EP0021545B1 - Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzungen und sich nicht verstopfender Ausgabebehälter dafür - Google Patents

Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzungen und sich nicht verstopfender Ausgabebehälter dafür Download PDF

Info

Publication number
EP0021545B1
EP0021545B1 EP19800200610 EP80200610A EP0021545B1 EP 0021545 B1 EP0021545 B1 EP 0021545B1 EP 19800200610 EP19800200610 EP 19800200610 EP 80200610 A EP80200610 A EP 80200610A EP 0021545 B1 EP0021545 B1 EP 0021545B1
Authority
EP
European Patent Office
Prior art keywords
abrasive
liquid detergent
containing liquid
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.)
Expired
Application number
EP19800200610
Other languages
English (en)
French (fr)
Other versions
EP0021545A1 (de
Inventor
Lyle Brown Tuthill
Esther Ruth Fitzgerald
Sharon Janosik Mitchell
Jonathan Spinner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26731520&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0021545(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0021545A1 publication Critical patent/EP0021545A1/de
Application granted granted Critical
Publication of EP0021545B1 publication Critical patent/EP0021545B1/de
Expired legal-status Critical Current

Links

Images

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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/44—Closures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D47/00—Closures with filling and discharging, or with discharging, devices
    • B65D47/04—Closures with discharging devices other than pumps
    • B65D47/06—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages
    • B65D47/12—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages having removable closures
    • B65D47/121—Stoppers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D47/00—Closures with filling and discharging, or with discharging, devices
    • B65D47/04—Closures with discharging devices other than pumps
    • B65D47/06—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages
    • B65D47/12—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages having removable closures
    • B65D47/127—Snap-on caps
    • B65D47/128—Snap-on caps with internal parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D47/00—Closures with filling and discharging, or with discharging, devices
    • B65D47/04—Closures with discharging devices other than pumps
    • B65D47/20—Closures with discharging devices other than pumps comprising hand-operated members for controlling discharge
    • B65D47/26—Closures with discharging devices other than pumps comprising hand-operated members for controlling discharge with slide valves, i.e. valves that open and close a passageway by sliding over a port, e.g. formed with slidable spouts
    • B65D47/261—Closures with discharging devices other than pumps comprising hand-operated members for controlling discharge with slide valves, i.e. valves that open and close a passageway by sliding over a port, e.g. formed with slidable spouts having a rotational or helicoidal movement
    • B65D47/268—Closures with discharging devices other than pumps comprising hand-operated members for controlling discharge with slide valves, i.e. valves that open and close a passageway by sliding over a port, e.g. formed with slidable spouts having a rotational or helicoidal movement the valve member pivoting about an axis perpendicular to the container mouth axis
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the invention relates to liquid detergent compositions containing specified amounts and types of insoluble abrasives which are especially useful in the washing of dishes.
  • the compositions contain high-sudsing surfactants and may also contain detergency builders which complement the action of the abrasive.
  • the invention also relates to the combination of such liquid detergents and a package which provides convenient dispensing of the detergent composition without clogging.
  • Scouring cleansers generally contain a relatively high level of abrasive. When such scouring cleansers are used as adjuncts in the dishwashing process such products provide abracing power to make the removal of cooked, burnt or dried-on foods on kitchenware easier and more convenient.
  • liquid scouring cleansers containing water-insoluble abrasives have become available. Such liquid compositions are disclosed in U.S.
  • Canadian Patent 1,048,365 discloses granular detergent compositions suitable for dishwashing containing 20% to 35% surfactant and 5% to 20% of abrasive material having a particle diameter in the range of 200 to 850 micrometers.
