EP2196531B1 - Pastille de détergent revêtue d'un polymère - Google Patents
Pastille de détergent revêtue d'un polymère Download PDFInfo
- Publication number
- EP2196531B1 EP2196531B1 EP08021163.4A EP08021163A EP2196531B1 EP 2196531 B1 EP2196531 B1 EP 2196531B1 EP 08021163 A EP08021163 A EP 08021163A EP 2196531 B1 EP2196531 B1 EP 2196531B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- detergent
- acid
- detergent composition
- water
- 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.)
- Not-in-force
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0082—Coated tablets
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- 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
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
Definitions
- the present invention relates to a coated detergent and/or additive composition e.g. for the dish washing or laundry machine or water softener tablets coated with a water or temperature dissolvable polymer material and a process of manufacturing thereof.
- the traditional form of detergent and/or additive compositions for use in dish washing or washing machines 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 machine or in an adequate dispensing device which is then placed in said machine.
- One common embodiment is to provide detergent tablets as packaged pieces, either in a package which has to be opened before the tablet is put in the dish washing machine or washing machine, or packaged in a water soluble package left around the tablet when putted in the machine.
- Water soluble packages comprising an agent to be dispensed in an aqueous medium are well known.
- 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.
- Unwrapped tablets having a coating primarily are provided for laundry dishwashing compositions, particularly for increasing mechanical resistance of the tablet and for stabilise them.
- WO00/66701 describe shaped detergent tablets coated with several types of water soluble polymers, particularly with (co)polymers comprising acid monomers and/or unsaturated monomers.
- US 6,576,599 discloses dishwashing tablets having a water insoluble coating for improving mechanical stability of the tablets.
- WO 04/ 20569 A1 describes a detergent particle having a base layer of a fine powder dispersed in a binder on the surface of the particle, said base layer is coated with a surface modifier.
- EP 1 903 099 A1 describes coated tablets, particularly automatic dishwashing tablets coated with proteins, sugars or shellac.
- DE 10050958 A1 and WO 62/32780 A2 both describe detergent tablets coated or packaged with a polyethylene glycol graft copolymer.
- DE 10207427 A1 describes a readily dissolvable coating composition based on polyvinyl alcohol-polyether graft copolymers and a further compound having a hydroxy-, amid- or ester function.
- the object of the present invention was to provide a detergent composition providing safe and easy handling for the user and good dissolution properties of the tablet.
- a unit coated detergent composition wherein the detergent composition is coated with a water dissolvable or dispersible coating comprising at least 1% up to 99% of polyvinyl alcohol-polyethylene glycol graft copolymer and a low molecular weight compound selected from sugars comprising 1 to 10 sugar units or any amino acid, preferably natural amino acids or a mixture of sugars, a mixture of amino acids or a mixture of sugars and amino acids.
- detergent in the following any 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, e.g. compressed detergent compositions or tablets comprising a compressed as well as a non-compressed portion.
- Said tablet may have any shape, including so-called “mould tablets” having a cavity for filling with detergent ingredients not contained in the compressed portion. Such mould tablets are well known in the art.
- Even the compressed portion of the tablet may comprise several phases like e.g. different layers comprising different detergent ingredient compositions.
- said detergent tablet is formed In a shape to ensure the uniform or the step-wise 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, laundry or water softening. Such ingredients may include for example surfactants, suds suppressers, bleach systems, chelating agents, builders, enzymes, fillers and perfumes, however, is not limited to these.
- One particular preferred embodiment of the present invention is a shaped body for automatic dishwashing formed of a particulate detergent composition, wherein the detergent composition comprises any of the ingredients which are typical for such compositions.
- the detergent composition comprises any of the ingredients which are typical for such compositions.
- Such ingredients are not limiting the invention, however, examples of suitable ingredients are mentioned below.
- a predosed quantity of detergent is coated on at least one surface side with a water soluble or dissolvable polymer material and a low molecular weight compound as defined in claim 1 to provide a coated detergent shaped body as a "unit coated detergent".
- unit coated detergent means an amount of detergent composition suitable for one wash. Nevertheless, two or more unit coated 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 coating is made of a water dissolvable or water and temperature dissolvable material.
