IE60580B1 - Creamy scouring compositions - Google Patents
Creamy scouring compositionsInfo
- Publication number
- IE60580B1 IE60580B1 IE253887A IE253887A IE60580B1 IE 60580 B1 IE60580 B1 IE 60580B1 IE 253887 A IE253887 A IE 253887A IE 253887 A IE253887 A IE 253887A IE 60580 B1 IE60580 B1 IE 60580B1
- Authority
- IE
- Ireland
- Prior art keywords
- composition
- weight
- accordance
- organic solvent
- compositions
- Prior art date
Links
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
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
-
- 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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2068—Ethers
Landscapes
- 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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Stable, viscous creamy scouring compositions are disclosed, which are substantially free of terpene solvents, and contain a narrowly-defined solvent derived from propylene glycol. The compositions of the invention show excellent cleaning ease-of-rinsing, shine performance, and are not aggressive to cleansed surfaces and packaging materials.
Description
The present invention relates to stable, viscous abrasive-containing scouring compositions, which show excellent cleaning, ease-of-rinsing, and shine performance, and are not aggressive to surfaces to be cleansed therewith and packaging materials.
These compositions are substantially free of terpene solvents, and contain a narrowly-defined solvent derived from propylene glycol.
It is well-known to formulate scouring compositions, in 10 liquid or creamy form, containing solvents.
In particular, creamy scouring compositions containing an abrasive and a binary solvent system constituted of terpenes and polar solvents have been disclosed in European Patent Application 0,126,545, published on November 26, 1984. In these compositions, the terpenes show both cleaning and desirable emulsification properties, which enhance product viscosity.
It has become desirable, however, to replace terpenes by soluents which ar® fully compatible with all types of surfaces to be cleansed therewith, ©nd packaging materials, and at th© same time exhibit good cleaning and emulsification properties .
It has now been found that viscous terpene solvent free creamy scouring cleanser compositions showing remarkable cleaning efficiency, ease-of-rinsing and surface-compatibility, can be formulated which contain a narrowly-defined solvent derived from propylene glycol.
US-3,591,510 discloses the us® of solvents of this type in liquid hard surface cleaning compositions free of abrasive. ΕΡ-Ά-0 040 882 mentions the us© of propylene glycol-derived solvents, in combination with terpenes and benzyl alcohols, in liquid hard surface cleaners free of abrasive .
It is an object of th® present invention to provide viscous creamy cleanser compositions which are fully compatible with surfaces te be cleansed therewith and packaging materials. It is a further object of th® present invention to provide a cleanser composition with excellent cleaning, ease-of-rinsing and shine performance.
The present invention relates to a viscous creamy scouring cleanser being substantially free of terpene soluents, containing a surface-active agent, an abrasive. and an organic solvent and if desired conventional additives, characterised in that said cleanser is free of or contains not more than 2% by weight of terpene solvents and that the organic solvent is represented by the formula: CH, RO(CH2CHO)nH wherein R is a to C„ alkyl, alkenyl or alkyl aryl group, preferably a to C·alkyl group, and n is an integer from 1 to a, preferably 1 or 2 ; and that the Mohs hardness of the abrasive is 7 or less.
The surface-active agents, th© abrasives, the solvent and the optional ingredients ar® described in more detail hereinafter.
Unless indicated to the contrary, the ^-indications stand for % by weight".
Surface-active Agents Uater-soluble detersive surfactants useful herein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants and mixtures thereof. Typical of these are the alkyl benzene sulfates and sulfonates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known in th© detergency art.
In general, such detersive surfactants contain an alkyl group in the range; the anionic detersive surfactants are most commonly used in the form of their sodium, potassium or triethanolammonium salts. Th© nonionics generally contain from 3 to 17 ethylene oxide groups per mole of hydrophobic moeity. Especially preferred in the compositions of th© present invention are: CJ7-C15 alkyl benzene sulfonates, C,C„§ paraffin-sulfonates and the ethoxylated alcohols of the formula RGCCK^CH^O)^ H? with R being a ci2~Ci5 alkyl chain and n being a number from 6 to 10.
Anionic surfactants are frequently present at levels from 0.3 to 8%, preferably 2 to 4%, of the composition. Nonionic surfactants, are used at levels between 0.1% to 6% by weight of the composition. Mixtures of th® like surfactants can also be used. The total level of surface-active ©gent is preferably from 3% to 5%.
Abrasive - The abrasive types employed herein are selected from water-insoluble, non-gritfey materials well-known in the literature for their relatively mild abrasive properties.
