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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/667—Neutral esters, e.g. sorbitan 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
  • C11D1/66—Non-ionic compounds
  • C11D1/74—Carboxylates or sulfonates esters 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/06—Phosphates, including polyphosphates
• • 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
  • C11D3/08—Silicates
• • 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
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • 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
  • C11D3/2086—Hydroxy 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
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

• the present invention relates to the cleaning of fabrics in soaking conditions, i.e. in conditions where the fabrics are left to soak in a soaking liquor comprising water and detergent ingredients, either as a first step before a typical washing operation, or as a single step.
• Fabric soaking operations have been described in the art. In such soaking operations, fabrics are left in contact with a soaking liquor for a prolonged period of time ranging from a few hours to overnight.
• This laundering process has the advantage that it maximizes the contact time between the fabrics and the key active ingredients of the soaking liquor. It also has the advantage that it reduces or eliminates the need for a typical laundering operation involving the need for mechanical agitation, or that it improves the efficiency of the subsequent typical laundering operation.
• Such soaking operations are typically efficient to remove tough outdoor dirt from fabrics, such as particulate soil, mud, silt and clays.
• Such dirt is particularly difficult to remove from fabrics. Indeed, it is believed that the very fine dirt grains like silt, typically in the range between 0.002 and 0.050 mm, and clay, typically below 0.002mm in size, can insert among fabric fibers and steadily stick to the surface of the fibers. This problem is particularly acute with socks which are most exposed to silt and clay pick-up.
• this object can be met by soaking fabrics in an aqueous soaking liquor comprising a soaking detergent composition, said composition comprising a sorbitan ester as defined hereinafter in combination with high levels of a building and soil suspending system.
• the present invention encompasses the soaking detergent as well as a process of soaking fabrics in a soaking liquor formed with said soaking detergent.
• compositions comprising:
• the present invention encompasses a process of soaking fabrics, wherein said fabrics are immersed in a soaking liquor comprising water and an effective amount of the composition above.
• the present invention encompasses a composition and a process of soaking fabrics.
• the composition hereinafter referred to as the soaking composition is used in the soaking process.
• the present invention encompasses a composition which comprises a sorbitan ester, and a high level of a building and soil suspending system.
• the first essential ingredient is a sorbitan ester according to the formula C 6 H 9 O 2 (C 2 H 4 O) x R 1 R 2 R 3, wherein x is an integer of from 0 to 40, R 1 , R 2 are independently OH or (C n H n+1 )COO, and R 3 is (C n H n+1 )COO group, where n is an integer of from 11 to 17.
• x is 0 or 20
• the most preferred compositions herein comprise polyethoxylated (20) sorbitan tristearate, i.e. C 6 H 9 O 2 (C 2 H 4 O) 20 (C 17 H 35 COO) 3, or polyethoxylated (20) sorbitan monostearate, i.e. C 6 H 9 O 2 (C 2 H 4 O) 20 (OH) 2 (C 17 H 35 COO), or sorbitan monostearate, i.e. C 6 H 9 O 2 (OH) 2 (C 17 H 35 COO), or sorbitan monopalmitate, i.e. C 6 H 9 O 2 (OH) 2 (C 15 H 31 COO), or mixtures thereof.
• Glycosperse TS 20 from Lonza (polyethoxylated sorbitan tristearate)
• Glycosperse S 20 from Lonza (polyethoxylated sorbitan monostearate)
• Radiasurf 7145 from Fina from sorbitan monostearate
• Radiasurf 7135 from Fina (sorbitan monopalmitate)
• Armotan MP from Akzo (sorbitan monopalmitate).
• the soaking composition herein there should be from 0.01% to 10% of said sorbitan ester, preferably from 0.01% to 5%, most preferably from 0.5% to 5%.
• the building and soil suspending system is the building and soil suspending system
• the second essential ingredient herein is a building and soil suspending system comprising a compound selected from citric acid or citrates, silicates, zeolites, polycarboxylates, phosphates, and mixtures thereof. It is also essential that said system be present at a high total amount, of from 5% to 50% by weight of the total composition, preferably from 10% to 40%, most preferably from 15% to 30%.
• Citric acid can be used in its acidic form or in the form of its salts (mono-, di-, tri- salts) and in all its anhydrous and hydrated forms, or mixtures thereof.
• Suitable silicates for use herein include alkali metal salts of silicate, or mixtures thereof.
• Preferred alkali metal salt of silicate to be used herein is sodium silicate.
• alkali metal salt of silicate can be used herein, including the crystalline forms as well as the amorphous forms of said alkali metal salt of silicate or mixtures thereof.
• Suitable crystalline forms of sodium silicate to be used are the crystalline layered silicates of the granular formula NaMSi x O 2x+1 .yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or mixtures thereof. Crystalline layered sodium silicates of this type are disclosed in EP-A-164 514 and methods for their preparation are disclosed in DE-A-34 17 649 and DE-A-37 42 043.
• x in the general formula above has a value of 2, 3 or 4 and is preferably 2.
• M is sodium and y is 0 and preferred examples of this formula comprise the a , b , g and d forms of Na 2 Si 2 O 5 .
• These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is d - Na 2 Si 2 O 5 , NaSKS-6.