- the unit coated detergent according to the present invention may contain between 5 grams and 60 grams of detergent.
- This unit coated detergent of the present invention is placed in the machine without any further handling step. This is possible, since said coating is made of a water solvable, dissolvable or dispersible material.
- Providing the detergent in coated form has several advantages. First, said unit coated 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 coated 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. Either in case of water solvable films wrapped around the detergent unit people may be confused and try to open said wrapping.
- the coating of the unit coated detergent is made of a material which is water soluble or dissolves in water or is dispersible in water, is harmless for the user and can be processed at high speed during manufacture of the coating of detergent compositions and allows fast and residue-free dissolution of the tablet.
- the coating is provided at least on one surface side of the shaped body, preferably on at least two surface sides, e.g. on the both "top surfaces", which means the upper and the lower surface of the detergent tablet, including or excluding any non-compressed portion of the tablet, which means that either compressed portion is coated, non-compressed portion is not or both portions are coated. Further preferred the coating is applied on all surfaces of the detergent tablet.
- said coating material comprises at least 1% to 99% of a polyvinyl alcohol-polyethylene glycol graft copolymer and a low molecular compound selected from sugars comprising 1 to 10 sugar units or any amino acid or a mixture of sugars, a mixture of amino acids or a mixture of amino acids or a mixture of sugars and amino acids.
- a particularly preferred polyvinyl alcohol-polyethylene glycol graft copolymer according to the invention is the polymer Kollicoat® IR from BASF, Germany.
- the polymeric ingredient portion of the coating may consist essentially of said polymer and a low molecular compound selected from sugars comprising 1 to 10 sugar units or any amino acid or a mixture of sugars, a mixture of amino acids or a mixture of amino acids or a mixture of sugars and amino acids. or can be a combination of said polymer with
- compositions mentioned under items A.) and C.) optionally can comprise a binder material.
- the coating comprises at least 1% by weight or at least 5% by weight, preferably at least 15 % by weight, more preferably at least 35 % by weight, most preferably at least 50 % by weight and up to 99 % by weight, up to 95 % by weight, up to 90% by weight or maybe up to 75 % by weight of the polyvinyl alcohol - polyethylene glycol graft copolymer.
- the coating may comprise any of the materials mentioned in A.) and C.), preferred of the materials mentioned in A.) or B.), particularly preferred the materials mentioned in A.)
- the materials mentioned in A.) are mostly preferred for the reason that the materials are easily providing a coating, are clearly non-toxic, non-expensive and can be easily and fast dissolved in water or in wash load, particularly in heated water/wash load like in an automatic dishwashing apparatus.
- the coating composition comprises at least 1% by weight or at least 5% by weight, preferably at least 15% by weight, more preferably at least 35% by weight, most preferably at least 50% by weight of the low molecular weight compound as defined in claim 1, and up to 99 %, or up to 95 %, preferably up to 75 %, more preferably up to 50 % by weight of said low molecular compounds.
- the coating comprises further any of the materials of A) or C) said compounds as well are added in these weight ranges.
- the coating can consist of the above mentioned ingredients or can contain as further ingredients any of them mentioned below.
- the water soluble low molecular weight compound is any type of sugar, amino acid or other low molecular acids, e.g. citric acid.
- One particular advantage of these materials is on one side the water solubility /dispersibility on the other hand the non-toxicity of the compounds.
- water-soluble/dissolvable/dispersible is herein defined when more than 99% of a coating (layer) of such material dissolves within 15 minutes, preferably within 5 min in a beaker containing 1 L of deionised water at 40° C which is stirred with a stirrer revolving at 200 r. p.m. It is pointed out that materials can be used as ingredients for the coating which itself may not be soluble, but e.g. dispersible, as long as the coating comprising said material is dissolved by water.
- Preferred additional water soluble / dissolvable / dispersible materials are cellulose, particularly preferred cellulose fibres or microcristalline cellulose with an average particle size in dry state of below 1000 ⁇ m, preferably below 500 ⁇ m, more preferred 250 ⁇ m or smaller and particularly preferred of between 20 and 150 ⁇ m; starch or starch derivatives, pectine like glycogene or - most preferred - proteins or peptides (at least 10mer), particularly gelatine or derivatives or peptide fragments thereof.
