EP1971633B1 - Umhüllte reinigungsmittelzusammensetzungen und herstellungsverfahren - Google Patents

Umhüllte reinigungsmittelzusammensetzungen und herstellungsverfahren Download PDF

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Publication number
EP1971633B1
EP1971633B1 EP07700205.3A EP07700205A EP1971633B1 EP 1971633 B1 EP1971633 B1 EP 1971633B1 EP 07700205 A EP07700205 A EP 07700205A EP 1971633 B1 EP1971633 B1 EP 1971633B1
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EP
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Prior art keywords
composition according
water soluble
foil
detergent
copolymer
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EP07700205.3A
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English (en)
French (fr)
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EP1971633A1 (de
Inventor
Robbert De Boer
Janco Van Ommen
Henk Schuldink
Henk Beenen
Marco Ruiter
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Dalli Werke GmbH and Co KG
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Dalli Werke GmbH and Co KG
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Priority to EP07700205.3A priority Critical patent/EP1971633B1/de
Priority to PL07700205T priority patent/PL1971633T3/pl
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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 relates to a packaged detergent and/or additive composition e.g. for the dish washing machine wrapped in a water dissolvable material comprising a polyvinyl alcohol copolymer and a process of manufacturing thereof.
  • the traditional form of detergent and/or additive compositions for use in dish washing is granules or non particulate solids such as bars or tablets or briquettes.
  • the term tablet will refer to any form of non particulate solids.
  • said detergent and/or additive tablets or granules are respectively placed or poured in the dispenser located in said dish washing machine or in an adequate dispensing device which is then placed in said washing machine.
  • Water soluble packages comprising an agent to be dispensed in an aqueous medium are well known.
  • Polyvinyl alcohol (PVOH) is known as a watersoluble packaging material.
  • Examples of such containers comprising PVOH as a packaging material include detergent pouch packages suitable for automatic dishwashers and washing machines.
  • CA-A-1,112,534 discloses a packet made of a water-soluble material in film form enclosing within it a paste of automatic dishwasher-compatible detergent composition.
  • EP-A 700 989 describes a unit packaged detergent.
  • Said unit packaged detergent is a detergent packaged in a water soluble polymer film or sheet in such a form that it is suitable for one wash. This unit packaged detergent is placed in the detergent disperser of the machine without unwrapping the contained detergent from the packaging.
  • said unit packaged detergent prevents wasting through spillage of the detergent and/or additive composition.
  • said unit packaged detergent eliminates the need for the user to estimate the dosage of said composition required and ensures that the correct dosage of said composition per wash cycle is used by the user.
  • the fingers of a user do not come in contact with the wrapped detergent composition.
  • WO 04/20509 describes a water soluble non-homogenous polymer containing water soluble fillers for wrapping detergent compositions.
  • the polymer is used in an injection moulding process using a water soluble resin comprising a water soluble polymer and a water soluble filler.
  • DE-A 199 34 983 describes the use of polyvinyl alcohol as a soil release ingredient of a detergent composition, particularly in detergent compositions for laundry.
  • the object of the present invention was to provide a detergent composition wrapped in a water soluble foil providing excellent cleaning results.
  • a further object of the invention is to provide a fast and easy production process for said wrapped composition.
  • a unit packaged detergent composition wherein the detergent composition is wrapped a foil comprising in a water soluble material having a water content of below of 7.5% comprising a water soluble copolymer wherein the copolymer is a random or a block copolymer of a polyvinyl alcohol and a process of manufacturing such a packaged detergent composition.
  • detergent and/or additive compositions will be encompassed by the term "detergent”.
  • This detergent composition may be in the form of granules or of any non particulate solids such as bars or tablets or briquettes.
  • tablet encompasses in the following any form of non particulate solids.
  • Said tablet may have any shape.
  • said solid non particulate detergent tablet is formed in a shape to ensure the uniform dissolution of the tablet in the wash liquor.
  • the detergent and/or additive composition may comprise any ingredients known in the art for dish washing or laundry. Such ingredients may include for example surfactants, suds suppressers, bleach systems, chelating agents, builders, enzymes, fillers and perfumes, however, is not limited to these.
  • a predosed quantity of detergent is wrapped in a packaging to form a unit packaged detergent.
  • unit packaged detergent means a packaged amount of detergent suitable for one wash. Nevertheless, two or more unit packaged detergents according to the present invention may be used in a single wash to meet different washing conditions, like dirtiness of washing, amount of washing, volume of washing machine, hardness of water, temperature of water and type of detergent.
  • Said packaging is made of a water dissolvable material.
  • the unit packaged detergent according to the present invention may contain between 5grams and 30grams of detergent.