  • the present invention comprises a liquid detergent composition containing by weight:
  • the detergent compositions of the present invention contain three essential components:
  • compositions of this invention contain from 20% to 35% of an anionic surfactant or mixtures thereof.
  • anionic detergents can be broadly described as the water-soluble salts, particularly the alkali metal, alkaline earth metal, ammonium and amine salts, of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from 8 to 22 carbon atoms and a radical selected from sulfonic acid and sulfuric acid ester radicals. Included in the term alkyl is the alkyl portion of high acyl radicals.
  • anionic synthetic detergents which can form the surfactant component of the compositions of the present invention are the sodium, ammonium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C S- C 1s carbon atoms) sodium or potassium alkyl benzene or toluene sulfonates, in which the alkyl group contains from 9 to 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); sodium or potassium paraffin sulfonates and olefin sulfonates in which the alkyl or alkenyl group contains from 10 to 20 carbon atoms; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate,
  • alkyl sulfate salts which can be employed in the instant detergent compositions include sodium lauryl alkyl sulfate, sodium stearyl alkyl sulfate, sodium palmityl alkyl sulfate, sodium decyl sulfate, sodium myristyl alkyl sulfate, potassium lauryl alkyl sulfate, potassium stearyl alkyl sulfate, potassium decyl sulfate, potassium palmityl alkyl sulfate, potassium myristyl alkyl sulfate, sodium dodecyl sulfate, potassium dodecyl sulfate, potassium tallow alkyl sulfate, sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, potassium coconut alkyl sulfate and mixtures of these surfactants.
  • Highly preferred alkyl sulfates are sodium coconut alkyl sul
  • Suitable alkylbenzene or alkyltoluene sulfonates include the alkali metal (lithium, sodium, potassium), alkaline earth (calcium, magnesium) and alkanolamine salts of straight-or branched-chain alkylbenzene or alkyltoluene sulfonic acids-Alkylbenzene sulfonic acids useful as precursors for these surfactants include decyl benzene sulfonic acid, undecyl benzene sulfonic acid, dodecyl benzene sulfonic acid, tridecyl benzene sulfonic acid, tetrapropylene benzene sulfonic acid.
  • Preferred sulfonic acids as precursors of the alkyl-benzene sulfonates useful for compositions herein are those in which the alkyl chain is linear and averages about 12 carbon atoms in length.
  • Examples of commercially available alkyl benzene sulfonic acids useful in the present invention include Conoco SA 515 and SA 597 marketed by the Continental Oil Company and Calsoft LAS 99 marketed by the Pilot Chemical Company.
  • alkyl ether sulfates having the formula RO(C 2 H 4 O) x SO 3 M wherein R is alkyl or alkenyl of 10 to 20 carbon atoms, x is 1 to 30, and M is a water-soluble cation.
  • the alkyl ether sulfates useful in the present invention are condensation products of ethylene oxide and monohydric alcohols having from 10 to 20 carbon atoms. Preferably, R has 12 to 18 carbon atoms.
  • the alcohols can be derived from natural fats, e.g., coconut oil or tallow, or can be synthetic. Such alcohols are reacted with 1 to 30, and especially 1 to 12, molar proportions of ethylene oxide and the resulting mixture of molecular species is sulfated and neutralized.
  • alkyl ether sulfates of the present invention are sodium coconut alkyl triethylene glycol ether sulfate, magnesium tallow alkyl triethylene glycol ether sulfate, and sodium tallow alkyl hexaoxy ethylene sulfate.
  • Preferred alkyl ether sulfates are those comprising a mixture of individual compounds, said mixture having an average alkyl chain length of from 12 to 16 carbon atoms and an average degree of ethoxylation of from 1 to 12 moles of ethylene oxide.
  • anionic surfactants useful herein are the compounds which contain two anionic functional groups. These are referred to as di-anionic surfactants.
  • Suitable dianionic surfactants are the disulfonates, disulfates, or mixtures thereof which may be represented by the following formula: where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C 15 to C 20 disodium 1,2-alkyldisulfates, C 15 to C 20 dipotassium-1,2-alkyldisulfonates or disulfates, di-sodium 1,9-hexadecyl disulfates, C 15 to C 20 disodium 1,2-alkyl- disulfonates, disodium 1 ,9-stearyldisulfates and 6,10-octadecyldisulfates.
