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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/201—Monohydric alcohols linear
• • 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
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/94—Mixtures with anionic, cationic or non-ionic 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
• • 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
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/2017—Monohydric alcohols branched
• • 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
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols
  • C11D3/2044—Dihydric alcohols linear
• • 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
• • 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
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/90—Betaines
• • 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
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/92—Sulfobetaines ; Sulfitobetaines
• • 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
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/2034—Monohydric alcohols aromatic
• • 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
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2041—Dihydric alcohols

Definitions

• the present invention relates to a cleaning composition which provides an effective cleaning and shine performance on surfaces, especially hard surfaces.
• compositions which provide cleaned shiny surfaces is a problem known in the art to the formulator of a cleaning composition. More particularly, the problem of providing shiny surfaces is often compromised by residues of the compositions which are left on said surfaces and which appear as streaks as water evaporation is completed. The problem of the residuality is even more noticeable where the composition is used to clean surfaces made of glossy materials, such as glossy ceramic tiles, windows and mirrors, or such materials as polyurethane-coated PVC which is widely used in Northern America. Furthermore, nowadays, many products are formulated or can be used as no-rinse products. In such conditions or with such products, the problem of residuality has become more acute.
• composition which comprises a surfactant system comprising an alkyl sulphate surfactant and a betaine or a sulphobetaine surfactant in specific ratios and wherein the pH of the composition is of at least 4.
• the present invention relates to a cleaning composition
• a cleaning composition comprising a surfactant system comprising an alkyl sulphate and a betaine or a sulphobetaine surfactant in a weight ratio of alkyl sulphate to betaine or sulphobetaine of 5.5:1 to 100:1, and wherein the pH of the composition is of at least 4.
• the composition comprises a solvent for enhanced cleaning and shine performance of the composition.
• the composition further comprises a peroxygen bleach for providing the composition with effective disinfecting performance.
• An essential feature of the invention is a surfactant system, said system comprising an alkyl sulphate and a betaine or a sulphobetaine surfactant in specific weight ratios of alkyl sulphate to betaine or a sulphobetaine surfactant.
• Alkyl sulphate surfactants to be used herein are those of formula ROSO 3 - M + , wherein R represents an alkyl group containing from 6 to 24 carbon atoms, more preferably 6 to 16 and most preferably 8 to 14 carbon atoms. M represents a water-solubilising cation.
• the alkyl group can be in straight or branched configuration, and preferably in straight configuration.
• Alkyl sulphate is commercially available from Rhone Poulenc under the tradename Rhodapon® or from Albright & Wilson under the tradename EMPICOL®.
• Rhodapon® or from Albright & Wilson under the tradename EMPICOL®.
• EMPICOL® 0137/A A preferred commercial alkyl sulphate for use herein is EMPICOL ® 0137/A.
• composition according to the present invention comprises a betaine or a sulphobetaine surfactant, or derivatives thereof, or mixtures thereof.
• a further advantage of the invention is the mild action profile of said betaine and/or sulphobetaine surfactants. Accordingly, the compositions herein may be particularly suitable for the cleaning of delicate surfaces, e.g. delicate laundry or surfaces in contact with food and/or babies. Furthermore, betaine and/or sulphobetaine surfactants are also extremely mild to the skin, and thus contribute to the convenience of use of the compositions of the present invention by the user.
• Suitable betaine/sulphobetaine surfactants to be used in the compositions of the present invention are the betaine/sulphobetaine wherein the molecule contains both basic and acidic groups which form an inner salt giving the molecule both cationic and anionic hydrophilic groups over a broad range of pH values.
• Some common examples of these detergents are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
• Preferred betaine or sulphobetaine surfactants have the formula wherein R1 is an alkyl radical containing from about 1 to about 24 carbon atoms, preferably from 8 to 18, and more preferably from 12 to 14, wherein R2 and R3 contain from 1 to 3 carbon atoms, and preferably 1 carbon atom, wherein n is an integer of from 1 to 10, preferably from 1 to 6 and more preferably is 1, Y is selected from the group consisting of carboxyl and sulfonyl radicals and wherein the sum of R1, R2 and R3 radicals is from about 14 to about 24 carbon atoms, or mixtures thereof.
