound and as a kind of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have a medium one Particle size 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.
  • the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the summary name 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.
  • Suitable phosphates are, for example, sodium dihydrogen phosphate, NaH 2 PO, in the form of the dihydrate (density 1.91, preferably “3 , melting point 60 °) or in the form of the monohydrate (density 2.04, preferably “ 3 ), the disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 4 , which is anhydrous or with 2 mol. (Density 2.066 like “3 , water loss at 95 °), 7 mol. (Density 1, 68 like " 3 , melting point 48 ° with loss of 5 H 2 0) and 12 Mol.
  • Water decahydrate (corresponding to 19- 20% P 2 0 5 ) and in anhydrous form (corresponding to 39-40% P 2 0 5 )
  • trisodium phosphate tertiary sodium phosphate
  • Na 3 P0 4 trisodium phosphate
  • a further preferred phosphate is tripotassium phosphate (tertiary or tri-base potassium phosphate), K 3 P0 4.
  • Tetrasodium diphosphate is also preferred (Sodium pyrophosphate), Na 4 P 2 0 7 , which i n anhydrous form (density 2.534 "3 , melting point 988 °, also given 880 °) and as decahydrate (density 1, 815-1, 836 like " 3 , melting point 94 ° with loss of water), and the corresponding potassium salt potassium diphosphate (potassium pyrophosphate ), h P ⁇ O / .
  • Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graamsches salt, Kurrolsches and Maddrellsches salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentanate triphosphate Na 5 P 3 O 0 (sodium polyphosphate)
  • sodium polyphosphate sodium polyphosphate
  • the corresponding potassium salt, pentapotassium phosphate, K 5 P 3 O 10 potassium tripolyphosphate
  • the potassium polyphosphates are widely used in the detergent and cleaning agent industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These are formed, for example, when hydrolysing sodium metaphosphate with KOH
  • sodium tripolyphosphate potassium tripolyphosphate or mixtures of these two
  • mixtures of sodium tripolyphosphate and sodium potassium polyphosphate or mixtures of potassium tripolyphosphate and sodium potassium polyphosphate or mixtures of sodium tripolyphosphate phosphate and potassium phosphate phosphate can be used
  • phosphates are used as washing or cleaning-active substances in washing or cleaning agents
  • preferred agents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium tin phosphate (sodium or potassium tripolyphosphate), in Amounts from 5 to 80% by weight, preferably from 15 to 75% by weight and in particular from 20 to 70% by weight, in each case based on the weight of the washing or cleaning agent
  • potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1 1, preferably more than 2 1, preferably more than 5 1, particularly preferably more than 10 1 and in particular more than 20 1. It is particularly preferred to use exclusively potassium tripolyphosphate without admixtures use other phosphates
  • alkali carriers Alkahmetal hydroxides, alkahmetal carbonates, alkahmetal bicarbonates, alkahmetalsesquicarbonates, the alkali silicates mentioned, alkali metasilicate, and mixtures of the aforementioned substances, for example, are alkali carriers a builder system containing a mixture of tripolyphosphate and sodium carbonate Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disodium because of their low chemical compatibility with the other ingredients of washing or cleaning agents compared to other builder substances
  • Alkali metal hydroxides preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4% by weight and in particular below 2% by weight, in each case based on the total weight of the washing or detergent. Agents which contain less than 0.5% by weight and in particular no alkali metal hydroxides, based on their total weight, are particularly preferred.
  • Organic cobuilders include, 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), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures 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 value 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, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 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 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the (co) polymeric polycarboxylate content of washing or cleaning agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • 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 ,
  • copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Ethylenediamine-N, N'-disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of neutral reacting sodium salts, e.g.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • anionic, cationic and amphoteric surfactants are also included in the group of surfactants.
  • 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 radical is branched linearly or preferably in the 2-position methyl may 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 . 1 -alcohols with 3 EO or 4 EO, C 9-11 -alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 . 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 alcohol with 3 EO and C 12 . 18 alcohol with 5 EO.
