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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3932—Inorganic compounds or complexes
• • 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
  • C11D3/39—Organic or inorganic per-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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring

Definitions

• This invention relates to the activation of bleaches employing peroxy compounds, including hydrogen peroxide or hydrogen peroxide adducts which liberate hydrogen peroxide in aqueous solution, as well as peroxy acids; to compounds that activate or catalyse peroxy compounds; to bleach compositions including detergent bleach compositions which contain a catalyst for peroxy compounds; and to process for bleaching and/or washing of substrates employing the above mentioned types of compositions.
• peroxy compounds including hydrogen peroxide or hydrogen peroxide adducts which liberate hydrogen peroxide in aqueous solution, as well as peroxy acids
• bleach compositions including detergent bleach compositions which contain a catalyst for peroxy compounds
• process for bleaching and/or washing of substrates employing the above mentioned types of compositions employing the above mentioned types of compositions.
• the present invention is concerned with the novel use of a specific class of manganese complexes as effective catalyst for the bleach activation of peroxy compound bleaches.
• Applicants copending US Patent Application 798396 describes mononuclear manganese of formula [L Mn IV (OR)3] Y where Mn is manganese in the +4 oxidation state; R is a C1-C20 radical selected from alkyl, cycloalkyl, aryl, benzyl and radical combinations thereof; at least two R radicals may also be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese; L is a ligand selected from a C3-C60 radical having at least 3 nitrogen atoms coordinating with the manganese; and Y is an oxidatively-stable counterion; and their use as bleach catalysts.
• X is less crucial for the catalytic activity, but may be of importance for the physical properties of the complex, such as solubility and stability.
• Examples of preferred ligands are: 1,4,7-triazacyclononane (TACN); 1,4,7-trimethyl-1,4,7-triazacyclononane (1,4,7-Me3TACN); 2-methyl-1,4,7-triazacyclononane (2-Me-TACN); and 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (1,2,4,7-Me4TACN); and 1,2,2,4,7-pentamethyl-1,4,7, triazacyclononane (1,2,2,4,7-Me5TACN); 2-benzyl-1,4,7-trimethyl-1,4,7-triazacyclonane; and 2-decyl-1,4,7-trimethyl-1,4,7-triazacyclonane.
• TACN 1,4,7-triazacyclononane
• 1,4,7-trimethyl-1,4,7-triazacyclonane (1,4,7-Me3TACN
• ligands may be synthesised by the methods described in K Wieghardt et al., Inorganic Chemistry 1982, 21 , page 3086 et seq, incorporated herein by reference.
• the mononuclear manganese complexes of the invention may also be obtained and presented as a solution by adding a Mn-salt, such as Mn(NO3)2, to an acid solution of the ligand, e.g. 1,4,7-Me3TACN, in water.
• a Mn-salt such as Mn(NO3)2
• an acid solution of the ligand e.g. 1,4,7-Me3TACN
• the solution as obtained can be added to a bleaching solution containing a peroxycompound to give comparable results to those obtained with the isolated Mn-complexes.
• the mononuclear manganese complexes of the present invention find particular application in bleach compositions and in bleach compositions.
• a bleach composition comprising a peroxy compound, and a complex of formula (I) as hereinbefore defined.
• the composition will also comprise a surface active material and detergent additives such as builders.
• An advantage of the bleach catalysts of the invention is that they are hydrolytically and oxidatively stable and function in a variety of detergent formulations.
• the catalysts of the invention enhance the bleaching action of hydrogen peroxide bleaching agents and of organic and inorganic peroxyacid compounds.
• bleach catalysts are compatible with detergent enzymes, such as proteases, cellulases, lipases, amylases, oxidases etc.
• the bleach composition according to the invention are effective on a wide range of stains including both hydrophilic and hydrophobic stains.
• the invention provides a method of bleaching a stained substrate, the method comprising contacting the stained substrate in aqueous media with a bleaching agent selected from the group of peroxy compound bleaches including hydrogen peroxide, hydrogen peroxide-liberating or generating compounds, peroxyacids and their salts, and peroxyacid bleach precursors and mixtures thereof, and a manganese complex of formula (I), as hereinbefore defined, each in an effective amount to interact with one another and provide a cleaning effect upon the substrate.
• a bleaching agent selected from the group of peroxy compound bleaches including hydrogen peroxide, hydrogen peroxide-liberating or generating compounds, peroxyacids and their salts, and peroxyacid bleach precursors and mixtures thereof, and a manganese complex of formula (I), as hereinbefore defined, each in an effective amount to interact with one another and provide a cleaning effect upon the substrate.
