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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • 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
  • C11D3/2075—Carboxylic acids-salts thereof
• • 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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38618—Protease or amylase in liquid compositions only

Definitions

• the formulator of a dishwashing detergent composition faces the challenge of deriving a formulation which meets a number of distinct consumer relevant performance demands.
• such a composition should be effective at removing soils from dirty "dishes" when used in a dishwashing process.
• the term "dishes” is used herein in a generic sense, and encompases essentially any items which may be found in a dishwashing load, including chinaware, glassware, plasticware, hollowware and cutlery, including silverware.
• Manual dishwashing compositions typically contain no bleaching components, which are by contrast common components of laundry, machine dishwashing and hard-surface cleaner compositions.
• Manual dishwashing compositions are typically formulated to perform well at near neutral pH.
• Machine dishwashing, non- bleach containing hard surface cleaner compositions and laundry compositions are typically alkaline with a pH of usually 9-11.
• Bleach containing hard surface cleaner compositions are often acidic with a pH of less than 6.
• a further manual dishwashing habit involves contacting soiled dishes with a concentrated detergent product (e.g. using a spray dispenser), and allowing the product to remain on the surface of the dishes for a period of time.
• the dishes may subsequently be rinsed by immersion in a water bath or passing under a stream of running water, with optionally manual rubbing of the surface of the dishes with, e.g. a sponge or cloth, or using the rinse cycle of an automatic dishwashing machine.
• the dishes may be subjected to washing steps, utilising further detergent product, which may involve either a manual dishwashing method, or a washing method utilising an automatic dishwashing machine.
• composition containing anionic surfactant and divalent cation (particularly Ca or Mg) having an acidic pH gives remarkable performance benefits, particularly greasy cleaning performance benefits, when employed in a dishwashing method in which, essentially, concentrated detergent product is applied directly to the surface of the dishes, preferably followed by rinsing of the dishes.
• a fluid detergent composition suitable for use in a dishwashing method in which the detergent composition is applied to the dishes in essentially concentrated form, containing (a) from 1% to 80% by weight of the composition of anionic surfactant; and
• composition is formulated such that the pH of a 1% solution of the composition in water, at 20°, is no more than 6.
• composition is in the form of a liquid or a gel.
• composition contains organic solvent components.
• composition contains no builder salts.
• composition contains no bleaching components.
• said compositon contains additional surfactant selected from nonionic, cationic, zwitterionic, ampholytic and amphoteric surfactants.
• a 1% by weight solution of said composition has a pH of from 3 to 6.
• Said composition can be formulated to contain enzyme components.
• the anionic surfactant may be, essentially any anionic surfactant, including anionic sulfate, sulfonate or carboxylate surfactant.
• Alkyl ethoxy sulfate surfactants suitable for use herein comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C*LO ⁇ C 16 alcohol with an average of from 0.5 to 20, preferably from 0.5 to 12, ethylene oxide groups.
• C 12 -C14 alkyl sulfate which has been ethoxylated with an average of from 0.5 to 4 moles of ethylene oxide per molecule is especially preferred.
• Alkyl polyethoxy polcarboxylate surfactants suitable for use herein include those having the formula: R - O - ( CH - CH - 0) X - R3
• Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2- ethyl-1-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l- octanoic acid and 2-pentyl-l-heptanoic acid.
• Other anionic surfactants are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2- ethyl-1-decanoic acid, 2-propyl-l-nonanoic acid, 2-butyl-l- octanoic acid and 2-pentyl-l-heptanoic acid.
• compositions containing polyhydroxy fatty acid amide Preferably, from 0.05% to 5%, more preferably from 0.25% to 4% most preferably from 0.5% to 3% by weight of the composition of calcium ions may be included in the detergent compositions herein. It has additionally been found for compositions containing polyhydroxy fatty acid amide that the presence of calcium greatly improves the cleaning of greasy soils.
• the calcium ions can, for example, be added as a chloride, hydroxide, oxide, formate or acetate, or nitrate salt. If the anionic surfactants are in the acid form, the calcium can be added as a calcium oxide or calcium hydroxide slurry in water to neutralise the acid.