  • the 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.
  • 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.
  • 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.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • 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
  • 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 oxyalkyl radical having 1 to 8 carbon atoms
  • C 1-4 -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 propylated Derivatives of this remainder.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the cleaning agents according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
  • 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 radical 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, C 9 .n alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 -alcohol with 3 EO and C 12 -i 8 -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 include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants which have a melting point above room temperature are particularly preferred, nonionic surfactants having a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43.3 ° C, are particularly preferred.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 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 alkoxylated nonionic surfactants, in particular 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 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted.
  • non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms, preferably a C 18 - alcohol and at least 12 moles, at least preferably 15 mol and in particular at least 20 moles of ethylene oxide won.
  • the so-called “narrow rank ethoxylates" are particularly preferred.
  • ethoxylated nonionic surfactants which are derived from C 6 . 2 o-monohydroxyalkanols or C 6 . 20 alkylphenols or C 16 . 2 o-fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide were obtained per mole of alcohol.
  • 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 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass 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.
  • Preferred dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Make up 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 inverse 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 copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • the nonionic surfactant of the formula (II) In detergents or cleaning agents, preferably in dishwashing detergents, the nonionic surfactant of the formula (II)
  • R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.
  • 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 5. 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 18 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 15.
  • each R 3 in the above formula can be different if x> 2.
  • the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 represents H and x assumes values from 6 to 15.
  • R 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 5, preferably with surfactants of the type
  • x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • 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.
  • automatic dishwashing agents according to the invention are preferred which contain surfactants of the general formula III as nonionic surfactant (s)
  • 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 III can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in formula III above 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.
  • preferred dishwasher detergents according to the invention are those in which R 1 in formula III for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up 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 automatic dishwashing 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 group having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used with particular preference according to the invention.
  • nonionic surfactants are the end group-capped poly (oxyalkylated) nonionic surfactants of the formula (IV)
  • R 1 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
  • R 2 represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 Carbon atoms, which preferably have between 1 and 5 hydroxyl groups and are preferably further functionalized with an ether group
  • R 3 is 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 40.
  • R 3 is H.
  • R 1 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms
  • R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.
  • end group-capped poly (oxyalkylated) nonionic surfactants are preferred which, according to the formula (VI) R 0 [CH 2 CH 2 0] x CH 2 CH (OH) R 2 (VI)
  • R 1 which represents linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 have up to 30 carbon atoms R 2 , which is a monohydroxyher intermediate group -CH 2 CH (OH) - adjacent.
  • R 2 which is a monohydroxyher intermediate group -CH 2 CH (OH) - adjacent.
  • x stands for values between 1 and 40.
  • Such end-capped poly (oxyalkylated) nonionic surfactants can be obtained, for example, by reacting a terminal epoxide of the formula R 2 CH ( ⁇ ) CH 2 with an ethoxylated alcohol of the formula R 1 0 [CH 2 CH 2 0] x-1 CH 2 CH 2 OH obtained.
  • the stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-mentioned nonionic surfactants represent statistical mean values which can be an integer or a fraction 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.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C 9 . 13- Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as for example from C 12 . 18 -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 alcohols such as 2-methyl-branched C 9 n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 .
  • 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 . 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which differ derive ethoxylated fatty alcohols with a narrow homolog distribution, particularly preferred. It is also possible to use alk (en) yl succinic acid with preferably 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • anionic surfactants are part of machine dishwashing detergents, their content, based on the total weight of the detergents, is preferably less than 4% by weight, preferably less than 2% by weight and very particularly preferably less than 1% by weight. Automatic dishwashing detergents that do not contain anionic surfactants are particularly preferred.
  • cationic and / or amphoteric surfactants can also be used.
  • cationic compounds of the formulas VII, VIII or IX can be used as cationic active substances:
  • the content of cationic and / or amphoteric surfactants is preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. %. Automatic dishwashing detergents that do not contain cationic or amphoteric surfactants are particularly preferred.