  • This unit packaged detergent of the present invention is placed in the machine without unwrapping the contained detergent from the packaging. This is possible, since said packaging is made of a water dissolvable material, as described above. To avoid the unwrapping the detergent from the packaging has several advantages. First, said unit packaged detergent prevents wasting through spillage of the detergent and/or additive composition. Spillage may occur during the measuring and/or dispensing into the dispenser of the washing machine or into a dispensing device. Second, said unit packaged detergent eliminates the need for the user to estimate the dosage of said composition required and ensures that the correct dosage of said composition per wash cycle is used by the user. Therefore, separate measuring and/or dosing devices are superfluous. Third, the fingers of a user do not come in contact with the detergent composition, which means that the user avoids to soil its fingers and/or hands.
  • the packaging of the unit packaged detergent is made of a material which dissolves in water, however, outside of water has a stiffness high enough to be processed at high speed during packaging of the detergent compositions.
  • the material is made essentially from a polymer compound and might include several additives.
  • the preferred stiffness of the polymeric material can obtained for example by reducing the water content of the material to a water content of below 7.5%, preferably 7% or less, particularly preferred 5% or less.
  • the water soluble polymer When used as a material for the formation of a water soluble / dispersible article the water soluble polymer has been found to be particularly suitable, specifically by displaying a very short dissolution/dispersion time and also by producing a low amount of residue in use. It will be appreciated that the resin is not a heterogeneous admixture of components but instead is homogenous.
  • water-soluble when referring to the polymer, water-soluble is herein defined when greater than 99% of such material dissolves within 15 minutes in a beaker containing 1 L of deionised water at 40° C which is stirred with a stirrer revolving at 200 r. p.m.
  • the water soluble polymer is preferably a film forming polymer.
  • the water soluble polymer may comprise a homopolymer or a copolymer. Where the water soluble polymer comprises a copolymer the copolymer may be a random or block copolymer.
  • the water soluble polymer comprises polyvinyl alcohol, polyvinyl pyrrolidone, partially hydrolysed polyvinyl acetate, polyvinyl acetate, a cellulose polymer (such as a cellulose ether e.g. hydroxypropyl cellulose), modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether or styrene.
  • a cellulose polymer such as a cellulose ether e.g. hydroxypropyl cellulose
  • modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts maleic anhydride, acrylamide, alkylene, vinylmethyl ether or styrene.
  • Preferred are copolymers of polyvinylalcohol
  • the water soluble polymer preferably has dispersant, anti-redeposition, soil releasing or other detergency properties.
  • the water soluble polymer may comprise a sulphonated polymer.
  • the water soluble polymer may comprise a polyamine or a modified polyamide compound.
  • Preferred examples include those derived from aspartic acid.
  • the water soluble polymer system may comprise a weakener, like for example glycerine.
  • the water soluble polymer system may comprise a soil release agent.
  • polymeric soil release agents include those having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to 30 oxypropylene units, said hydrophile segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 1 to 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH:)nOCH:CH 2 O-, where M is sodium and n is an integer from 4-6.
  • Other soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.
  • Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow).
  • Cellulosic soil release agents for use herein also include those selected from the group consisting of Ct-C4 alkyl and C4 hydroxyalkyl cellulose.
  • Further suitable surfactants include water-soluble cationic ethoxylated amine compounds with particulate soil/claysoil removal and/or anti-redeposition properties. Particularly preferred of these cationic compounds are ethoxylated cationic monoamines, diamines or triamines.
  • the water soluble polymer system may also further comprise partially water soluble or insoluble builder compounds, i.e. in addition to a water soluble / water dispersible builder.
  • Partially soluble and insoluble builder compounds are particularly suitable for disruption of the resin upon dissolution.
  • partially water soluble builders include the crystalline layered silicates. Preferred are the crystalline layered sodium silicates. Crystalline layered sodium silicates of this type preferably have a two dimensional 'sheet' structure, such as the so cabled 8-layered structure.
  • Further examples of largely water insoluble builders include the sodium aluminosilicates. Suitable aluminosilicates include the aluminosilicate zeolites.
  • the filler may comprise a crystal growth inhibitor.
  • Suitable types of crystal growth inhibitors include organodiphosphonic acids.
  • the organo diphosphonic acid is preferably a CICJ, diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1-hydroxy-1,1-diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • HEDP ethane 1-hydroxy-1,1-diphosphonic acid
  • a preferred polymer system in accordance with the invention meets one or more of the following physical parameters:
  • the additives are substantially water soluble so that the overall system retains its water solubility / water dispersibility.
  • the water soluble polymer system may contain a plasticizer with a content of less than 10 wt %, most preferably less than 5%.
  • Suitable types of plasticizers include solvents.
  • solvents include alkylene glycol mono lower alkyl ethers, glycerol, propylene glycols, ethoxylated or propoxylated ethylene or propylene, glycerol esters, glycerol triacetate, lower molecular weight polyethylene glycols, lower molecular weight methyl esters and amides.