- Suitable compounds are "low molecular weight compounds" like C 3 -C 6 sugars in aldose or ketose form like allose, altrose, glucose, mannose, gulose, idose, galactose, talose, psicose, fructose, sorbose, tagatose, xylulose, ribulose, ribose, arabinose, xylose, lyxose, threose, erythrose, erythrulose, dihydroxy acetone or glycerol aldehyde or disaccharides like for example saccharose, lactose, maltose or Isomalt or oligosaccharides comprising 3 to 10 sugar units or amino acids, preferably natural amino acids (commonly contained in natural proteins) without being restricted to the mentioned examples.
- One particularly preferred low molecular weight compound is the sugar Isomalt ST, comprising 6-O- ⁇ -D-glucopyranosyl-D-sorbite and 1-O- ⁇ -D-glucopyranosyl-D-mannite dihydrate units. Further information about said sugar is available under www.chemistryworld.de/schene/prs-html/analysen/2444-snz.htm.
- polymorphic SiO2 e.g.of theAerosil type from Degussa, Germany
- water soluble / dissolvable / dispersible compounds may be used in combination with an additional water soluble or dispersible polymer.
- water soluble/dispersible polymer it will be appreciated that the water soluble polymer may comprise a homopolymer or a copolymer.
- the copolymer may be a random or block copolymer.
- a suitable additional water soluble polymer may comprise a cellulose derivative such as a cellulose ether e.g. hydroxypropyl cellulose, carboxymethyl cellulose, or the polymer comprises monomers of polyvinyl alcohol, polyvinyl pyrrolidone, partially hydrolysed polyvinyl acetate, polyvinyl acetate, modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether or styrene.
- Such polymers can either be homo- or copolymers of the mentioned monomer units.
- polyvinyl pyrrolidone homopolymers or copolymers of polyvinylalcohol preferably copolymers of polyvinylalcohol and polycarboxylates, most preferred are copolymers of polyvinylalcohol with maleic acid or (meth)acrylic acid.
- the additional water soluble polymer preferably has dispersant, anti-redeposition, soil releasing or other detergency properties.
- the additional water soluble polymer may further be a polymer comprising sulfonic acid groups like e.g. the polymers described in EP-A 1 299 513 , EP-A 1 363 986 , WO 95/12654 or EP-A 0 877 002
- 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 coating system in accordance with the invention meets one or more of the following physical parameters:
- the water soluble coating system may contain a plasticizer with a content of more than 0.01 %, preferably more than 0.1 %, more preferred more than 0.5% and most preferred 1% or more and up to 30%, preferably less than 30 wt %, more preferably 10% or less than 10%.
- Suitable types of plasticizers include solvents.
- solvents include water, alkylene glycol mono lower alkyl ethers, glycerol, polyalcohols, propylene glycols, ethoxylated or propoxylated ethylene or propylene, glycerol esters, glycerol triacetate, polyethylene glycols, methyl esters and amides.
- plasticizers is glycerol.
- Another preferred type of plasticizers comprises the medium molecular weight polyethylene glycols (PEGs). Such materials preferably have molecular weights of at least 150. PEGs of molecular weight ranging from 200 to 3000 are most preferred.
- PEGs of molecular weight ranging from 200 to 3000 are most preferred.
- Yet another preferred type of plasticizers 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 dodecanoate.
- 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 compounds 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'-dihydroxylsobutyric 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 com 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.
- a plasticizing agent allows the reduction of the water content in the coating composition before/during the application of the composition to the detergent tablet. Since the detergent tablet consists itself of water dissolvable/dispersible components it is not desirable to apply a high water amount to the tablet during the coating process. Further the plasicizer provides the coating after drying with an increased smoothness and elasticity, resulting in less brittleness and more comfortable handling of the tablet.
- the coating may include a colourant.
- Colourant when present as a component in the resin is preferably present at a level of from 0.001wt % to 2wt %, preferably from 0.01wt % to 1.7wt %, most preferably from 0.1wt % to 1.5wt %.
- 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 and liquid colourants e.g. of the type Liquitit ® of Miliken
- the coating liquid usable for the coating process for preparing the coating layer may further also contain;
- any additives are substantially water soluble or dispersible so that the overall system retains its water solubility / water dispersibility.