  • the group of polymers includes in particular the wash- or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the rinse aid polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can also be used in washing or cleaning agents.
  • Polymers effective as softeners are, for example, the polymers containing sulfonic acid groups, which are used with particular preference.
  • Copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers can be used particularly preferably as polymers containing sulphonic acid groups.
  • 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 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Preferred among these monomers are those of the formulas Xla, Xlb and / or Xlc,
  • 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).
  • copolymers are made of
  • 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,
  • copolymers consist of i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers of the formulas Xla, Xlb and / or Xlc containing sulfonic acid groups:
  • the copolymers can contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • copolymers which have structural units of the formula XII are preferred.
  • polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups.
  • the sulfonic acid group is copolymerized
  • Acrylic acid derivative with methacrylic acid leads to another polymer, the use of which is also preferred.
  • the corresponding copolymers contain the structural units of the formula XIII
  • 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 changed.
  • Copolymers are those which have structural units of the formula XIV
  • those copolymers are preferred which have structural units of the formulas XII and / or XIII and / or XIV and / or XV and / or XVI and / or XVII
  • the sulfonic acid groups in the polymers can be wholly or partly in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
  • metal ions preferably alkali metal ions and in particular by sodium ions.
  • the use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention is preferably 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer, in the case of copolymers which contain only monomers from groups i) and ii) from group i) and 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,
  • the molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred detergent or cleaning agent compositions 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 15,000 gmol '1 .
  • amphoteric or cationic polymers continue to be used. These particularly preferred polymers are characterized in that they have at least one positive charge. Such polymers are preferably water-soluble or water-dispersible, that is to say they have a solubility in water at 25 ° C. above 10 mg / ml.
  • Cationic or amphoteric polymers particularly preferably contain at least one ethylenically unsaturated monomer unit of the general formula
  • R 1 to R 4 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, a heteroatomic group with at least one positively charged group, a quaternized nitrogen atom or at least one amine group with a positive charge in the pH range between 2 and 11 or for -COOH or -COOR 5 , where R 5 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • 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.
  • amphoteric polymers contain, as monomer units, derivatives of diallylamine, in particular dimethyldiallylammonium salt and / or methacrylamidopropyl (trimethyl) ammonium salt, preferably in the form of the chloride, bromide, iodide, hydroxide, phosphate, sulfate, hydrosulfate, ethyl sulffasts, methyl sulfate, mesylate, tosylate, formate or acetates in combination with monomer units from the group of ethylenically unsaturated carboxylic acids.
  • Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H 2 0 2 in water.
  • Further useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) 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, ⁇ -
  • Phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-
  • Chlorine or bromine-releasing substances can also be used as bleaching agents. Suitable materials that release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • Bleach activators are used in detergents or cleaning agents, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 ° C and below.
  • 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 tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, 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 triacetyloxy and 2,5-diacetyloxy and 2,5-glycolacetyl, ethylene glycol 2,5-dihydrofuran.
  • 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 nitriles of the formula
  • R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2 .
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , - CH 2 -CH 3 , -CH 2 -CH 2 - CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2
  • bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids with 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-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetine, Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulf
  • bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as 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.
  • bleach activators from the group of polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyloxy- or isononosulfonates, are preferred.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide
  • acylated phenolsulfonates in particular n-nonanoyloxy- or isononosulfonates
  • n- or iso-NOBS n- or iso-NOBS
  • n-methyl-morpholinium-acetonitrile-methyl sulfate MMA
  • up to 10% by weight in particular 0.1% by weight to 8% by weight, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing agents used.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, the manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of the bleach activator-containing agents. But in special cases, more bleach activator can be used.
  • Glass corrosion inhibitors prevent the appearance of cloudiness, streaks and scratches but also the iridescence of the glass surface of machine-cleaned glasses.
  • Preferred glass corrosion inhibitors come from the group of magnesium and / or zinc salts and / or magnesium and / or zinc complexes.
  • a preferred class of compounds that can be used to prevent glass corrosion are insoluble zinc salts.
