EP1740689B1 - Procedes pour la production de detergents et de nettoyants - Google Patents

Procedes pour la production de detergents et de nettoyants Download PDF

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Publication number
EP1740689B1
EP1740689B1 EP05733723.0A EP05733723A EP1740689B1 EP 1740689 B1 EP1740689 B1 EP 1740689B1 EP 05733723 A EP05733723 A EP 05733723A EP 1740689 B1 EP1740689 B1 EP 1740689B1
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EP
European Patent Office
Prior art keywords
cavity
film material
washing
cleaning
molded article
Prior art date
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EP05733723.0A
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German (de)
English (en)
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EP1740689A1 (fr
Inventor
Wolfgang Barthel
Salvatore Fileccia
Ulf Arno Timmann
Thomas Holderbaum
Sandra Behr
Dirk Gerst
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL05733723T priority Critical patent/PL1740689T3/pl
Publication of EP1740689A1 publication Critical patent/EP1740689A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets

Definitions

  • the present invention is in the field of detergents or cleaners.
  • the present invention relates to a process for the preparation of detergents or cleaners, in particular of metering units of detergents or cleaners.
  • Detergents or cleaners are now available to the consumer in a variety of forms.
  • this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions.
  • These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport.
  • the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing.
  • the corresponding means are comprehensively described in the prior art.
  • compacted detergents or cleaners also have a number of disadvantages.
  • Especially tableted supply forms are characterized by their high compression often by a delayed disintegration and thus a delayed release of their ingredients.
  • solid or liquid detergents or cleaners which have a water-soluble or water-dispersible packaging are increasingly being described in recent years. These agents are characterized as the tablets by a simplified dosage, since they can be dosed together with the outer packaging in the washing machine or dishwasher, on the other hand, but at the same time they also allow the preparation of liquid or powder detergents or cleaning agents Compared to the compact data by a better resolution and faster effectiveness.
  • the EP 1 314 654 A2 (Unilever ) a dome-shaped pouch with a receiving chamber containing a liquid.
  • EP 1 256 623 A1 Subject of the European application EP 1 256 623 A1 (Procter & Gamble) is a kit of at least two bags of different composition and optics. The bags are separate and not as a compact single product.
  • the object of the present application was to provide a process for the preparation of detergents or cleaners, which enables the joint preparation of solid and liquid or flowable detergent or cleaner compositions in separate areas of a compact dosing unit.
  • the final process product should be characterized by an attractive appearance.
  • thermoforming body is formed, which can be filled in connection.
  • a shaped body is provided.
  • Such moldings are obtainable, for example, by compaction methods such as tableting, by extrusion, such as extrudate extrusion, by injection molding or by casting.
  • moldings which are produced by tabletting or by casting are particularly preferred.
  • the moldings contain or consist of washing or cleaning-active substances or substance mixtures.
  • washing or cleaning agent tablets is carried out in a manner known to those skilled in the art by compressing particulate starting substances.
  • the premix is compressed in a so-called matrix between two punches to form a solid compressed product.
  • This process hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the tabletting is preferably carried out on so-called rotary presses.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • Preferred processes in the context of the present invention are characterized in that the pressing takes place at pressing pressures of 0.01 to 50 kNcm -2 , preferably of 0.1 to 40 kNcm 2 and in particular of 1 to 25 kNcm -2 .
  • the production of preferred casting bodies according to the invention is carried out, for example, by casting a washing or cleaning-active preparation into a mold and subsequently demolding the solidified cast body to form a (mold) shaped body.
  • a "mold” are preferably tools that have cavities that can be filled with pourable substances. Such tools may be formed, for example, in the form of individual cavities but also in the form of plates having a plurality of cavities.
  • the single cavities or cavity plates are preferably mounted on horizontally circulating conveyor belts in industrial processes which allow continuous or discontinuous transport of the cavities, for example along a number of different workstations (e.g., casting, cooling, filling, sealing, demolding, etc.).
  • the washing or cleaning active preparations are potted in the preferred process and subsequently solidified to a dimensionally stable body.
  • solidification characterizes any curing mechanism which delivers a body which is solid at room temperature from a deformable, preferably flowable mixture or such substance or mass, without the need for pressing or compacting forces.
  • Solidification in the context of the present invention is therefore, for example, the curing of melts of solid substances at room temperature by cooling.
  • Solidification processes in the context of the present application are also the curing of formable materials by time-delayed water binding, by evaporation of solvents, by chemical reaction, crystallization, etc. and the reactive curing of flowable powder mixtures to form stable hollow bodies.
  • dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers.
  • the dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers.
  • the dispersant or at least 50 wt .-% of the polymer mixture of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidone, vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.
  • dispersions which contain, as dispersants, a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, the weight fraction of the poly (ethylene) glycol being based on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight.
  • the dispersions in which the dispersant contains more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very particularly preferably more than 98% by weight.
  • Dispersing agents which also contain poly (propylene) glycol in addition to poly (ethylene) glycol preferably have a ratio of the weight proportions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1 and in particular between 7: 1 and 2: 1 on.
  • nonionic surfactants which are used alone, but particularly preferably in combination with a nonionic polymer.
  • Detailed information on the usable nonionic surfactants can be found in the description of washing or cleaning-active substances below.
  • Dispersions preferably used as detergent tablets according to the invention are characterized in that they are dissolved in water (40 ° C.) in less than 9 minutes, preferably less than 7 minutes, preferably less than 6 minutes, more preferably less than 5 minutes and in particular dissolve in less than 4 minutes.
  • 20 g of the dispersion are introduced into the interior of a dishwashing machine (Miele G 646 PLUS).
  • the main rinse of a standard rinse program (45 ° C) is started.
  • the determination of the solubility is carried out by the measurement of the conductivity, which is recorded via a conductivity sensor.
  • the dissolution process is completed when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau.
  • the conductivity measurement starts with the replacement of the circulation pump in the main wash cycle.
  • the amount of water used is 5 liters.
  • the moldings produced, for example, by tableting or casting may take any geometric form, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , pentagonal, octagonal and octagonal prismatic as well as rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped bodies according to the invention have corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and bevelled ("touched”) edges is preferred.
  • the moldings can also be produced in multiple phases.
  • two-layered or three-layered shaped bodies, in particular two-layered or three-layered tablets, have proven particularly useful here.
  • tablets and / or compacts for example roll compacts, and / or extrudates, and / or injection-molded bodies and / or casting bodies and / or molded articles composed of these shaped bodies are used in step a) of the process according to the invention.
  • the shaped body may have a coating.
  • the coating can cover both the entire molded body and individual areas of the molded body.
  • moldings which have a coating on their entire surface.