• Crystalline layered silicates are incorporated in granular soaking compositions herein, either as dry mixed solids, or as solid components of agglomerates with other components.
• Suitable amorphous forms of sodium silicate to be used herein have the following general formula: NaMSi x O 2x+1 wherein M is sodium or hydrogen and x is a number from 1.9 to 4, or mixtures thereof.
• M is sodium or hydrogen and x is a number from 1.9 to 4, or mixtures thereof.
• Preferred to be used herein are the amorphous forms of Si 2 O 5 Na 2 O.
• Suitable Zeolites for use herein are aluminosilicates including those having the empirical formula: Mz(zAlO2.ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate.
• Preferred zeolites which have the formula: Naz ⁇ (AlO2)z (SiO2)yù.xH2O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
• aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
• a method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
• Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
• the crystalline aluminosilicate ion exchange material has the formula: Na12 ⁇ (AlO2)12(SiO2)12ù.xH2O wherein x is from 20 to 30, especially about 27.
• This material is known as Zeolite A.
• the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
• Suitable phosphate builders for use herein include sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
• Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
• Suitable polycarboxylate builders for use herein include ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
• Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,120,874 and 4,102,903.
• Other useful detergency builders include the ether hydroxypolycarboxylates, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
• polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
• polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl
• succinic acid builders include the C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof.
• a particularly preferred compound of this type is dodecenylsuccinic acid.
• succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadeoenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
• Suitable polycarboxylate buiders for use herein include builders according to formula I wherein Y is a comonomer or comonomer mixture; R 1 and R 2 are bleach- and alkali-stable polymer-end groups; R 3 is H, OH or C 1-4 alkyl; M is H, alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is from 0 to 2; and n is at least 10, or mixtures thereof.
• the first category belongs to the class of copolymeric polymers which are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid, mesaconic acid and salts thereof as first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha -C 1-4 alkyl acrylic acid as second monomer.
• the polymers belonging to said first class are those where p is not 0 and Y is selected from the acids listed hereinabove.
• Preferred polymers of this class are those according to formula I hereinabove, where Y is maleic acid.
• R 3 and M are H
• n is such that the polymers have a molecular weight of from 1000 to 400 000 atomic mass units.
• the second category of preferred polymers for use herein belongs to the class of polymers in which, referring to formula I hereinabove, p is 0 and R 3 is H or C 1-4 alkyl.
• n is such that the polymers have a molecular weight of from 1000 to 400 000 atomic mass units.
• R 3 and M are H.
• alkali-stable polymer end groups R 1 and R 2 in formula I hereinabove suitably include alkyl groups, oxyalkyl groups and alkyl carboxylic acid groups and salts and esters thereof.
• n the degree of polymerization of the polymer can be determined from the weight average polymer molecular weight by dividing the latter by the average monomer molecular weight.
• n 182 (i.e. 15,500 / (116 x 0.3 + 72 x 0.7)).
• highly preferred polymers for use herein are those of the first category in which n averages from 100 to 800, preferably from 120 to 400.
• Preferred builder and soil suspending system foruse herein is anhydrous citric acid, or polymers of maleic or acrylic acid, or copolymers of maleic and acrylic acid.
• the soaking composition of the present invention may further comprise a variety of other ingredients.
• the composition may further comprise an oxygen bleach.
• oxygen bleaches provide a multitude of benefits such as bleaching of stains, deodorization, as well as disinfectancy, and the sorbitan esters according to the present invention have a further particular advantage that they are resistant to oxydation by oxygen bleaches.
• the oxygen bleach in the composition may come from a variety of sources such as hydrogen peroxide or any of the addition compounds of hydrogen peroxide, or organic peroxyacid, or mixtures thereof.
• addition compounds of hydrogen peroxide it is meant compounds which are formed by the addition of hydrogen peroxide to a second chemical compound, which may be for example an inorganic salt, urea or organic carboxylate, to provide the addition compound.
• the addition compounds of hydrogen peroxide include inorganic perhydrate salts, the compounds hydrogen peroxide forms with organic carboxylates, urea, and compounds in which hydrogen peroxide is clathrated.
• oxygen beaches include persulphates, particularly potassium persulphate K 2 S 2 O 8 and sodium persulphate Na 2 S 2 O 8 .
• inorganic perhydrate salts include perborate, percarbonate, perphosphate and persilicate salts.
• the inorganic perhydrate salts are normally the alkali metal salts.
• alkali metal salt of percarbonate, perborate or mixtures thereof are the preferred inorganic perhydrate salts for use herein.
• Preferred alkali metal salt of percarbonate is sodium percarbonate.
• Soaking compositions in the present invention may comprise from 0% to 60% by weight of composition of a hydrogen peroxyde source, preferably from 0% to 40% and more preferably from 10% to 40%.
• the soaking compositions herein comprise an oxygen bleach
• suitable compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2 143 231.
