EP0190880A2 - Wäschewaschmittel - Google Patents

Wäschewaschmittel Download PDF

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Publication number
EP0190880A2
EP0190880A2 EP86300624A EP86300624A EP0190880A2 EP 0190880 A2 EP0190880 A2 EP 0190880A2 EP 86300624 A EP86300624 A EP 86300624A EP 86300624 A EP86300624 A EP 86300624A EP 0190880 A2 EP0190880 A2 EP 0190880A2
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EP
European Patent Office
Prior art keywords
water
laundry
pouch
particulate component
product according
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.)
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Application number
EP86300624A
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English (en)
French (fr)
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EP0190880A3 (en
EP0190880B1 (de
Inventor
David Ellis
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Procter and Gamble Ltd
Procter and Gamble Co
Original Assignee
Procter and Gamble Ltd
Procter and Gamble Co
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Publication of EP0190880A3 publication Critical patent/EP0190880A3/en
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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
    • C11D17/04—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
    • C11D17/046—Insoluble free body dispenser
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates

Definitions

  • the invention relates to laundry products.
  • it relates to laundry products suitable for cleaning fabrics in a washing machine and which contain a laundry composition in particulate form.
  • the present invention provides a laundry product comprising:
  • the laundry composition is thus formulated in a multicomponent form, a first particulate component comprising a meso-phase forming organic surfactant and a second particulate component comprising a builder and being essentially free of meso-phase forming surfactant.
  • the weight ratio of the first particulate component to the second particulate component is generally from about 10:1 to about 1:50, preferably from about 5:1 to about 1:20, and more preferably from about 1:1 to about 1:10.
  • the first component generally has an ionic organic surfactant content of at least about 15%, preferably at least about 25%, more preferably at least about 50% by weight thereof.
  • the second component generally has a water-soluble or water-dispersible inorganic or organic builder content of at least about 50%, preferably at least about 85%, more preferably at least about 95% by weight thereof.
  • the ionic organic surfactant content of the second component is generally less than about 5% by weight thereof.
  • the first particulate component additionally comprises an agent for elevating the Krafft temperature of the meso-phase forming organic surfactant such as a water-soluble electrolyte.
  • the second particulate component preferably incorporates a non-meso-phase forming organic surfactant, preferably selected from the class of nonionic organic surfactants.
  • the meso-phase forming organic surfactant exhibits an intermediate meso-phase region at low water levels (5% by weight or less)
  • the non-meso-phase forming organic surfactant exists in this domain as an isotropic liquid.
  • the phase-forming characteristics of the organic surfactants can be identified in conventional manner using a polarizing microscope.
  • a wide range of organic surfactants can be incorporated in the first particulate component, inclusive of anionic, cationic, ampholytic and zwitterionic detersive surfactants and mixtures thereof.
  • the total level of these materials is generally from about 2% to about 40%, preferably from about 5% to about 25% by weight of the total laundry composition.
  • Suitable synthetic anionic surfactants are water-soluble salts of C 8 -C 22 alkyl benzene sulphonates, C 8 -C 22 alkyl sulphates, C 10-18 alkyl polyethoxy ether sulphates, C 8-24 paraffin sulphonates, alpha- C 12-24 olefin sulphonates, alpha-sulphonated C 6 -C 20 fatty acids and their esters, C 10 -C 18 alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, especially those prepared from coconut oil, C 8 -C 12 alkyl phenol polyethoxy ether sulphates, 2-acylox y C9-C23 alkane-1-sulphonate, and beta-alkyloxy C 8 -C 20 alkane sulphonates.
  • a particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts or organic sulphuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulphonic acid or sulphuric acid ester group.
  • alkyl is the alkyl portion of acyl groups).
  • this group of synthetic detergents are the sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher alcohols (C 8-18 ) carbon atoms produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl benzene sulphonates, in which the alkyl group contains from about 9 to about 15, especially about 11 to about 13, carbon atoms, in straight chain or branched chain configuration, e.g.
  • alkane chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium or alkanolammonium cations; sodium is preferred.
  • Suitable fatty acid soaps herein can be selected from the ordinary alkali metal (sodium, potassium), ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24, preferably from about 10 to about 22 and especially from about 16 to about 22 carbon atoms in the alkyl chain.
  • Fatty acids in partially neutralized form are also suitable for use herein, especially in liquid compositions.
  • Sodium and potassium soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from tallow and hydrogenated fish oil.
  • Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from about 5:1 to about 1:5, preferably from about 5:1 to about 1:1, more preferably from about 5:1 to about 1.5:1.
  • an alkyl benzene sulphonate having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, the cation being an alkali metal, preferably sodium; and either an alkyl sulphate having from 10 to 20, preferably 12 to 18 carbon atoms in the alkyl radical or an ethoxy sulphate having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6, having an alkali metal cation, preferably sodium.