  • compositions of this invention contain from 2% to 15%, preferably from 3% to 8%, most preferably 4%, of a suds stabilizing nonionic surfactant or mixtures thereof.
  • a suds stabilizing nonionic surfactant or mixtures thereof is essential to satisfactory performance and acceptance as a complete dishwashing product.
  • the nonionic surfactant will be in a weight ratio to the anionic surfactants of from 1:10 to 1:2, most preferably from 1:7 to 1:3.
  • Nonionic surface active agents operable in the instant compositions can be any of three basic types ⁇ the alkylene oxide condensates, the amides and the semi-polar nonionics.
  • alkylene oxide condensates are broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • alkylene oxide condensates examples include:
  • amide type of nonionic surface active agent examples include the ammonia, monoethanol and diethanol amides of fatty acids having an acyl moiety of from 8 to 18 carbon atoms.
  • acyl moieties are normally derived from naturally occurring glycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
  • amine oxides examples include the amine oxides, phosphine oxides and sulfoxides. These materials are described more fully in Berry, U.S. Patent 3,819,528. Particularly preferred are amine oxides of the formula: wherein R, is a C, o- ,a alkyl and R 2 and R 3 are methyl or ethyl.
  • the level and type of surfactant used in the compositions of this invention provide an initial suds cover to a dishwashing solution and a suds cover after the washing of 8 plates when used at a concentration of 0.07% in 7.57 litres of 46°C water containing 120 mg/I water hardness measured as CaC0 3 , each plate carrying 4.0 ml of a triglyceride containing soil. Suds are generated by mechanical agitation and the suds cover and height measured. A dinner plate carrying the soil is washed successively with the introduction of 4.0 ml of soil each time. An essentially complete suds cover of the washing solution is more important than suds height, but, preferably, the suds cover after the washing of 8 plates is at least 1.27 cm in height.
  • the sudsing characteristic of the preferred high-sudsing compositions of the invention is that necessary to provide the user of the product with an indication of cleaning potential in a dishwashing solution. Soils encountered in dishwashing act as suds depressants and the presence or absence of suds from the surface of a dishwashing solution is a convenient guide to product usage.
  • Mixtures of anionic surfactants and nonionic surfactants, especially amides and amine oxide nonionic surfactants are utilized in the compositions of the invention because of their high sudsing characteristics, their suds stability in the presence of food soils and their ability to indicate accurately an adequate level of product usage in the presence of soil.
  • compositions of the invention may contain optional surfactants other than anionic and nonionic surfactants such as ampholytic, zwitterionic and cationic surfactants.
  • Ampholytic surfactants can be broadly described as derivatives of aliphatic amines which contain a long chain of 8 to 18 carbon atoms and an anionic water-solubilizing group, e.g. carboxy, sulfo or sulfate. Examples of compounds falling within this definition are sodium-3-dodecylamino propane sulfonate, and dodecyl dimethylammonium hexanoate.
  • Zwitterionic surface active agents operable in the instant composition are broadly described as internally-neutralized derivatives of aliphatic quaternary ammonium and phosphonium and tertiary sulfonium compounds in which the aliphatic radical can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono.
  • Cationic surfactants such as quaternary ammonium compounds can find optional use in the practice of the invention to the extent they are compatible with the other surfactants in the particular composition.
  • the abrasive agent can be any of the water-insoluble abrasive materials known in the art which have a particle diameter of from 15 to 150, preferably from 35 to 125, microns and a hardness on the Mohs scale of from 2 to 7.
  • materials such as a gate, mica, calcite, garnet, quartz, kieselguhr, silica, marble, tripoli, flint, feldspar, emery, pumice, alumina, perlite, expanded perlite, volcanic ash, diatomaceous earth, bentonite, amorphous silica from dehydrated silica gels, precipitated silica, plastics such as polystyrene and polyacrylates, and natural and synthetic aluminosilicates and mixtures thereof.
