Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
  • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
  • D06F39/02—Devices for adding soap or other washing agents
  • D06F39/024—Devices for adding soap or other washing agents mounted on the agitator or the rotating drum; Free body dispensers
• • 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
  • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
• • 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

Definitions

• This invention relates to packaged non-aqueous liquid cleaning products.
• Liquid cleaning compositions which are substantially free of water are described in the art.
• the lack of water in such products enables the incorporation therein of unstable or incompatible ingredients such as bleaches or enzymes- although the present invention is applicable even to products which do not contain such ingredients.
• Such products are designed for the cleaning of hardsurfaces, for dishwashing or for fabric washing.
• the present invention especially applicable to such products as are designed for fabric washing.
• a packaged non-aqueous liquid cleaning product comprising a container and a non-aqueous liquid cleaning composition therein, the container being closed by a water-soluble or water-dispersible closure member.
• the container may take any form consistent with it being included in the machine together with the articles to be cleaned. It may be formed of flexible or rigid material. We have found that a particularly convenient container is of a material that does not dissolve or dispense in water, for example it may have the form of a plastic material bottle having a relatively narrow neck which is closed by the closure member. The use of biodegradable material and/or material of natural origin for the container is preferred.
• the closure member may take any convenient form and may be flexible or relatively rigid. It should effectively close the container and while in place prevent spillage of the contents from the container and the ingress of any significant amount of moisture form the surrounding air.
• the closure member may be secured to the container by any suitable means, such as by being glued thereto or by being physically held in place for example by being a press fit into an aperture of the container.
• the closure member is a tablet.
• the closure member should be formed of such a material that will not significantly disintegrate in contact with the non-aqueous liquid, such contact being l ⁇ kely to decur in storage or in transport.
• the closure member When the closure member is soluble it should be formed of a material which has such a rate of solubility that, in use, the majority of the contents of the container are released into the wash liquor promptly, say within 5 minutes, such as within 2 minutes.
• Polyvinylalcohol is a suitable material for forming such a closure member.
• the disintegration of the closure member may be encouraged by forming it of such a material or mixture of materials which on contact with water will generate gas, swell or, in the case of the wash liquor having an elevated temperature, melt.
• the closure member may comprise a water- soluble solid acid such as citric acid or tartaric acid and a water-soluble carbonate or bicarbonate salt so that on contact with water the carbon dioxide generated serves to rapidly disintegrate the closure member.
• the closure member may include a swellable material, such as a smectite clay, which will swell in contact with water thereby serving to hasten the disintegration of the closure member.
• Wax ⁇ like materials while not in themselves water-soluble, but which at the elevated temperatures of the wash liquor will become molten may also be included to aid disintegration of the closure member.
• Wax-like materials while not in themselves of the wash liquor will become molten may also be included to aid disintegration of the closure member at these temperatures.
• the closure member may include a material having a high heat of hydration such that on contact with the wash liquor a localised region of elevated temperature is generated thereby to further encourage disintegration.
• the closure member Before use the closure member may be protected against attack from atmospheric moisture, which might occur for example on storage, by being provided with a cover formed of water-impermeable material, such as plastics or aluminium foil designed to be removed or punctured by the consumer prior to adding the package to the washing machine.
• a cover formed of water-impermeable material such as plastics or aluminium foil designed to be removed or punctured by the consumer prior to adding the package to the washing machine.
• the closure member comprises one or more ingredients which have a useful function in the cleaning process, in particular ingredients which benefit from being dissolved or dispersed in the wash liquor before the bulk of the non-aqueous liquid and/or are difficult to incorporate in the liquid itself, perhaps because of physical or chemical instability.
• the closure eber comprises one or more ingredients selected from detergency builder, bleach precursors, peroxygen or peracid bleaches, enzymes, polymers for controlling the deposition of soil or insoluble particulate material onto the articles to be cleaned, foam inhibitors and perfumes.
• Non-aqueous liquid cleaning compositions generally comprise a liquid phase containing a surfactant and/or a solvent and a particulate solid phase dispersed therein.
• the liquid phase of the product preferably contains a surfactant.
• the surfactant may make up all or only part of the liquid phase, the remainder being constituted by a liquid non-surfactant material such as a solvent.
• the surfactant may be chosen from the liquid surfactants described "Surface Active Agents” Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon•s Emulsifiers and Detergents” published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache 2nd Edn., Carl Hanser Verlag, 1981.
• nonionic surfactants are especially suitable, most preferably polyalkoxylated nonionic surfactants.