• betaine surfactants examples include C12-C18 alkyl dimethyl betaine such as the coconut betaine and C10-C16 alkyl dimethyl betaine such as the lauryl betaine.
• Coconut betaine and Lauryl betaine are commercially available from Seppic and Albright & Wilson respectively, under the trade name of Amonyl 265® and Empigen BB/L® respectively.
• compositions herein comprise at least 0.005% by weight of the total composition of said betaine or sulphobetaine surfactant, or derivatives thereof, or mixtures thereof, preferably from 0.01% to 10%, and more preferably from 0.1% to 5%.
• the weight ratios of alkyl sulphate to betaine or sulphobetaine are an important feature of the invention. Hence, ratios outside the range below, such as those where the betaine or sulphobetaine surfactant is in a higher proportion than the alkyl sulphate, would not provide the cleaning and shine benefit but only the cleaning benefit while still leaving greasy residues. On the other hand, a ratio above 100:1 of alkyl sulphate to betaine or sulphobetaine surfactant would result in a surface showing spotty residues of the crystalline type.
• alkyl sulphate and betaine or sulphobetaine surfactant be present within the composition in a weight ratio of alkyl sulphate to betaine of 5.5:1 to 100:1, preferably from 10:1 to 50:1.
• a weight ratio of alkyl sulphate to betaine of 15:1 to 30:1 is most preferred.
• compositions comprising the specific surfactant system mentioned above and having a pH below 4 have been found to produce a precipitate in the solution.
• the pH of the composition is measured at 20°C in the neat composition where the composition is an aqueous composition or measured as a 1% solution in distilled water at 20°C where the composition is a solid composition.
• the pH of the composition is of at least 4.
• the compositions according to the present invention are aqueous liquid cleaning compositions.
• Said aqueous compositions preferably have a pH as is of not more than 12.0, more preferably from 4 to 10.
• the pH of the compositions can be adjusted by using organic or inorganic acids, or alkalinising agents.
• composition of the invention may, optionally, contain additional components such as solvents, peroxygen bleach, chelants and mixtures thereof.
• solvents When used, solvents will, advantageously, give an enhanced cleaning and shine performance to the composition.
• Suitable solvents for incorporation in the compositions according to the present invention include propylene glycol derivatives such as n-butoxypropanol or n-butoxypropoxypropanol, 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 preferred water-soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as butyl carbytol.
• Water-soluble CELLOSOLVE® solvents are compounds of the 2-alkoxyethoxyethanol class, with 2-butoxyethoxyethanol being preferred.
• Other suitable solvents are benzyl alcohol, ethanol, isopropyl alcohol and diols such as 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol and mixture thereof.
• Preferred solvents for use herein are n-butoxypropoxypropanol, butyl carbitol® and mixtures thereof.
• a most preferred solvent for use herein is butyl carbitol®.
• the solvents will typically be present within the undiluted composition of the invention at a level of 0.01% to 10% by weight, preferably 3% to 7% by weight of the composition.
• a peroxygen bleach is a peroxygen bleach.
• Peroxygen bleach especially hydrogen peroxide, persulfate and the like, in the compositions of the present invention advantageously contribute to the disinfection properties of said compositions.
• said peroxygen bleach may attack the vital function of the micro-organism cells, for example, it may inhibit the assembling of ribosomes units within the cytoplasm of the micro-organism cells.
• said peroxygen bleach like hydrogen peroxide is a strong oxidizer that generates hydroxyl free radicals which attack proteins and nucleic acids.
• the presence of said peroxygen bleach, especially hydrogen peroxide provides strong stain removal benefits which are particularly noticeable for example in laundry and hard surfaces applications.
• a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water.
• Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicate, persulphate such as monopersulfate, perborates and peroxyacids such as diperoxydodecandioic acid (DPDA), magnesium perphthalic acid and mixtures thereof.
• DPDA diperoxydodecandioic acid
• a preferred peroxygen bleach is hydrogen peroxide, or a water soluble source thereof, or mixtures thereof.
• a most preferred peroxygen bleach is hydrogen peroxide.
• peroxides can be used as an alternative to hydrogen peroxide and sources thereof or in combination with hydrogen peroxide and sources thereof.
• Suitable classes include dialkylperoxides, diacylperoxides, preformed percarboxylic acids, organic and inorganic peroxides.