  • a preferred type of surfactant for use herein comprises the mono-, di-, trim, or tetra-C 2 -C 3 alkylene glycol mono C 2 -C 6 alkyl ethers.
  • Such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol mono ethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol mono butyl ether and dipropylene glycol monobutyl ether are especially preferred.
  • PEGs polyethylene glycols
  • PEGs polyethylene glycols
  • Such materials preferrably have molecular weights of at least 150. PEGs ofmolecular weight ranging from 200 to 600 are most preferred.
  • Yet another preferred type of surfactant comprises lower molecular weight methyl esters. Such materials are those of the general formula: R-C(0)- OCH 3 wherein R ranges from 1 to 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecancate.
  • Suitable types of plasticisers also include nonionic surfactants.
  • Preferred nonionic surfactants incorporated into the resin provide a suds suppression benefit.
  • the alkyl ethoxylate condensation products of an alcohol with from 1 to 80 moles of an alkylene (liner/branched aliphatic / aromatic optionally subsituted C 2 to C 20 alkylene) oxide are suitable for this use.
  • the alkyl chain of the alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • Suitable surfactants include POLY-TERGENT(R) SLF-18B nonionic surfactants by Olin Corporation.
  • Ethoxylated C 6 -C 18 fatty alcohols and C 6 -C 18 mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein.
  • the ethoxylated fatty alcohols are the C 10 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the C 12 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
  • the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and exhibits water insolubility.
  • Examples of compounds of this type include certain of the commercially-available Pluronic (TM) surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000.
  • this type of nonionic surfactant include certain of the commercially available Tetronic(TM) compounds, marketed by BASF.
  • the polymer system may comprises a mixed nonionic surfactant system.
  • Suitable lubricants include fatty esters of mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • the fatty acid portion of the fatty ester can be obtained from mono- or poly-carboxylic acids having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • monocarboxylic fatty acids include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid, lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valerie acid, lactic acid, glycolic acid and beta,beta'-dihydroxyisobutyric acid.
  • Suitable polycarboxylic acids include: n-butyl-malonic acid, isocitric acid, citric acid, maleic acid, malic acid and succinic acid.
  • the fatty alcohol radical in the fatty ester can be represented by mono- or polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon chain.
  • suitable fatty alcohols include; behenyl, arachidyl, cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol, isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol, pentaerythritol, sorbitol or sorbitan.
  • the fatty acid and/or fatty alcohol group of the fatty ester adjunct material has from 1 to 24 carbon atoms in the alkyl chain.
  • Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan esters wherein the fatty acid portion of the ester normally comprises a species selected from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
  • the glycerol esters are also highly preferred.
  • Specific examples of fatty alcohol esters for use herein include: stearyl acetate, palmityl all-lactate, cocoyl isobutyrate, oleyl maleate, oleyl dimaleate, and tallowyl proprionate.
  • Fatty acid esters useful herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol mono stearate, ethylene glycol mono stearate, sorbitan esters.
  • Suitable sorbitan esters include sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed tallow alkyl sorbitan mono- and all-esters.
  • Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, glycerol monobehenate, and glycerol distearate are preferred glycerol esters herein.
  • Further suitable agents include triglycerides, mono or diglycerides, and wholly or partially hydrogenated derivatives thereof, and any mixtures thereof.
  • Suitable sources of fatty acid esters include vegetable and fish oils and animal fats. Suitable vegetable oils include soy bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.
  • Waxes including microcrystalline waxes are possible lubricants, although much less preferred in the present invention due to their poor solubility in water.
  • Preferred waxes have a melting point in the range from 35° C to 110° C and comprise generally from 12 to 70 carbon atoms.
  • Preferred are petroleum waxes of the paraffin and microcrystalline type which are composed of long-chain saturated hydrocarbon compounds.
  • the resin may include a colourant.
  • Colourant when present as a component in the resin is preferably present at a level of from 0.001wt % to 1.5wt %, preferably from 0.01wt % to 1.0wt %, most preferably from 0.1wt % to 0.3wt %.
  • the colourant may comprise a dye or a pigment.
  • suitable dyes include reactive dyes, direct dyes, azo dyes.
  • Preferred dyes include phthalocyanine dyes, anthraquinone dye, quinoline dyes, monoazo, disazo and polyazo. More preferred dyes include anthraquinone, quinoline and monoazo dyes.
  • Preferred dyes include SANDOLAN E-HRL 180% (tradename), SANDOLAN MILLING BLUE (tradename), TURQUOISE ACID BLUE (tradename) and SANDOLAN BRILLIANT GREEN (tradename) all available from Clariant UK, HEXACOL QUINOLINE YELLOW (tradename) and HEXACOL BRILLIANT BLUE (tradename) both available from Paintings, UK, ULTRA MARINE BLUE (tradename) available from Holliday or LEVAFIX TURQUISE BLUE EBA (tradename) available from Bayer, USA.
