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EP1740690B2 - Verfahren zur herstellung von wasch-oder reinigungsmitteln - Google Patents

Verfahren zur herstellung von wasch-oder reinigungsmitteln Download PDF

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Publication number
EP1740690B2
EP1740690B2 EP05733100.1A EP05733100A EP1740690B2 EP 1740690 B2 EP1740690 B2 EP 1740690B2 EP 05733100 A EP05733100 A EP 05733100A EP 1740690 B2 EP1740690 B2 EP 1740690B2
Authority
EP
European Patent Office
Prior art keywords
washing
water
cleaning
soluble
cleaning agent
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.)
Active
Application number
EP05733100.1A
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German (de)
English (en)
French (fr)
Other versions
EP1740690B1 (de
EP1740690A1 (de
Inventor
Thomas Holderbaum
Arno DÜFFELS
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
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL05733100T priority Critical patent/PL1740690T5/pl
Publication of EP1740690A1 publication Critical patent/EP1740690A1/de
Publication of EP1740690B1 publication Critical patent/EP1740690B1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid compositions

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 dosing 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, but on the other hand they also allow the preparation of liquid or powdered detergents or cleaners, which compared to the Kompaktaten characterized by a better resolution and faster effectiveness.
  • the EP 1 314 664 A2 (Unilever) a dome-shaped pouch with a receiving chamber containing a liquid
  • the prior art has also disclosed molds which comprise more than one receiving chamber or more than one ready-made form.
  • EP 1 256 623 A1 Procter & Gamble is a kit of at least two bags with different composition and different optics, The bags are separated and not as a compact single product before:
  • the object of the present application was to provide a process for the preparation of detergents or cleaners with water-soluble or water-dispersible packaging, by which the amounts of the water-soluble or water-dispersible material used can be minimized, wherein the water-soluble or water-dispersible packaging is stable even without the use of conventional adhesives or adhesion promoters Should have sealing seams.
  • the resulting process products should further enable the co-packaging of solid and liquid or flowable detergent compositions in separate areas of a compact dosing unit.
  • the final process product should be characterized by an attractive appearance.
  • a washing or cleaning agent in which a detergent or cleaning product molding and the water-soluble or water-dispersible packaging material are adhesively bonded together by a heat seal and the detergent tablets a coating with a water-soluble or water-dispersible organic polymer on its entire surface having.
  • a first subject of the present application is therefore a washing or cleaning agent, comprising at least one detergent or cleaning product molding and at least one water-soluble or water-dispersible film material, characterized in that the washing or cleaning agent molded body and the film material are adhesively bonded together by a heat-sealing seam and the Detergent or detergent tablet has a coating with a water-soluble or water-dispersible organic polymer on its entire surface .
  • the sealing seam in the cleaning agents according to the invention does not bind two film materials, for example for sealing a bag or pouch containing a washing or cleaning agent, but instead bonds the film material directly to the washing or cleaning agent.
  • the adhesive bond of the film material and detergent tablets preferably leads to the formation of a cavity bounded by this film material and this body, which cavity in turn can be filled, preferably with another washing or cleaning agent.
  • the composition of the detergent tablets differs from the composition of the detergent or cleaning agent filled in the cavity.
  • the heat-sealing seam of the compositions according to the invention preferably has the form of a circumferential sealed seam, that is, a self-contained sealed seam.
  • the thickness of the sealing seam is preferably between 0.1 and 5 mm, preferably between 0.5 and 3 mm and particularly preferably between 1 and 2 mm.
  • the heat seal is formed by bringing the film material and the molded body into contact with one another and then heating them in a spatially defined region.
  • the heat-sealing is preferably carried out at a temperature above 40 ° C, more preferably above 60 ° C, most preferably above 80 ° C and especially above 100 ° C.
  • the film material and the adjacent region of the shaped body for a maximum of 5 seconds, preferably for 0.1 to 4 seconds, more preferably for 0.2 to 3 seconds and especially 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.
  • the heat-sealing of the washing or cleaning agent shaped article with the water-soluble or water-dispersible film material can be effected not only by the action of hot air or the action of a laser beam but also by means of heated sealing tools.
  • sealing tools When sealed by sealing tools ("sealing jaws"), the film material and the molded body are heated in the area of the later sealed seam.
  • the sealing tool can be guided to the surface of the molding and support the sealing process by additional pressure.
  • preferred washing or cleaning agents are characterized in that the shaped body has a breaking pressure above 1 bar, preferably above 2.5 bar and in particular above 4 bar.
  • the breaking pressure is determined by placing the shaped body between two plane-parallel surfaces and moving them towards each other.