  • Cationic surfactants suitable for use herein include quaternary ammonium surfactants and surfactants of a semi-polar nature, for example amine oxides.
  • Suitable quaternary ammonium surfactants are selected from mono C 8 -C 16 , preferably C 10 -C 14 N- alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl and the corresponding di-C6-C10 N-alkyl or alkenyl ammonium surfactants.
  • Suitable amine oxides are selected from mono C 8 -C 20' preferably C 10 -C 14 N-alkyl or alkenyl amine oxides and prcpylene-1,3-diamine dioxides wherein the remaining N positions are again substituted by methyl, hydroxyethyl or hydroxypropyl.
  • the second particulate component of the laundry composition is based on a water-soluble or water-dispersible inorganic or organic builder component or mixture thereof, and is preferably hydratable, the degree of hydration preferably being such that in the final granule, the builder is hydrated to an extent of no more than about 90%, preferably from about 10% to about 85%, more preferably from about 30% to about 70% of its total hydration capacity (based on the highest hydrate or hydrates which are stable at room temperature).
  • the hydratable builder consists predominantly (at least 50%) of material having no hydrate transition point below about 40°C.
  • Suitable builder salts useful herein can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof.
  • the level of these materials is generally from about 15% to about 90%, preferably from about 20% to about 60% by weight of the total laundry composition.
  • suitable water-soluble, inorganic alkaline builder salts include the alkali metal carbonates, borates, phosphates, pyrophosphates, tripolyphosphates and bicarbonates.
  • Organic builder/chelating agents that can be incorporated include organic polycarboyxlates and amincpolycarboyxlates and their salts, organic phosphonate derivatives such as those disclosed in US- A-3,213,030, US-A-3,433,021, US-A-3,292,121 and US-A-2,599,807, and carboxylic acid builder salts such as those disclosed in US-A-3,308,067.
  • Preferred chelating agents include citric acid, nitrilotriacetic (NTA) and ethylenediamine tetra acetic acids (EDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), nitrilo(trimethylene phosphonic acid) (NIMP), ethylenediamine tetra(methylene phosphonic acid) (EDTMP) and diethylenetriamine penta(methylene phosphonic acid) (IETPMP) and salts thereof.
  • NTA nitrilotriacetic
  • EDTA ethylenediamine tetra acetic acids
  • HEEDTA hydroxyethylethylenediaminetriacetic acid
  • NIMP nitrilo(trimethylene phosphonic acid)
  • ETMP ethylenediamine tetra(methylene phosphonic acid)
  • IETPMP diethylenetriamine penta(methylene phosphonic acid) and salts thereof.
  • IETPMP diethylene
  • a further class of builder salts is the insoluble alumino silicate type which functions by cation exchange to remove polyvalent mineral hardness and heavy metal ions from solution.
  • a preferred builder of this type has the formulation Na z (AlO 2 ) z (SiO 2 ) y .xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5 and x is an integer from about 15 to about 264.
  • Compositions incorporating builder salts of this type form the subject of GB-A-1,429,143, DE-A-2,433,485, and DE-A-2,525,778.
  • the laundry compositions herein can be supplemented by all manner of detergent and laundering components, either as part of the first or second particulate components, or in separate particulate admixtures.
  • the first particulate component can be supplemented by agents for raising the Krafft temperature of the meso-phase forming organic surfactant, for example the water-soluble inorganic or organic builder salts specified above, or by hydrotropes such as urea, guanidine hydrochloride, or the alkali metal benzene, toluene, xylene or cumene sulfonates.
  • such materials comprise no more than about 75% by weight, preferably no more than about 50% by weight of the first particulate component.
  • the second particulate component can be supplemented by a non-meso-phase forming organic surfactant, especially an organic nonionic surfactant.
  • the nonionic surfactants are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from about 8 to 17, preferably from about 9.5 to 13.5, more preferably from about 10 to about 12.5.
  • HLB hydrophilic-lipophilic balance
  • nonionic surfactants include the condensation products of primary or secondary aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 2 to about 40 moles, preferably 2 to about 9 moles of ethylene oxide per mole of alcohol.
  • the aliphatic alcohol comprises between 9 and 18 carbon atoms and is ethoxylated with between 2 and 9, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol.
  • the preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.g.
  • myristyl, cetyl, stearyl alcohols or partly branched such as the Lutensols, Dobanols and Neodols which have about 25% 2-methyl branching (Lutensol being a Trade Name of BASF, Dobanol and Neodol being Trade Names of Shell), or Synperonics, which are understood to have about 50% 2-methyl branching (Synperonic is a Trade Name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica.
  • Lutensol being a Trade Name of BASF
  • Dobanol and Neodol being Trade Names of Shell
  • Synperonics which are understood to have about 50% 2-methyl branching (Synperonic is a Trade Name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica.
  • nonionic surfactants falling within the scope of the invention include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-2.5, Dobanol 91-3, Dobanol 91-4, Dobanol 91-6, Dobaml 91-8, Dobanol 23-6.5, Synperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having from 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atoms.