• Preferred examples of such compounds are tetracetyl ethylene diamine, (TAED), sodium 3, 5, 5 trimethyl hexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described for instance in US 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in European patent application 91870207.7.
• N-acyl caprolactam selected from the group consisting of substituted or unsubstituted benzoyl caprolactam, octanyl caprolactam, nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam.
• the soaking compositions herein may comprise mixtures of said bleach activators.
• Preferred mixtures of bleach activators herein comprise n-nonanoyloxybenzenesulphonate (NOBS) together with a second bleach activator having a low tendency to generate diacyl peroxide, but which delivers mainly peracid.
• Said second bleach activators may include tetracetyl ethylene diamine (TAED), acetyl triethyl citrate (ATC), acetyl caprolactam, benzoyl caprolactam and the like, or mixtures thereof.
• Said mixtures of bleach activators are preferably used in the embodiment of the present invention where the soaking liquors are controlled to a pH below 9.5.
• mixtures of bleach activators comprising n-nonanoyloxybenzenesulphonate and said second bleach activators, allow to boost particulate soil cleaning performance while exhibiting at the same time good performance on diacyl peroxide sensitive soil (e.g. beta-carotene) and on peracid sensitive soil (e.g. body soils).
• diacyl peroxide sensitive soil e.g. beta-carotene
• peracid sensitive soil e.g. body soils
• the soaking compositions herein may comprise from 0% to 15% by weight of the total composition of n-nonanoyloxybenzenesulphonate, preferably from 1% to 10% and more preferably from 3% to 7% and from 0% to 15% by weight of the total composition of said second bleach activator preferably from 1% to 10% and more preferably from 3% to 7%.
• Suitable amino carboxylate chelating agents which may be used herein include diethylene triamino pentacetic acid, ethylenediamine tetraacetates (EDTA), N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine hexaacetates, and ethanoldiglycines, alkali metal ammonium and substituted ammonium salts thereof or mixtures thereof.
• chelating agents include ethylenediamine-N,N'-disuccinic acids (EDDS) or alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof.
• EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
• suitable chelating agents may be the organic phosphonates, including 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 in the form of their metal alkali salt.
• the organic phosphonate compounds where present are in the form of their magnesium salt.
• the soaking compositions in the present invention may accordingly comprise from 0% to 5% by weight of the total compositions of said chelating agents, preferably from 0% to 3%, more preferably from 0.05% to 2%.
• Soaking compositions in the present invention may further comprise other optional ingredients such as surfactants, fillers, optical brighteners, enzymes, other chelants, dispersants, surfactants, soil release agents, photoactivated bleaches such as Zn phthalocyanine sulphonate, dyes, dye transfer inhibitors, pigments and perfumes.
• Said optional ingredients can be added in varying amounts as desired.
• compositions herein can be manufactured in solid, preferably granular, or liquid form.
• the present invention encompasses a process of soaking fabrics.
• process of soaking fabrics refers to the action of leaving fabrics to soak in a soaking liquor comprising water and a composition as described hereinabove, for a period of time sufficient to clean said fabrics.
• the soaking process can be performed independently from any other process, such as a typical laundering operation, or a first step before a second, typical laundering step.
• fabrics are left to soak for a period of time ranging from 10 minutes to 24 hours, preferably from 30 min to 24 hours, most preferably 4 hours to 24 hours
• After the fabrics have been immersed in said soaking liquor for a sufficient period of time they can be removed and rinsed with water.
• the fabrics can also be washed in a normal laundering operation after they have been soaked, with or without having been rinsed inbetween the soaking operation and the subsequent laundering operation.
• a soaking composition described hereinabove is diluted in an appropriate amount of water to produce a soaking liquor.
• Suitable doses may range from 45 to 50 grams of soaking compositoin in 3.5 to 5 liters of water, down to 90 to 100 grams of soaking composition in 20 to 45 liters of water.
• one dose is 45-50 grams in 3.5 to 5 Lt for a concentrated soak (bucket/sink).
• the dose is 90-100 grams in about 20 (Europe) to 45 (US) liter of water.
• the fabrics to be soaked are then immersed in the soaking liquor for an appropriate period of time. There are factors which may influence overall performance of the process on particulate dirt/soils.
• soaking time is overnight, i.e. 12 hours up to 24 hours.
• soaking time is overnight, i.e. 12 hours up to 24 hours.
• Another factor is the initial warm or warmluke temperature. Indeed higher initial temperatures of the soaking liquors ensure large benefits in performance.
• the process herein is suitable for cleaning a variety of fabrics, but finds a preferred application in the soaking of socks, which are particularly exposed to silt and clay pick-up.
• Soaking liquors are formed by diluting each time 45 g of said compositions in between 3.5 lit. to 5.0 lit. of water. 0.5 to 2 Kg of fabrics are then each time immersed in said soaking liquor for a time ranging from 10 minutes to 24 hours. Finally, the fabrics are removed from the soaking liquors, rinsed with water and washed with a regular washing process, handwash or washing machine wash, with a regular detergent, with or without re-using the soaking liquor, then said fabrics are left to dry.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Inorganic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Hydroponics (AREA)