  • the pressing force of the plates acts orthogonal to the plane of the heat-sealing seam.
  • the fracture pressure then results taking into account the area of the plates used from the force at which the shaped body breaks.
  • a first constituent of the agents according to the invention is a detergent or cleaner tablet.
  • Such shaped bodies are obtainable, for example, by compaction methods such as tableting, by extrusion, such as extrudate extrusion or by casting.
  • extrusion such as extrudate extrusion 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 methods are characterized in that the compression at pressing pressures of 0.01 to 50 kNcm -2 , preferably from 0.1 to 40 kNcm -2 and in particular from 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 method and solidify subsequently 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.
  • dispersion in this application a system of several phases is referred to, one of which is dispersed continuously (dispersion medium) and at least one further (dispersed substances).
  • Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers.
  • the dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers.
  • the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group consisting of polyvinylpyrrolidones, 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.
  • all substances which are solid or wash-active at room temperature are suitable as dispersed substances, but especially washing or cleaning substances from the group of builders (builders and co-builders), the washing or cleaning-active polymers, the bleaching agent Bleach activators, the glass corrosion inhibitor, the silver protectant and / or the enzymes.
  • washing or cleaning substances from the group of builders (builders and co-builders), the washing or cleaning-active polymers, the bleaching agent Bleach activators, the glass corrosion inhibitor, the silver protectant and / or the enzymes.
  • 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 wash cycle of a standard rinse program (45 ° C) is started. Solubility is determined by measuring the conductivity, which is recorded by 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 shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-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.
  • detergents or cleaners according to the invention which are in the form of a washing or cleaning agent tablet are single-phase or multi-phase detergents or cleaning tablets are particularly preferred.
  • tablets and / or compacts for example roll compacts, and / or extrudate and / or cast bodies are used as shaped bodies in step a) of the process according to the invention.
  • the detergent tablets according to the invention may be completely or partially coated by the water-soluble or water-dispersible film material.
  • the film material which is adhesively bonded to the shaped body by a heat-sealing seam, can therefore cover both the entire molded body and individual regions of the shaped body.
  • Particularly preferred detergent tablets according to the invention are covered with a film material over their entire surface. Moldings in which the film material only covers parts of the surface of the molding, for example individual side surfaces, in particular those side surfaces with a cavity, are also preferred.
  • the coating of the shaped body can contribute to the improvement of its shaped body optics and / or to influence its dissolution behavior.
  • the coating covers the entire molded body. According to the invention, moldings which have a coating on their entire surface.
  • the coating materials used in the present application are the water-soluble or water-dispersible natural or synthetic organic polymers.
  • Water-soluble polymers in the context of the invention are those polymers which are soluble in water at room temperature in excess of 2.5% by weight.
  • the moldings are preferably coated with a polymer or polymer mixture, wherein the polymer (and accordingly the entire coating) or at least 50% by weight of the polymer mixture (and thus at least 50% of the coating) is selected from certain polymers.
  • the coating consists entirely or at least 50% of its weight of water-soluble polymers from the group of nonionic, amphoteric, zwitterionic, anionic and / or cationic polymers.
  • polymers are water-soluble amphopolymers.
  • Amphoteric polymers ie polymers which contain both free amino groups and free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule and amphoteric polymers. COO - - or -SO 3 - groups, and summarized those polymers containing -COOH or SO 3 H groups and quaternary ammonium groups.
  • An example of an inventively employable Am phopolymer is the available under the name Amphomer ® acrylic resin containing a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group acrylic acid , Methacrylic acid and their simple esters.
  • amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and, if appropriate, further ionic or nonionic monomers, as described, for example, in the German Offenlegungsschrift 39 29 973 and the cited prior art.
  • unsaturated carboxylic acids for example acrylic and methacrylic acid
  • cationically derivatized unsaturated carboxylic acids for example acrylamidopropyltrimethylammonium chloride
  • further ionic or nonionic monomers as described, for example, in the German Offenlegungsschrift 39 29 973 and the cited prior art.
  • Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium as they are commercially available under the name Merquat ® 2001 N, are inventively particularly preferred amphopolymers.
  • amphoteric polymers are for example sold under the names Amphomer ® and Amphomer ® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.
  • Suitable zwitterionic polymers are, for example, acrylamidopropyltrimethylammonium chloride / acrylic acid or methacrylic acid copolymers and their alkali metal and ammonium salts. Further suitable zwitterionic polymers are methacroylethylbetaine / methacrylate copolymers, sold under the name Amersette ® (AMER-CHOL) are commercially available.