• compositions herein comprise at least 0.01% by weight of the total composition of said peroxygen bleach or mixtures thereof, preferably from 0.1% to 15%, and more preferably from 1% to 10%.
• the following disinfecting test method may be applied to measure the disinfection property of the composition:
• Disinfection properties of a composition may be measured by the bactericidal activity of said composition.
• a test method to evaluate the bactericidal activity of a composition is described in European Standard, prEN 1276, CEN/TC 216 N 59, dated November 1995 issued by the European Committee for Standardisation, Brussels.
• European Standard, prEN 1276, CEN/TC 216 N 59 specifies a test method and requirements for the minimum bactericidal activity of a disinfecting composition. The test is passed if the bacterial colonies forming units (cfu) are reduced from a 10 7 cfu (initial level) to a 10 2 cfu (final level after contact with the disinfecting product), i.e. a 10 5 reduction of the viability is necessary.
• Chelating agents are also additional components which may be suitable for use herein.
• Preferred chelating agents are those selected from the group of aminophosphonates.
• Suitable amino phosphonate compounds for use herein include amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates.
• the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
• Preferred amino phosphonate chelants to be used herein is diethylene triamine penta methylene phosphonate. Such phosphonate chelant is commercially available from Monsanto under the trade name DEQUEST®.
• Said cheating agents especially phosphonate cheating agents like diethylene triamine penta methylene phosphonates, are particularly preferred in the compositions according to the present invention as they have been found to further contribute to the disinfecting properties of hydrogen peroxide.
• compositions according to the present invention comprise up to 5% by weight of the total composition of a cheating agent, or mixtures thereof, preferably from 0.002% to 3% by weight and more preferably from 0.002% to 1.5% by weight of the composition.
• compositions herein may further comprise a variety of other optional compounds including antimicrobial compounds such as Eugenol commercially available for example from Sigma, Systems - Bioindustries (SBI) - Manheimer Inc, builders, buffers, bactericides, enzymes, hydrotropes, colorants, stabilizers, bleach activators, soil suspenders, dye transfer agents, brighteners, perfumes, anti dusting agents, dispersant, dye transfer inhibitors, pigments, perfumes and dyes.
• antimicrobial compounds such as Eugenol commercially available for example from Sigma, Systems - Bioindustries (SBI) - Manheimer Inc, builders, buffers, bactericides, enzymes, hydrotropes, colorants, stabilizers, bleach activators, soil suspenders, dye transfer agents, brighteners, perfumes, anti dusting agents, dispersant, dye transfer inhibitors, pigments, perfumes and dyes.
• compositions according to the present invention may be formulated either as solids or liquids.
• the compositions In the case where the compositions are formulated as solids, they will be mixed with an appropriate solvent, typically water, before use.
• the compositions In liquid form, the compositions are preferably but not necessarily formulated as aqueous compositions. Liquid compositions are preferred herein for convenience of use.
• compositions herein may be packaged in a variety of suitable detergent packaging known to those skilled in the art.
• the liquid compositions herein may desirably be packaged in manually operated spray dispensing containers, which are usually made of synthetic organic polymeric plastic materials.
• the present invention also encompasses liquid cleaning compositions of the invention packaged in a spray dispenser, preferably in a trigger spray dispenser.
• said spray-type dispensers allow to uniformly apply to a relatively large area of a surface to be cleaned the liquid cleaning compositions suitable for use according to the present invention; thereby contributing to the cleaning properties of said compositions.
• Such spray-type dispensers are particularly suitable to clean vertical surfaces.
• Suitable spray-type dispensers to be used according to the present invention include manually operated foam trigger-type dispensers sold for example by Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are disclosed, for instance, in US-4,701,311 to Dunnining et al. and US-4,646,973 and US-4,538,745 both to Focarracci. Particularly preferred to be used herein are spray-type dispensers such as T 8500® commercially available from Continental Spray International or T 8100® commercially available from Canyon, Northern Ireland. In such a dispenser the liquid composition is divided in fine liquid droplets resulting in a spray that is directed onto the surface to be treated.