  • the article preferably comprises a cleaning composition.
  • the cleaning composition may be an automatic dishwashing detergent or additive, a laundry detergent or additive, a hard surface cleaning composition (such as an all-purpose cleaner) or a toilet reservoir cleaner.
  • the article When used in a dishwasher application the article has been found to be particularly suitable since the packaging resin is formed of highly water soluble components; in use the article has been found to overcome the problem of residue formation on items being cleaned, said residue being formed of packaging material having poor solubility.
  • the cleaning composition may be a powder, a tablet or a liquid, but if a liquid, is preferably a low water formulation, preferably having a maximum water content of 5 wt%, in order to maintain the integrity of the article. It will be appreciated that a higher water content may be present where the water is chemically or physically bound (i.e. by a high ionic strength solution).
  • the cleaning composition may consist of among others a builder system, a bleach system, an enzyme system, a viscosity modifier, a perfume or odor control system, one or more colourants, an acidity modifier, a bactericide / fungicide, a surfactant system, an enzyme system and a polymer system.
  • the composition may be formulated having regard to the fact that the user will not come into contact with the composition, whether by inhalation or by skin contact.
  • the composition may include an enzyme, without concern about physical contact between the composition containing the enzyme, and the user.
  • a fast dissolving rate is achieved by decreasing the thickness of said water dissolvable material and/or increasing the temperature of the water.
  • the present invention uses water dissolvable polymeric materials of thicknesses between 10 ⁇ m and 80 ⁇ m, more preferably between 20 ⁇ m and 60 ⁇ m.
  • said unit packaged detergent may be provided in a bag which contains substantially in a loose manner the detergent or as an additional layer on the outer surface of a detergent tablet (tablet is wrapped).
  • said unit packaged detergents are delivered in a container made of any material, like carton, plastic or metal if required supplied with a coating.
  • said unit packaged detergents may be packed and sold as individually packed units separated from each other or in a string, each unit packaged detergents being individually separable by a perforation line. Therefore, each unit packaged detergent can be individually torn off from said string and placed without unwrapping the contained detergent in the washing machine.
  • said packaging material of the unit packaged detergent may be translucent, opaque or having a printed side.
  • said unit packaged detergent may comprise an additive which provides an unbearable bitter taste.
  • This additive may be coated onto said unit packaged detergent. This improves the prevention that children may accidentally ingest the complete packaging detergent.
  • the unit packaged detergent according to the present invention may be manufactured in the following way:
  • the wrapping / packaging speed for example on a high speed horizontal form fill seal flowwrapper system (for example from Theeberg, SIG, Fuji, Bosch) is higher and therefore the manufacturing process has a higher output while remaining the stability of the packing process.
  • Packaging output raises from about 550 tablets per minute to about 725 tablets per minute. Thickness of the foil in this packaging process was 40 ⁇ m.
  • the unit packaged detergent according to the present invention may be used in the following manner:
  • a boron free automatic dishwashing detergent with a 4-in-1 formulation known in the art with and without a water soluble foil is tested on the performance of primary cleaning.
  • the detergent is tablet shaped, consisting of three layers and has a weight of 20.0 grams.
  • the water soluble foil has a weight of about 0.3 grams.
  • the water soluble foil consists mainly of polyvinylalcohol - maleic acid (PVOH/MA) copolymer.
  • the cleaning performance test is carried out according to the Fresenius test method 0406 vers 1 with a water hardness of 21°GH.
  • the selected cleaning program is '50°C normal' on a 'Miele G651SC' dishwashing machine.
  • Soiling of oat flakes, minced meat, milk, tea, tomato/cheese, egg yolk and rice starch on various soil carriers are prepared and toughened. These soilings are cleaned in a dishwashing machine. The soiling left behind after washing is judged gravimetrically (in % removal) or visually on a scale were 1 is no removal and 10 is complete removal of the soil. This test is repeated five times.
  • a boron free automatic dishwashing detergent with a 4-in-1 formulation known in the art with and without an water soluble foil is tested on the performance of the rinse aid function.
  • the detergent is tablet shaped, consisting of three layers and has a weight of 20.0 grams.
  • the water soluble foil has a weight of about 0.3 grams.
  • the water soluble foil consists mainly of PVOH/MA copolymer.
  • the rinse aid performance test is carried out according to the Fresenius Standardmethode 10_2000 vers. 02, with a water hardness of 21°GH.
  • the selected cleaning program is '55°C universal' on a 'Miele G666SC turbothermic plus' dishwashing machine.