- the shaped body article preferably comprises a cleaning composition or a water softener 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.
- Such a coated article has been found to be particularly suitable since the coating material is formed of components allowing a fast decomposition of the coating; 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 comprise of among others a builder system, a bleach system, a silver protecting system, a protecting system for glass (against glass corrosion), 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, and a polymer system comprising a polymer supporting spotting characteristics and/or a polymer supporting filming characteristics (like for example discussed in EP-A 1299 513 , 1 363 986 , WO 95/12854 or EP-A 0 877 002 ) and a tablet disintegrate without being limited to these ingredients.
- a builder system a bleach system, a silver protecting system, a protecting system for glass (against glass corrosion), 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,
- ingredients of the composition do not limit the present invention and any suitable detergent composition for different purposes can be used.
- Typical components of automatic dishwashing compositions are disclosed for example in EP-A 1 268129 , EP-A 1 299 513 , EP-A 1 571 198 , EP-A 1 520 908 and EP-A 1 524 313 . All the components described therein may be part of the compositions coated according to the present invention.
- 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.
- dishwashing compositions particularly preferred dishwashing compositions comprising bleaching systems, complexing agents and/or a polymer system providing good spotting and filming characteristics.
- a fast dissolving rate is achieved by a thin coating of said water dissolvable material.
- the present invention uses coatings of water dissolvable materials with amounts of from 0.07 mg/cm 2 to 15 mg/cm 2 resulting e.g. preferably in thicknesses between 5 ⁇ m and 1000 ⁇ m, more preferably between 20 ⁇ m and 600 ⁇ m.
- the coating corresponds to about 0.01 % by weight to 5% by weight, preferably about 0.01 % by weight to 2.8% by weight of the total amount of the detergent unit.
- said unit coated detergent may comprise an additive which provides an unbearable bitter taste, particularly in case the coating comprises any sugar.
- This additive may be coated onto said detergent composition, either as part of the water soluble coating or as a separate coating . This improves the prevention that children may accidentally ingest the complete detergent.
- the water soluble material provided as powder or prepared as a solution, melt or dispersion or a combination thereof comprising all components desired to be in the coating, is coated onto the material by any suitable method.
- the material is coated by powdering, spraying, dipping, immersing or similar or any combination of said techiques.
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Claims (7)
- Composition détergente unitaire revêtue, dans laquelle la composition détergente est revêtue d'un revêtement susceptible d'être dissous ou dispersé dans l'eau comprenant d'au moins 1 % jusqu'à 99 % d'un copolymère greffé poly(alcool vinylique) - polyéthylène glycol et un composé de faible masse moléculaire choisi parmi des sucres comprenant 1 à 10 motifs de sucre ou un quelconque acide aminé, de préférence des acides aminés naturels ou un mélange de sucres, un mélange d'acides aminés ou un mélange de sucres et d'acides aminés.
- Composition détergente unitaire revêtue selon la revendication 1, dans laquelle le revêtement comprend au moins 50 % à 99 % d'un copolymère greffé poly(alcool vinylique) - polyéthylène glycol et un quelconque autre matériau de revêtement.
- Composition détergente unitaire revêtue selon la revendication 1 ou 2, dans laquelle la quantité de matériau de revêtement fournissant le revêtement est comprise entre 0,07 et 15 mg/cm2.
- Composition détergente unitaire revêtue selon l'une quelconque des revendications 1 à 3, dans laquelle la composition détergente est une composition pour lave-vaisselle, une composition détergente pour le linge ou une composition adoucissante de l'eau.
- Composition détergente unitaire revêtue selon la revendication 4, dans laquelle la composition pour lave-vaisselle est sous forme d'une pastille, ayant au moins une partie comprimée et éventuellement une partie non comprimée.
- Composition détergente unitaire revêtue selon l'une quelconque des revendications 1 à 5, dans laquelle le revêtement est fourni sur au moins une face superficielle du corps façonné, de préférence sur au moins deux faces superficielles, mieux encore sur au moins l'une des deux "faces de dessus", ce qui signifie la surface supérieure et inférieure de la pastille de détergent, y compris ou à l'exclusion de toute partie non comprimée de la pastille.