• the effective level of the complex expressed in terms of parts per million (ppm) of the manganese in an aqueous bleaching solution, will normally range from 0.001 ppm to 100 ppm, preferably from 0.01 ppm to 20 ppm, most preferably from 0.1 ppm to 10 ppm. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp-bleaching. The lower levels quoted are primarily intended and preferably used in domestic laundry operations.
• compositions comprising a peroxy compound bleach and the bleach catalyst are effective over a wide pH range of between 7 and 13, with optimal pH range lying between 8 and 11.
• the peroxy bleach compounds which can be utilized in the bleaching composition and detergent bleach composition of the present invention include hydrogen peroxide, hydrogen peroxide-liberating compounds, hydrogen peroxide-generating systems, peroxyacids and their salts, and peroxyacid bleach precursor systems, and mixtures thereof.
• Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates persilicates and persulphates. Mixtures of two or more of such compounds may also be used. Particularly preferred are sodium percarbonate and sodium perborate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred to sodium perborate tetrahydrate because of its excellent storage stability combined with its ability to dissolve very quickly in aqueous bleaching solutions. Sodium percarbonate may be preferred for environmental reasons.
• Alkylhydroxy peroxides are another class of peroxide bleaching agents. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.
• Organic peroxyacids may also be suitable as the peroxide bleaching agent.
• Such materials normally have the general formula: wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or group or a quaternary ammonium group.
• Typical monoperoxy acids useful herein include, for example.
• Typical diperoxyacids useful herein include, for example:
• inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS).
• MPS potassium monopersulphate
• peroxide compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor.
• a peroxyacid bleach precursor may improve the overall whiteness of white fabrics.
• Such materials may also be used because of the hygiene benefits they confer on materials treated therewith.
• Peroxyacid bleach precursors are known and amply described in literature, such as in British Patents 836,988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; European Patent Specification Nos 0185522; 0174132 and 0120591; and US Patents 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
• peroxyacid bleach precursors are the quaternary ammonium substituted peroxyacid precursors disclosed in US Patents 4,751,015 and 4,397,757, and in European Patent Specification Nos 284,292, 331,229 and 303,520.
• peroxyacid bleach precursors of this class are: 2-(N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate - (SPCC); N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride - (ODC); 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
• SPCC 2-(N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate -
• ODC N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride -
• 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate and N,N,
• a further special class of cationic peroxyacid bleach precursors is formed by the cationic nitriles as disclosed in European Patent Specification No 303520, 458396 and 464880.
• peroxyacid bleach precursors may be used in the present invention.
• the preferred materials are esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
• Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoloxy benzene sulphonate (SBOBS); N,N,N'N'-tetraacetyl ethylene diamine (TAED); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyloxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.
• SBOBS sodium-4-benzoloxy benzene sulphonate
• TAED N,N,N'N'-tetraacetyl ethylene diamine
• TAED sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate
• Particularly suitable materials are the so-called sulphonimides as disclosed in European Patent Specification Nos 453,003 and 446,982.
• a detergent bleach composition of the invention can be formulated by combining effective amounts of the components.
• effective amounts means the components are present in quantitites such that each of them is operative for its intended purpose when the resulting mixture is combined with water to form an aqueous medium which may be used to wash and clean clothes, fabrics and other articles.
• the detergent bleach composition can be formulated to contain, for example, from about 2% to 30% by weight, preferably from 5 to 25% by weight, of a peroxide compound.
• Peroxyacids may be used in somewhat lower amounts, for example from 1% to about 15% by weight, preferably from 2% to 10% by weight.
• Peroxyacid precursors may be used in combination with a peroxide compound at approximately the same level as peroxyacids, i.e. 1% to 15%, preferably from 2% to 10% by weight.
• the complex will be present in the bleach and detergent bleach compositions in amounts so as to provide the required level of in the wash liquor.
• the manganese content in the formulation is from 0.0005% to about 0.5% by weight, preferably 0.001% to 0.25% by weight.
• the Mn content in the formulation When used in a detergent bleach composition to be dosed at low levels, for example by Japanese and US consumers at dosages of about 1 and 2 g/l respectively the Mn content in the formulation is at 0.0025 to 0.5% by weight, preferably 0.005 to 0.25%. At higher product dosages as used, for example, by European consumers, the Mn content in the formulation is from 0.0005 to 0.1% by weight, preferably from 0.001 to 0.05%.
• the bleach catalyst of the invention is compatible with substantially any known and common surface-active agents and detergency builder materials.