It is highly preferred that the abrasives used herein not b® undesirably scratchy". Abrasive materials hauing a Mohs hardness of 7, or below?' are used; abrasives having a Mohs hardness of 3, or below, can be used to avoid scratches on aluminum or stainless steel finishes. Suitable abrasives herein include inorganic materials? ©specially such materials as calcium carbonate and diatomaceous earth, as well as materials such as Fuller’s earth, magnesium carbonate, China clay, attapulgit®, calcium hydroxyapatite, calcium orthophosphate, dolomite and fhe like.- Th© aforesaid inorganic materials can be qualified as strong abrasives. Synthetic organic abrasives such as urea-formaldehyde, methyl methacrylate melamine-formaldehyde resins, polyethylene spheres and polyvinylchloride can be advantageously used in order to avoid scratching on certain surfaces, especially plastic s surfaces. When such soft abrasives -are used, strong builders can be incorporated in the composition.
Typically, abrasives have a particle size range of j. -1000 pm and are used at concentrations of 5% to 30% in the compositions. Thickeners are frequently added to suspend the abrasives.
The organic solvent ~ Th® organic solvent to be used in the present composition has the general formula RO(CH,CHO) H wherein R is an alkvl, alkenyl, or alkyl-aryl group having from 1 to 8 carbon atoms, and n is an integer from I to 4. Preferably, R is a alkyl group containing 1 to 4 carbon atoms, and n is l or 2. Especially preferred R groups are n-butyl or isobutyl. Host preferred species are 1- n-butoxypropane-2-ol (n~i); and 1(2-n-butoxy-l-methylethoxy)propane-2-ol (n=2), and mixtures thereof. l-n-butoxypropane-2-ol is ©specially preferred.
Th® organic solvent herein is preferably vised at levels of frcm 2 to 10% by weight of the composition,more preferably 4 to 6%.
The solvent system can optionally contain, in combination with the solvent described hereinabove, water-soluble CARBITOL*· solvents or water-soluble CELLOSOLVE* solvents. Water-soluble CARBITOL* solvents are compounds of the 2~(2-alkoxyethoxy)ethanol class wherein / the alkoxy group is derived from ethyl, propyl or butyl; a 7 preferred water-soluble carbitol is 2- {2-butoxyethoxy)ethan©X also known as butyl carbitol. ft Water-soluble CELLOSOLVE · solvents are compound of the * Trade Mark 2-alkoxy ethanol class, with 2-butoxy ethanol being preferred.
Suitable solvents to be used with the solvents of the invention are also benzyl alcohol, and diols such as 2-ethyl-l,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
The above-described co-solvents can be used in levels ranging from 0.1 to 5% of the composition.
The compositions herein are substantially free of terpene-solvents. Inasmuch as solvents are generally used at levels exceeding 2%, terpenes cannot be incorporated in the claimed compositions in such proportions. It is understood, however, that relatively minor sub-additive levels of terpenes, e.g., below 0.6% (calculated on the total cleanser composition), can be present originating from conventional ingredients such as perf limes .
Optional Ingredients - In addition to th® essential ingredients listed hereinbefore, th® present composition can contain additional components, which can be highly desirable For example, it is highly preferred that th® compositions contain a detergent builder and/or metal ion seguestrant. Compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates, (NTA), ethylene diamine tetracetate (EDTA), amino-polyphosphonates (DEQUES!), water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, and mixtures thereof. These builders are preferably not used in combination 5Asifch strong abrasives like calcium carbonate, but are recommended in combination with soft organic abrasives like polyvinylchloride.
Metal ion sequestrants ©f lower metal sequestration constant can advantageously be used in combination with strong or soft abrasives. Thos© metal ion sequestrants include polycarboxylates, citrates. Preferred builders/sequestrants for use in the present invention are NTA, EDTA, citrates and mixtures thereof. The builders/sequestrant will be present at levels of from i% to 15%, preferably from 2% to 7%.
It is highly preferred, as well, to include soaps in the compositions of the invention. Soaps prepared from coconut oil fatty acids are preferred.
Soaps are used in amounts ranging from 0.2% to 3% by weight of the composition, preferably in an amount in excess of 1%, typically from 1% to 2% by weight.
This level is clearly above levels currently used in similar compositions, since it has surprisingly been discovered that the presence of soaps at these higher levels not only provides suds control, but also has a thickening effect on the compositions containing the specific organic solvent of the invention. This finding allows to keep th® amount of thickener at a very low level, thus substantially reducing certain drawbacks of thickeners, such as rinsing difficulties resulting from their use at substantial levels.