  • the polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.
  • the nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.
  • the ionic monomers may be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.
  • the crosslinking agents used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho, meta and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose with 2 to 5 allyl groups per molecule of saccharin.
  • cationic polymers preferably used as part of the coating polymers.
  • the cationic polymers the permanent cationic polymers are preferred.
  • "permanently cationic” refers to polymers which have a cationic group, irrespective of the pH of the agent (ie both the coating and the shaped body). These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.
  • Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers.
  • Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.
  • a particularly preferred coating material for shaped bodies in the context of the present application is polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • the statements made below in the description with regard to the preferred container materials apply, to which reference is made at this point in order to avoid repetitions.
  • the detergent tablets may have a cavity.
  • 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 well opening surface may be planar. In such a trough opening, all boundary points of the trough opening lie in one plane. In a preferred embodiment, the surface forming the trough opening is not planar.
  • Such an embodiment can be realized for example by a shaped body having an uneven surface. Alternatively, a shaped body can be provided, whose depression opening extends over at least two boundary surfaces of a shaped body.
  • the cavity is an opening which connects two opposite sides of the molding together. If a tablet is used as the shaped body, then the shaped body with such a breakthrough corresponds to a so-called ring tablet.
  • Breakthrough shaped moldings are particularly preferably used in which the opening areas of the opening on the opposite sides of the molded body are less than 80%, preferably less than 60%, preferably less than 40%, based on the larger of the two opening areas. more preferably differ by less than 20% and in particular by less than 10%.
  • the cross-section of the aperture may be angular or round.
  • Cross sections with one, two, three, four, five, six or more corners are feasible, but such moldings are in Particularly preferred frame 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 2 and 20 ml, preferably between 2 and 15 ml, more preferably between 2 and 10 ml and in particular between 2 and 7 ml.
  • detergent tablets or detergent tablets which have a cavity are particularly preferred.
  • Very particular preference is given to detergents or cleaners according to the invention in which the shaped body has a cavity which is at least partly closed by the film material which is adhesively bonded to the shaped body by a heat-sealing seam.
  • the cavity of the washing or cleaning agent shaped body is filled.
  • 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 (e ) filled in the cavity of the washing or cleaning agent shaped body.
  • 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 is dependent 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 pressed during perforating through perforated disks (Extrusion) or plastically deformed on perforated rolls.
  • extrudates The products of extruder granulation are also referred to as extrudates.
  • Enzymes, bleaches, bleach activators, bleach catalysts, silver protectants or glass corrosion inhibitors are particularly suitable as constituents of the washing or cleaning-active preparations filled into the cavity of the detergent or cleaner body.
  • 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.
  • a further preferred subject matter of the present application is therefore a washing or cleaning agent comprising at least one detergent or cleaning product body and at least one water-soluble or water-dispersible film material, characterized in that the washing or cleaning agent shaped body has a cavity in the form of a cavity which is active with a washing or cleaning agent Substance filled and sealed with a film material, wherein the film material is adhesively bonded by a heat seal with the detergent or Reinigugnsffenform emotions.
  • the molding may also have a breakthrough instead of a trough, with particular preference molded body in the form of a ring tablet are used.
  • shaped bodies can be produced, for example, by casting or by extrusion extruding, in addition to the tabletting described above.
  • the present application therefore further relates to a washing or cleaning agent comprising at least one washing or cleaning agent shaped body in the form of a ring tablet and at least one water-soluble or water-dispersible sheet material, characterized in that the cavity of the washing or cleaning agent shaped body with a washing or cleaning-active substance is filled, wherein the film material is adhesively bonded by a heat-sealing seam with the washing or cleaning agent molding and preferably at least one, particularly preferably both openings of the cavity of the molding sealed.
  • a laundry detergent or detergent tablet was adhesively bonded to a water-soluble or water-dispersible film material by means of a heat seal, wherein the water-soluble or water-dispersible film material was used in the form of a commercial film.
  • the water-soluble or water-dispersible film material is shaped into a hollow body which is an injection-molded and / or blow-molded and / or deep-drawn part.
  • deep-drawn part refers to such containers which are obtained by deep-drawing a first film-like wrapping material.
  • the deep drawing is preferably carried out by bringing the wrapping material over a receiving trough located in a die forming the deep-drawing tray and shaping the wrapping material into this receiving trough by the action of pressure and / or vacuum.
  • the shell material may be pre-treated before or during the molding by the action of heat and / or solvent and / or conditioning by relative to ambient conditions changed relative humidity and / or temperatures.