  • Suitable coating materials are all materials known to the person skilled in the art.
  • Preferred coating materials in the context of the present application are the water-soluble or water-insoluble natural or synthetic organic polymers, water-soluble or water-dispersible organic polymers being particularly preferred.
  • Also suitable for the coating of the moldings are the salts of organic or inorganic acids. Of the group of organic acids, in particular the salts of mono-, di-, tri, tetra- or polycarboxylic acids are preferred.
  • Preferred methods according to the invention are accordingly characterized in that the shaped body has a coating.
  • cavity in the context of the present invention, both troughs and through the molding through holes or holes, which connect two sides of the molding, preferably opposite sides of the molding, for example, the bottom and roof surface of the molding together.
  • the shape of the cavity which is preferably a well, may be chosen freely, with tablets being preferred in which at least one well is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral , conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral shapes.
  • Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized.
  • wells with rounded corners and edges or with rounded corners and chamfered edges are preferred.
  • the bottom surface of the trough can be flat or inclined.
  • the cavity is an opening, which connects two opposite sides of the molding together.
  • a corresponding shaped body can be referred to as a ring body.
  • the aperture areas of the aperture in the surface of this annular body may be the same size but may differ in size.
  • the shaped body with such a breakthrough corresponds to a so-called ring tablet.
  • Particularly preferred such shaped bodies are used with breakthrough, in which the opening areas of the opening on the opposite sides of the molding, based on the larger of the two opening surfaces by less than 80%, preferably less than 60%, preferably less than 40%, more preferably less than 20% and in particular differ less than 10%.
  • ring tablets are used, in which the opening areas of the aperture have the same size.
  • the cross-section of the aperture may be angular or round.
  • Cross sections with one, two, three, four, five, six or more corners can be realized, however, such shaped bodies are particularly preferred in the context of the present application, which have a breakthrough without corners, preferably a breakthrough with a round or oval cross-section.
  • a "cross section” refers to a surface which is perpendicular to a straight connecting line between the center points of the two opposite opening surfaces of the shaped body.
  • the molding may have more than one cavity. Moldings having two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or more cavities are particularly preferred in the present application. If the shaped body has more than one cavity, these cavities can be both the wells described above and the breakthroughs described above. Shaped bodies which have more than one cavity, wherein at least one of the cavities is a trough and at least one further of the cavities is a breakthrough, are particularly preferred in the context of the present application.
  • the volume of the cavity is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.
  • these cavities can be filled proportionally with a solid or liquid, washing or cleaning-active substance.
  • Such methods in which the cavity of the shaped body is partially filled with a washing or cleaning substance before applying the first sheet material in step b), are particularly preferred in the context of this application.
  • flowable washing and cleaning active preparations preferably liquid (s), in particular melts, and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or Kompaktat (s) used.
  • the cavity is filled prior to placing the first film material in step b) partially with a washing or cleaning active powder, granules or extrudate.
  • liquid in the present application denotes substances or substance mixtures as well as solutions or suspensions which are in the liquid state of matter.
  • Powder is a general term for a form of division of solids and / or mixtures obtained by comminution, that is, grinding or crushing in the mortar (pulverization), grinding in mills or as a result of atomization or freeze-drying.
  • a particularly fine division is often called atomization or micronization; the corresponding powders are called micro-powders.
  • powders have lower particle sizes below 5000 .mu.m, preferably less than 3000 .mu.m, preferably less than 1000 .mu.m, very particularly preferably between 50 and 1000 .mu.m and in particular between 100 and 800 .mu.m.
  • Powders can be compacted and agglomerated by extrusion, pressing, rolling, briquetting, pelleting and related processes.
  • Each of the methods known in the prior art for the agglomeration of particulate mixtures is in principle suitable for producing the solids contained in the agents according to the invention.
  • agglomerates used as solid (s) are, in addition to the granules, the compacts and extrudates.
  • Granules are aggregates of granules.
  • a granule (granule) is an asymmetric aggregate of powder particles.
  • Granulation methods are widely described in the art.
  • Granules can be prepared by wet granulation, by dry granulation or compaction and by melt solidification granulation.
  • the most common granulation technique is wet granulation, since this technique is subject to the fewest restrictions and leads most safely to granules with favorable properties.
  • the wet granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably carried out in mixers, fluidized beds or spray towers, said mixer can be equipped, for example, with stirring and kneading tools.
  • combinations of fluidized bed (s) and mixer (s) or combinations of different mixers can also be used for the granulation.
  • the granulation takes place Depending on the starting material and the desired product properties under the action of low to high shear forces.
  • melt solidification melting
  • aqueous, slurries spray drying
  • solid substances which are sprayed at the top of a tower in a defined droplet size, solidify in free fall or dry and on Floor of the tower incurred as granules.
  • Melt solidification is generally particularly suitable for shaping low-melting substances which are stable in the melting temperature range (eg urea, ammonium nitrate and various formulations such as enzyme concentrates, pharmaceuticals etc.), the corresponding granules are also referred to as prills.
  • Spray drying is used especially for the production of detergents or detergent ingredients.
  • extruder or perforated roll granulations in which powder mixtures optionally mixed with granulating liquid are plastically deformed during perforation by perforated disks (extrusion) or on perforated rolls.
  • the products of extruder granulation are also referred to as extrudates.
  • Builders, enzymes, bleaches, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors are particularly suitable as ingredients of the washing or cleaning-active formulations introduced into the cavities between steps a) and b).
  • Bleaches, in particular peroxygen compounds such as percarbonates or perborates, bleach activators or silver protectants, are particularly preferably introduced.
  • These ingredients are preferably filled into the cavity as part of solid washing or cleaning active preparations between steps a) and b). These ingredients are described in more detail later in the text. To avoid repetition, reference is made at this point to the comments there.
  • the volume of the substances introduced between steps a) and b) is preferably between 0.5 and 12 ml, particularly preferably between 0.5 and 8 ml, very particularly preferably between 0.5 and 6 ml and in particular between 0.5 and 4 ml.
  • the cavity of the shaped body is preferably filled between 1 and 80% by volume, preferably between 5 and 60% by volume, very particularly between 10 and 50% by volume and in particular between 20 and 50% by volume.
  • step b) of the method according to the invention a film material is placed on the molding surface over the opening of the cavity.
  • the first film material used in step b) is a water-soluble or water-dispersible film material, preferably a polymeric water-soluble or water-dispersible film material.
  • the film material in step b) comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and their mixtures.
  • PVAL polyvinyl alcohol
  • PVP polyvinylpyrrolidone
  • polyethylene oxide polyethylene oxide
  • gelatin gelatin
  • cellulose and derivatives thereof and their mixtures.