  • the amount of abrasive included in the compositions is in the range of from 1% to 20% of the total composition by weight.
  • Preferred compositions contain from 5% to 10% by weight of abrasive.
  • compositions of this invention can contain up to 20%, preferably from 5% to 15%, by weight of detergency builders either of the organic or inorganic types.
  • detergency builders either of the organic or inorganic types.
  • water-soluble inorganic builders which can be used, alone or in admixture with themselves and organic alkaline sequestrant builder salts, are alkali metal carbonates, polyphosphates, and silicates. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate, and sodium hexametaphosphate.
  • organic builder salts which can be used alone, or in admixture with each other or with the preceding inorganic alkaline builder salts, are alkali metal polycarboxylates, e.g., water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates (NTA) and sodium and potassium N-(2-hydroxyethyl)-nitrilo diacetates.
  • alkali metal polycarboxylates e.g., water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium nitrilo triacetates (NTA) and sodium and potassium N-(2-hydroxyeth
  • compositions of this invention can contain insoluble builder salts selected from certain zeolites or aluminosilicates.
  • aluminosilicate which is useful in the compositions of the invention is water-insoluble crystalline aluminosilicate ion exchange material of the formula: wherein Z and y are at least 6, the molar ratio of Z to y is from 1.0 to 0.5 and x is from 10 to 264, said material having a particle size diameter of from 0.1 micrometer to 10 micrometers, a calcium ion exchange capacity of at least 200 mg. CaC0 3 eq./gram and a calcium ion exchange rate of at least 34.1 mg Ca ++ /litre/minute/gram.
  • This ion exchange builder is more fully described in Belgian Patent 814,874.
  • a preferred aluminosilicate of this type is Zeolite A.
  • a second water-insoluble aluminosilicate ion exchange material useful herein is water-insoluble amorphous hydrated aluminosilicate material of the emperical formula: wherein M is sodium, potassium, ammonium, or substituted ammonium, Z is from 0.5 to 2, y is 1 and said material having a particle size diameter of less than 100, preferably less than 10 micrometers, a magnesium ion exchange capacity of at least 50 milligrams equivalent of CaCO hardness per gram of anhydrous aluminosilicate and a Mg ++ exchange rate of at least 17.1 mg/liter/minute/gram/liter; and mixtures thereof.
  • This ion exchange builder is more fully described in Gedge et al's French Patent 2,237,839.
  • compositions of this invention contain from 20% to 75% water.
  • Alcohols such as ethyl alcohol, and hydrotropes, such as sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, trisodium sulfosuccinate and related compounds (as disclosed in U.S. Patent 3,915,903), and urea, can be utilized in the interests of achieving a desired product phase stability, viscosity, and yield value.
  • hydrotropes such as sodium and potassium toluene sulfonate, sodium and potassium xylene sulfonate, trisodium sulfosuccinate and related compounds (as disclosed in U.S. Patent 3,915,903), and urea
  • suspending or thickening agents such as those disclosed in U.S.
  • Patent 3,393,153 including colloidal silica having a mean particle diameter ranging from 0.01 micrometers to 0.05 micrometers colloidal clays such as bentonites or chemically treated bentonites, isomorphous silicates, especially those with a high magnesium content, and particulate polymers such as polystyrene, oxidized polystyrene having an acid number of from 20 to 40, sulfonate polystyrene having an acid number of from 10 to 30, polyethylene, oxidized polyethylene having an acid number of from 10 to 30; sulfonated polyethylene having an acid number of from 5 to 25; polypropylene, oxidized polypropylene having an acid number of from 10 to 30 and sulfonated polypropylene having an acid number of from 5 to 25, all of said particulate polymers having mean particle diameters ranging from 0.01 micrometers to 30 micrometers.
  • colloidal clays such as bentonites or chemically treated bentonites, isomorphous silicates, especially those with
  • suspending and thickening agents include copolymers of styrene with monomers such as maleic anhydride, nitrilonitrile, methacrylic acid and lower alkyl esters of methacrylic acid, copolymers of styrene with methyl or ethyl acrylate, methyl or ethyl maleate, vinyl acetate, acrylic, maleic or fumaric acids and mixtures thereof.