• Nonionic detergent surfactants are well-known in the art. They normally consist of a water-solubilizing polyalkoxylene or a mono- or di-alkanolamide group in chemical combination with an organic hydrophobic group derived, for example, from alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms, dialkylphenols in which each alkyl group contains from 6 to 12 carbon atoms, primary, secondary or tertiary aliphatic alcohols (or alkyl-capped derivatives thereof) , preferably having from 8 to 20 carbon atoms, monocarboxylic acids having from 10 to about 24 carbon atoms in the alkyl group and polyoxypropylenes.
• alkylphenols in which the alkyl group contains from about 6 to about 12 carbon atoms
• dialkylphenols in which each alkyl group contains from 6 to 12 carbon atoms
• primary, secondary or tertiary aliphatic alcohols or alkyl-capped derivatives thereof
• fatty acid mono- and dialkanolamide ⁇ in which the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms.
• the alkyl group of the fatty acid radical contains from 10 to about 20 carbon atoms and the alkyloyl group having from 1 to 3 carbon atoms.
• the polyalkoxylene moiety preferably consists of from 2 to 20 groups of ethylene oxide or of ethylene oxide and propylene oxide groups.
• particularly preferred are those described in the applicants' published European specification EP-A-225,654, especially for use as all or part of the liquid phase.
• ethoxylated nonionics which are the condensation products of fatty alcohols with from 9 to 15 carbon atoms condensed with from 3 to 11 moles of ethylene oxide.
• condensation products of Cn_-i3 alcohols with (say) 3 to 7 moles of ethylene oxide may be used as the sole nonionic surfactants or in combination with those of the described in the last-mentioned European specification. especially as all or part of the liquid phase.
• Suitable nonionics which may be incorporated, preferably at most in minor quantities, comprise the alkyl polysa ⁇ charides (polyglycosides/ oligosaccharides) such as described in any of specifications US 3,640,998; US 3,346,558; US 4,223,129; EP-A-92,355; EP-A-99,183; EP-A-70,074, '75, » 76, '77; EP-A-75,994, » 95, *96.
• alkyl polysa ⁇ charides polyglycosides/ oligosaccharides
• Nonionic detergent surfactants normally have molecular weights of up to about 11,000. When mixtures of different nonionic detergent surfactants are used, it is preferred that the mixture is liquid at room temperature. Mixtures of nonionic detergent surfactants with other detergent surfactants such as anionic, cationic or ampholytic detergent surfactants and soaps may also be used.
• anionic detergent surfactants which may be used, preferably at most, in minor quantities, are alkali metal, ammonium or alkylolamaine salts of SLjLkylbenzene ⁇ ulphonates having from 10 to 18 carbon atdj ⁇ s in the alkyl group, alkyl and alkylether sulphates having from 10 to 24 carbon atoms in the alkyl group, the alkylether sulphates having from 1 to 5 ethylene oxide groups, olefin sulphonates prepared by sulphonatipn of C ⁇ o ⁇ C24 alpha-olefins and subsequent neutralization and hydrolysis of the sulphonation - reaction product.
• surfactants which may be used, preferably at most in minor quantities, include alkali metal soaps of a fatty acid, preferably one containing 12 to 18 carbon atoms. Typical such acids are oleic acid, ricinoleic acid and fatty acids-derived from caster oil or mixtures thereof. The sodium or potassium soaps of these acids can be used. As well as fulfilling the role of surfactants, soaps can act as further detergen ⁇ y builders or fabric conditioners, other examples of which will be described in more detail hereinbelow. It can also be remarked that the oils mentioned in this paragraph may themselves constitute all or part of the liquid phase, whilst the corresponding low molecular weight fatty acids (triglycerides) can be dispersed as solids or function as structurants.
• cationic detergent surfactants are aliphatic or aromatic alkyl-di (alkyl) ammonium halides and examples of soaps are the alkali metal salts of ⁇ 2 ⁇ C24 fatty acids.
• Ampholytic detergent surfactants are e.g. the sulphobetaines. Combinations of surfactants from within the same, or from different classes may be employed to advantage for optimising structuring and/or cleaning performance.
• Non-surfactants which are suitable for inclusion in the liquid phase include ethers, polyethers, alkylamines and fatty amines, (especially di- and tri-alkyl- and/or fatty- N- substituted derivatives thereof, alkyl (or fatty) carboxylic acid lower alkyl esters, ketones, aldehydes, and glycerides.
• Specific examples include di- alkyl ethers, polyethylene glycols, polyethylene oxides, glymes alkyl ketones (such as acetone) , glycerol, glycerol triacetate, propylene glycol, and sorbitol.