  • the dishwashing machine is loaded with crystal glasses, china plates, glass plates, SAN plates and stainless steel knives. These items are washed in an dishwashing machine were 50 grams additional soil is added. After each cleaning cycle the items are judged visually on spots and streaks on a scale where 0 is very large stripes and/or very numerous large spots and 8 is free of spots and stripes. The test is repeated three times the results are cumulative.
  • a boron free automatic dishwashing detergent with a 4-in-1 formulation known in the art with and without a water soluble foil is tested on the performance of primary cleaning.
  • the detergent is tablet shaped, consisting of three layers and has a weight of 20.0 grams.
  • the water soluble foil has a weight of about 0.3 grams.
  • the water soluble foil consists mainly of polyvinylalcohol - methacrylic acid (PVOH/MAA) copolymer.
  • the cleaning performance test is carried out according to the Fresenius test method 0406 vers 1 with a water hardness of 21°GH.
  • the selected cleaning program is '50°C normal' on a 'Miele G651SC' dishwashing machine.
  • Soiling of oat flakes, minced meat, milk, tea, tomato/cheese, egg yolk and rice starch on various soil carriers are prepared and toughened. These soilings are cleaned in a dishwashing machine. The soiling left behind after washing is judged gravimetrically (in % removal) or visually on a scale were 1 is no removal and 10 is complete removal of the soil. This test is repeated five times.
  • a boron free automatic dishwashing detergent with a 4-in-1 formulation known in the art with and without an water soluble foil is tested on the performance of the rinse aid function.
  • the detergent is tablet shaped, consisting of three layers and has a weight of 20.0 grams.
  • the water soluble foil has a weight of about 0.3 grams.
  • the water soluble foil consists mainly of PVOH/MAA copolymer.
  • the rinse aid performance test is carried out according to the Fresenius Standardmethode 10_2000 vers. 02, with a water hardness of 21°GH.
  • the selected cleaning program is '55°C universal' on a 'Miele G666SC turbothermic plus' dishwashing machine.
  • the dishwashing machine is loaded with crystal glasses, china plates, glass plates, SAN plates and stainless steel knives. These items are washed in an dishwashing machine were 50 grams additional soil is added. After each cleaning cycle the items are judged visually on spots and streaks on a scale where 0 is very large stripes and/or very numerous large spots and 8 is free of spots and stripes. The test is repeated three times the results are cumulative.

Claims (22)

  1. Eine als Einheitsdosis verpackte Geschirrreinigungszusammensetzung, die in einer Folie verpackt ist, die ein wasserlösliches Material mit einem Wassergehalt von unterhalb 7,5 % umfasst, das ein wasserlösliches Copolymer umfasst, wobei das Copolymer ein statistisches oder ein Blockcopolymer ist und das Copolymer ein Copolymer eines Polyvinylalkohols umfasst.
  2. Die Zusammensetzung gemäß Anspruch 1, wobei der Wassergehalt des wasserlöslichen Materials 7 % oder weniger, weiter bevorzugt 5 % oder weniger, ist.
  3. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei das Polymer ein filmbildendes Polymer ist.
  4. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei das Polymer Polyvinylpyrrolidon, partiell hydrolysiertes Polyvinylacetat, Polyvinylacetat, ein Cellulosepolymer, Celluloseether, Hydroxypropylcellulose, modifizierte Acryl-, Fumar-, Malein-, Itacon-, Aconit-, Mesacon-, Citracon- und Methylenmalonsäure oder deren Salze, Maleinsäureanhydrid, Acrylamid, Alkylen, Vinylmethylether oder Styrol umfasst.
  5. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei das Copolymer ein Copolymer von Polyvinylalkohol mit modifizierter Acrylsäure ist.
  6. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei das Polymer dispergierende, Anti-Wiederablagerungs-, Soil-Release- oder andere Reinigungsmitteleigenschaften hat.
  7. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei das Polymer ein sulphoniertes Polymer umfasst.
  8. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei das Polymer ein Polyamin oder eine modifizierte Polyamidverbindung, die bevorzugt von Aspartinsäure abgeleitet ist, umfasst.
  9. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Folie außerdem einen Weichmacher, bevorzugt Glycerin, umfasst.
  10. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Folie außerdem ein Soil-Release-Mittel umfasst.
  11. Die Zusammensetzung gemäß Anspruch 10, wobei das Soil-Release-Mittel ausgewählt aus der Gruppe umfassend polymere Soil-Release-Mittel, celluloseartiges Soil-Release-Mittel und wasserlösliche kationische ethoxylierte Aminverbindungen.
  12. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Folie außerdem teilweise wasserlösliche oder unlösliche Builderverbindungen, bevorzugt ein kristallines Natriumschichtsilicat oder ein Natriumaluminosilicat, umfasst.