- Procédé de préparation d'un corps unitaire façonné selon l'une quelconque des revendications 1 à 6 comprenant la pulvérisation d'un matériau de revêtement tel que défini dans l'une quelconque des revendications 1 ou 2 sur au moins une face superficielle du corps façonné.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ES08021163.4T ES2523029T3 (es) | 2008-12-05 | 2008-12-05 | Pastilla de detergente revestida de polímero |
PL08021163T PL2196531T3 (pl) | 2008-12-05 | 2008-12-05 | Pokryta polimerem tabletka detergentu |
EP08021163.4A EP2196531B1 (fr) | 2008-12-05 | 2008-12-05 | Pastille de détergent revêtue d'un polymère |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08021163.4A EP2196531B1 (fr) | 2008-12-05 | 2008-12-05 | Pastille de détergent revêtue d'un polymère |
Publications (2)
Publication Number | Publication Date |
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EP2196531A1 EP2196531A1 (fr) | 2010-06-16 |
EP2196531B1 true EP2196531B1 (fr) | 2014-09-03 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08021163.4A Not-in-force EP2196531B1 (fr) | 2008-12-05 | 2008-12-05 | Pastille de détergent revêtue d'un polymère |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2196531B1 (fr) |
ES (1) | ES2523029T3 (fr) |
PL (1) | PL2196531T3 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8927477B2 (en) * | 2010-08-06 | 2015-01-06 | Re.Le.Vi. S.P.A. | Sanitary agent covered by a film |
US9683199B2 (en) * | 2010-11-10 | 2017-06-20 | Colgate-Palmolive Company | Fabric conditioners containing soil releasing polymer |
ITRE20110036A1 (it) * | 2011-05-24 | 2012-11-25 | Re Le Vi Spa | Sistema per l'applicazione di un agente sanitario adesivo ad una parete di un apparato sanitario |
DE102012214607A1 (de) * | 2012-08-16 | 2014-02-20 | Henkel Ag & Co. Kgaa | Wasserlösliche Verpackung mit Bittermittel I |
DE102012214608A1 (de) * | 2012-08-16 | 2014-02-20 | Henkel Ag & Co. Kgaa | Wasserlösliche Verpackung mit Bittermittel II |
EP3077454A1 (fr) | 2013-12-06 | 2016-10-12 | Monosol, LLC | Traceur fluorescent pour films hydrosolubles, procédés associés et articles associés |
US20160340623A1 (en) | 2014-02-11 | 2016-11-24 | Eurvest Sa | Sanitary self-adhesive products |
EP3334816B1 (fr) | 2015-08-11 | 2019-01-23 | Unilever Plc. | Emballage hydrosoluble |
BR112018002484B1 (pt) | 2015-08-11 | 2022-05-03 | Unilever Ip Holdings B.V. | Embalagem solúvel em água e uso de uma embalagem solúvel em água |
TR201904947T4 (tr) * | 2015-08-11 | 2019-05-21 | Unilever Nv | Suda-çözünebilen paket. |
EP3138901A1 (fr) * | 2015-09-04 | 2017-03-08 | The Procter & Gamble Company | Article de dose unitaire soluble dans l'eau comprenant un agent aversif |
FR3044678B1 (fr) * | 2015-12-04 | 2017-12-08 | Eurotab | Tablette detergente enrobee |
ES2750024T3 (es) | 2016-02-09 | 2020-03-24 | Unilever Nv | Embalaje soluble en agua |
US11807834B2 (en) | 2017-10-13 | 2023-11-07 | Conopco, Inc. | Aqueous spray composition |
EP3694963A1 (fr) | 2017-10-13 | 2020-08-19 | Unilever PLC | Composition aqueuse de pulvérisation |
CN111201308A (zh) | 2017-10-13 | 2020-05-26 | 荷兰联合利华有限公司 | 水性喷雾组合物 |