• compositions for use in a product of the invention may contain the liquid phase in an amount of at least 10% by weight of the total composition.
• the amount of the liquid phase present in the composition may be as high as about 90%, but in most cases the practical amount will lie between 20 and 70% and preferably between 30 and 60% by weight of the composition.
• the compositions for use in a container according to the present Invention preferably also contain one or more other functional ingredients, for example selected from detergency builders, bleaches, and (for hard surface cleaners) .abrasives.
• the detergency builders are materials which counteract the effects of calcium, or other ion, water hardness, by precipitation, by an ion sequestering or ion-exchange effect. They comprise both inorganic and organic builders. They may also be sub-divided into the phosphorus-containing and non-phosphorus type, the latter being preferred in the present invention for environmental reasons.
• Inorganic builders comprise the various carbonate, silicate-, borate- and aliminosilicate-type materials, particularly the alkali-metal salt forms. Mixtures of these may also be used.
• non-phosphorus-containing inorgnaic builders when present, include water-soluble alkali metal carbonates, bicarbonates, borates, silicates, metasilicates, and crystalline and amorphous alumino silicates. Specific examples include sodium and potassium silicates and zeolites.
• organic builders include the alkali metal, ammonium and substituted, citrates, succinates, malonates, fatty acid sulphonates, carboxymethoxy succinates, ammonium polyacetates, carboxylates, p ⁇ lycarboxylates, aminopolycarboxylates, polyacetyl carboxylates and polyhydroxsulphonates.
• Specific examples include sodium potassium, lithium, ammonium and substituted ammonium salts of ethylenedi ⁇ iminetetraacetic acid, nitrllotr-ta ⁇ etic acid, oxydisuccinic acid, melitic acid, benzene poly ⁇ arboxylic acids and citric acid.
• organic phosphonate type sequestering agents such as those sold by Monsanto under the tradename of the Dequest range and alkanehydroxy phosphonates.
• a carboxylic acid polymer may be present, such as a water-soluble homopolymer or a copolymer having a molecular weight of at least 500. It may be derived from a mono-carboxylic acid or from a di- or poly-carboxylic acid. The polymer will be used in its water-soluble alkali metal salts form.
• One group of polymer materials found to be of value comprises homopolymer ⁇ derived from a monomer of the formula
• R is hydrogen, hydroxyl, Ci - C4 alkyl or alkoxy, acetoxy or -CH2COOM
• R2 is hydrogen, C1-C4 alkyl, or -COOM
• M is an alkali metal.
• this group include the sodium and potassium salts or polyacrylic, polymethacrylic, polyitaconic, polymaleic and polyhydroxyacrylic acids and also the hydrolysis products of the corresponding polymerised acid anhydrides.
• the polymer obtained by hydrolysis of maleic anhydride falls within this group.
• a second group of polymeric materials comprises the copolymers of two or more carboxylic monomers of the above formula.
• this group include the sodium and potassium salts of copolymers of maleic anhydride with acrylic acid, methacrylic acid, crotonic acids, itaconic acid and its anhydride, aconitic acid.
• a third group of polymeric materials comprises the copolymers of one carboxylic monomer of the above formula and one or more non-carboxylic acid monomers such as ethylene, propylene, styrene, -methyl styrene, acrylonitrile, a ⁇ rylamide, vinylacetate, methyl vinyl ketone, a ⁇ rolein and esters of carboxylic acid monomers such as ethyl aerylate and methacrylate.
• non-carboxylic acid monomers such as ethylene, propylene, styrene, -methyl styrene, acrylonitrile, a ⁇ rylamide, vinylacetate, methyl vinyl ketone, a ⁇ rolein and esters of carboxylic acid monomers such as ethyl aerylate and methacrylate.
• Suitable bleaches include the halogen, particularly chlorine bleaches such as are provided in the form of alkalimetal hypohalites, e.g. hypochlorites.
• the oxygen bleaches are preferred, for example in the form of an inorganic persalt, preferably with an precursor, or as a peroxy acid compound.
• the precursor makes the bleaching more effective at lower temperatures, i.e. in the range from ambient temperature to about 60*C, so that such bleach systems are commonly known as low-temperature bleach systems and are well known in the art.
• the inorganic persalt such as sodium perborate/ both the monohydrate and the tetrahydrate, acts to release active oxygen in solution, and the precursor is usually an organic compound having one or more reactive acyl residues, which cause the formation of peraej_ds, the latter providing for a more effective bleaching action at lower temperatures than the peroxy bleach compound alone.