  • Secondary linear alkyl ethoxylates are also suitable in the present compositions, especially those ethoxylates of the Tergitol series having from about 9 to 15 carbon atoms in the alkyl group and up to about 11, especially from about 3 to 9, ethoxy residues per molecule.
  • nonionic surfactants include the condensation products of C 6 -C 12 alkyl phenols with from about 3 to 30, preferably 5 to 14 moles of ethylene oxide, and the compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, such synthetic nonionic detergents being available on the market under the Trade Name of "Plurcnic" supplied by Wyandotte Chemicals Corporation.
  • Especially preferred nonionic surfactants for use herein are the C 9 -C 15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C 12 - C 15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.
  • alkali metal, or alkaline earth metal, silicate can also be present.
  • the alkali metal silicate is preferably from about 3% to about 15% by weight of the total composition.
  • Suitable silicate solids have a molar ratio of SiO 2 /alkali meta1 2 0 in the range from about 0.5 to about 3.3, more preferably from about 1.0 to about 2.0.
  • the laundry compositions herein can also contain bleaching components.
  • the bleach is selected from inorganic peroxy salts, hydrogen peroxide, hydrogen peroxide adducts, and organic peroxy acids and salts thereof.
  • Suitable inorganic peroxygen bleaches include sodium perborate mono- and tetrahydrate, sodium percarbonate, sodium persilicate, urea-hydrogen peroxide addition products and the clathrate 4Na 2 SO 4 :2H 2 O 2 :lNaCl.
  • Suitable organic bleaches include peroxylauric acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecanedioic acid, diperoxyazelaic acid, mono- and diperoxyphthalic acid and mono- and diperoxyisophthalic acid and salts (especially the magnesium salts) thereof.
  • the bleaching agent is generally present at a level of from about 5% to about 35%, preferably from about 10% to about 25% by weight of total laundry composition.
  • Peroxyacid bleach precursors suitable herein are disclosed in UK-A-2040983, highly preferred being peracetic acid bleach precursors such as tetraacetylethylene diamine, tetraacetylmethylenediamine, tetraacetylhexylenediamine, sodium p-acetoxybenzene sulphonate, tetraacetylglycouril, pentaacetylglucose, octaacetyllactose, methyl 0-acetoxy benzoate, sodium 3,5,5-trimethylhexanoyloxybenzene sulfonate, sodium 3,5,5-trimethylhexanoyloxybenzoate, sodium 2-ethylhexanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate and sodium octanoyloxybenzenesulfonate.
  • the level of bleach precursor is generally from about 0.5% to
  • compositions herein include suds suppressors, enzymes, fluorescers, photoactivators, soil suspending agents, anti-caking agents, pigments, perfumes, fabric conditioning agents etc.
  • Suds suppressors are represented by materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties.
  • Suitable silicone suds controlling agents include polydimethylsiloxanes having a molecular weight in the range from about 200 to about 200,000 and a kinematic viscosity in the range from about 20 to about 2,000,000 mm 2 /s, preferably from about 3000 to about 30,000 mm2/s, and mixtures of siloxanes and hydrophobic silanated (preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to about 20 millimicrons and a specific surface area above about 50 m 2 /g.
  • Suitable waxes include microcrystalline waxes having a melting point in the range from about 65°C to about 100°C, a molecular weight in the range from about 4000-1000, and a penetration value of at least 6, measured at 77°C by ASTM-D1321, and also paraffin waxes, synthetic waxes and natural waxes.
  • Suitable phosphate esters include mono- and/or di-C 16 -C 22 alkyl or alkenyl phosphate esters, and the corresponding mono- and/or di alkyl or alkenyl ether phosphates containing up to 6 ethoxy groups per molecule.
  • Enzymes suitable for use herein include those discussed in US-A-3,519,570 and US-A-3,533,139.
  • Suitable fluorescers include B lankophor MBlE (Bayer AG) and Tincpal CBS and EMS (Ciba Geigy).
  • Photoactivators are discussed in EP-A-57088, highly preferred materials being zinc phthalocyanine, tri- and tetra-sulfonates.
  • Suitable fabric conditioning agents include smectite-type clays as disclosed in GB-A-1400898 and di-C 12 -C 24 alkyl or alkenyl amines and ammonium salts.
  • Antiredeposition and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of this type are disclosed in GB-A-1,596,756.
  • Preferred polymers include copolymers or salts thereof of maleic anhydride with ethylene, methylvinyl ether, acrylic acid or methacrylic acid, the maleic anhydride constituting at least about 10 mole percent, preferably at least about 20 mole percent of the ccpolymer.
  • the laundry compositions herein have a bulk density of at least about 0.5g/cc, preferably at least about 0.6g/cc, and more preferably at least about 0.7g/cc.
  • bulk density is measured on a pouch basis.
  • the contents of at least one pouch or set of pouches should meet the preferred bulk density limitations.
  • at least about 50%, and more preferably at least about 80% by weight of the laundry composition is in one or more pouches meeting the bulk density parameters.
  • the first particulate component is preferably made by an extrusion process, the extrudates being from about 1 to about 6, preferably from about 1.5 to about 3.5mm in length and from about 0.4 to about 3, preferably from about 0.8 to about 1.8mm in diameter.
  • the second particulate component is preferably made by spray-drying an aqueous slurry of detergency builder to a density of at least about 0.3g/cc, spraying-on the non-meso-phase forming organic surfactant, where present, and comminuting the spray-dried granules in for example a Patterson-Kelley twin shell blender.
  • the aqueous slurry for spray drying preferably comprises from about 30% to about 60% water and from about 40% to about 70% of the detergency builder; it is heated to a temperature of from about 60°C to about 90°C and spray dried in a current of air having an inlet temperature of from about 200°C to about 400°C, preferably from about 275°C to about 350°C, and an outlet temperature of from about 95°C to about 125°C, preferably from about 100°C to about 115°C.