  • the pressure action can be carried out by two parts of a tool, which behave as positive and negative to each other and deform a spent between these tools film when squeezed.
  • the action of compressed air and / or the weight of the film and / or the weight of an active substance applied to the upper side of the film is also suitable as pressure forces.
  • the deep-drawn shell materials are preferably fixed after deep drawing by using a vacuum within the receiving wells and in their achieved by the deep-drawing process space shape.
  • the vacuum is preferably applied continuously from deep drawing to filling until sealing and in particular until the separation of the receiving chambers.
  • a discontinuous vacuum for example, for deep drawing of the receiving chambers and (after an interruption) before and during the filling of the receiving chambers, possible.
  • the continuous or discontinuous vacuum can vary in its thickness and, for example, take higher values at the beginning of the process (during deep drawing of the film) than at its end (during filling or sealing or singulation).
  • the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices.
  • the shell material preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 60 ° C. 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 , preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C.
  • the dies used and the receiving troughs located in these dies are preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C.
  • the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers.
  • Cooling is particularly suitable cooling fluids, preferably water, which are circulated in special cooling lines within the die.
  • This cooling as well as the previously described continuous or discontinuous application of a vacuum has the advantage of preventing shrinkage of the deep-drawn containers after deep drawing, which not only improves the appearance of the process product, but also at the same time the escape of the filled into the receiving chambers means over the Edge of the receiving chamber, for example, in the sealing areas of the chamber, is avoided. Problems with the sealing of the filled chambers are thus avoided.
  • the deep-drawing process can be between methods in which the shell material is guided horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or separating and methods in which the shell material via a continuously rotating Matrizenformwalze (optionally optionally with a counter-guided Patrizenformwalze, which lead the forming upper punch to the cavities of the Matrizenformwalze) is different.
  • the first-mentioned process variant of the flat bed process is to operate both continuously and discontinuously, the process variant using a molding roll is usually continuous. All of the mentioned deep drawing methods are suitable for the production of the inventively preferred means.
  • the receiving troughs located in the matrices can be arranged "in series" or staggered.
  • the deep drawing bodies may have one, two, three or more receiving chambers. These receiving chambers can be arranged side by side and / or one above the other in the deep-drawn part.
  • the agent according to the invention in particular automatic dishwashing detergent, is formulated in a water-soluble or water-dispersible thermoformed body which, in addition to the solid detergent and / or cleaning agent according to the invention, in particular automatic dishwashing detergent, in a separate receiving chamber further comprises a liquid or gel detergent or detergent mixture contains.
  • the water-soluble or wasseridispergierbaren container can be prepared by injection molding in addition to deep drawing.
  • Injection molding refers to the forming of a molding material such that the mass contained in a mass cylinder for more than one injection molding plastically softens under heat and flows under pressure through a nozzle into the cavity of a previously closed tool.
  • the method is mainly applied to non-hardenable molding compounds which solidify in the tool by cooling.
  • Injection molding is a very economical modern process for producing non-cutting shaped articles and is particularly suitable for automated mass production.
  • thermoplastic molding compounds are heated to liquefaction (up to 180 ° C) and injected under high pressure (up to 140 MPa) in closed, two-piece, that is from Gesenk (earlier Die) and core (formerly male) existing, preferably water-cooled molds, where they cool and solidify.
  • Suitable molding compositions are water-soluble polymers, for example the abovementioned cellulose ethers, pectins, polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or starch.
  • Detergents or cleaning agent tablets and molds are preferably adhesively bonded together along a circumferential sealing seam.
  • the adhesive connection can of course also take place along a simple sealed seam, which is not self-contained and makes it possible to fold the shaped body and the hollow mold along this sealing seam.
  • Such particularly preferred embodiments of the invention agents are characterized by an advantageous appearance and high flexibility in the dosage, in particular the dosage of the dispensing or dosing of washing machines or dishwashers.
  • the molded body and the hollow body may be adhesively bonded together along two or more separate sealing seams.
  • the washing or cleaning agent shaped body has a cavity which at least partially surrounds the hollow body.
  • Wells are in turn wells as well as breakthroughs, in other words, washing or cleaning tablets are in the form of a well tablet as well as detergent tablets in the form of a ring tablet.
  • the water-soluble or water-dispersible hollow bodies which are adhesively bonded to the shaped body by a heat-sealing seam, are located at least partially in the cavity.
  • the hollow body may for example be inserted into the cavity, but may also be secured in this cavity by an additional adhesive, snap or snap connection.
  • the hollow body has the cavity at least 50% by volume, preferably at least 70% by volume, more preferably at least 80% by volume and in particular at least 90 vol .-% fills.