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable.
  • the water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • the coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • the film material used in the process according to the invention at least partially comprises a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and in particular 82 to 88 mol%.
  • the first film material used in the process according to the invention comprises at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight. of a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and more preferably 82 to 88 mol%.
  • Polyvinyl alcohols having a specific molecular weight range are preferably used as the film material, wherein 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 about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
  • Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
  • polyvinyl alcohols are as the film material ® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ®, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).
  • the water solubility of PVAL can be altered by post-treatment with aldehydes (acetalization) or ketones (ketalization).
  • Polyvinyl alcohols which are acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly advantageous and particularly advantageous on account of their pronounced cold water solubility.
  • To use extremely advantageous are the reaction products of PVAL and starch.
  • the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.
  • Films made of PVAL are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
  • PVP Polyvinylpyrrolidones
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • Commercially available PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous solutions.
  • Polyethylene oxides PEOX for short, are polyalkylene glycols of the general formula H- [O-CH 2 -CH 2 ] n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
  • the amino acid composition of gelatin is broadly similar to that of the collagen from which it was obtained and varies depending on its provenance.
  • film materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose, and mixtures thereof.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Starch is composed of two components of different molecular weight: from about 20 to 30% straight chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched chain amylopectin (MW about 300,000 to 2,000,000).
  • small amounts of lipids, phosphoric acid and cations are still included. While the amylose forms long, helical, entangled chains with about 300 to 1,200 glucose molecules as a result of the binding in the 1,4-position, the chain branched in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like structure with about 1,500 to 12,000 molecules of glucose.
  • starch-derivatives which are obtainable from starch by polymer-analogous reactions are also suitable for the preparation of water-soluble coatings of the detergent, detergent and cleaner portions in the context of the present invention.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But even starches in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as starch derivatives.
  • the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and ethers, and amino starches.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5,000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • HPMC hydroxypropyl methylcellulose
  • degree of substitution average number of methoxy groups per anhydroglucose unit of cellulose
  • molar substitution average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose
  • Preferred methods according to the invention are characterized in that at least one of the film materials used is transparent or translucent.
  • the film material used, for example, for deep-drawing and / or sealing is preferably transparent.
  • transparency means that the transmittance within the visible spectrum of the light (410 to 800 nm) is greater than 20%, preferably greater than 30%, more preferably greater than 40% and in particular greater than 50%.
  • a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent within the meaning of the invention.
  • Preparations made according to the invention, for the production of which transparent film material has been used, may contain a stabilizing agent.
  • Stabilizing agents in the context of the invention are materials which protect the ingredients at least partially enclosed by the film material from decomposition or deactivation by light irradiation. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
  • antioxidants are particularly suitable stabilizing agents in the context of the invention.
  • the formulations may contain antioxidants.
  • antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
  • Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic palmitate, organosulfur compounds such as the esters of 3,3'-thiodipropionic acid with C 1-18 alkanols, especially C 10-18 alkanols, metal ion deactivators capable of auto-oxidation catalyzing metal ions such as copper, to complex such as nitrilotriacetic acid and its derivatives and their mixtures.
  • Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.
  • UV absorbers can improve the light stability of the formulation ingredients.
  • Organic substances unsunscreen
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) 4-hydroxy-5- (methylpro-pyl) monosodium salt (Ciba Fast ® H), phenyl-substituted in the 3-position acrylates (cinnamic acid derivatives ), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • the biphenyl and especially stilbene derivatives which are available commercially as Tinosorb ® FD or Tinosorb ® FR available ex Ciba.
  • 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl sal
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds.
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and in addition oxides of iron, zirconium, silicon, manganese, aluminum and cerium, and mixtures thereof.
  • silicates (talc) barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments may also be surface-treated, ie hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
  • Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones.
  • micronized zinc oxide is used.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • fluorescent dyes include the 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and Benzimidazole systems and substituted by heterocycles pyrene derivatives.
  • Preferred process variants are characterized in that the film materials used in step b) of the process according to the invention have a thickness between 5 and 2000 .mu.m, preferably between 10 and 1000 .mu.m, more preferably between 15 and 500 .mu.m, very particularly preferably between 20 and 200 .mu.m and in particular between 25 and 100 microns have.
  • the films used may be single-layer or multi-layer films (laminate films). Regardless of their chemical or physical structure, the water content of the film materials is preferably below 10 wt .-%, more preferably below 7 wt .-%, most preferably below 5 wt .-% and in particular below 4 wt .-%.
  • step c) of the method according to the invention the first film material is deep-drawn into the cavity; by creating a negative pressure in the cavity of the molded body.
  • the packaging film used is conditioned before molding.
  • the packaging film is pretreated before thermoforming in step c) by heating and / or solvent application. If the film material is pretreated by the action of heat before or during the deep drawing into the cavity of the shaped body, this is preferably for this purpose 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, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C.
  • pumps are particularly preferably used for a rough vacuum water jet, remplisstechniksdampfstrahl-, Wasserring- u. Piston pumps.
  • rotary slide valves slide gate valves
  • trochoidal and sorption pumps as well as so-called Roots blowers and cryopumps.
  • Roots blowers To set a fine vacuum, rotary vane pumps, diffusion pumps, Roots blowers, positive displacement, turbomolecular, sorption, ion getter pumps (getters) are preferred.
  • the negative pressure generated is between -100 and -1013 mbar, preferably between -200 and -1013 mbar, particularly preferably between -400 and -1013 mbar and in particular between -800 and -1013 mbar.
  • the negative pressure can be generated in the cavity by different procedures.
  • the cavity is one of the breakthroughs described at the outset.
  • Ring shaped bodies or ring tablets are those shaped bodies which have two interconnected openings in their surface. These interconnected openings form a passage penetrating the body or tablet, which preferably connects two mutually opposite sides.
  • ring tablets are used in the process according to the invention for producing the washing or cleaning agent dosing units, deep drawing of the film material takes place in the opening of these ring tablets in a particularly preferred embodiment after a molding tool has been introduced into the opening of the ring tablet.
  • This mold may be inserted into the aperture before or after the first film material is placed on the mold surface over the aperture of the ring tablet.
  • the introduction of the mold can also be done simultaneously with the laying of the film material.
  • the mold is used in this process variant as a "placeholder" and reduces the void volume of the opening, in which the film material can be thermoformed. Consequently, the receiving chamber formed by the deep drawing of the foil material does not become the entire breakthrough but only the void volume remaining in the breakthrough after the insertion of the forming tool fill out.
  • the receiving chamber formed from the film material consequently fills the breakthrough only in part.
  • the method steps b) and c) in this preferred variant of the method can be carried out in the reverse order or at the same time.