• the ratio by weight of the peroxy bleach compound to the precursor is from about 15:l to about 2:1, preferably from about 10:1 to about 3.5:1.
• the amount of the bleach system i.e. peroxy bleach compound and precursor
• the amount of the bleach system may be varied between about 5% and about 35% by weight of the total -Liquid, it is preferred to use from about 6% to about 50% of the ingredients forming the bleach system.
• the preferred level of the peroxy bleach compound in the composition is between about 5.5% and about 27% by weight, while the preferred level of the precursor is between about 0.5% and about 40%, most preferably between about 1% and about 5% by weight.
• Typical examples of the suitable peroxyblea ⁇ h compounds are alkali etal peroborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.
• They are generally compounds which contain N-acyl or O-acyl residues in the molecule and which exert their activating action on the peroxy compounds on contact with these in the washing liquor.
• precusors within these groups are polyacylated alkylene diamines, such as N ⁇ N ⁇ N 1 - tetraacetylethylene diamine (TAED) and N,N,N 1 ,N 1 - tetraacetylethylmethylene diamine (TAMD) ; acylated glycolurils, such as tetraacetylglycoluril (TAGU) ; triacetylcyanurate and sodium sulphophenyl ethyl carbonic acid ester.
• polyacylated alkylene diamines such as N ⁇ N ⁇ N 1 - tetraacetylethylene diamine (TAED) and N,N,N 1 ,N 1 - tetraacetylethylmethylene diamine (TAMD)
• acylated glycolurils such as tetraacetylglycoluril (TAGU)
• a particularly preferred precursor is N,N,N 1 ,N 1 -tetra- acetylethylene diamine (TAED) .
• the organic peroxyacid compound bleaches are preferably those which are solid at room temperature and most preferably should have a melting point of at least 50*C. Most commonly, they are the organic peroxya ⁇ ids and water-soluble salts thereof having the general formula
• R is an alkylene or substituted alkylene group containing 1 to 20 carbon atoms or an arylene group containing from 6 to 8 carbon atoms
• Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
• the liquid phase comprises an ester formed from an organic acid and an alkoxylated alcohol nonionic detergent
• the ester can act as a percursor for a persalt bleach included in the composition, thus obviating the need for any other conventional precursor.
• These esters can also lower the pour point of the composition.
• composition for use in a product of the invention contains abrasive for hard surface cleaning (i.e. is a liquid abrasive cleaner), these will inevitably be incorporated as particulate solids. They may be those of the kind which are water insoluble. Water soluble abrasives may also be used.
• compositions of the invention optionally may also contain one or more minor ingredients such as fabric conditioning agents, enzymes, perfumes (including deoperfumes) , micro-biocides, colouring agents, fluorescers, soil-suspending agents (anti-redeposition agents), corrcsion inhibitors, enzyme stabilizing agents, and lather depressants.
• the solids content of the non-aqueous cleaning composition for use in a product of the invention may be within a very wide range, for example from 1-90%, usually from 10-80% and preferably from 15- 70%, especially 15-50% by weight of the final composition.
• the solids should be in particulate form and ideally should have an average particle size of less than 300 microns, preferably less than 200 microns, more preferably less than 100 microns, especially less than 10 microns.
• the particule size may even be of sub-micron size.
• the proper particle size can be obtained by using materials of the appropriate size or by milling the total product in a suitable milling apparatus.
• the solid phase may be dispersed in the non-aqueous cleaning compositions for use in the present invention by any means known in the art.
• the non-aqueous cleaning compositions for use in the present invention also contain one or more dispersants for modifying the rheology of the dispersion.
• dispersants for modifying the rheology of the dispersion.
• deflocculants described in European patent specification EP-A-266 199 (Unilever PLC, Case No. C 7090) , for example dodecyl benzene sulphonic acid or lecithin.
• dispersants which may be used are the highly voluminous inorganic carrier materials described in GB patent specifications 1 205 711 and 1 270 040, chain structure-type clays as described in EP-A-34 387 cationic quaternary amine salt surfactants, urea, a substituted-urea or -guanidine according to GB 2 179 346 or J 61 227 829, or substituted urethanes, according to J 61 227 830.
• compositions are substantially non-aqueous, i.e. they contain little or no free water, preferably no more than 5%, preferably less than 3%, especially less than 1% by weight of the total composition. It has been found by the applicants that the higher the water content, the more likely it is for the viscosity to be too high, or even for setting to occur. However, this may at least in part be overcome by use of higher amounts of, or more effective deflocculants or other dispersants.