• the surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
• the total level of the surface-active material may be from 0.5% up to 50% by weight, and is preferably from about 1% to 40% by weight of the composition, most preferably 4 to 25% by weight.
• Synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl groups.
• suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C9-C18) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of
• nonionic surface-active compounds examples include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; the condensation products of aliphatic (C8-C18) primary, secondary linear or branched alcohols with ethylene oxide, generally 3-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
• alkyl polyglycosides long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
• amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If amphoteric or zwitterionic detergent compounds are used it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
• soaps may also be incorporated in the compositions of the invention.
• the bleach performance of the bleaching and detergent bleach composition is improved if the amount of long-chain C16 - C22 fatty acid soaps is kept to a minimum.
• Short chain C12 - C14 fatty acid soaps may be included preferably at levels not more than about 10% by weight.
• the detergent bleach composition comprises a surface-active material, a peroxide bleaching agent, a complex of general formula (I) as hereinbefore defined, 0 to 25% by weight of anionic surfactant and 7.5 to 55% by weight of nonionic surfactant, the weight ratio of nonionic surfactant to anionic surfactant being at least 0.75.
• the detergent bleach composition of the invention will normally also contain a detergency builder.
• Builder materials may be selected from calcium sequestrant materials; precipitating materials; calcium ion-exchange materials and mixtures thereof.
• Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of ether polycarboxylates, such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid; ethylene diamine tetraacetic acid; benzene polycarboxylic acids; citric acid; and polyacetal carboxylates as described in US Patents 4,144,226 and 4,146,495.
• alkali metal polyphosphates such as sodium tripolyphosphate
• the alkali metal salts of ether polycarboxylates such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid
• ethylene diamine tetraacetic acid ethylene diamine tetraacetic acid
• precipitating builder materials examples include sodium orthophosphate, sodium carbonate and sodium carbonate/ calcite.
• Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are well-known examples.
• compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potasssium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
• the organic or inorganic builder materials such as sodium or potasssium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
• a phosphate builder is used, preferably a peroxyacid is present as the bleach agent.
• the builder materials may be present at a level of, for example, from 5 to 80% by weight, preferably from 10 to 60% by weight.
• the detergent compositions of the invention may also contain conventional additives in the amounts at which such materials are normally employed in fabric washing detergent compositions.
• these additives include buffers, such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids, lather depressants, such as alkyl phosphates and silicones, anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers, other stabilizers, such as ethylene diamine tetraacetic acid (EDTA) and the phosphonic acid derivatives (i.e.
• buffers such as carbonates
• lather boosters such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids
• lather depressants such as alkyl phosphates and silicones
• anti-redeposition agents such as sodium carboxymethyl cellulose and alkyl
• Dequest R types fabric softening agents, inorganic salts, such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, enzymes, such as proteases, cellulases, lipases, amylases and oxidases, germicides and colourants.
• transition metal sequestrants such as EDTA and the phosphoric acid derivatives, e.g. ethylene diamine tetra-(methylene phosphonate) EDTMP are particularly important.
• Another optional but highly desirable additive with multi-functional characteristics is a polymeric material having a molecular weight of from 1,000 to 2,000,000 and which can be a homo- or co-polymer of acrylic acid, maleic acid, or salt or anhydride thereof, vinyl pyrrolidone, methyl-or ethyl-vinyl ethers, and other polymerisable vinyl monomers.
• polymeric materials are polyacrylic acid or polyacrylate; polymaleic acid/acrylic acid copolymer; 70:30 acrylic acid/hydroxyethyl maleate copolymer; 1:1 styrene/maleic acid copolymer; isobutylene/maleic acid and diisobutylene/ maleic acid copolymers; methyl- and ethyl-vinylether/ maleic acid copolymers; ethylene/maleic acid copolymer; polyvinyl pyrrolidone; and vinyl pyrrolidone/maleic acid copolymer.
• Such a polymeric additive is usually present at a level from about 0.1% to about 3% by weight.
• the composition contains not more than 5% by weight of carbonate, expressed as sodium carbonate, more preferably not more than 2.5% by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
• Detergent bleach compositions of the invention when formulated as free-flowing particles, e.g. in powdered or granulated form, can be produced by any of the conventional techniques employed in the manufacture of detergent compositions, for instance by slurry-making, followed by spray-drying, to form a detergent base powder to which heat-sensitive ingredients including the peroxy compound bleach, conventional additives, and the complex can be added as dry substances.