  • this breakthrough partially but not completely filled.
  • Particularly preferred are those processes in which the mold between 5 and 95 vol .-%, preferably between 10 and 90 vol .-%, preferably between 15 and 85 vol .-% and in particular between 20 and 80 vol .-% of the opening the ring tablet fills out.
  • Suitable materials for the production of molds are in particular metals or metal alloys and, preferably, polymers.
  • metallic molds with, preferably polymeric, coatings can be used.
  • Such coatings are suitable, for example, for increasing the chemical or physical stability of the molds, for example against corrosion or mechanical stress.
  • polymeric coatings are suitable for preventing adhesion to the surface of the mold.
  • the mold introduced into the aperture of the ring tablet is adapted, in terms of its spatial shape, to the spatial shape of the aperture of the ring tablet.
  • the mold is preferably close to the inner wall of the ring tablet, that is, on the wall of the opening to.
  • Particularly preferred are those methods in which the distance between the introduced in the breakthrough mold and the inner wall of the Ring tablet is less than 10 mm, preferably less than 5 mm, preferably less than 3 mm and in particular between 0.1 and 2 mm.
  • the molding tool preferably has a rotationally symmetrical horizontal cross section.
  • Particularly preferred molds are characterized by a triangular or quadrangular, preferably square, horizontal cross-section. The corners of these molds are preferably rounded.
  • the horizontal cross section of the mold introduced into the annular shaped body is oval or circular.
  • the upper side of the molding tool that is to say the side of the molding tool facing the first film material placed on the opening of the ring tablet, can be designed in different ways. Since the in step c) applied to the opening of the Ringtablette sheet material in step d) of this preferred embodiment is deep drawn in the at least partially filled with the molding breakthrough, preferably deep-drawn so that this film material fits tightly against the top of the mold, can by the spatial configuration of the upper side of the molded body is also directly influenced by the spatial configuration of the bottom surface of the receiving chamber produced by the deep-drawing process. So results from the use of a mold with a flat top one. taking into account the shrinkage of the deep-drawn sheet material that naturally occurs during thermoforming processes, essentially flat bottom surface of the receiving chamber.
  • molds with a flat, concave or convex top but in particular molds are used with a concave top.
  • the upper side of the molding tool has both planar and curved sections, as concave and / or convex sections.
  • the introduced in the breakthrough of the ring tablet mold is designed such that by applying a negative pressure to the mold, the gas space between the mold and the applied to the opening of the ring tablet film material can be evacuated. Therefore, preferred molding tools have notches, grooves or holes, by means of which by applying a negative pressure, the gas space between the mold and the first placed on the opening of the ring tablets first Foil material at least partially evacuated and in this way the film material can be deep-drawn into the opening.
  • the sheet material deep-drawn into the opening of the ring tablet can naturally fill the space in the breakthrough, which does not by the Mold is taken.
  • the breakthrough of the ring tablets is therefore also only partially filled.
  • the deep drawing is preferably carried out by applying a negative pressure, but can for example also be effected by the action of a punch.
  • the receiving chamber formed by the deep drawing of the first film material is preferably filled with a flowable substance.
  • the flowable substances may be solids or liquids, with particular preference liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or Kompaktat (e) are used. A more detailed description of these flowable substances is given below in the text.
  • this receiving chamber is preferably sealed.
  • Suitable sealing materials are, for example, solidifying melts or liquids or, preferably, precisely fitting shaped bodies. With particular preference, however, water-soluble film materials are used as sealing materials.
  • the sealing takes place by means of heat, preferably by laser welding or heat sealing.
  • the sealing can be carried out in principle in the region of the shaped body of the ring tablet itself and / or in the region of the opening.
  • the metering units have a, preferably circumferential, sealing seam, which is in direct contact with the shaped body; in the second case, the, preferably circumferential, sealing seam lies in the region of the opening and does not touch the shaped body.
  • thermoformed first sheet material with the used for sealing further water-soluble sheet material by means of heat sealing, wherein the receiving chamber occluding, preferably circumferential sealing seam, with particular preference, the shaped body is not affected, that is generated for example in the region of the opening.
  • the tightness of the sealed receiving chambers can be significantly increased in comparison to conventional methods.
  • metallic molds are used.
  • the molds used are heated.
  • Ring tablet and filled receiving chamber are preferably adhesively bonded together.
  • This adhesive connection can be made, for example, by gluing the ring tablet to the first film material placed over the opening of the ring tablet in step c) or by heat-sealing the first film material to the surface of the ring tablet.
  • the breakthrough of the ring tablet is not filled below the water-soluble receiving chamber.
  • the mold is removed after completion of the seal from the opening and the cavity located in the opening below the filled receiving chamber filled with another, preferably flowable, washing or cleaning-active substance.
  • the partially filled ring tablet is preferably first turned over.
  • the second opening of the opening is preferably also sealed, with the sealing materials mentioned above, in particular water-soluble film materials, being used with particular preference.
  • Process variants are particularly preferred in which a washing or cleaning-active liquid or a washing or cleaning-active gel is introduced into at least one of the process steps e) or h).
  • a washing or cleaning-active liquid or a washing or cleaning-active gel is introduced in step e), while in step h) a flowable, washing or cleaning-active solid, preferably a powder or granules or a Extrudate, is filled.
  • the first film material in step c) or in step d) of the process according to the invention is preferably deep-drawn by applying a negative pressure.
  • the negative pressure in the cavity is produced by applying a negative pressure to a hole or notch which connects the cavity to the part of the surface of the shaped body (outside the cavity) which does not extend through the first foil material Step b) is covered.
  • a hole may, for example, be a bore which connects the cavity to a side surface or the lower side of the molded body.
  • Such a bore preferably has a diameter below 5 mm, preferably below 3 mm and in particular below 2 mm.
  • the cavity can also be connected by more than one hole with one or more outsides.
  • the molded body also have more than one bore.
  • the shaped body can furthermore have notches. These notches or grooves open into the opening of the cavity opening and lead from there preferably to a side surface of the molding.
  • the width of these notches is preferably less than 10 mm, preferably less than 7 mm, more preferably less than 4 mm and in particular less than 2 mm.
  • the depth of the notches is preferably in the range between 1 and 15 mm, preferably between 1 and 10 mm and in particular between 1 and 5 mm.
  • the first film material is applied by applying a negative pressure to a hole or indentation which connects the cavity to the part of the surface of the molded article (outside the cavity), not through the first film material from step b) is covered, deep drawn into the cavity.
  • the negative pressure in the cavity can be generated by applying a negative pressure to the shaped body surface (outside the cavity).
  • a negative pressure to the shaped body surface (outside the cavity).