  • the hollow body preferably has a filling, more preferably a liquid filling.
  • a filling more preferably a liquid filling.
  • liquid fillings which, based in each case on the total weight of the liquid filling, are at least 10% by weight, preferably at least 20% by weight, more preferably at least 40% by weight and in particular at least 80% by weight have multiple surfactants.
  • the stability and quality of the heat-sealing seam, which the washing or cleaning agent molding connects with the water-soluble or water-dispersible film material can be influenced by the composition of the washing or cleaning agent molded body. It has proven to be advantageous if the shaped body or the shaped body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat-sealing seam, has a surfactant content below 20% by weight, preferably below 16% by weight, preferably below 12 wt .-%, more preferably below 8 wt .-% and in particular below 4 wt .-%.
  • the enzyme content, bleach content and bleach activator content in the molded article or molded article phase adhesively bonded to the water-soluble or water-dispersible film material by the heat-sealing seam are also kept within narrow limits.
  • washing or cleaning agents characterized in that the shaped body or the shaped body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat-sealing seam, has an enzyme content below 6% by weight, preferably below 4.5% by weight. -%, preferably below 3.0 wt .-% and in particular below 1.0 wt .-%.
  • washing or cleaning agents characterized in that the shaped body or the shaped body phase, which is adhesively bonded to the liquid-filled hollow body by a heat-sealing seam, has a bleaching agent content below 15% by weight, preferably below 12% by weight, preferably below 9 wt .-%, more preferably below 6 wt .-% and in particular below 3 wt .-%.
  • washing or cleaning agents are also particularly advantageous in that the shaped body or the shaped body phase, which is adhesively bonded to the water-soluble or water-dispersible film material by a heat-sealing seam, has a bleach activator content below 5% by weight, preferably below 3. 5 wt .-%, more preferably below 2.0 wt .-% and in particular below 1.0 wt .-%.
  • the quality and stability of the heat-sealing seam between detergent tablets and water-soluble or water-dispersible film material can be increased by increasing the builder content and / or the polymer content of the shaped body or the molded body phase having the heat-sealing seam ,
  • the shaped body or the shaped body phase which is adhesively bonded to the liquid-filled hollow body by a heat-sealing seam has a builder content of more than 10% by weight, preferably more than 15% by weight. preferably above 20 wt .-%, more preferably above 25 wt .-% and in particular above 30 wt .-%.
  • Detergents or cleaning agents have furthermore proved to be advantageous, characterized in that the shaped body or the shaped body phase, which is adhesively bonded to the liquid-filled hollow body by a heat-sealing seam, has a polymer content above 0.5% by weight, preferably above 1 , 0 wt .-%, more preferably above 2.0 wt .-% and in particular above 4 wt .-%.
  • 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.
  • the heat sealing is preferably carried out at a temperature above 40 ° C, more preferably above 60 ° C, even more preferably above 80 ° C and especially above 100 ° C.
  • the water-soluble or water-dispersible film material provided in step b) is shaped into a hollow body which is an injection-molded and / or blow-molded and / or deep-drawn part,
  • 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 according to the invention preferably comprise further washing and cleaning substances, in particular washing and cleaning substances from the group of bleaches, bleach activators, builders, surfactants, enzymes, polymers, disintegration aids, electrolytes, pH Surfactants, perfumes, perfume carriers, dyes, hydrotropes, foam inhibitors, corrosion inhibitors and glass corrosion inhibitors.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse aid polymers and / or polymers which act as softeners.
  • the washing or cleaning-active polymers for example the rinse aid polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • Effective polymers as softeners are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • Suldonsaure tendency-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 (R 2 ) C C (R 3 ) CCOH in which 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 is - COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, melhallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3 -Sulfopropylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts of said
  • ethylenically unsaturated ⁇ compounds are used as further ionic or nonionogenic monomers into consideration.
  • disintegration aids so-called tablet disintegrants
  • tablet proliferation agents or Decay accelerators are prepared according to Römpp (9th edition, Vol. 6, p. 4440 ) and Voigt " Textbook of Pharmaceutical Technology "(6th edition, 1987, pp. 182-184 ) Excipients, which ensure the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in resorbable form.

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EP05733100.1A 2004-04-28 2005-04-20 Verfahren zur herstellung von wasch-oder reinigungsmitteln Active EP1740690B2 (de)

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PL1740690T3 (pl) 2013-03-29
EP1740690A1 (de) 2007-01-10
PL1740690T5 (pl) 2016-11-30
US20080248989A1 (en) 2008-10-09

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