  • the mole ratio of ester and/or acid to styrene is preferably in the range from 4 to 40 styrene units per ester and/or acid unit.
  • Such materials preferably have a mean particle diameter range of from 0.05 micrometers to 1 micrometer and molecular weights ranging from 500,000 to 2,000,000.
  • Cellulosic polymers such as carboxymethyl cellulose and hydroxypropyl cellulose and gums such as guar gum and gum tragacanth are also suitable suspending and thickening agents.
  • the detergent compositions of this invention can contain, if desired, any of the usual adjuvants, diluents and additives, for example, perfumes, enzymes, dyes, antitarnishing agents, antimicrobial agents, and the like, without detracting from the advantageous properties of the compositions.
  • Alkalinity sources and pH buffering agents such as alkali metal carbonates and bicarbonates, monoethanolamine, triethanolamine, alkali metal hydroxides, etc., can also be utilized.
  • a preferred pH range for a 196 solution in water is from 6 to 11.
  • the liquid detergent compositions of the invention contain abrasives as suspended solids and may contain other solid or liquid ingredients that provide desired product stability characteristics and that affect product viscosity.
  • the products of the invention are thixotropic or pseudoplastic and resistant to settling out of the abrasive or other solids yet sufficiently fluid for dispensing with the package of the invention.
  • the compositions have a Brookfield viscosity of from 400 mPas. to 2500 mPas. when measured at 50 rpm and a yield value of from 5 to 600 ⁇ 10 -5 M per square centimeter at 25°C.
  • compositions of the invention are their yield value.
  • non-Newtonian liquids the consistency is a function of the material, pressure, temperature, and also the shear stress applied to the system.
  • a Bingham plastic system is capable of supporting indefinitely insoluble particulate material which has a density greater than that of the supporting medium, so long as the material has such a particle size and density that the shear stress which each particle places on the supporting medium does not exceed the yield value.
  • the yield value can be lost temporarily, but in such a case, the original composition can be reconstituted by mixing. If a chemical reaction either consumes a vital component or produces a damaging one, the loss of yield value can be permanent.
  • the yield value of the liquid detergent compositions of this invention ranges from 5x10- 5 to 600x 0-5 N per square centimeter. If the yield value is too low, the insoluble, particulate material will not be suspended, because the weight of the individual particles, distributed over the area which supports the particles, will exceed the yield value. However, if the yield value is too great, the composition will become thick and unmanageable because as the yield value increases, so will the apparent viscosity.
  • a preferred range of yield values to support the insoluble particulate material used in the liquid detergent compositions of this invention is from 100 ⁇ 10 -5 to 400x 10- 5 Newtons per square centimeter.
  • compositions can present a dispensing problem because of a slow "drain back" characteristic that leads to product retention and subsequent clogging in various parts of a dispensing closure. This difficulty is greatly intensified when the closure is not sealed after use and water and other solvents evaporate from the product retained in the closure.
  • the essential package elements are: 1) a flexible package container to provide the squeeze dispensing characteristics typical of a variety of consumer products including dishwashing liquids and liquid abrasive cleansers; and 2) a clog resistant closure.
  • Typical dishwashing liquid detergents have a viscosity within the range of from 30 mPas to 300 mPas, contain no suspended solids other than low levels of opacifiers and are not thixotropic or pseudoplastic to any great extent. Closure clogging is not a serious problem and directional control of dispensed product is of no particular concern.
  • closures for abrasive liquid cleaning preparations involve consideration of the thixotropic nature of such products because of product retention in the closure aperture.
  • the closure design is distinguished by elements particularly suited to the dispensing of the product of the invention.