  • Insoluble zinc salts in the sense of this preferred embodiment are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20 ° C.
  • Examples of insoluble zinc salts which are particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn 2 (OH) 2 C0 3 ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn 3 (P0 4 ) 2 ), and zinc pyrophosphate (Zn 2 (P 2 0 7 )).
  • the zinc compounds mentioned are preferably used in amounts which have a zinc ion content of between 0.02 and 10% by weight, preferably between 0.1 and 5.0% by weight and in particular between 0.2 and 1.0 % By weight, based on the total agents containing glass corrosion inhibitor.
  • the exact content of the zinc salt or zinc salts in the agents naturally depends on the type of zinc salts - the less soluble the zinc salt used, the higher its concentration in the agents.
  • the particle size of the salts is a criterion to be observed so that the salts do not adhere to glassware or machine parts. Means are preferred in which the insoluble zinc salts have a particle size below 1.7 millimeters.
  • the insoluble zinc salt preferably has an average particle size which is significantly below this value in order to further minimize the risk of insoluble residues, for example an average particle size of less than 250 ⁇ m. This, in turn, is all the more the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing particle size.
  • the average particle size is preferably below 100 ⁇ m. For even more poorly soluble salts, it can be even lower; For example, average particle sizes below 100 ⁇ m are preferred for the very poorly soluble zinc oxide.
  • Another preferred class of compounds are magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid. These have the effect that even with repeated use the surfaces of glassware do not change corrosively, in particular no clouding, streaks or scratches but also no iridescence of the glass surfaces.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of the unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or polymeric carboxylic acids are preferred.
  • the spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such Salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
  • the first group of zinc salts include, for example, zinc citrate, zinc oleate and zinc stearate, and the group of soluble salts
  • Zinc salts include, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate.
  • At least one zinc salt of an organic carboxylic acid particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and / or zinc citrate, as the glass corrosion inhibitor.
  • Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
  • the zinc salt content of cleaning agents is preferably between 0.1 to 5% by weight, preferably between 0.2 to 4% by weight and in particular between 0.4 to 3% by weight, or the content of zinc in oxidized form (calculated as Zn 2+ ) between 0.01 to 1% by weight, preferably between 0.02 to 0.5% by weight and in particular between 0.04 to 0.2% by weight. -%, each based on the total weight of the agent containing glass corrosion inhibitor.
  • Corrosion inhibitors serve to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area 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.
  • 3-amino-5-alkyl-1, 2,4-triazoles which are preferably used according to the invention: 5, -propyl, butyl, pentyl, heptyl, octyl, nonyl -, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-Tolyl-, - (4-tert.butylphenyl) -, - (4- Methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, -3-amino-1, 2,4-triazole.
  • the alkylamino-1, 2,4-triazoles or their physiologically tolerable salts are used in a concentration of 0.001 to 10% by weight, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04 wt .-% used.
  • Preferred acids for the salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid.
  • 5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-versatic-10-acid-alkyl-3-amino-1, 2,4-triazoles and mixtures are very particularly effective of these substances.
  • detergent formulations often contain agents containing active chlorine, which can significantly reduce the corroding of the silver surface.
  • 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 found Use.
  • transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • redox-active substances can be used. These substances are preferably inorganic redox-active substances from the group of the manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, the metals preferably in one of the oxidation states II, III , IV, V or VI are present.
  • the metal salts or metal complexes used are said to be at least partially soluble in water.
  • the counterions suitable for salt formation include all customary one, two or three times negatively charged inorganic anions, e.g. B. oxide, sulfate, nitrate, fluoride, but also organic anions such. B. stearate.
  • Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and, if appropriate, additionally one or more of the abovementioned.
  • Anions exist.
  • the central atom is one of the above Metals in one of the above Oxidation states.
  • the ligands are neutral molecules or anions that are monodentate or multidentate; the term "ligand" in the sense of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail.
  • Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
  • metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1- diphosphonate]
  • the metal salts and / or metal complexes are selected from the group MnS0, Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1-diphosphonate], V 2 0 5 , V 0 4 , V0 2 , TiOS0 4 , K 2 TiF 6 , K 2 ZrF 6 , CoS0 4 , Co (N0 3 ) 2 , Ce (N0 3 ) 3 and mixtures thereof, so that preferred Automatic dishwashing agents according to the invention are characterized in that the metal salts and / or metal complexes are selected from the group MnS0, Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1, 1-diphosphonate], V 2 0 5 ,
  • metal salts or metal complexes are generally commercially available substances which can be used in the agents according to the invention for the purpose of protecting against silver corrosion without prior cleaning. For example, that's from S0 3 production
  • the inorganic redox-active substances are preferably coated, i.e. completely covered with a waterproof material that is easily soluble at cleaning temperatures to prevent their premature decomposition or oxidation during storage.
  • a waterproof material that is easily soluble at cleaning temperatures to prevent their premature decomposition or oxidation during storage.
  • Preferred coating materials which are applied by known processes are paraffins, micro waxes, waxes of natural origin such as carnauba wax, candella wax, beeswax, higher-melting alcohols such as hexadecanol, soaps or fatty acids.
  • the coating material which is solid at room temperature, is applied in a molten state to the material to be coated, e.g.
  • the melting point must be selected so that the coating material easily dissolves or melts quickly during the silver treatment.
  • the melting point should ideally be in the range between 45 ° C and 65 ° C and preferably in the range 50 ° C to 60 ° C.
  • the metal salts and / or metal complexes mentioned are contained in cleaning agents, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, in each case based on the total agent containing corrosion inhibitor.
  • Enzymes can be used to increase the washing or cleaning performance of washing or cleaning agents. 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 I x 10 ⁇ to 5 percent by weight based on active protein. The Protein concentration can be determined using known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferred.
  • subtilisins BPN 'and Carlsberg the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lent ⁇ s, subtilisin DY and the enzymes thermitase, proteinase K and the enzyme 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 5483.
  • 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 B. amyloliquefaciens or from B. stearothermophilus and their further developments which are improved for use in detergents and cleaning agents.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST.
  • this oc-amylase is available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ® .
  • Amyloliquefaciens is sold by Novozymes under the name BAN ® , and derived variants of the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ® , also from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from ß. to highlight agaradherens (DSM 9948).
  • CCTase cyclodextrin glucanotransferase
  • DSM 9948 agaradherens
  • Another commercial product is the Amylase-LT ® .
  • Lipases or cutinases can furthermore be used according to the invention, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors.
  • suitable precursors 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 can be used, which were originally isolated 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.
  • Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA , The from ß. subtilis .beta.-glucanase obtained is available under the name Cereflo ® from Novozymes.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenol oxidases) can be used according to the invention.
  • 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 originate, for example, either originally from microorganisms, for example of the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced according to known biotechnological processes by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the enzymes in question are preferably purified by methods which are established per se, 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.
  • the enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, 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.
  • Capsules of this type are applied by methods known per se, 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 can be protected against damage, such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • damage such as inactivation, denaturation or decay, for example by physical influences, oxidation or proteolytic cleavage, especially during storage.
  • 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-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters.
  • 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-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, among other things, against physical influences or pH fluctuations.
  • Polymers containing polyamine N-oxide act as enzyme stabilizers.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance.
  • Cross-linked N-containing compounds also act as enzyme stabilizers.
  • a sulfur-containing reducing agent is, for example, sodium sulfite.
  • Combinations of stabilizers are preferably used, for example 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 effect of peptide-aldehyde stabilizers is increased by the combination with boric acid and / or boric acid derivatives and polyols and is further enhanced by the additional use of divalent cations, such as calcium ions.
  • One or more enzymes and / or enzyme preparations preferably solid protease preparations and / or amylase preparations, in amounts of 0.1 to 5% by weight are preferred. preferably from 0.2 to 4.5 and in particular from 0.4 to 4% by weight, based in each case on the total enzyme-containing agent.