BR112020007293A2 (pt) | 2017-10-13 | 2020-09-29 | Unilever N.V. | produto spray para tecido, método para conferir frescor ao tecido e uso do produto spray para tecido |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10207427A1 (de) * | 2002-02-21 | 2003-09-04 | Basf Ag | Schnelllöslicher Filmüberzug basierend auf Polyvinylalkohol-Polyether-Pfropfcopolymeren in Kombination mit Hydroxy-, Amid-, oder Esterfunktionen enthaltenden Komponenten |
EP1903099A1 (fr) * | 2006-09-22 | 2008-03-26 | Dalli-Werke GmbH & Co. KG | Compositions détergentes enrobées et leur procédé de fabrication |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0726935B1 (fr) | 1993-11-03 | 2000-08-30 | The Procter & Gamble Company | Limitation de la precipitation de carbonate de calcium dans les lave-vaisselle |
ES2158885T3 (es) | 1994-09-12 | 2001-09-16 | Procter & Gamble | Un detergente envasado unitario. |
CA2236605A1 (fr) | 1997-05-09 | 1998-11-09 | Yves Duccini | Agents anti-tartre |
JP2002513076A (ja) | 1998-04-27 | 2002-05-08 | ザ、プロクター、エンド、ギャンブル、カンパニー | 輪郭表面を有する被覆非粒状洗剤製品 |
DE19920118B4 (de) | 1999-05-03 | 2016-08-11 | Henkel Ag & Co. Kgaa | Wasch- und Reinigungsmittelformkörper mit Beschichtung und Verfahren zu seiner Herstellung |
CA2404579C (fr) | 2000-03-29 | 2009-08-11 | National Starch And Chemical Investment Holding Corporation | Polymeres inhibant la formation de depots de carbonate et de phosphate de calcium dans des lave-vaisselle |
DE10050622A1 (de) | 2000-07-07 | 2002-05-02 | Henkel Kgaa | Klarspülmittel II a |
DE10050958A1 (de) * | 2000-10-13 | 2002-04-18 | Basf Ag | Verwendung von wasserlöslichen oder wasserdispergierbaren Polyetherblöcken enthaltenden Pfropfpolymerisaten als Beschichtungs- und Verpackungsmittel für Wasch-, Reinigungs- und Wäschebehandlungsmitte |
ATE305886T1 (de) * | 2000-10-18 | 2005-10-15 | Reckitt Benckiser Nv | Waschmittel verpackt mit ethoxyliertem polyvinylalkohol |
DE10109799A1 (de) | 2001-03-01 | 2002-09-05 | Henkel Kgaa | 3in1-Geschirrspülmittel und Verfahren zur Herstellung derselben |
JP4189213B2 (ja) | 2002-08-30 | 2008-12-03 | 花王株式会社 | 洗剤粒子 |
EP1520908A1 (fr) | 2003-10-01 | 2005-04-06 | Dalli-Werke GmbH & Co. KG | Composition pour lave-vaisselle avec des propriétés de rinçage améliorées |
EP1571198A1 (fr) | 2004-03-02 | 2005-09-07 | Dalli-Werke GmbH & Co. KG. | Composés au manganèse liés à des polymères dans des compositions détergentes |
WO2008080774A1 (fr) * | 2006-12-29 | 2008-07-10 | Basf Se | Agent d'enrobage sous forme de film, formé de particules à dispersion rapide, à base de copolymères greffés de polyvinylalcool-polyéther |
-
2008
- 2008-12-05 EP EP08021163.4A patent/EP2196531B1/fr not_active Not-in-force
- 2008-12-05 PL PL08021163T patent/PL2196531T3/pl unknown
- 2008-12-05 ES ES08021163.4T patent/ES2523029T3/es active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10207427A1 (de) * | 2002-02-21 | 2003-09-04 | Basf Ag | Schnelllöslicher Filmüberzug basierend auf Polyvinylalkohol-Polyether-Pfropfcopolymeren in Kombination mit Hydroxy-, Amid-, oder Esterfunktionen enthaltenden Komponenten |
EP1903099A1 (fr) * | 2006-09-22 | 2008-03-26 | Dalli-Werke GmbH & Co. KG | Compositions détergentes enrobées et leur procédé de fabrication |
Also Published As
Publication number | Publication date |
---|---|
ES2523029T3 (es) | 2014-11-20 |
PL2196531T3 (pl) | 2015-02-27 |
EP2196531A1 (fr) | 2010-06-16 |
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