• the detergent base powder compositions, to which the complex is added can itself be made in a variety of other ways, such as the so-called part-part processing, non-tower route processing, dry-mixing, agglomeration, granulation, extrusion, compacting and densifying processes etc., such ways being well known to those skilled in the art and not forming an essential part of the present invention.
• the complex may be added separately to a wash/bleach water containing the peroxy bleaching agent.
• the complex is included as a detergent additive product.
• Such additive products are intended to supplement or boost the performance of conventional detergent compositions and may contain any of the components of such compositions, although they will not comprise all of the components present in a fully formulated detergent composition.
• Additive products in accordance with this aspect of the invention will normally be added to an aqueous liquor containing a source of (alkaline) hydrogen peroxide, although in certain circumstances the additive product may be used as separate treatment in a pre-wash or in the rinse.
• Additive products in accordance with this aspect of the invention may comprise the complex alone or, preferably, in combination with a carrier, such as a compatible aqueous or non-aqueous liquid medium or a particulate substrate or a flexible non-particulate substrate.
• a carrier such as a compatible aqueous or non-aqueous liquid medium or a particulate substrate or a flexible non-particulate substrate.
• compatible particulate substrates include inert materials, such as clays and other aluminosilicates, including zeolites, both of natural and synthetic origin.
• Other compatible particulate carrier materials include hydratable inorganic salts, such as carbonates and sulphates.
• the complex can also be formulated in detergent bleach compositions of other product forms, such as flakes, tablets, bars and liquids and particularly non-aqueous liquid detergent compositions.
• non-aqueous liquid detergent compositions in which the complex may be incorporated are known in the art and various formulations have been proposed, e.g. in US Patents 2,864,770; 3,368,977; 4,772,412; GB Patents 1,205,711; 1,370,377; 2,914,536; DE-A-2,233,771 and European Patent Specification No. 0,028,849.
• compositions which normally comprise a non-aqueous liquid medium, with or without a solid phase dispersed therein.
• the non-aqueous liquid medium may be a liquid surfactant, preferably a liquid nonionic surfactant; a non-polar liquid medium, e.g. liquid paraffin; a polar solvent, e.g. polyols, such as glycerol, sorbitol, ethylene glycol, optionally combined with low-molecular monohydrix alcohols, e.g. ethanol or isopropanol; or mixtures thereof.
• the solid phase can be builders, alkalis, abrasives, polymers, clays, other solid ionic surfactants, bleaches, fluorescent agents and other usual solid detergent ingredients.
• the bleach system in the wash solution was added at a concentration of 8.6 mmol/l PBM which corresponds to 14.3% by weight of PBM if a detergent bleach formulation is dosed at 6g/l.
• Test cloths were immersed for 30 minutes in each of the compositions of the examples. After rinsing with tap water, the cloths were dried in a tumble drier. The reflectance (R 460* ) was measured on a Zeiss Elrephometer before and after treatment. The difference ( ⁇ R 460* ) in the value gives a measure of the effectiveness of the treatment.
• the level of mononuclear Mn complex corresponds to 0.03% by weight of catalyst if a detergent composition is dosed at 6 g/l.

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Citations (4)

• 1991
  • 1991-12-20 GB GB919127060A patent/GB9127060D0/en active Pending
• 1992
  • 1992-03-04 GB GB929204706A patent/GB9204706D0/en active Pending
  • 1992-12-17 CA CA002085720A patent/CA2085720A1/en not_active Abandoned
  • 1992-12-17 NO NO92924895A patent/NO924895L/no unknown
  • 1992-12-18 AU AU30297/92A patent/AU3029792A/en not_active Abandoned
  • 1992-12-18 ZA ZA929850A patent/ZA929850B/xx unknown
  • 1992-12-18 BR BR9205100A patent/BR9205100A/pt not_active Application Discontinuation
  • 1992-12-18 ZA ZA929851A patent/ZA929851B/xx unknown
  • 1992-12-18 EP EP92311580A patent/EP0549272A1/en not_active Withdrawn
  • 1992-12-19 KR KR1019920024785A patent/KR930012103A/ko not_active Application Discontinuation
  • 1992-12-19 KR KR92024784A patent/KR960002630B1/ko not_active IP Right Cessation
  • 1992-12-19 CN CN92115249A patent/CN1074237A/zh active Pending
  • 1992-12-21 JP JP4340639A patent/JPH05263098A/ja active Pending
  • 1992-12-21 MX MX9207471A patent/MX9207471A/es unknown
• 1993
  • 1993-02-03 TW TW082100713A patent/TW232706B/zh active

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