  • disintegration aids so-called tablet disintegrants
  • 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.
  • Disintegration aids are preferably used in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, based in each case on the total weight of the agent containing disintegration aids.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent compositions contain such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, from a formal point of view, 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 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.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as another 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.
  • Subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • Disintegration aids preferred in the context of the present invention preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, are present in the disintegrant-containing agents in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight. and in particular from 4 to 6% by weight, in each case based on the total weight of the disintegrant-containing composition.
  • gas-developing effervescent systems can also preferably be used as tablet disintegration aids.
  • the gas-developing shower system can consist of a single substance which releases a gas when it comes into contact with water.
  • magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water.
  • the gas-releasing bubble system itself consists of at least two components that react with one another to form gas. While here a variety of systems is conceivable and executable, such as nitrogen, oxygen or Release hydrogen, the bubbling system used in the washing and cleaning agent compositions according to the invention can be selected on the basis of both economic and ecological aspects.
  • Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
  • the alkali metal carbonates or bicarbonates 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.
  • the preferred shower system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight. -% of an acidifying agent, based in each case on the total weight of the agent.
  • Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent.
  • the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
  • acidifying agents in the effervescent system preference is given to acidifying agents in the effervescent system from the group of the organic di-, tri- and oligocarboxylic acids or mixtures.
  • perfume compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexyl benzylatepylpropionate, stally.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g.
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example 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.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, and no pronounced substantivity to the substrates to be treated with the dye-containing agents, such as, for example, glass, ceramics, plastic dishes or textiles not to stain them.
  • the solvents include, in particular, the non-aqueous organic solvents, with particular preference given to using non-aqueous solvents from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, 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 ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propyl -3- methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.
  • Suitable foam inhibitors are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable anti-deposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as Methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid and / or known from the prior art of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • the sulfonated derivatives of the phthalic acid and terephthalic acid polymers are particularly preferred.
  • Optical brighteners can be added to detergents or cleaning agents in order to eliminate graying and yellowing of textiles treated with these agents. These substances absorb on the fiber 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 pure with the yellow tone of the grayed or yellowed laundry White results.
  • Suitable compounds originate from the substance classes of the 4,4 '- diamino-2,2'-stilbenedisulfonic (flavonic), 4,4'-biphenylene -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole , Benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.
  • flavonic 4,4 '- diamino-2,2'-stilbenedisulfonic
  • 4,4'-biphenylene -Distyryl Methylumbelliferone
  • coumarins dihydroquinolinones
  • 1, 3-diaryl pyrazolines 1, 3-diaryl pyrazolines
  • naphthalimides benzoxazole
  • Benzisoxazole and benzimidazole systems as well as the
  • Graying inhibitors in textile cleaning agents have the task of keeping the dirt detached from the fibers 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 in the particulate agents are cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.
  • Antimicrobial agents are used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides, etc. Important substances from these groups are for example benzalkonium chlorides, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, it being possible to dispense with the use of these agents entirely.
  • the formulations can also have fabric-softening clay minerals, which can be selected from a large number of minerals, in particular the layered silicates.
  • the smectite group has proven to be advantageous.
  • the term smectite includes both clays in which aluminum oxide is present in a silicate grid and clays in which magnesium oxide occur in a silicate grid.
  • Typical smectites have the following general formula: Al 2 (Si 2 0 5 ) 2 (OH) 2 « nH 2 0 and compounds with the following formula Mg 3 (Si 2 0 5 ) 2 (OH) 2 » nH 2 0. Smectites are usually in an extensive three-layer structure.
  • suitable smectites include those selected from the class of montmorillonites, hectorites, volchonskites, nontronites, saponites and sauconites, especially those with alkali or alkaline earth metal ions in the crystal lattice structure.
  • Preferred is a three-layer, expandable aluminum silicate, which is characterized by a dioctahedral crystal lattice, whereas the extensive three-layer magnesium silicate structure has a trioctahedral crystal lattice.