• the composition contained in the body of said dispenser is directed through the spray-type dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism. More particularly, in said spray-type dispenser head the composition is forced against an obstacle, e.g. a grid or a cone or the like, thereby providing shocks to help atomise the liquid composition, i.e. to help the formation of liquid droplets.
• an obstacle e.g. a grid or a cone or the like
• compositions of the present invention may also be executed in the form of wipes.
• wipes it is meant herein disposable paper towels incorporating a liquid composition according to the present invention.
• the present invention also encompasses wipes, e.g. disposable paper towels, incorporating a liquid composition according to the present invention.
• said wipes are impregnated, more preferably wetted with said liquid compositions.
• said wipes are packaged in a plastic box.
• the advantage of this execution is a faster usage of a cleaning composition by the user, this even outside the house, i.e. there is no need to pour the liquid compositions according to the present invention on the surfaces to be treated and to dry it out with a cloth.
• wipes allow cleaning of surfaces in one step.
• the present invention encompasses a process for cleaning surfaces wherein a composition according to the present invention is applied onto said surfaces.
• surface it is meant herein any surface including hard-surfaces like bathroom, kitchen, floors, table tops, refrigerators, walls, tiles, wash surfaces and the like.
• compositions may be applied to the surface to be disinfected in its neat form or in its diluted form.
• diluted form it is meant herein that the compositions to be used in the cleaning process herein being either in a liquid or solid form may be diluted by the user typically up to 1000 times their weight of water, preferably up to 300 times, more preferably into 80 to 30 times their weight of water, and most preferably 60 to 40 times.
• Standard enamel plates were soiled by applying on them a grease/particulate matter and then baking them.
• the tested compositions were then applied on a sponge and then placed onto a Gardner Machine.
• the Gardner machine measured the number of strokes needed to reach 95-99% clean plates. The performance was measured as such (i.e undiluted) and upon dilution at 1.5% in water.
• test product Five millimeters of test product are applied to one face of a wetted sponge.
• the wetted sponge is applied in one motion with even pressure from top to bottom of a previously cleaned, with isopropyl alcohol, black tile.
• the tile with the applied product(s) is allowed to dry for ten minutes before grading by expert judges.
• the control reference is made by repeating the above test with a wetted sponge but without the tested product.
• composition was made by mixing the listed ingredients in the listed proportions : A B C E Alkyl sulphate 1 1 1 1 betaine 0.05 0.05 0.05 0.05 butyl carbitol® - 5 - 5 hydrogen peroxide - - 2 2 Water and minors up to 100 H 2 SO 4 up to pH 4
• compositions are in accordance with the invention: F G H I Alkyl sulphate 1 2 8 5 betaine 0.05 0.1 0.5 0.2 butyl carbitol® - 5 - 5 hydrogen peroxide - - 1 2 Water and minors up to 100 H 2 SO 4 up to pH 5 J K L M Alkyl sulphate 1 2 8 5 betaine 0.05 0.1 0.5 0.2 butyl carbitol® - 5 - 5 hydrogen peroxide - - 1 2 Water and minors up to 100 H 2 SO 4 up to pH 9

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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)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)
• Cosmetics (AREA)

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Citations (5)

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• 1996
  • 1996-05-03 EP EP96870056A patent/EP0805197A1/fr not_active Withdrawn
• 1997
  • 1997-04-28 TR TR1998/02215T patent/TR199802215T2/xx unknown
  • 1997-04-28 CZ CZ983514A patent/CZ351498A3/cs unknown
  • 1997-04-28 WO PCT/US1997/007080 patent/WO1997042278A1/fr not_active Application Discontinuation
  • 1997-04-28 AU AU28159/97A patent/AU2815997A/en not_active Abandoned
  • 1997-04-28 BR BR9709584-2A patent/BR9709584A/pt unknown
  • 1997-04-28 HU HU0002498A patent/HUP0002498A3/hu unknown
  • 1997-04-28 CN CN97195199A patent/CN1232488A/zh active Pending
  • 1997-04-28 CA CA002252716A patent/CA2252716A1/fr not_active Abandoned
  • 1997-04-28 JP JP09539973A patent/JP2000514847A/ja active Pending
  • 1997-04-29 ZA ZA9703710A patent/ZA973710B/xx unknown
  • 1997-05-02 AR ARP970101815A patent/AR006940A1/es unknown
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