Thickeners should preferably be included in the compositions of the invention, in order to suspend the abrasive. However the level will b© kept under 2«, preferably from 0.2% to 1.5%. Common thickener® such as the polyacrylates, xanthan gums, carboxymethy1 celluloses, swellable smectite clays, and the like, can be used herein.
Optional components are also represented by ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical ingredients include pH regulants, perfumes, dyes, optical brighteners, soil suspending agents, detersive enzymes, gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, and the like.
Another optional ingredient for use herein is represented by conventional detergent hydrotropes. Examples of suitable hydrotropes are urea, monoethanolamine, diethanolamine, triethanolamine and the sodium potassium, ammonium and alkanol ammonium salts of xylene-, toluene-, ethylbenzene- and isopropyl-benzene sulfonates. It is a particular feature of the present invention, however, that stable formulations can be prepared without the need for hydrotropic materials of this kind.
The compositions herein typically contain up to about 90% water as a carrier. By way of example th© water-level can vary in the range from e.g. 50% to 80%. Water-alchol (e.g., ethanol, isopropanol, butanol, etc.) mixtures can also be used. Alkylated polysaccharides can be used to increase th® stability and performance characteristics of the compositions.
The compositions herein are preferably formulated in the alkaline pH range, generally in th© range of pH Θ-Π, preferably about 10-10.8. Caustics such as sodium hydroxide and sodium carbonate can be used to adjust and buffer the pH as desired.
The following examples are given by way of illustrating the compositions herein, but ar® not intended to be limiting of the scope of the invention.
Abbreviations MaPS Sodium Cs., to C„, paraffin sulfonate 13 lo Sodium salt of linear C.M-C0 alkyl benzene sulfonate LAS 5 LAB Linear C1Q_^9 alkyl benzene Lutensol* A07 Condensate of 1 mol© C19~C,4 fatty alcohol with 7 moles of ethylen© oxide Dobanol* 45/7 C,,-C,c oxoalcohol with 7 moles of 14 15 ethylene oxide per mole of alcohol 10 HCnFft Marrow cut, hardened, coconut fatty ac MT A Sodium nitrilotriacetate EDTA Ethylene diamine tetraacetate CaCOg Calcium carbonate Sokolarf PHC 25 Crosslinked polyacrylate thickener 15 ETHD 2-Ethyl-l,3-hexanediol Tf^PD 2,2.4-trimethyl"!~3"P@ntanediol PUC Polyvinylchloride * Trade Mark V Ζ -5 Creamy cleansers were prepared by mixing the listed ingredients in the stated Ingredients proportions (% by weight). Comp. A Ex. I LAS 0.5 4.0 hSaPS 3.0 - Lutensol® A07 0.3 - w&7co. 3.0 HC FA Π 0.2 1.2 Benzyl alcohol 1.5 - Orange terpenes 2.0 - l-Butoxypropane-2-ol - 5.0 AJTA - 4.0 CaC0? 30.0 - PUC .... 10.0 Sokolatf PHC25 0.6 0.4 Water * minors up to 100 The above compositions were comparatively tested on synthetic soils representative of typical hard surface household soils. The test-soils were prepared as follows. a) HBTS soil: is composed of 250 ml isopropyl alcohol, 75g calcium stearate powder and 0.5g carbon black. It is applied on an enamel-coated metal plate (cleaned with a detergent and then with alcohol) with a paint roller, and the plates are baked at 180°C for 20 minutes. b) KO soil: is composed of 25% HSJ/ soil with carbon black (2), 37.5%, CriscoR (1) oil, 37.5% Puritan* Cl) oil. This soil is rolled onto stainless steel plates (beforehand cleaned with a detergent and then with alcohol) using a paint roller. A very thin uniform layer is needed since the soil is difficult to cure.
A Trade Mark The plates are placed in the oven at 115®C (soft soil) or 170°C (hard soil) for 2 hours and than allowed to age at least l day. , (1) commercial cooking oil sold by The Procter & Gamble $ Company (2) commercial soil sold by Chem Pack Inc., U.S.A.
The testing conditions were as follows: The test was run with the aid of an Erichsen washability machine. A sponge of approximately 9.5 x 5 x 4 cm was used after being carefully washed under hot running water and squeezed through drying rolls. 5g of the undiluted cleanser to be tested was spread over one side of the sponge. The number of strokes of the cleaning machine uaried with th® type of soil. Performance readings were done as soon as visible cleaning dirfrences became noticeable. The gradings were done visually by three judges working independently.