  • the weight average particle size of the spray dried granules is from about 0.15 to about 3mm, preferably from about 0.5mm to about 1.4mm. After comminution, the weight average particle size is from about 0.1 to about 0.5mm, preferably from about 0.15 to about 0.4mm.
  • the laundry composition is contained in a water-permeable pouch or multi-pouch delivery system.
  • Suitable materials for forming the delivery system include water-permeable, high wet strength paper, non-woven fabrics and plastic film having a basis weight of from about 5 to about 70, preferably from about 10 to about 50, more preferably from about 15 to about 40g/m .
  • the fibres or filaments of the fabric can be natural (e.g. wool, silk, wood pulp, jute, hemp, cotton, linen, sisal, or ramie) or synthetic (e.g. rayon, cellulose, ester, polyvinyl derivatives, polyolefins, polyamides or polyesters) or mixtures of any of the above.
  • each pouch of the product will preferably have at least one water-permeable outer-facing wall.
  • the porosity of the pouch or multi-pouch delivery system in relation to the laundry composition contained therein will normally be such that at least about 80%, preferably at least about 90% by weight of the laundry composition is released from the delivery system into the wash water in a period of less than about 20 minutes, preferably less than about 12 minutes, and more preferably less than about 6 minutes (testing being performed in the 30°C cycle of an AEG Lavamat Bella 100CE - 15 litres of water; ambient water temperature 5°C; heat-up time to 30°C - 10 mins.; wash load - 4 clean bedding sheets; product placed initially between 3rd and 4th sheets).
  • the size of the pores, apertures or capillaries of the pouch material, in relation to the particle size distribution of the laundry composition, on the other hand, should be such as to minimize dusting.
  • the pouch material is preferably free of perforations and has a pore size of less than about lmm, preferably less than about 100 ⁇ m, more preferably less than about 10 ⁇ m. Also, preferably no more than about 1% by weight of the particles of the laundry composition are of a size to pass through the pouch material and cause dusting.
  • the laundry products of the invention have a volume fill of at least about 40%, preferably at least about 50%, and more preferably at least about 60%. It is a feature of the invention that the laundry products specified herein maintain excellent product dispensing even at very high volume fill and high product density.
  • a laundry product comprising:
  • Pouch volume fill is defined herein as the total volume of product composition contained in the delivery system expressed as a percentage of the total pouch volume. In the case of multi-pouch delivery systems, these quantities are determined by integrating the product composition volumes and pouch volumes for the individual pouches. The product composition volume/pouch is equal to the quotient of the product composition weight/pouch and product bulk density. Pouch volume, on the other hand, is determined herein by multiplying pouch area and pouch depth. Pouch area is determined by reference to a plane projection of the internal surface of the pouch such as to provide maximum projected area and pouch depth is the corresponding maximum internal lateral dimension of the pouch (unfilled).
  • the delivery system comprises a number of separate pouches or compartments in a linear side-by-side arrangement or in a two-dimensional side-by-side array.
  • Multi-pouch delivery systems of this type promote further improvements in product dissolution as well as allowing for separate storage of ingredients which normally interact with one another.
  • the products are preferably made by a lamination technique in which quantities of the laundry composition are sandwiched between two lamina of water-permeable pouch material bonded one to another in a pattern of intersecting, pouch-defining, grid lines, there preferably being at least 4, more preferably from 5 to 21 lines, especially from about 6 to about 9 lines in each grid direction.
  • one or more pouches can contain a quantity of both the first and second particulate components or only one of the two components, as desired.
  • the pouch volume as defined above is in the range from about 0.5 to about 30cc, preferably from about 1 to about l5cc, and especially from about 3 to about 9cc, and the total pouch volume is in the range from about 60 to about 400cc, preferably from about 100 to about 300cc, and more preferably from about 150 to about 250cc.
  • Multi-pouch laundry products according to the invention are prepared as follows.
  • the first particulate component is prepared by extrusion in a Simon-Heeson extruder and the second particulate component is prepared by spray-drying with subsequent spray-on of the nonionic surfactant and comminution in a Patterson-Kelley twin-shell blender.
  • Pouch compositions Pl to P7 are each perfumed prior to incorporation in the laundry product, Pl and P4 being perfumed with a peroxyacid-stable perfume and the remaining pouch compositions being perfumed with a peroxysalt-stable but peroxyacid-labile perfume.
  • the multi-pouch delivery system consists of a 48 pouch paper laminate having a pouch volume of about 5cc/pouch. The contents of each pouch have a bulk density of about 0.7g/cc.
  • the above products have excellent product dissolution characteristics under typical cool water washing machine conditions.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP19860300624 1985-02-02 1986-01-30 Wäschewaschmittel Expired EP0190880B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB858502700A GB8502700D0 (en) 1985-02-02 1985-02-02 Laundry products
GB8502700 1985-02-02