• non-aqueous liquid Since the objective of a non-aqueous liquid will generally be to enable the formulator to avoid the negative influence of water on the components, e.g. causing incompatibility of functional ingredients, it is clearly neseessary to avoid the accidental or delibarate addition of water to the product at any stage in its life. For this reason, special precautions are necessary in manufacturing procedures and pack designs for use by the consumer.
• all raw materials should be dry and (in case of hydratable salts) in a low hydration state, e.g. anhydrous carbonate builder and sodium perborate monohydrate, where the latter is employed in the composition.
• the dry, substantially anhydrous solids are blended with the liquid phase in a dry vessel.
• this blend is passed through a grinding mill or a combination of mills, e.g. a colloid mill, a corundum disc mill, a horizontal or vertical agitated ball mill, to achieve a particle size of 0.01 to 100 microns, preferably 0.5 to 50 microns, ideally 1 to 10 microns.
• a preferred combination of such mills is a colloid mill followed by a horizontal ball mill since these can be operated under the conditions required to provide a narrow size distribution in the final product.
• particulate material already having the desired particle size need not be subjected to this procedure and if desired, can be incorporated during a later stage of processing.
• FIG. 1 of the drawings is a vertical cross-section through the product showing the contents thereof, the closure member and the protective cover;
• Figure 2 is a perspective view from above and two sides of the same packaged product but with the contents thereof, the closure member and the protective cover removed.
• the packaged product comprises a bottle shaped container 1 having a neck portion 2 formed to define a relatively narrow opening.
• An annular lip 3 supports a disc-shaped tablet 4 constituting a closure member for the container.
• the tablet is made as described below.
• the top face of the tablet is level with the upper annular face of the neck portion 2, so that a protective cover 5 secured to the upper annular face of the neck portion lies flat against the upper face of the tablet 4.
• a non-aqueous cleaning composition 6 within the container is a non-aqueous cleaning composition 6 in an amount which represents the dose for a single wash in an automatic fabric washing machine.
• This amount may be from 50 ml to 250 ml and is typically about 70-90 ml.
• the volume of the container 1 is chosen accordingly so as to leave a free space 7 with a dimension which is optimum for efficient dispensing while maintaining the total volume of the product as low as possible.
• the container 1 is formed of a semi-rigid material such as low-density polyethylene.
• the protective cover 5 is formed of plastics material film, secured to the container by way of releasable adhesive.
• Suitable compositions for the tablet 4 are (% by weight) Table Comoosition: A B C
• Polyethylene glycol 6000 8.0 18.0 8.0
• the polyethylene glycol, sodium benzoate and magnesium stearate are used to obtain a strong homogeneous tablet, which is produced by compressing a dry mixture of the ingredients.
• the weight of the tablet was 2.0 g.
• Suitable non-aqueous liquid cleaning compositions are (% by weight)
• Nonionic surfactant 1 27.5 33.0 30.0
• PLURAFAC RA30 which is a C3.3/15 fatty alcohol alkoxylated with an average of 4 to 5 moles ethylene oxide and 2 to 3 moles propylene oxide (ex ICI) .
• Alkyl ie. dodecyl
• benzene sulphonic acid as free acid
• SOKALAN CP5 which is an acrylic acid/maleic acid copolymer in the sodium salt form with an average molecular weight of 70,000 and an acrylic acid : maleic acid ratio of 1:1 (ex BASF).
• the volume of this composition in the container was 90 ml(120g), while the overall container volume was 120 ml.
• the protective cover 5 is removed by the consumer and the product is then placed in the drum of an automatic washing machine, together with a fabric load.
• the machine washing cycle is started and as the wash liquor comes in contact with the tablet 4 the latter fizzes and disintegrates.
• the movement of the machine drum causes the container to topple over, discharging the cleaning composition into the wash liquor.
• the wash cycle continues in the usual manner and at the end thereof the empty container 1 is removed from the machine together with the clean fabric load.

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

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• 1989
  • 1989-04-24 GB GB898909253A patent/GB8909253D0/en active Pending
• 1990
  • 1990-04-03 WO PCT/EP1990/000525 patent/WO1990012864A1/en active IP Right Grant
  • 1990-04-03 ES ES199090905464T patent/ES2046777T3/es not_active Expired - Lifetime
  • 1990-04-03 EP EP90905464A patent/EP0479788B1/de not_active Expired - Lifetime
  • 1990-04-03 DE DE90905464T patent/DE69004572T2/de not_active Expired - Fee Related

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