• Techniques for controlling pH at recommended usage levels include the use of buffers, alkali, acids, etc., and are well known to those skilled in the art. Dilute hydrochloric acid is preferred for downward pH adjustment, and sodium hydroxide for upward pH adjustment.
• Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non- limiting classes of useful nonionic surfactants are listed below.
• Nonionic polvhydroxy fatty acid amide surfactant Nonionic polvhydroxy fatty acid amide surfactant
• R 1 is H, C1-C 4 hydrocarbyl, 2-hydroxy ethyl, 2- hydroxy propyl, or a mixture thereof, preferable C1-C 4 alkyl, more preferably C- ⁇ or C 2 alkyl, most preferably C-*_ alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight-chain C 7 -C-L 9 alkyl or alkenyl, more preferably straight-chain Cg-C- ⁇ alkyl or alkenyl, most preferably straight-chain alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
• condensation produc s of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
• examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
• condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
• this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
• Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containng from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
• the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
• the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
• a polyalkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety.
• the preferred alkyleneoxide is ethylene oxide.
• Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 18' preferably from 10 to 16, carbon atoms.
• the alkyl group is a straight-chain saturated alkyl group.
• the alkyl group can contain up to about 3 hydroxyl groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
• Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galatoses.
• Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.
• R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
• the glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position) . The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-,3-, 4- and/or 6-position, preferably predominantly the 2-position.
• Nonionic fatty acid amide surfactant Nonionic fatty acid amide surfactant
• Fatty acid amide surfactants suitable for use herein are those having the formula:
• R 6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R 7 is selected from the group consisting of hydrogen, C- -C ⁇ alkyl, C1-C 4 hydroxyalkyl, and
• Ampholytic surfactants can be incorporated into the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
• One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 for examples of ampholytic surfactants.
• Suitable amphoteric surfactants for use herein include the alkyl amphocarboxylic acids of the formula:
• R is a Cg-C 18 alkyl group
• Rj is of the general formula:
• R 1 is a (CH 2 ) x COOM or CH 2 CH2OH, and x is 1 or 2 and M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions.
• the preferred R alkyl chain length is a C- ⁇ o to C1 4 alkyl group.
• a preferred amphocarboxylic acid is produced from fatty imidazolines wherein the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
• Amine oxide surfactant Amine oxides useful, as amphoteric surfactants, in the present invention include those compounds having the formula:
• R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms;
• R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, preferably 2 carbon atoms, or mixtures thereof;
• x is from 0 to 3, preferably 0;
• each R 5 is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable 1, ethylene oxide groups.
• the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
• amine oxide surfactants in particular include C ⁇ o ⁇ 1 8 alkyl dimethyl amine oxides and C -Ci2 alkoxy ethyl dihydroxyethyl amine oxides.
• examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide.
• Preferred are C ⁇ Q -C ⁇ alkyl dimethylamine oxide, and C-Lo- 18 acylamido alkyl dimethylamine oxide.
• Zwitterionic surfactants can also be incorporated into the detergent compositions herein. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.
• the betaines useful, as zwitterionic surfactants, in the present invention are those compounds having the formula R(R') 2 N + R 2 COO" wherein R is a Cg-C-Lg hydrocarbyl group, preferably a C 10 " c 16 alkyl group or C 10 -i 6 acylamido alkyl group, each R 1 is typically C1-C3 alkyl, preferably methyl,m and R 2 is a C1-C5 hydrocarbyl group, preferably a C-L-C 3 alkylene group, more preferably a ⁇ -C 2 alkylene group.
• betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; 0- ⁇ 2 - 14 acyla idopropylbetaine; Cg_i 4 acylamidohexyldiethyl betaine; 4 [ C ⁇ 4 - ⁇ acylmethylamidodiethylammonio]-l-carboxybutane; C- ⁇ g. ⁇ g acylamidodimethylbetaine; C 12 -1 6 acylamidopentanediethyl- betaine; [C 12 - 16 acylmethylamidodimethylbetaine.