Publications (3)

Publication Number Publication Date
EP0190880A2 true EP0190880A2 (de) 1986-08-13
EP0190880A3 EP0190880A3 (en) 1988-01-27
EP0190880B1 EP0190880B1 (de) 1992-05-13

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Family Applications (1)

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EP19860300624 Expired EP0190880B1 (de) 1985-02-02 1986-01-30 Wäschewaschmittel

Country Status (3)

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EP (1) EP0190880B1 (de)
DE (1) DE3685228D1 (de)
GB (1) GB8502700D0 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0236136A2 (de) * 1986-03-07 1987-09-09 Unilever Plc Produkt zum Austeilen von Behandlungsmitteln in einer Wasch- oder Geschirrspülmaschine
GB2203458A (en) * 1987-04-15 1988-10-19 Unilever Plc Fabric-softening composition
GB2254857A (en) * 1991-02-22 1992-10-21 Unilever Plc Sachet for laundry treatment

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011502A1 (de) * 1978-11-17 1980-05-28 Unilever Plc In einem geschlossenen Sack aus folienartigem Material enthaltene körnige Waschmittelzusammensetzung
WO1980001077A1 (en) * 1978-11-17 1980-05-29 Unilever Nv Detergent products

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011502A1 (de) * 1978-11-17 1980-05-28 Unilever Plc In einem geschlossenen Sack aus folienartigem Material enthaltene körnige Waschmittelzusammensetzung
WO1980001077A1 (en) * 1978-11-17 1980-05-29 Unilever Nv Detergent products

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0236136A2 (de) * 1986-03-07 1987-09-09 Unilever Plc Produkt zum Austeilen von Behandlungsmitteln in einer Wasch- oder Geschirrspülmaschine
EP0236136A3 (en) * 1986-03-07 1989-10-18 Unilever Plc Product for dispensing treatment agents in a washing or dishwashing machine
GB2203458A (en) * 1987-04-15 1988-10-19 Unilever Plc Fabric-softening composition
GB2203458B (en) * 1987-04-15 1991-10-02 Unilever Plc A composition for softening fabrics
GB2254857A (en) * 1991-02-22 1992-10-21 Unilever Plc Sachet for laundry treatment

Also Published As

Publication number Publication date
DE3685228D1 (en) 1992-06-17
GB8502700D0 (en) 1985-03-06
EP0190880A3 (en) 1988-01-27
EP0190880B1 (de) 1992-05-13

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