  • the domed or hemispherical nozzle design with its absence of actue angles, i.e. "corners” does not allow any appreciable product buildup and has the beneficial effect of concentrating and focusing any compressive force applied to the flexible container in a manner to keep the nozzle region and aperture clear of product buildup. The release of pressure from the container after dispensing clears the aperture.
  • FIG. 1 An example of the dispensing closure of the present invention is illustrated in Figures 1 through 3 wherein like parts are identified by the same number.
  • the closure is generally indicated at 1 having a body portion 2 and a bail-like sealing member 3.
  • the body portion 2 has a downwardly depending annular portion or skirt 4.
  • the inside surface of the annular portion 4 is provided with threads 5 adapted to mate and engage corresponding threads on the neck or finish of a container (not shown).
  • Means other than threading as are well known in the art may be employed to engage the closure 1 with the neck or finish of a container within the scope of the present invention.
  • the outside surface of the annular portion 4 can, if desired, be provided with grooves, ridges or the like both for decorative purposes and to facilitate grasping of the shell for threading it onto the container finish.
  • the interior surface of the top portion of the body portion 2 can have a downwardly depending annual rib 6 to abut and form a seal with the top surface of the container finish.
  • a chimney 7 is located centrally of the top portion of the body portion 2.
  • the chimney is generally cylindrical in configuration and is provided with an axial bore 8, open at its lower end to communicate with the interior of the container and is surmounted at its upper end with a domed or hemispherical portion 9 terminating in an aperture 10 for dispensing the product from the container and closure.
  • the diameter of the axial bore 8 also defines the interior horizontal diameter of the domed portion which preferably is at least 0.51 cm.
  • the bail-like sealing member 3 has an arcuate conformation and rotatable joints 11, 12 with the top portion of the closure body portion 2. In other embodiments, the joint is located on the outside wall of the chimney by means, for example, of protuberant posts from the chimney engaging sockets on the sealing member.
  • the sealing member 3 has a gripping portion 13 centrally located and a downwardly projecting protrusion 14 adapted to plug the aperture 10 when the sealing member 3 is in an closed position.
  • the sealing member may be adapted to provide a more positive seal of the protrusion 14 with the aperture 10 during shipment than is desirable during the period of consumer use.
  • the posts 15, 16 can be engaged into sockets 17, 18 for shipment and sale.
  • the container may be made of such materials as polyethylene, polypropylene or polyvinyl chloride. Particularly suitable are materials capable of formation into containers by blow molding.
  • the parts of the closure can be made from plastic materials such as polyethylene, polystyrene, polycarbonates or polypropylene that can be formed into desired shapes by injection molding. Materials resistent to cold flow such as the polycarbonates are particularly suitable for the sealing member.
  • Liquid detergent compositions were prepared containing the ingredients listed below:
  • compositions listed above contain approximately 45 to 55% water and have a pH value in the range of 8.0 to 10.0.
  • compositions are entirely satisfactory when used in dilute solutions as a dishwashing detergent compositions and are substantially superior to typical liquid dishwashing detergent compositions when used undiluted or in concentrated solution for removal of tightly attached soils.
  • compositions A and B were stored in packages of the invention with a closure having a circular cross-section aperture with a diameter of 0.305 cm.
  • Product was dispensed from 624 ml containers as packed and after storage of 3, 8, 10, 17 and 30 days. When the aperture was covered between uses, there was essentially no evidence of clogging to restrict or misdirect product flow when the container was subjected to a pressure of 26.65 N applied 10.2 cm from the base of the container. When the aperture was left open between uses, performance was impaired but generally satisfactory. Control samples utilizing the "push-pull" liquid detergent closure of U.S. Patents 3,227,332 and 3,201,013 and the liquid abrasive cleanser closures of U.S. Patents 3,981,421 and 4,065,037 did not provide dispensing characteristics as satisfactory.