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Cited By (7)

Citations (5)

Family Cites Families (9)

• 1995
  • 1995-04-03 EP EP95870028A patent/EP0736594A1/fr not_active Withdrawn
• 1996
  • 1996-03-12 WO PCT/US1996/003329 patent/WO1996031584A1/fr not_active Application Discontinuation
  • 1996-03-12 KR KR1019970707000A patent/KR19980703595A/ko not_active Application Discontinuation
  • 1996-03-12 JP JP8530293A patent/JPH11503189A/ja active Pending
  • 1996-03-12 HU HU9802073A patent/HUP9802073A3/hu unknown
  • 1996-03-12 CA CA002217212A patent/CA2217212A1/fr not_active Abandoned
  • 1996-03-12 PL PL96322591A patent/PL322591A1/xx unknown
  • 1996-03-12 AU AU51893/96A patent/AU5189396A/en not_active Abandoned
  • 1996-03-12 MX MX9707646A patent/MX9707646A/es unknown
  • 1996-03-12 CN CN96194246A patent/CN1185801A/zh active Pending
  • 1996-03-12 CZ CZ973128A patent/CZ312897A3/cs unknown
  • 1996-03-12 TR TR97/01101T patent/TR199701101T1/xx unknown
  • 1996-03-12 BR BR9604782A patent/BR9604782A/pt not_active Application Discontinuation
  • 1996-03-19 ZA ZA962210A patent/ZA962210B/xx unknown

Patent Citations (5)

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