  • the abovementioned washing or cleaning agent tablets are suitable for such a process.
  • particulate starting mixtures can thus produce moldings which have sufficient porosity to generate by applying a negative pressure on the surface of the shaped body, which is not covered by the film material within the cavity sufficient negative pressure to the Deep-draw opening of the cavity covering foil material in this cavity.
  • the first sheet material is produced by applying a negative pressure to the part of the surface of the shaped body (outside the cavity), which is not covered by the sheet material from step b) deep drawn into the cavity.
  • the negative pressure in the cavity is produced by the air in the cavity below the film material applied in step b) "passing through the tablet", that is to say by applying a negative pressure to holes specially provided for this purpose, Notches or holes, or by taking advantage of tablet porosity was removed from this cavity.
  • the negative pressure in the cavity is produced by removing the air in the cavity below the film placed in step b) through holes in this film material from the cavity.
  • Processes according to the invention in which the negative pressure is generated both in the cavity, ie below the film material applied in step b) and also outside the cavity, above the film material applied in step b), are particularly preferred.
  • Such a particularly advantageous process procedure can be realized, for example, by the fact that the molded body covered with the film material is brought into a vacuum chamber.
  • the film web applied in step b) is sealed with the filled container in such a way that the container is closed on all sides and in particular no air can pass through the openings of the film web applied in step c) into the container. If the sealed container is then removed from the vacuum chamber, the atmospheric pressure acting on the container from outside causes the outer walls of the container, in particular the film web applied in step b), to fit tightly against the molded body into the cavity.
  • the film material is molded into the cavity to form a receiving trough.
  • This receiving trough is then filled in the subsequent step d) with a detergent or cleaning substance.
  • the shape and the volume of the receiving trough will of course depend on the shape and the volume of the cavity of the molded article on which the process is based.
  • volume of the receiving trough formed by the film material is at least 40% by volume, preferably at least 60% by volume, very particularly preferably at least 80% by volume, in particular at least 90% by volume and particularly preferably at least 95 vol .-% of the volume of the cavity of the molding in step a) or in step a ').
  • the shaped body and the foil material are adhesively bonded together in a preferred embodiment of the method according to the invention.
  • the adhesive bond preferably takes place in spatial proximity to the opening of the cavity into which the film material was deep-drawn in step c).
  • Particularly preferred is the adhesive compounds along a circumferential sealed seam. This sealed seam can be realized by a number of different procedures. However, preference is given to those processes in which the adhesive compound is formed by the action of adhesives and / or solvents and / or compressive or squeezing forces.
  • molded body before, simultaneously with or after the deep drawing of the first film material in step c) is adhesively bonded to this first film material by a bond and / or a heat seal.
  • a circumferential sealing seam that is, a self-contained sealing seam is particularly preferred.
  • the heat seal is effected by the action of heated sealing tools.
  • the heat seal is effected by the action of a laser beam.
  • the heat seal is effected by the action of hot air.
  • a washing or cleaning-active substance is filled onto the film material in the cavity.
  • washing or cleaning substances are suitable solids as well as liquids.
  • the washing or cleaning-active substance can be filled onto the film material in the cavity by means of all dosing methods known to those skilled in the art.
  • step d) prefabricated molded bodies, for example cast bodies, tablets or extrudates are placed on the film material in the cavity.
  • a tablet or a ring tablet is used as the shaped body in step a)
  • the end product of this preferred variant of the method corresponds to a core tablet or a bullet-shaped tablet in which the cavity of the tablet obtained in step a ) is filled with a casting, another tablet or an extrudate, wherein the tablet and the inserted core are separated from each other by the in step c) deep-drawn in the cavity sheet material.
  • the washing or cleaning-active substance filled in step d) preferably has a density above 1.0 g / cm 3, preferably above 1.1 g / cm 3, particularly preferably above 1.2 g / cm 3, very particularly preferably above 1.3 g / cm3 and in particular above 1.4 g / cm 3.
  • the volume ratio of the shaped body provided in step a) to the volume of substance introduced into the cavity in step d) is preferably between 1: 1 and 20: 1 and in particular between 3: 1 and 15: 1.
  • particulate substances for example powders, granules or extrudates
  • these particulate substances or substance mixtures have an average particle size below 5000 ⁇ m, preferably less than 3000 ⁇ m, preferably less than 1000 ⁇ m, very particularly preferably between 50 and 1000 ⁇ m and in particular between 100 and 800 ⁇ m.
  • the flowable washing or cleaning substance is a liquid.
  • substances or mixtures of substances in their liquid state of aggregation are referred to as liquid.
  • the term "liquid” therefore also comprises, in addition to liquid pure substances, also solutions, suspensions, emulsions or melts. Preference is given to using substances or mixtures of substances which are in the liquid state at 20 ° C.
  • the liquids contain at least one substance from the group of nonionic surfactants and / or polymers and / or organic solvents. The liquid may in turn have several phases.
  • the cavity is preferably filled with a liquid.
  • This liquid-filled cavity is then preferably sealed.
  • a gas or gas mixture is additionally enclosed during the sealing in the cavity.
  • this gas or gas mixture may be an inert gas (e.g., argon or nitrogen), a reactive gas such as carbon dioxide, but also, for example, natural ambient air.
  • this gas or gas mixture may be an inert gas (e.g., argon or nitrogen), a reactive gas such as carbon dioxide, but also, for example, natural ambient air.
  • the cavity is filled with a liquid in step d) and subsequently sealed with the inclusion of a gas bubble are particularly preferred.
  • the volume of the gas bubble is preferably between 1 and 25% by volume, preferably between 2 and 20% by volume and in particular between 4 and 10% by volume of the volume of the sealed cavity.
  • the shaped bodies provided in step a) have a coating of a water-soluble or water-dispersible material, preferably an envelope of a water-soluble or water-dispersible film material, more preferably of a water-soluble or water-dispersible polymer-based film material.
  • Particularly preferred film materials are the materials described above from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof.
  • This enclosure may include the shaped body completely or only partially.
  • Particularly preferred are processes in which the shaped body in step a) is partially surrounded by a water-soluble or water-dispersible film material.
  • Such a partial coating can be realized, for example, by deforming a first water-soluble or water-dispersible film material, for example by deep drawing to form a receiving chamber and the shaped body is moved in step a) in this resulting receiving chamber.
  • the water-soluble or water-dispersible receiving chamber may also be made by injection molding a water-soluble or water-dispersible material.
  • step a) After the shaped body has been moved into this receiving chamber in step a), the remaining steps of the method according to the invention are carried out as described above, with the difference that in this variant of the method, the shell material of the shaped body from step a) in the course of the process with the first or second preferably water-soluble film material from steps b) or e) to connect adhesively and in this way to achieve a complete enclosure of the provided in step a), a ') and d) washing or cleaning-active substances.