Th® performance benefits were established via paired comparison with duplicates as follows. A 0-4 scale was used whereby: 0 means no difference; ϊ - probable difference; 2 = consistent difference; 3 <= clear difference; 4 = big difference .
Th® testing results were as listed below. Prior art composition A was the reference against which th® composition of example 1 was compared.
Soil Comp, ft Ex. I KO Ref. + 0.5 HSTS Ref. 4-2.0 Λ The above test clearly confirms the significant performance benefits derivable from th® inuentiue compositions us . related art composition.
In addition. the following compositions are prepared: Inqradiants Ex. ΙΪ Ex. XII Ex. IV Ex. V Ex. VI Ex. VII Ex. VIII LAS 4.0 4.0 0.5 3.0 0.5 3.0 4.0 5 daPS - - 3.0 1.0 3.0 1.0 - Lutensol'w A07 — - 0.3 - 0.2 - - WaCOs 3.0 - 3.0 - 3.0 3.0 - HCnffi 1.2 1.2 1.2 1.5 1.5 1.2 1.2 Benzyl alcohol - - - 1.0 - - 10 Butyl carbito1 .... - - 1.0 - - ETHO - - 1.0 - - - TMPO - • - " - 1.0 1.0 - 1-Butoxypropane-2-ol l(2-Butoxy-l-saethyl— ·=· 2.0 3.0 2.0 s.o 15 ethoxy)propane-2-ol 5.0 5.0 - 4.0 - - MTA 4.0 4.0 3.0 1.0 2.0 - - EDTA - 1.0 1.0 1.0 - 2.0 Citrate - - 1.0 3.0 2.0 3.0 - CaC©3 30.0 - 30.0 - - 30.0 - 20 PVC - 10.0 - 10.0 10.0 - 10.0 Sokolasf PHG25 Water t minors 0.4 0.4 0.4 ---CO P 0.4 fe a 0.4 1 0 0 0.4 0.4 * Trade Mark
Claims (8)
1. fi viscous, creamy scouring cleanser containing a surface-active agent, an organic solvent, an abrasive, and if desired conventional additives, characterized in, that said cleanser is free of or contains not more than 2% by weight of terpene-solvents; and that the organic solvent is represented by the formula; RO(CH 2 CHO) n H wherein R is a C„ to C g alkyl, alkenyl or alkyl aryl group, preferably a to C alkyl group, and n is an integer from 1 to 4; and that the Mohs hardness of the abrasive is 7 or less.
2. A composition in accordance with Claim 1 wherein R is a Cj to C, alkyl group, and n is ί or 2.
3. A composition in accordance with Claims 1 and 2 wherein the organic solvent is l-n-butoxypropan®-2-ol or is 1(2-n-butoxy-l-methyl ®thoxy)propane-2-ol, or is a mixture thereof.
4. A composition in accordance with Claims 1-3 wherein the organic solvent is present at levels of from 2% fco 10% by weight.
5. A composition in accordance with Claims 1-4 which contains from 1 to 15% by weight of a detergent builder and/or metal ion seguestrant.
6. A- composition in accordance with Claim 5 wherein said detergent builder and/or metal ion sequestrant material is selected from nitrilotriacetate, ethylene diamine tetraacetate, citrate, and mixtures thereof.
7. fl composition in accordance with Claims 1-6 which „ contains from 0.2% to 3% of a fatty acid soap. Ί ®. fl viscous creamy scouring cleanser composition in accordance with any of the preceding Claims, containing 5 - from 3%, to 5% by weight of organic surface-actiue agent; - from 1% to 2% by weight of fatty acid soap; - from 4% to 6% by weight of an organic solvent selected from i-n-butoxypropane-2-ol, l<2-n-butoxy-I~methyl ethoxy)propane-2-ol, and mixtures thereof; 10 _ from 2% to 7% by weight of a determent builder and/or metal ion sequestrant material selected from nitrilotriacetate, ethylene diamine tetraacetate, citrate, and mixtures thereof.