• Preferred betaines are Ci 2 - ⁇ g dimethyl-ammonio hexanoate and the C 10 - l g acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
• R is a hydrocarbon group having from 7 to 22 carbon atoms
• A is the group (C(O))
• n is 0 or 1
• R*L is hydrogen or a lower alkyl group
• x is 2 or 3
• y is an integer of 0 to 4
• Q is the group -R 2 COOM wherein R 2 is an alkylene group having from 1 to 6 carbon atoms and M is hydrogen or an ion from the groups alkali metals, alkaline earth metals, ammonium and substituted ammonium
• B is hydrogen or a group Q as defined.
• the sultaines useful in the present invention are those compounds having the formula (R(R--*) 2 N + R 2 S ⁇ 3 ⁇ wherein R is a c 6 ⁇ c 1 8 hydrocarbyl group, preferably a C ⁇ -C ⁇ g alkyl group, more preferably a Ci 2 ⁇ 1 3 alkyl group, each R 1 is typically l ⁇ c 3 alkyl, preferably methyl, and R 2 is a C-j ⁇ -C hydrocarbyl group, preferably a C*L-C3 alkylene or, preferably, hydroxyalkylene group.
• compositions of the invention will most preferably contain an organic solvent system present at levels of from 1% to 30% by weight, preferably from 3% to 25% by weight, more preferably form 5% to 20% by weight of the composition.
• the organic solvent system may be a mono, or mixed solvent system; but is preferably in mixed solvent system.
• at least the major component of the solvent system is of low volatility.
• Suitable organic solvent for use herein has the general formula
• R is an alkyl, alkenyl, or alkyl aryl group having from 1 to 8 carbon atoms, and n is an integer from 1 to 4.
• R is an alkyl group containing 1 to 4 carbon atoms, and n is 1 or 2.
• R groups are n-butyl or isobutyl.
• 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 carbitol.
• Water-soluble CELLOSOLVE solvents are compounds of the 2-alkoxyethoxy ethanol class, with 2- butoxyethoxyethanol being preffered.
• Suitable solvents are benzyl alcohol, and diols such as 2-ethyl-l,3-hexanediol and 2,2,4-trimethl-l,3- pentanediol.
• the low molecular weight, water-soluble, liquid polyethylene glycols are also suitable solvents for use herein.
• Preferred amides are Cg-C 2 o alkyl mono- or di-C2 ⁇ C 3 alkanolamides, especially monoethanolamides, diethanolamides, and isopropanolamides.
• Preferred suds enhancing agents are C ⁇ Q -IS acyl amide alkyl dimethyl amine oxides, betaines, condensation products of aliphatic alcohols with ethylene oxides, and alkylpolysaccharides, and mixtures thereof.
• a hydrotrope is typically added to the compositions of the present invention, and may be present at levels of from 0.5% to 10%, preferably from 1% to 5%, by weight.
• Useful hydrotropes include sodium, potassium, and ammonium xylene sulfonates, sodium, potassium, and ammonium toluene sulfonate, sodium potassium and ammonium cumene sulfonate, and mixtures thereof.
• hydrotropes include polycarboxylates. Some polycarboxylates have calcium chelating properties as well as hydrotropic properties. Particularly useful hydrotropes are alkylpolyethoxy polycarboxylate surfactants of the type as previously described herein.
• alkyl amphodicarboxylic acid of the generic formula: (CH 2 ) X COO- RCNHCH 2 CH 2 N ⁇
• R is a Cg to C- ⁇ g alkyl group, x is from 1 to 2
• M is preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanolammonium, most preferably from sodium, potassium, ammonium, and mixtures thereof with magnesium ions.
• the preferred alkyl chain length (R) is a C 10 to C 14 alkyl group and the dicarboxylic acid functionally is diacetic acid and/or dipropionic acid.
• alkyl amphodicarboxylic acid is the amphoteric surfactant Miranol R 2CM Cone.manufactured by Miranol, Inc., Dayton, NJ.
• compositions of the present invention are particularly useful when formulated to contain a lime soap dispersant compound which acts to disperse any insoluble lime soap salts which may be formed between the fatty acids produced by the lipolytic hydrolysis of fats/oils and calcium ions in the wash soluble, thereby preventing the deposition of these salts as spots or films on the articles in the wash, or as an unseemly ring around the rim of the sink.
• Certain lime soap dispersant compounds may also provide improved product stability particularly where the product is formulated as a liquid product containing calcium ions.