  • the clay minerals contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, magnesium ions and the like. The clay minerals are usually distinguished on the basis of the cations that are predominantly or exclusively absorbed.
  • a sodium bentonot is such a clay mineral in which sodium is predominantly present as the absorbed cation.
  • Such absorbed cations can carry out exchange reactions with other cations in aqueous solutions.
  • a typical exchange reaction involving a smectite type is the following:
  • Smectites such as, for example, nontonite have an ion exchange capacity of approximately 70 meq / 100 g
  • montmorillonites which have an exchange capacity of above 70 meq / 100 g
  • Particularly preferred clay minerals in the context of the present invention are therefore expanded three-layer smectite types with an ion exchange capacity of at least 50 meq / 100 g.
  • Organophilic clay minerals can also be used in the present invention.
  • Such hydrophobically modified clay minerals in which inorganic metal ions are exchanged for organic ions by the previously described exchange process are also preferred.
  • the modified clay minerals are very miscible with organic solvents and have the property of storing organic solvents between the layers.
  • Suitable examples of organophilic clay minerals are Benton SD-1, SD-2 and SD-3 from Rheox.
  • Bentonites have proven to be particularly preferred. Bentonites are contaminated clays that are formed by weathering volcanic tuffs. Due to their high montmorillonite content, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonites according to the intended use. Bentonites are a common clay component in tropical soils and are used as sodium bentonite e.g. mined in Wyoming / USA. Sodium bentonite has the most favorable application properties (swellability), so that its use is preferred in the context of the present invention. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca bentonites are artificially converted into the more swellable Na bentonites by exchanging Ca for Na.
  • montmorillonites are clay minerals belonging to the phyllosilicates and here to the dioctahedral smectites, which crystallize monoclinic-pseudohexagonal. Montmorillonite predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not plastic, by the general formulas
  • AI 2 [(OH) 2 / Si 4 O 10 ] -nH 2 O or AI 2 0 3 -4Si0 2 H 2 0-nH 2 0 or AI 2 [(OH) 2 / Si 4 O 10 ] (at 150 ° dried)
  • Montmorillonites have a three-layer structure, which consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral layer.
  • the layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, ammonium compounds, hydroxyaluminosilicate ions, etc.
  • Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity. So AI can be exchanged for Mg, Fe 2+ , Fe 3+ , Zn, Cr, Cu and other ions. As a result of such Substitution results in a negative charge on the layers, which is balanced by other cations, especially Na + and Ca 2+ .
  • Calcium or magnesium bentonites are usually non-swellable and usually less effective plasticizers. However, it is advantageous to combine non-swellable bentonites with carrier materials, such as, for example, polyethylene glycol, in order to achieve a considerably improved soft feel of the textiles treated with them. Calcium or magnesium bentonites which are used in the presence of a sodium source, such as NaOH or NaC0 3 , are also advantageous.
  • the clay is a treated montmorillonite-containing clay which has the following properties:
  • a clay containing montmorillonite is particularly preferred, which is obtained by the following process steps: a) drying the clay to a water content of 25-35% by weight, b) extruding the dried material into a paste; c) drying the paste to a moisture content of 10-14% by weight and d) calcining at a temperature between 120 and 250 ° C.
  • the chemical composition of the bentonite to be used as the starting material is preferably the following:
  • a detailed description of the process for the treatment of bentonite can be found in WO 00/03959, the disclosure of which is fully incorporated in this application.
  • the crystalline structure of montmorillonite is more or less resistant to acid treatment.
  • Acid treatment in the context of the invention means that a sample of the clay (for example 1 g / l) in a 1N HCl solution is exposed to a temperature of 80 ° C. for 15 hours. It must be mentioned that most clays can be destroyed by acid treatment with, for example, fluoride. In the context of the present invention, however, acid treatment means HCI treatment.
  • Montmorillonites (magnesium saturated / air dried) usually have a maximum diffraction distance of 14-15 in the 001 plane when treated with X-rays. This maximum diffraction distance usually does not change by treating the clay with HCI.