  13. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Folie außerdem ein Schmiermittel als ein rheologiemodifizierendes Additiv enthält, bevorzugt ausgewählt aus der Gruppe umfassend Fettsäureester, die aus ein- oder mehrwertigen Alkoholen mit 1 bis 40 Kohlenstoffatomen in der Kohlenwasserstoffkette mit Mono- oder Polycarbonsäuren mit einer oder mehreren Säuregruppen mit 1 bis 40 Kohlenstoffatomen in der Kohlenwasserstoffkette erhalten werden.
  14. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Folie außerdem einen Weichmacher als rheologiemodifizierendes Additiv enthält, bevorzugt mit einem Gehalt von weniger als 10 Gew.-% und/oder bevorzugt ausgewählt ist aus der Gruppe umfassend Lösungsmittel, nichtionische Tenside oder ein Mischsystem nichtionischer Tenside.
  15. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Folie außerdem ein Färbemittel enthält.
  16. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Folie eine Dicke von zwischen 10 µm und 80 µm, bevorzugt zwischen 20 µm und 60 µm (Mikrometer) aufweist.
  17. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei das wasserlösliche Material oder die Folie mit einem Additiv beschichtet ist, das einen unerträglich bitteren Geschmack abgibt.
  18. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Geschirrreinigerzusammensetzung borfrei ist.
  19. Die Zusammensetzung gemäß einem der vorhergehenden Ansprüche, wobei die Geschirrreinigerzusammensetzung eine Tablettenform aufweist.
  20. Verwendung einer Folie, die ein wasserlösliches Material mit einem Wassergehalt von weniger als 7,5 % umfasst, enthaltend das wasserlösliche Copolymer gemäß einem der vorhergehenden Ansprüche zum Einhüllen einer Geschirrreinigerzusammensetzung.
  21. Ein Verfahren zum Herstellen der verpackten Geschirrreinigerzusammensetzung gemäß der Ansprüche 1 bis 19 unter Verwendung einer Folie, die ein wasserlösliches Material mit einem Wassergehalt von weniger als 7,5 % umfasst, das ein wasserlösliches Copolymer gemäß einem der Ansprüche 1 bis 19 enthält.
  22. Verfahren gemäß Anspruch 21, wobei ein horizontales Hochgeschwindigkeits-Schlauchbeutelverpackungssystem verwendet wird.
EP07700205.3A 2006-01-14 2007-01-10 Umhüllte reinigungsmittelzusammensetzungen und herstellungsverfahren Active EP1971633B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP07700205.3A EP1971633B1 (de) 2006-01-14 2007-01-10 Umhüllte reinigungsmittelzusammensetzungen und herstellungsverfahren
PL07700205T PL1971633T3 (pl) 2006-01-14 2007-01-10 Opakowane kompozycje detergentowe i sposób ich wytwarzania

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06000790A EP1808482A1 (de) 2006-01-14 2006-01-14 Umhüllte Reinigungszusammensetzungen und Herstellungsverfahren
PCT/EP2007/000149 WO2007080105A1 (en) 2006-01-14 2007-01-10 Wrapped detergent compositions and manufacture process
EP07700205.3A EP1971633B1 (de) 2006-01-14 2007-01-10 Umhüllte reinigungsmittelzusammensetzungen und herstellungsverfahren

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EP1971633A1 EP1971633A1 (de) 2008-09-24
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Families Citing this family (6)

* Cited by examiner, † Cited by third party
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WO2013130466A1 (en) 2012-02-28 2013-09-06 The Procter & Gamble Company Method for forming packages
US10259602B2 (en) 2012-02-28 2019-04-16 The Procter And Gamble Company Method for forming packages
CN104487353B (zh) 2012-07-24 2017-06-09 宝洁公司 用于将产品封装进容器中的方法和设备
US10053656B2 (en) 2013-08-14 2018-08-21 Budich International Gmbh Multiphase detergent tablet
US9783330B2 (en) 2014-03-06 2017-10-10 The Procter & Gamble Company Method and apparatus for shaping webs in a vertical form, fill, and sealing system
US9643812B2 (en) 2014-03-06 2017-05-09 The Procter & Gamble Company Method for pleating or shaping a web

Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300546A (en) 1965-10-05 1967-01-24 American Cyanamid Co Water soluble envelope prepared from a graft polymer of alkyl acrylate on a polyvinyl alcohol/polyvinyl acetate co-polymer