• a lime soap dispersant compound herein is defined as a compound, which has a lime soap dispersing power (LSDP) , as of no more than 8, preferably no more than 7, most preferably no more than 6.
• the lime soap dispersant compound is typically present at a level of from 0.1% to 40% by weight, more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight of the compositions.
• Amylases include, for example, alpha-amylases obtained from a special strain of B licheniforms, described in more detail in GB 1,269,839 (Novo).
• Commercially available amylases include for example, Rapidase, sold by International Bio-Synthetics Inc, and Termamyl, sold by Novo Industries A/S.
• a lipase unit is defined as the amound of lipase which produces 1 umol of titratable butyric acid per minute in a pH stat, where pH is 7.0, temperature is 30°C, and substrate is an emulsion of ributyrin and gum arabic in the presence of Ca++ and NaCl in phosphate buffer.
• Preferred enzyme-containing compositions herein may comprise from 0.001% to 10%, preferably from 0.005% to 8%,most preferably from 0.01% to 6%, by weight of an enzyme stabilizing system.
• the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
• Such stabilizing systems can comprise calcium ion, boric acid, propylene.glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
• compositions herein may further comprise from 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
• chlorine bleach scavengers While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during dishwashing is usually large; accordingly, enzyme stability in-use can be problematic.
• Suitable chlorine scavenger anions are widely available, indeed ubiquitous, and are illustrated by salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
• Antioxidants such as carbamate, ascorbate, etc. , organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA) , and mixtures thereof can likewise be used.
• EDTA ethylenediaminetetracetic acid
• MEA monoethanolamine
• scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired.
• polycarboxylate polymer thickeners are the Carbopol 600 series resins available from B.F. Goodrich. Especially preferred are Carbopol 616 and 617. It is believed that these resins are more highly cross-linked than the 900 series resins and have molecular weights between about 1,000,000 and 4,000,000. Mixtures of polycarboxylate polymers as herein described may also be used in the present invention. Particularly preferred is a mixture of Carbopol 616 and 617 series resins.
• Opacifiers such as Lytron (Morton Thiokol, Inc.), a modified polystyrene latex, or ethylene glycol distearate can be added, preferably as a last step. Lytron can be added directly as a dispersion with mixing. Ethylene glycol distearate can be added in a molten state with rapid mixing to form pearlescent crystals. Opacifiers useful herein, particularly for light duty liquids, are typically present at levels from about 0.2% to about 10%, preferably from about 0.5% to about 6% by weight.
• the composition used in the detergent pre-soak method contains suds suppressor at a level of from 0.01% to 15% by weight.
• the suds suppressor may be any of these commonly known in the art including known silicone and fatty acid suds suppressors. Examples
• soiled plastic slides were prepared by taking five preweighed clean 6.5cm x 5cm plastic slides, applying approximately 2g of greasy soil (9:1 mixture of vegetable oil, corn oil) to each slide, and placing the slides in a fridge overnight. Each slide was then weighed, to obtain the exact mass of soil applied, and placed in a separate Petri dish. One of the compositions I - V was then added to each soiled slide-containing Petri dish, such that the soiled slide was fully immersed in the detergent. Each slide was allowed to remain so immersed for 15 minutes, before being removed from the Petri dish and clipped, using a bulldog clip, onto a bar which was suspended between two retort stands, at a height of 28cm above the bench.
• Each suspended slide was then sprayed for 20 seconds with a uniform spray of water, originating from a 'garden spray' positioned 50cm from the slide.
• Each slide was then dried, by placing in an oven at 40°C, and reweighed to calculate the mass of soil removed by the soaking/rinsing process. The full test procedure was repeated four times for ecah test composition.
• the average mass of soil removed for each composition was indexed to a standard reference, taken to be the mass of soil removed for composition IV.
• the following grease removal indices were obtained:

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• 1994
  • 1994-09-01 AU AU77188/94A patent/AU7718894A/en not_active Abandoned
  • 1994-09-01 WO PCT/US1994/009890 patent/WO1995007969A1/en not_active Application Discontinuation
  • 1994-09-01 EP EP94927987A patent/EP0719320A4/de not_active Ceased
  • 1994-09-01 CN CN94193903A patent/CN1057791C/zh not_active Expired - Fee Related

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