  • acid-sensitive montmorillonites are preferred, for example montmorillonites, the crystalline structure of which is destroyed when they are treated with HCl.
  • montmorillonites the crystalline structure of which is destroyed when they are treated with HCl.
  • the use of such clay minerals has a softening effect and also ensures better dispersibility in the aqueous wash liquor or the aqueous textile treatment liquid.
  • the destruction of the crystalline structure can be determined by measuring the diffraction distance, so that the maximum diffraction distance to be expected for crystalline montmorilonites in the 001 plane of 14-15 does not appear for the destroyed montmorillonites.
  • acid sensitivity is related to an increased exchange of aluminum for magnesium in the octahedral layer of the montmorillonite clay.
  • the above-mentioned acid-sensitive montmorillonites have the advantage that they enable a reduced tendency to gel and an improved dispersibility in the wash liquor. In addition, it has been observed that such clay minerals produce an improved soft feel.

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Abstract

L'invention concerne un procédé permettant de produire un agent emballé, au cours duquel une feuille est déformée par moulage répété dans des cavités de formage profond présentant différents volumes. Le procédé selon l'invention est conçu pour produire des emballages comportant plusieurs récipients de réception.
PCT/EP2004/009022 2003-08-21 2004-08-12 Procede de production d'agents de lavage ou de nettoyage Ceased WO2005021381A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2003138369 DE10338369A1 (de) 2003-08-21 2003-08-21 Verfahren zur Herstellung von Wasch- oder Reinigungsmitteln
DE10338369.7 2003-08-21

Publications (1)

Publication Number Publication Date
WO2005021381A1 true WO2005021381A1 (fr) 2005-03-10

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2004/009022 Ceased WO2005021381A1 (fr) 2003-08-21 2004-08-12 Procede de production d'agents de lavage ou de nettoyage

Country Status (2)

Country Link
DE (1) DE10338369A1 (fr)
WO (1) WO2005021381A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1120119B (de) * 1955-11-03 1961-12-21 Max Braun Fa Verfahren und Vorrichtung zum Herstellen eines offenen Hohlkoerpers nach Art einer Schale aus einer Folie oder Platte aus organischem thermoplastischem Kunststoff nach der Methode des Vakuum-Tiefziehens
US5224601A (en) * 1990-07-18 1993-07-06 Rhone-Poulenc Ag Company Water soluble package
WO2002085738A1 (fr) * 2001-04-20 2002-10-31 Reckitt Benckiser (Uk) Limited Recipients solubles dans l'eau contenant au moins deux compartiments
US20030077005A1 (en) * 2001-10-08 2003-04-24 The Procter & Gamble Company Process for production of pouches
WO2004080810A1 (fr) * 2003-03-13 2004-09-23 Henkel Kommanditgesellschaft Auf Aktien Detergent ou nettoyant sous forme de portions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2361688A (en) * 2000-04-28 2001-10-31 Procter & Gamble Multi-compartment water soluble pouch for detergents

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1120119B (de) * 1955-11-03 1961-12-21 Max Braun Fa Verfahren und Vorrichtung zum Herstellen eines offenen Hohlkoerpers nach Art einer Schale aus einer Folie oder Platte aus organischem thermoplastischem Kunststoff nach der Methode des Vakuum-Tiefziehens
US5224601A (en) * 1990-07-18 1993-07-06 Rhone-Poulenc Ag Company Water soluble package
WO2002085738A1 (fr) * 2001-04-20 2002-10-31 Reckitt Benckiser (Uk) Limited Recipients solubles dans l'eau contenant au moins deux compartiments
US20030077005A1 (en) * 2001-10-08 2003-04-24 The Procter & Gamble Company Process for production of pouches
WO2004080810A1 (fr) * 2003-03-13 2004-09-23 Henkel Kommanditgesellschaft Auf Aktien Detergent ou nettoyant sous forme de portions

Also Published As

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