  • the resulting final process product is not only distinguished by the separation of the active substances introduced in steps a) and a ') or d), but also makes possible the Preparation of readily soluble and thus highly active active substances in powder form or in the form of liquid compositions in a prefabricated dosing unit.
  • the water-soluble or water-dispersible receiving chamber is preferably adhesively bonded in a further process step with the first film material from step b).
  • the adhesive connection is preferably carried out subsequent to the deep-drawing of the first film material in step c), but can also take place with preference in the Anschlu8 to the steps b) or d).
  • the cavity can be a depression or a breakthrough.
  • the latter method variant is carried out with a shaped body which has a breakthrough as a cavity.
  • the process product of this process variant is then a ring-core tablet ("bull-eye tablet"), the breakthrough is closed on both sides by means of a water-soluble or water-dispersible material, the breakthrough itself by another water-soluble or water-dispersible Material, which may be identical to the aforementioned water-soluble or water-dispersible material, but may also differ from this material, is divided into two separate chambers, which preferably have a different filling.
  • this sealing takes place by applying a second film material to the cavity opening and subsequent heat sealing and / or ultrasonic sealing and / or high-frequency sealing.
  • This second film material may be the same or a different film material from the first film material used in step b).
  • the second film material may differ from the first film material, for example, by its thickness and / or its composition.
  • the sealing of the second film material via the cavity opening can also take place by gluing the second film material to the first film material or to the shaped article.
  • solvents particularly preferably water or aqueous solutions, are suitable for sealing the cavity opening of the bonding.
  • the sealed cavity preferably has an overpressure.
  • a crowning can be achieved, for example, by adding gas-releasing components to the washing or cleaning-active substances filled in step d).
  • the film material used for the sealing bulges and forms a visually appealing, convex curvature.
  • the molded article is adhesively bonded to the first film material and / or to the second film material by the heat-sealing and / or ultrasonic sealing and / or high-frequency sealing and / or gluing.
  • Process product is thus in particular a molded article with a breakthrough (ring-core tablet or "bull-eye tablet”), the breakthrough is closed on both sides by means of a water-soluble or water-dispersible material, the breakthrough itself by another water-soluble or water-dispersible Material is divided into two separate chambers, which preferably have a different filling.
  • a solid washing or cleaning substance more preferably a solid washing or cleaning substance in the form of a powder, granules or extrudate
  • the second chamber contains a liquid detergent or cleaning substance.
  • the water-soluble or water-dispersible materials, which close the breakthrough on both sides or subdivide the breakthrough into two separate chambers may be identical, but may also differ from one another.
  • the volume of the chambers located in the breakthrough is preferably between 0.5 and 15 ml, preferably between 0.5 and 12 ml, more preferably between 0.5 and 8 ml and in particular between 0.5 and 6 ml Chambers to each other is preferably between 10: 1 and 1:10, preferably between 8: 1 and 1: 8, more preferably between 6: 1 and 1: 6 and in particular between 4: 1 and 1: 4.
  • the shaped bodies with filled breakthrough described above enable the combined formulation of solid and liquid washing and cleaning substances using minimal amounts of packaging materials.
  • water-soluble or water-dispersible packaging materials these means are also suitable for direct metering into the metering chamber or the interior of a dishwasher or washing machine.
  • the shaped bodies of this particular embodiment according to the invention are distinguished by at least three phases (shaped body, first washing or cleaning substance in chamber 1, second detergent or cleaning substance in chamber 2) and thus allows the visualization complex drug combinations (eg "2in1" - or "3in1" automatic dishwashing or combination products of a laundry detergent and conditioner such as a softener, a dye transfer inhibitor or a crease inhibitor.
  • the process end products are preferably separated and compounded. If, for example, a film web is used as first or second film material, which film is processed to more than one of the metering units according to the invention, then this film material is cut into shape during or after completion of the process.
  • Inventive method characterized in that the first or second sheet material in the course of the process, preferably after a Sealing step is severed by a mechanical and / or thermal process to form a cutting line, wherein the cutting line preferably extends circumferentially on the surface of the molding, are particularly preferred.
  • the process according to the invention may also be followed by packaging of the process end products in "flow packs", stand-up pouches or cardboard packaging.
  • a film material preferably a water-soluble or water-dispersible film material
  • a film material is thermoformed to form a receiving chamber in the cavities of detergent tablets or detergent tablets.
  • Process products are therefore furthermore metering units for detergents or cleaners, comprising a molding having at least one cavity, a film material deep-drawn into the cavity to form a receiving chamber, and a washing or cleaning substance located on the film material in the cavity.
  • the film material is applied tightly against the inner walls of the cavity.
  • the shaped body is preferably a tablet, a compact, an extrudate, an injection molding or a casting.
  • the preferred manufacturing method of these moldings and their preferred spatial forms reference is made at this point to avoid repetition of the statements above in the description.
  • the volume of the cavity is preferably between 0.1 and 20 ml, preferably between 0.2 and 15 ml, more preferably between 1 and 10 ml and in particular between 2 and 7 ml.
  • the dosing units according to the invention comprise, in addition to a shaped body, a receiving trough filled with washing or cleaning-active ingredients and preferably made of a water-soluble or water-dispersible foil material.
  • the dosing unit thus has two phases separated from one another. These separate phases allow, for example, the separation of incompatible ingredients or the joint dosage of detergents or cleaning agents with different states of aggregation or Kon Stammionsformen.
  • the dosing unit is characterized in that the receiving chamber formed from the thermoformed sheet material with a flowable, preferably a liquid washing or cleaning substance, more preferably with one or more active substance (s) from the group of Group of nonionic surfactants and / or polymers and / or organic solvents, is filled.
  • a flowable preferably a liquid washing or cleaning substance, more preferably with one or more active substance (s) from the group of Group of nonionic surfactants and / or polymers and / or organic solvents
  • the flowable washing or cleaning substances may be solid or liquid.
  • Liquid (s) and / or gel (s) and / or powder and / or granules (e) and / or extrudate (s) and / or compact (e) are preferably used as flowable substances.
  • the flowable washing or cleaning substance is a liquid.
  • substances or mixtures of substances in their liquid state of aggregation are referred to as liquid.
  • the term "liquid” therefore also comprises, in addition to liquid pure substances, also solutions, suspensions, emulsions or melts. Preference is given to using substances or mixtures of substances which are in the liquid state at 20 ° C.
  • the liquids contain at least one substance from the group of nonionic surfactants and / or polymers and / or organic solvents.