US4115292A (en) 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US4119604A (en) 1976-08-18 1978-10-10 E. I. Du Pont De Nemours And Company Polyvinyl alcohol compositions for use in the preparation of water-soluble films
US4747976A (en) 1987-05-14 1988-05-31 The Clorox Company PVA films with nonhydrolyzable anionic comonomers for packaging detergents
EP0291198A2 (de) 1987-05-14 1988-11-17 The Clorox Company Folien aus mit nicht hydrolysierbaren anionischen Comonomeren modifizierten PVA,die Additive enthalten
JPH06240091A (ja) 1993-02-18 1994-08-30 Aisero Kagaku Kk ポリビニルアルコール系フィルム
EP0700989A1 (de) 1994-09-12 1996-03-13 The Procter & Gamble Company Portionsverpacktes Waschmittel
DE29801621U1 (de) 1998-01-31 1998-03-19 Fuchs & Boehme Gmbh Chem Fab Portionsverpackung
WO2000055068A1 (en) 1999-03-17 2000-09-21 Unilever Plc Water soluble package
CA2307429A1 (en) 1999-05-03 2000-11-03 Henkel Kommanditgesellschaft Auf Aktien Coated detergent tablets
CA2312157A1 (en) 1999-06-25 2000-12-25 Henkel Kommanditgesellschaft Auf Aktien An active-substance portion pack
WO2001079417A1 (en) 2000-04-14 2001-10-25 Unilever N.V. Water soluble package and liquid contents thereof
EP1155804A1 (de) 2000-05-19 2001-11-21 The Nippon Synthetic Chemical Industry Co., Ltd. Verfahren zur Herstellung eines geprägten Polyvinylalkoholfilms
WO2002016205A1 (en) 2000-08-25 2002-02-28 Reckitt Benckiser (Uk) Limited Water-soluble thermoformed containers comprising aqueous compositions
WO2002016222A1 (en) 2000-08-25 2002-02-28 Reckitt Benckiser (Uk) Limited Water-soluble thermoformed containers comprising aqueous compositions
WO2002042408A2 (en) 2000-11-27 2002-05-30 The Procter & Gamble Company Detergent products, methods and manufacture
WO2002058910A1 (en) 2001-01-26 2002-08-01 Reckitt Benckiser (Uk) Limited Process for preparing a laminated, thermoformed film
EP1251147A1 (de) 2001-04-20 2002-10-23 Kuraray Co., Ltd. Wasserlösliche Folie und Verpackung die diese verwendet
EP1256622A1 (de) 2001-05-08 2002-11-13 The Procter & Gamble Company Kit zum Handgeschirrspülen
US20030069155A1 (en) 2001-05-08 2003-04-10 Mangin Raphael Louis Kit of water-soluble or water dispersible pouches
EP1394065A1 (de) 2002-06-17 2004-03-03 Unilever N.V. Waschmittelbeutel
US20040072709A1 (en) 2000-10-18 2004-04-15 Ralf Wiedemann Cleaning compositions packaged in ethoxlated polyvinylalcohol materials
EP1418196A1 (de) 2002-11-11 2004-05-12 The Nippon Synthetic Chemical Industry Co., Ltd. Wasserlöslicher Film
US20040186035A1 (en) 2003-03-19 2004-09-23 The Procter & Gamble Company Water-soluble, liquid-containing pouch
US20050003982A1 (en) 2003-06-03 2005-01-06 Beckholt Dennis Allen Detergent pouch
EP1512701A1 (de) 2003-09-05 2005-03-09 The Procter & Gamble Company Polyvinylalkohol Copolymere und daraus formbare wasserlösliche Filme und Behälter
US20050202990A1 (en) 2000-05-11 2005-09-15 The Procter & Gamble Company Laundry system having unitized dosing
EP2003060A1 (de) 2007-06-15 2008-12-17 CFS Weert B.V. Verpackungsmaschine mit einem drehmomentgesteuerten Motor

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6197348A (ja) * 1984-10-17 1986-05-15 Kao Corp 耐湿、防湿性に優れた水溶性フイルム
DE19961661A1 (de) * 1999-06-25 2000-12-28 Henkel Kgaa Wirkstoffportionspackung
DE10223266C1 (de) * 2002-05-24 2003-11-20 Henkel Kgaa Verwendung Einspülkammer-dosierbare Tabletten-Portionen
US7022656B2 (en) * 2003-03-19 2006-04-04 Monosol, Llc. Water-soluble copolymer film packet

Patent Citations (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3300546A (en) 1965-10-05 1967-01-24 American Cyanamid Co Water soluble envelope prepared from a graft polymer of alkyl acrylate on a polyvinyl alcohol/polyvinyl acetate co-polymer
US4119604A (en) 1976-08-18 1978-10-10 E. I. Du Pont De Nemours And Company Polyvinyl alcohol compositions for use in the preparation of water-soluble films