8. 9 A viscous, creamy scouring cleanser according to 15 Claim 1, substantially as hereinbefore described with particular reference to the accompanying Examples.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US91056186A | 1986-09-22 | 1986-09-22 | |
GB868624156A GB8624156D0 (en) | 1986-10-08 | 1986-10-08 | Creamy scouring compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
IE872538L IE872538L (en) | 1988-03-22 |
IE60580B1 true IE60580B1 (en) | 1994-07-27 |
Family
ID=26291398
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
IE253887A IE60580B1 (en) | 1986-09-22 | 1987-09-21 | Creamy scouring compositions |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0261718B1 (en) |
DE (1) | DE3768398D1 (en) |
IE (1) | IE60580B1 (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8802086D0 (en) * | 1988-01-30 | 1988-02-24 | Procter & Gamble | Creamy scouring compositions |
US5330582A (en) * | 1989-11-08 | 1994-07-19 | Arakawa Chemical Industries, Ltd. | Method for cleaning rosin-base solder flux |
DE69003350T2 (en) * | 1989-11-08 | 1994-01-13 | Arakawa Chem Ind | Composition and method for removing rosin-based solder flux. |
US5630847A (en) * | 1995-03-30 | 1997-05-20 | The Procter & Gamble Company | Perfumable dry cleaning and spot removal process |
US5591236A (en) * | 1995-03-30 | 1997-01-07 | The Procter & Gamble Company | Polyacrylate emulsified water/solvent fabric cleaning compositions and methods of using same |
US5547476A (en) * | 1995-03-30 | 1996-08-20 | The Procter & Gamble Company | Dry cleaning process |
US5942484A (en) * | 1995-03-30 | 1999-08-24 | The Procter & Gamble Company | Phase-stable liquid fabric refreshment composition |
WO1996030581A1 (en) * | 1995-03-30 | 1996-10-03 | The Procter & Gamble Company | Dry cleaning article |
US5632780A (en) * | 1995-03-30 | 1997-05-27 | The Procter & Gamble Company | Dry cleaning and spot removal proces |
US5630848A (en) * | 1995-05-25 | 1997-05-20 | The Procter & Gamble Company | Dry cleaning process with hydroentangled carrier substrate |
US5912408A (en) * | 1995-06-20 | 1999-06-15 | The Procter & Gamble Company | Dry cleaning with enzymes |
US5687591A (en) * | 1995-06-20 | 1997-11-18 | The Procter & Gamble Company | Spherical or polyhedral dry cleaning articles |
US5681355A (en) * | 1995-08-11 | 1997-10-28 | The Procter & Gamble Company | Heat resistant dry cleaning bag |
US5789368A (en) * | 1996-01-26 | 1998-08-04 | The Procter & Gamble Company | Fabric care bag |
US6233771B1 (en) | 1996-01-26 | 2001-05-22 | The Procter & Gamble Company | Stain removal device |
US5840675A (en) * | 1996-02-28 | 1998-11-24 | The Procter And Gamble Company | Controlled released fabric care article |
US5891197A (en) * | 1996-08-02 | 1999-04-06 | The Proctor & Gamble Company | Stain receiver for dry cleaning process |
US5872090A (en) * | 1996-10-25 | 1999-02-16 | The Procter & Gamble Company | Stain removal with bleach |
US5762648A (en) * | 1997-01-17 | 1998-06-09 | The Procter & Gamble Company | Fabric treatment in venting bag |
US5849039A (en) * | 1997-01-17 | 1998-12-15 | The Procter & Gamble Company | Spot removal process |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3591509A (en) * | 1968-09-30 | 1971-07-06 | Procter & Gamble | Liquid hard surface cleaning compositions |
GB1533390A (en) * | 1976-04-08 | 1978-11-22 | Shell Int Research | Detergent compositions |
ATE32608T1 (en) * | 1980-05-27 | 1988-03-15 | Procter & Gamble | TERPEN SOLVENT MIXTURE USABLE FOR THE PREPARATION OF LIQUID CLEANING AGENT COMPOSITIONS. |
EP0126545B1 (en) * | 1983-04-19 | 1987-08-19 | The Procter & Gamble Company | Liquid scouring cleansers containing solvent system |
-
1987
- 1987-09-08 DE DE8787201698T patent/DE3768398D1/en not_active Expired - Fee Related
- 1987-09-08 EP EP19870201698 patent/EP0261718B1/en not_active Expired
- 1987-09-21 IE IE253887A patent/IE60580B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
IE872538L (en) | 1988-03-22 |
EP0261718B1 (en) | 1991-03-06 |
EP0261718A3 (en) | 1989-01-25 |
DE3768398D1 (en) | 1991-04-11 |
EP0261718A2 (en) | 1988-03-30 |
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Legal Events
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MM4A | Patent lapsed |