  • the number of these phases of metering units according to the invention can be increased by increasing the number of phases of the shaped body and / or the number of phases filled into the cavity.
  • the shaped body has two, three, four or more phases.
  • the washing or cleaning active material filled in the cavity has two, three, four or more phases.
  • a plurality of different washing or cleaning-active substances or substance mixtures can be filled into the one receiving chamber formed from the thermoformed sheet material.
  • An example of such a preferred embodiment is a dosing unit according to the invention, in which the receiving chamber formed from the thermoformed sheet material is filled with a two- or multi-phase liquid phase.
  • a multi-phase filling of this receiving chamber for example, be realized by two or more or above flowable, solid washing or cleaning-active substances are layered in the receiving chamber filled.
  • a dosing unit characterized in that the cavity additionally in part with a washing or cleaning active substance, preferably a substance from the group Builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors is filled, which is not in the formed from the thermoformed sheet material receiving chamber is particularly preferred.
  • a washing or cleaning active substance preferably a substance from the group Builders, enzymes, bleach, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors is filled, which is not in the formed from the thermoformed sheet material receiving chamber is particularly preferred.
  • the dosing unit in which the cavity underneath the deep-drawn sheet material is partially filled with a washing or cleaning-active substance, preferably a solid washing or cleaning-active substance.
  • the resulting dosing unit then comprises a mono- or multiphase shaped body with a cavity, a washing or cleaning substance filled into the cavity, which only partially fills the cavity, and a receiving chamber made of film material filled with a further detergent or cleaning substance Partially filled cavity was deep-drawn. If the cavity is a well, the washing or cleaning active substance filled in the cavity is enclosed between the bottom of the well and the receiving chamber formed from the thermoformed sheet material, and, if the filled receiving chamber is not at least partially transparent, in usually not visible from the outside.
  • the cavity is an opening with two openings facing one another, then the washing or cleaning-active substance filled in the cavity is through one of the openings filled with the washing or cleaning-active substance filled in the receiving chamber of deep-drawn sheet material visible, noticeable.
  • washing- or cleaning-active substances which are filled into the cavity of the shaped body outside the receiving chamber on deep-drawn sheet material are selected from the group of builders, enzymes, bleaches, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors.
  • Bleaches in particular peroxygen compounds such as percarbonates or perborates, bleach activators or silver protectants, are particularly preferably introduced.
  • These ingredients are preferably filled into the cavity as part of solid washing or cleaning active preparations between steps a) and b). These ingredients are described in more detail later in the text. To avoid repetition, reference is made at this point to the comments there.
  • these substances are preferably fixed in the receiving chamber. This fixation can be done for example by adhesion promoters.
  • a preferred Dosing unit according to the invention in which the receiving chamber filled with the washing or cleaning active substance and formed from the thermoformed sheet material is sealed. Suitable sealing materials are, for example, melts of organic polymers or sugar melts.
  • the receiving chamber formed by the deep-drawn sheet material and filled with the washing or cleaning substance is sealed with another sheet material.
  • this sheet material is preferably a water-soluble or water-dispersible sheet material.
  • both opening surfaces of the opening are sealed.
  • the sealing material may partially cover the shaped body surface, for example, in the targeted sealing of individual cavity openings with a water-soluble or water-dispersible sheet material.
  • the sealing material can also be used to completely encase the molded body.
  • Dosing units according to the invention are therefore particularly preferred, comprising a molding having at least one cavity, a film material deep-drawn into the cavity to form a receiving chamber, and a washing or cleaning substance present on the film material in the cavity, the molding additionally comprising a coating of a water-soluble or water-soluble material having water-dispersible material.
  • a water-soluble or water-dispersible coating may comprise, for example, a deep-drawn or injection-molded packaging.
  • the shaped body is adhesively bonded to the film material deep-drawn in the cavity and / or to the further film material used for sealing the thermoformed sheet material by means of heat sealing and / or ultrasonic sealing and / or high-frequency sealing.
  • the ingredients of the detergent or cleaning product according to the invention are spatially separated from the ingredients contained in the receiving chamber formed from the sheet material.
  • the resulting dosing unit is thus distinguished, in addition to the advantageous multiphase product appearance, by increased product and storage stability.
  • the detergents or cleaners according to the invention can be used for textile cleaning as well as for cleaning hard surfaces or dishes.
  • the detergents or cleaners prepared according to the invention preferably contain further washing and cleaning agents cleaning-active substances, in particular washing and cleaning-active substances from the group of bleaches, bleach activators, builders, surfactants, enzymes, polymers, disintegration aids, electrolytes, pH adjusters, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and glass corrosion inhibitors.
  • detergents and cleaners according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of these compositions.
  • preferred agents comprise one or more substances from the group of electrolytes, pH regulators, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (21)

  1. Procédé pour la fabrication d'une unité de dosage pour des agents de lavage ou de nettoyage, comprenant les étapes dans lesquelles
    a) on procure un corps moulé comprenant au moins une cavité ;
    b) on applique une première matière en feuille sur la surface du corps moulé par-dessus l'ouverture de la cavité ;
    c) on introduit la première matière en feuille par emboutissage dans la cavité en générant une dépression dans la cavité du corps moulé ;
    d) on introduit une substance possédant une activité de lavage ou de nettoyage sur la matière en feuille dans la cavité.
  2. Procédé selon la revendication 1, caractérisé en ce qu'il s'agit, en ce qui concerne le corps moulé, d'un comprimé, d'un produit de compactage, d'un produit d'extrusion, d'un corps moulé par injection, d'un corps moulé par coulage ou d'un corps moulé composé de ces corps moulés.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le corps moulé présente une enduction.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le rapport du volume du corps moulé au volume de la substance utilisée pour remplir la cavité à l'étape d) se situe entre 1:1 et 20:1, de préférence entre 3:1 et 15:1.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on remplit la cavité du corps moulé, avant l'application de la première matière en feuille à l'étape b), en partie avec une substance possédant une activité de lavage ou de nettoyage.
  6. Procédé selon la revendication 5, caractérisé en ce qu'il s'agit, en ce qui concerne la substance possédant une activité de lavage ou de nettoyage, d'une poudre, d'un granulé ou d'un extrudat possédant une activité de lavage ou de nettoyage, qui comprend de préférence une ou plusieurs substances actives choisies parmi le groupe comprenant des builders, des enzymes, des agents de blanchiment, des activateurs du blanchiment, des catalyseurs du blanchiment, des agents de protection de l'argent et des inhibiteurs de la corrosion du verre.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'on met en oeuvre, à titre de première matière en feuille à l'étape b), une matière en feuille soluble dans l'eau ou dispersible dans l'eau, de préférence une matière polymère en feuille soluble dans l'eau ou dispersible dans l'eau.