US4115292A (en) 1977-04-20 1978-09-19 The Procter & Gamble Company Enzyme-containing detergent articles
US4747976A (en) 1987-05-14 1988-05-31 The Clorox Company PVA films with nonhydrolyzable anionic comonomers for packaging detergents
EP0291198A2 (de) 1987-05-14 1988-11-17 The Clorox Company Folien aus mit nicht hydrolysierbaren anionischen Comonomeren modifizierten PVA,die Additive enthalten
JPH06240091A (ja) 1993-02-18 1994-08-30 Aisero Kagaku Kk ポリビニルアルコール系フィルム
EP0700989A1 (de) 1994-09-12 1996-03-13 The Procter & Gamble Company Portionsverpacktes Waschmittel
WO1996008555A1 (en) 1994-09-12 1996-03-21 The Procter & Gamble Company A unit packaged detergent
DE29801621U1 (de) 1998-01-31 1998-03-19 Fuchs & Boehme Gmbh Chem Fab Portionsverpackung
WO2000055068A1 (en) 1999-03-17 2000-09-21 Unilever Plc Water soluble package
CA2307429A1 (en) 1999-05-03 2000-11-03 Henkel Kommanditgesellschaft Auf Aktien Coated detergent tablets
CA2312157A1 (en) 1999-06-25 2000-12-25 Henkel Kommanditgesellschaft Auf Aktien An active-substance portion pack
WO2001079417A1 (en) 2000-04-14 2001-10-25 Unilever N.V. Water soluble package and liquid contents thereof
US20050202990A1 (en) 2000-05-11 2005-09-15 The Procter & Gamble Company Laundry system having unitized dosing
EP1155804A1 (de) 2000-05-19 2001-11-21 The Nippon Synthetic Chemical Industry Co., Ltd. Verfahren zur Herstellung eines geprägten Polyvinylalkoholfilms
WO2002016205A1 (en) 2000-08-25 2002-02-28 Reckitt Benckiser (Uk) Limited Water-soluble thermoformed containers comprising aqueous compositions
WO2002016222A1 (en) 2000-08-25 2002-02-28 Reckitt Benckiser (Uk) Limited Water-soluble thermoformed containers comprising aqueous compositions
US20040072709A1 (en) 2000-10-18 2004-04-15 Ralf Wiedemann Cleaning compositions packaged in ethoxlated polyvinylalcohol materials
WO2002042408A2 (en) 2000-11-27 2002-05-30 The Procter & Gamble Company Detergent products, methods and manufacture
WO2002058910A1 (en) 2001-01-26 2002-08-01 Reckitt Benckiser (Uk) Limited Process for preparing a laminated, thermoformed film
EP1251147A1 (de) 2001-04-20 2002-10-23 Kuraray Co., Ltd. Wasserlösliche Folie und Verpackung die diese verwendet
EP1256622A1 (de) 2001-05-08 2002-11-13 The Procter & Gamble Company Kit zum Handgeschirrspülen
US20030069155A1 (en) 2001-05-08 2003-04-10 Mangin Raphael Louis Kit of water-soluble or water dispersible pouches
EP1394065A1 (de) 2002-06-17 2004-03-03 Unilever N.V. Waschmittelbeutel
EP1418196A1 (de) 2002-11-11 2004-05-12 The Nippon Synthetic Chemical Industry Co., Ltd. Wasserlöslicher Film
US20040186035A1 (en) 2003-03-19 2004-09-23 The Procter & Gamble Company Water-soluble, liquid-containing pouch
WO2004085586A2 (en) 2003-03-19 2004-10-07 The Procter & Gamble Company Water-soluble, liquid-containing pouch
US20050003982A1 (en) 2003-06-03 2005-01-06 Beckholt Dennis Allen Detergent pouch
EP1512701A1 (de) 2003-09-05 2005-03-09 The Procter & Gamble Company Polyvinylalkohol Copolymere und daraus formbare wasserlösliche Filme und Behälter
EP2003060A1 (de) 2007-06-15 2008-12-17 CFS Weert B.V. Verpackungsmaschine mit einem drehmomentgesteuerten Motor

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Polyvinyl alcohol-developments", 1992, article "Polyvinyl alcohol acrylate and methacrylate copolymers and their applications in textile sizing and films", pages: 361 - 375, XP055265243
"Properties of polyvinyl alcohol films", FINCH POLYVINYL ALCOHOL, PROPERTIES AND APPLICATIONS, 1973, pages 378 - 384, XP055680811
FINCH, POLYVINYL ALCOHOL - DEVELOPMENTS, 1973, pages 422 - 432, XP055676844
FINCH, POLYVINYL ALCOHOL - PROPERTIES AND APPLICATIONS, pages 352 - 369, XP055676842

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Publication number Publication date
PL1971633T3 (pl) 2019-10-31
ES2731158T3 (es) 2019-11-14
WO2007080105A1 (en) 2007-07-19
EP1971633A1 (de) 2008-09-24
DK1971633T3 (da) 2019-08-05
EP1808482A1 (de) 2007-07-18

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