Landscapes

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

Claims (11)

1. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung, enthaltend, bezogen auf das Gewicht:
(a) 20% bis 35% eines anionischen oberflächenaktiven Mittels;
(b) 2% bis 15% eines schaumstabilisierenden, nichtionischen oberflächenaktiven Mittels ausgewählt aus der Gruppe bestehend aus Aminoxiden, Amiden und den Ethylenoxid-kondensaten von Alkoholen und Alkylphenolen;
(c) 1 % bis 20% eines wasserunlöslichen Scheuermittels mit einem Teilchendurchmesser von 15 bis 150 jUm und einer Härte auf der Mohs-Skala von 2 bis 7; und
(d) 20% bis 75% Wasser;

wobei diese Zusammensetzung einer Geschirrspüllösung eine anfängliche Schaumdecke und nach dem Waschen von 8 Tellern bei Anwendung in einer Konzentration von 0,07% in 7,57 1 Wasser von 46°C, das eine Wasserhärte, gemessen als CaC03, von 120 mg/I enthält, wobei jeder Teller 4,0 ml an triglyceridhaltigem Schmutz trägt, eine Schaumdecke liefert.
2. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung in einem Verstopfungen widerstehenden Ausgabebehälter, enthaltend:
(a) eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch 1 und
(b) einen Verstopfungen widerstehenden Behälter, der diese flüssige Reinigungsmittelzusammensetzung enthält, enthaltend;
(i) einen biegsamen Kunststoffbehälter, der so adaptiert ist, daß er einen Ansteig des Innendruckes durch Anwendung einer Druckkraft auf eine oder mehrere äußere Oberflächenbereiche liefert, und
(ii) einen Verstopfungen widerstehenden Spenderverschluß, der so adaptiert ist, daß er auf diesem biegsamen Kunststoffbehälter montiert wird, wobei dieser Verschluß aus einem Körperteil und einem bügelartigen Verschlußglied besteht, wobei der Körperteil aus einem ringförmigen Mantel, der das Behälterende umgibt, Einrichtungen zur Befestigung dieses Mantels an diesem Behälterende und einem gewölbten Düsenabschnitt mit einer zentralen Öffnung besteht, wobei diese Öffnung eine waagerechte Querschnittsfläche von 0,0051 cm2 bis 0,06 35 cm2, einen Mindestdurchmesser von 0,127 cm und eine Länge von nicht mehr als 0,635 cm aufweist, wobei dieses bügelartige Verschlußglied eine bogenförmige Gestalt aufweist und an jedem Ende eine drehbare Verbindung zu dem Körperteil hat, wobei dieses Verschlußglied einen zentral angeordneten Griffteil und an seiner Unterseite einen sich nach unten erstreckenden, vorstehenden Teil aufweist, der so adaptiert ist, daß er die Außenseite der Öffnung verschließt, wenn sich das Verschlußglied in geschlossener Stellung befindet.
3. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß den Ansprüchen 1 oder 2, worin das anionische oberflächenaktive Mittel ein Material ausgewählt aus der Gruppe bestehend aus Alkylsulfaten, Alkylethersulfaten, Alkylbenzolsulfonaten, Paraffinsulfonaten, Olefinsulfonaten und Gemischen daraus umfaßt.
4. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch 3, worin das schaumstabilisierende nichtionische oberflächenaktive Mittel ein Material ausgewählt aus der Gruppe bestehend aus Ethanolamiden, Aminoxiden und Gemischen daraus umfaßt.
5. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch 4, worin das Scheuermittel ein Material ausgewählt aus der Gruppe bestehend aus Quarz, Kieselerde, Diatomeenerde, Feldspat, Perlit hoher Dichte, Calcit und Gemischen daraus umfaßt.
6. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch 5, worin der Teilchendurchmesser des wasserunlöslichen Scheuermittels 40 bis 125 Mikrometer beträgt.
7. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch 6, worin das Scheuermittel ein Material ausgewählt aus der Gruppe bestehend aus Quarz, Kieselerde, Feldspat, Perlit, Calcit und Gemischen daraus, umfaßt.
8. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß den Ansprüchen 1 oder 2, welche weiterhin einen Detergensgerüststoff ausgewählt aus der Gruppe bestehend aus Alkalimetallpolyphosphaten, wasserlöslichen Polycarboxylate, Natriumaluminosilikate und Gemischen daraus enthält.
9. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß den Ansprüchen 1 oder 2, worin die Menge an Wasser 40 Gew.-% bis 75 Gew.-% beträgt.
10. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch 2, worin der gewölbte Teil des Körperteils des Verschlusses einen inneren, waagerechten Durchmesser von mindestens 0,51 cm aufweist.
11. Eine Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzung gemäß Anspruch 10, worin die Öffnung rund ist und einen Durchmesser von mindestens 0,20 cm aufweist.
EP19800200610 1979-06-29 1980-06-26 Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzungen und sich nicht verstopfender Ausgabebehälter dafür Expired EP0021545B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US5316279A 1979-06-29 1979-06-29
US11014880A 1980-01-07 1980-01-07
US53162 1987-05-21
US110148 1987-10-19

Publications (2)

Publication Number Publication Date
EP0021545A1 EP0021545A1 (de) 1981-01-07
EP0021545B1 true EP0021545B1 (de) 1983-10-12

Family

ID=26731520

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800200610 Expired EP0021545B1 (de) 1979-06-29 1980-06-26 Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzungen und sich nicht verstopfender Ausgabebehälter dafür

Country Status (2)