  8. Procédé selon la revendication 1, caractérisé en ce qu'on obtient la dépression dans la cavité du corps moulé par l'application d'une dépression sur la partie de la surface du corps moulé (à l'extérieur de la cavité), qui n'est pas recouverte par la matière en feuille de l'étape b).
  9. Procédé selon l'une quelconque des revendications 1 ou 8, caractérisé en ce qu'on obtient la dépression dans la cavité du corps moulé par l'application d'une dépression contre un trou ou une rainure qui relie la cavité à la partie de la surface du corps moulé (à l'extérieur de la cavité), qui n'est pas recouverte par la première matière en feuille de l'étape b).
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'on relie par adhérence le corps moulé avant, simultanément à ou après l'emboutissage de la première matière en feuille à l'étape c), à cette première matière en feuille via un collage et/ou via un thermosoudage.
  11. Procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'on introduit à l'étape d) une substance apte à l'écoulement possédant une activité de lavage ou de nettoyage.
  12. Procédé selon la revendication 11, caractérisé en ce qu'on introduit à l'étape d) un liquide qui contient de préférence une ou plusieurs substances actives choisies parmi le groupe des agents tensioactifs non ioniques et/ou des polymères et/ou des solvants organiques.
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'on scelle l'ouverture de la cavité dans la foulée de l'étape d) dans une étape e) supplémentaire.
  14. Procédé selon la revendication 13, caractérisé en ce que le scellement de l'ouverture de la cavité a lieu par l'application d'une deuxième matière en feuille sur l'ouverture de la cavité et via un thermosoudage et/ou un soudage aux ultrasons et/ou un soudage haute fréquence ultérieurs.
  15. Procédé selon la revendication 14, caractérisé en ce qu'on relie par adhérence via le thermosoudage et/ou le soudage aux ultrasons et/ou le soudage haute fréquence le corps moulé à la première matière en feuille et/ou à la deuxième matière en feuille.
  16. Procédé selon l'une quelconque des revendications 1 à 15, caractérisé en ce qu'on sépare la première ou la deuxième matière en feuille au cours du procédé, de préférence après une étape de scellement, via un procédé mécanique et/ou un procédé thermique par la réalisation d'une ligne de coupe, la ligne de coupe s'étendant de préférence en direction périphérique sur la surface du corps moulé.
  17. Procédé pour la fabrication d'une unité de dosage pour des agents de lavage ou de nettoyage, comprenant les étapes dans lesquelles :
    i. on procure un comprimé annulaire ;
    ii. on incorpore un moule via une première ouverture du renfoncement du comprimé annulaire, dans ce renfoncement ;
    iii. on applique une première matière en feuille, de préférence soluble dans l'eau, sur la surface du corps moulé par-dessus la deuxième ouverture du renfoncement ;
    iv. on introduit la première matière en feuille par emboutissage dans le renfoncement du comprimé annulaire pour obtenir une chambre de réception qui ne remplit que partiellement le renfoncement ;
    v. on introduit une substance possédant une activité de lavage ou de nettoyage dans la chambre de réception que l'on obtient à l'étape d).
  18. Procédé selon la revendication 17, caractérisé en ce que le moule présente sur son côté supérieur, une zone marginale plane périphérique.
  19. Procédé selon l'une quelconque des revendications 17 ou 18, caractérisé en ce qu'on scelle la chambre de réception remplie, dans une étape ultérieure f), le scellement ayant lieu de préférence par thermosoudage de la première matière en feuille avec la matière en feuille soluble dans l'eau dans la zone marginale plane du moule.
  20. Procédé selon l'une quelconque des revendications 17 à 19, caractérisé en ce qu'on retire le moule après le scellement de l'étape f), dans une étape ultérieure g) par la première ouverture hors du renfoncement, et on remplit la zone du renfoncement du comprimé annulaire occupée au préalable par le moule avec une autre substance possédant une activité de lavage ou de nettoyage.
  21. Procédé selon l'une quelconque des revendications 17 à 20, caractérisé en ce qu'on scelle la première ouverture du renfoncement dans une étape supplémentaire g).
EP05733723.0A 2004-04-28 2005-04-21 Procedes pour la production de detergents et de nettoyants Active EP1740689B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05733723T PL1740689T3 (pl) 2004-04-28 2005-04-21 Sposób wytwarzania środków piorących lub czyszczących

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004020839A DE102004020839A1 (de) 2004-04-28 2004-04-28 Verfahren zur Herstellung von Wasch- oder Reinigungsmittel
PCT/EP2005/004260 WO2005105974A1 (fr) 2004-04-28 2005-04-21 Procedes pour la production de detergents et de nettoyants

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EP1740689A1 EP1740689A1 (fr) 2007-01-10
EP1740689B1 true EP1740689B1 (fr) 2014-03-05

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Country Status (6)

Country Link
US (1) US20080004202A1 (fr)
EP (1) EP1740689B1 (fr)
DE (1) DE102004020839A1 (fr)
ES (1) ES2456016T3 (fr)
PL (1) PL1740689T3 (fr)
WO (1) WO2005105974A1 (fr)

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DE102005000782A1 (de) 2005-01-05 2006-07-20 Voith Paper Patent Gmbh Trockenzylinder
DE102005000795A1 (de) * 2005-01-05 2006-07-13 Voith Paper Patent Gmbh Vorrichtung und Verfahren zur Herstellung und/oder Veredelung einer Faserstoffbahn
DE102005022786B4 (de) * 2005-05-12 2016-09-15 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmitteldosiereinheit
DE102005025964A1 (de) * 2005-06-03 2006-12-07 Henkel Kgaa Wasch- oder Reinigungsmittel
EP1948702A2 (fr) 2005-11-17 2008-07-30 The Procter and Gamble Company Utilisation et application de copolymeres zwitterioniques definis
DE102007042450B4 (de) * 2007-09-06 2009-12-31 Andreas Siggelkow Wasserlösliche Verpackung mit Funktionsdepot sowie Verfahren zu ihrer Herstellung und Verwendung der Verpackung
SI2281853T1 (sl) * 2009-08-05 2012-09-28 Omya Development Ag Uporaba 2-amino-2-metil-1-propanola kot aditiva v vodnih suspenzijah materialov, ki obsegajo kalcijev karbonat
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Also Published As

Publication number Publication date
WO2005105974A1 (fr) 2005-11-10
ES2456016T3 (es) 2014-04-21
DE102004020839A1 (de) 2005-11-24
PL1740689T3 (pl) 2014-08-29
EP1740689A1 (fr) 2007-01-10
US20080004202A1 (en) 2008-01-03

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