Country Link
EP (1) EP0021545B1 (de)
DE (1) DE3065274D1 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60110794A (ja) * 1983-11-22 1985-06-17 ライオン株式会社 透明液体洗剤組成物
GB2168377A (en) * 1984-12-17 1986-06-18 Procter & Gamble Stable liquid dishwashing detergent containing abrasive, clay and low density particles
US4751016A (en) * 1985-02-26 1988-06-14 The Clorox Company Liquid aqueous abrasive cleanser
DE3601798A1 (de) * 1985-04-18 1986-10-23 Henkel KGaA, 40589 Düsseldorf Mehrzweckreinigungsmittel fuer harte oberflaechen
FR2650560A1 (fr) * 1989-08-02 1991-02-08 Maine Moulage Tete de conteneur tel qu'un tube
US5700331A (en) * 1996-06-14 1997-12-23 Colgate-Palmolive Co. Thickened cleaning composition
AR072859A1 (es) 2008-05-23 2010-09-29 Colgate Palmolive Co Metodos y composiciones liquidas de limpieza
DE102009045644A1 (de) * 2009-10-13 2011-04-14 Henkel Ag & Co. Kgaa Reinigungsmittel mit Bentoniten
US20120324655A1 (en) 2011-06-23 2012-12-27 Nalini Chawla Product for pre-treatment and laundering of stained fabric
US20160095496A1 (en) 2014-10-07 2016-04-07 The Procter & Gamble Company Method of pre-treating articles to be washed in a dishwashing machine
ES2773291T3 (es) 2015-01-15 2020-07-10 Ecolab Usa Inc Espuma para limpieza de larga duración

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3227332A (en) * 1963-09-27 1966-01-04 Procter & Gamble Captive closure
US4129527A (en) * 1974-11-07 1978-12-12 The Clorox Company Liquid abrasive detergent composition and method for preparing same
US3981421A (en) * 1975-06-30 1976-09-21 The Procter & Gamble Company Nonspurting dispensing closure
AU509862B2 (en) * 1976-07-01 1980-05-29 Albright & Wilson Australia )ltd Detergent compositions
DE2739776A1 (de) * 1976-09-07 1978-03-16 Procter & Gamble Reinigungsmittel
GB1534680A (en) * 1977-10-14 1978-12-06 Colgate Palmolive Co Cleaning compositions
DE2839857C3 (de) * 1978-09-13 1982-03-25 Henkel KGaA, 4000 Düsseldorf Backofen- und Grillreinigungsmittel und Verfahren zu ihrer Herstellung
US4352678A (en) * 1978-10-02 1982-10-05 Lever Brothers Company Thickened abrasive bleaching compositions

Also Published As

Publication number Publication date
DE3065274D1 (en) 1983-11-17
EP0021545A1 (de) 1981-01-07

Similar Documents

Publication Publication Date Title
US4457856A (en) Liquid detergent composition contains abrasive particles, anionic and nonionic surfactants
CA1140831A (en) Abrasive-containing liquid detergent composition and non-clogging dispensing package
CA1160131A (en) Liquid detergent composition
US4404128A (en) Enzyme detergent composition
EP0301883B1 (de) Flüssige Reinigungsmittelzusammensetzungen
AU747247B2 (en) Process for preparing pourable, transparent/translucent liquid detergent with continuous suspending system
AU746074B2 (en) Pourable transparent/translucent liquid detergent composition with suspended particles
US6369018B1 (en) Process for preparing pourable, transparent/translucent liquid detergent with non-continuous suspending system
EP0021545B1 (de) Scheuermittel enthaltende flüssige Reinigungsmittelzusammensetzungen und sich nicht verstopfender Ausgabebehälter dafür
EP0193375B1 (de) Flüssiges Reinigungsmittel
EP0292910A2 (de) Reinigungsmittelzusammensetzung für harte Oberflächen
CA1334919C (en) Liquid detergent compositions
AU635092B2 (en) Cleaning composition
CA1336386C (en) Liquid detergent composition
CA1160134A (en) Abrasive-containing liquid detergent composition
EP0034039B1 (de) Flüssige Reinigungsmittelzusammensetzung
CA1335646C (en) Liquid detergent compositions
EP0362916A2 (de) Flüssige Waschmittelzusammensetzungen
EP0030986A1 (de) Scheuermittel und Komplexbildner enthaltende flüssige Reinigungsmittelzusammensetzung
CA1143240A (en) Abrasive-containing liquid detergent composition
JPS5829899A (ja) 液体洗剤組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

17P Request for examination filed

Effective date: 19810626

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19831012

ET Fr: translation filed
REF Corresponds to:

Ref document number: 3065274

Country of ref document: DE

Date of ref document: 19831117

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19840328

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19840630

Year of fee payment: 5

Ref country code: BE

Payment date: 19840630

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19840716

Year of fee payment: 5

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

26 Opposition filed

Opponent name: UNILEVER PLC / UNILEVER N.V.

Effective date: 19840709

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 19850706

NLR2 Nl: decision of opposition
REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 19860630

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO