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
  • C11D3/3907—Organic 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
  • C11D3/50—Perfumes

Definitions

• the present invention generally relates to bleaching compositions having selected perfumes especially suitable for masking the "bleach" odor associated with such compositions More particularly, the invention relates to bleaching compositions containing a bleaching agent, a bleach activator and a perfume which effectively masks the odor of the composition before and during use
• inorganic peroxygen bleaches overcome many of the disadvantages found with chlorine bleaches, they have limitations on use in that they must be used at relatively high temperatures, such as 85°C or higher This drawback becomes significant in light of the washing practices in countries where lower wash temperatures are used which are generally less than about 60°C in order to reduce energy costs and prolong the life of the fabric This problem also renders the product ineffective when used to "pre-soak" especially soiled fabrics As a consequence, it is generally necessary to improve the low temperature performances of inorganic peroxygen bleaches through the addition of peroxygen bleach activators also known as peroxyacid precursors
• peroxygen or peroxyacid bleaches either alone or in combination with a bleach activator, as an alternative to the chlorine and inorganic peroxygen bleaches described above.
• Various products including peroxygen bleaches and activators therefor have been used, for example, detergent compositions containing a bleach/bleach activator system and bleach additive products which are added separately from the detergent composition.
• Other bleaching compositions include those which are used as a "pre-soak" product for extensively soiled fabrics. The previously mentioned detergent compositions and bleaching compositions can be used in this manner, as well.
• the pre-soak products or other bleach-containing products require the user to immerse the soiled fabrics and bleach-containing product into a washing solution that is typically contained in a bucket, sink or similar open container for 20 to 30 minutes (or longer) during which a strong "bleach" odor is emitted from the washing solution.
• Consumers are offended by such readily detectable bleach odor, a problem which is exacerbated when the product contains high levels of bleach. This problem has been very noticeable in products which contain peroxygen bleach and activators therefor.
• a bleaching composition which includes a bleaching agent, a bleach activator and a perfume that effectively masks the odor of such components.
• a composition which contains a perfume that effectively masks the odor of the bleaching agent and bleach activator, even when the composition is used as a pre-soak product and contains high levels of bleach.
• the invention meets the needs identified above by providing bleaching compositions and detergent compositions containing a bleaching agent and a bleach activator which include a selected perfume particularly suitable for masking the bleach odor emitted by such compositions before and during use.
• the compositions herein can optionally contain relatively high levels of bleaching agents and activators without significant detection of undesirable odors typically associated with such compositions.
• the compositions of the invention can be used in a wide variety of applications including presoak operations wherein soiled fabrics are soaked in open containers, i.e. bucket or sink, prior to conventional laundering operations. The consumer does not notice the bleach odors of the compositions when used in the aforementioned presoaking operations because of the perfume.
• the selected perfumes used in the compositions herein unexpectedly provide masking of the harsh odors normally associated with the bleach-containing compositions described herein.
• ODT Odor Detection Threshold
• AMU atomic weight and may also be expressed as g/mole. All percentages, ratios and proportions used herein are by weight, unless otherwise specified. All documents including patents and publications cited herein are incorporated herein by reference.
• a bleaching composition comprises: (a) a peroxygen bleaching agent; (b) a bleach activator; and (c) a perfume.
• the perfume contains, by weight of the perfume, (i) at least about 25% of a fragrance material selected from the group consisting of aldehydes with a molecular weight greater than 200 AMU, esters with a molecular weight above 200 AMU, alcohols with a molecular weight between 120 and 160 AMU and mixtures thereof, wherein at least about 10% by weight of the fragrance material has an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion; and (ii) at least about 1.0% of an adjunct material with an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion.
• the perfume is substantially free of halogenated fragrance materials and nitromusks.
• a granular detergent composition comprises: (a) from about 0.1% to about 40% by weight of a peroxygen bleaching agent selected from the group consisting of percarbonates, perborates, peroxides and mixtures thereof; (b) from about 0 1 % to about 20% by weight a bleach activator having the formula o
• R— C — LG wherein R is an alkyl group containing from about 5 to about 18 carbon atoms and LG is a leaving group, the conjugate acid of which has a pK a of from about 4 to about 13, wherein the LG has the formula
• Y is selected from the group consisting of SO ⁇ - M + , COO" M + , SO4- M + , PO4- M + PO3- M+, (N+R2 3 )X- and 0 ⁇ -N(R 2 2 ), M is a cation, X is an anion, and R 2 is an alkyl chain containing from about 1 to about 4 carbon atoms or H, and (c) from about 0 01 % to about 2% of a perfume containing, by weight of the perfume, (i) at least 25% of a fragrance material selected from the group consisting of aldehydes with a molecular weight greater than 200 AMU, esters with a molecular weight above 200 AMU, alcohols with a molecular weight between 120 and 160 AMU and mixtures thereof, wherein at least 10% by weight of the fragrance material has an Odor Detection Threshold (ODT) value of less than about 100 parts per trillion, and (u) at least 1 0% of an adjunct material with an
• a bleaching composition as described herein which is in the form of a liquid.
• a method of laundering soiled clothes comprising the step of contacting the soiled clothes with an aqueous washing solution containing a bleaching composition as described herein
• a presoaking method is also provided which comprises the steps of soaking the soiled clothes in an aqueous soaking solution of a bleaching composition as described herein and thereafter, contacting the clothes with an aqueous washing solution containing a detergent composition
• a bleaching composition which includes a bleaching agent, a bleach activator and a perfume that effectively masks the odor of such components before and during use. It is also an object of the invention to provide a bleaching composition which contains such a perfume that effectively masks the odor of the bleaching agent and bleach activator, even when the composition is used as a pre-soak product and contains high levels of bleaching agents and activators.
• compositions of the invention comprise a bleaching agent, a bleach activator and a selected perfume for masking the odor of the bleach components.
• the compositions herein can be in the form of granules, agglomerates, liquid, gel or a bar. Additionally, the. compositions can be used as a bleaching composition, fully formulated detergent composition, or as a bleach or detergent presoak product.
• Bleaching System
• the compositions of the invention must include a bleaching system comprising a bleaching agent and a bleach activator.
• the compositions preferably comprise from about 0.1% to about 40%, more preferably from about 20% to about 35%, and most preferably from about 30% to about 35%, by weight of the peroxygen bleaching agent.
• the detergent composition comprises from about 0.1 % to about 40%, more preferably from about 5% to about 15%, and most preferably from about 10% to about 15%, by weight of the bleach activator.
• one or more adjunct bleach activators may be used in the same amounts.
• the peroxygen bleaching agents can be any of those peroxygen bleaching agents useful for detergent compositions in textile cleaning that are known or become known.
• the bleaching agent is selected from the group consisting of percarbonates, perborates, peroxides and mixtures thereof. While intending not to be limiting, included within this group are sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium perborate (e.g. mono- or tetra-hydrate) and sodium peroxide. It should be understood that other peroxygen bleaches other than those described herein may be used in the detergent composition without departing from the scope of the invention The most preferred bleaching agent is sodium percarbonate
• the peroxygen bleaching agent used herein is combined with a bleach activator which leads to the in situ production in aqueous solution (i e during the laundering process) of the peroxy acid corresponding to the activator
• a bleach activator which leads to the in situ production in aqueous solution (i e during the laundering process) of the peroxy acid corresponding to the activator
• the bleaching mechanism generally, and the surface bleaching mechanism in particular, in the washing solution are not completely understood While not intending to be limited by theory, however, it is believed that the bleach activator undergoes nucleophilic attack by a perhydroxide anion, for example from aqueous hydrogen peroxide, to form a percarboxylic acid This reaction is commonly referenced in the art as perhydrolysis
• DAP diacylperoxide
• dingy soils are those which have built up on textiles after numerous cycles of usage and washing and thus, cause the white textile to have a gray or yellow tint
• the bleaching mechanism herein preferably produces an effective amount of peroxyacid and DAP to bleach both dingy stains as well as stains resulting from spaghetti and the like
• bleach activators within the scope of the invention render the peroxygen bleaches more efficient even at bleach solution temperatures wherein the bleach activators are not necessary to activate the bleach, for example at temperatures above 60°C As a consequence, less peroxygen bleach is required to obtain the same level of surface bleaching performance as compared with peroxygen bleach alone
• the bleach activator used in the granular detergent composition has the general formula o
• R— C — LG wherein R is an alkyl group, linear or branched, containing from about 1 to 11 carbon atoms and LG is a suitable leaving group
• a "leaving group” is any group that is displaced from the bleach activator as consequence of nucleophilic attack on the bleach activator by the perhydroxide anion, i.e. perhydrolysis reaction.
• a suitable leaving group is electrophilic and is stable such that the rate of the reverse reaction is negligible. This facilitates the nucleophilic attack by the perhydroxide anion.
• the leaving group must also be sufficiently reactive for the reaction to occur within the optimum time frame, for example during the wash cycle. However, if the leaving group is too reactive, the bleach activator will be difficult to stabilize. In the past, it has been difficult to formulate granular detergent compositions having the desired stability for a practical shelf-life.
• the conjugate acid of the leaving group in accordance with the present invention preferably has a pK a in a range from about 4 to about 13, more preferably from about 6 to about 11 , and most preferably from about 8 to about 11.
• the leaving group has the formula
• Y is selected from the group consisting of SO3" M + , COO" M + , SO4- M + , P0 4 " M + , PO3- M + , (N + R2 3 )X- and 0 ⁇ -N(R 2 2 ),
• M is a cation and X is an anion, both of which provide solubility to the bleach activator, and R 2 is an alkyl chain containing from about 1 to about 4 carbon atoms or H.
• M is preferably an alkali metal, with sodium being most preferred.
• X is a hydroxide, methylsulfate or acetate anion.
• R is an alkyl chain, linear or branched, containing from about 1 to about 11 carbon atoms
• the bleach activator has the formula
• TAED tetra acetyl ethylene diamme
• compositions of the invention preferably contain from about 0 001 % to about 5%, more preferably from about 0 01% to about 2%, and most preferably from about 0 1% to about 1 0%, by weight of a perfume as described herein
• the formulator has the luxury of choosing from a wide variety of perfume ingredients in order to arrive at a perfume formulation with the definition stated previously Several exemplary perfume formulations are set forth hereinafter
• the perfume preferably includes at least 25%, more preferably from about 40% to about 75%, and most preferably from about 60% to about 70%, by weight of the perfume, of certain aldehydes, esters, alcohols and mixtures thereof
• Suitable aldehydes with molecular weights greater than 200 AMU, esters with molecular weights greater than 200 AMU and alcohols with molecular weights between 120 - 160 AMU include, but are not limited to hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate; hexyl salicylate; phenyl ethyl alcohol; terpineol; 3,7-dimethyl-cs-2,6-octadien-1 -ol; 2,6-dimethyl-2-octanol; 2,6-dimethyl-7- octen-2-ol, 3,7-dimethyl-3-octanol; 3,7-d
• At least about 10%, more preferably from about 15% to about 30%, and most preferably from about 20% to about 25%, by weight of the perfume, of the aformentioned aldehydes, esters, alcohols and mixtures thereof have an Odor Detection Threshold value of less than about 100 parts per trillion.
• Suitable aldehydes with molecular weights greater than 200 AMU, esters with molecular weights greater than 200 AMU and alcohols with molecular weights between 120 - 160 AMU having such- measured Odor Detection Threshold (ODT) values include but are not limited to, benzyl salicylate; 2-methyl-3-(para tert butylphenyl)- propionaldehyde; 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1- carboxaldehyde; tricyclodecenyl propionate.
• the perfume also comprises at least about 1%, more preferably from about 5% to about 35%, and most preferably from about 20% to about 25%, by weight of the perfume, of an adjunct fragrance material with an Odor Detection Threshold values less than or equal to 100 parts per trillion include, but are not limited to, tricyclodecenyl acetate; anisaldehyde; 2- methyl-2-(para-iso-propylphenyl)-propionaldehyde; ethyl 3-methyl-3-phenyl glycidate; 4-(para-hydroxy phenyl) butan-2-one; 1-(2,6,6-trimethyl-2- cyclohexen-1-yl)-2-buten-1 -one; para methoxy acetophenone; para- methoxy-alpha-phenyl propene; methyl 2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalactone gamma.
• fragrance materials of synthetic or natural origin may be added to the perfume if desired and include but are not limited to dodecalactone gamma; methyl 2-(2- ⁇ entyl-3-oxo-cyclopentyl) acetate; beta naphthol methyl ether; methyl beta naphthyl ketone; couma n; decyl aldehyde; benzaldehyde; 4-tertiary-butyl cyclohexyl acetate; alpha, alpha- dimethyl phenethyl acetate; methyl phenyl carbinyl acetate; schiff s base of 4-(4-hydroxy-4-methyl pentyl)-3-cyclohexene-1 -carboxaldehyde and methyl anthranilate; cyclic ethylene glycol diester of tridecandioic acid; 3,7- dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl;
• adjunct ingredients can be included in the compositions disclosed herein.
• the levels of the ingredients will vary depending upon the context, e.g. liquid or granular, bleaching or detergent composition, etc.
• the bleaching or granular detergent compositions of the invention can include a wide variety of additional ingredients typically used in the art of detergency.
• the detergent composition can include from about 1% to about 80%, more preferably from about 5% to about 20%, and most preferably from about 10% to about 30%, by weight of a builder.
• the builder can be selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, crystalline layered and amorphous silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
• the alkali metal especially sodium, salts of the above.
• Preferred for use herein are the phosphates, carbonates, silicates, C 10 _ 1 g fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate, and mixtures thereof (see below).
• inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21 , and orthophosphates.
• polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1 , 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1 ,1 ,2-triphosphonic acid.
• Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581 ; 3,213,030; 3,422,021 ; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference.
• nonphosphorus, inorganic builders are sodium and. potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of Si0 2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
• Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
• polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
• Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference.
• Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
• Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant.
• polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization 96/31590 PC17US96/04023
• polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolyme ⁇ zation in alkaline solution, converted to the corresponding salt, and added to a detergent composition.
• Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071 , Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
• Water-soluble silicate solids represented by the formula Si ⁇ 2»M 2 0, M being an alkali metal, and having a SiO ⁇ M ⁇ O weight ratio of from about 0.5 to about 4.0, are useful salts in the compositions of the invention at levels of from about 0.1% to about 15%, more preferably from about 0.5% to about 2%, on an anhydrous weight basis.
• Anhydrous or hydrated paniculate silicate can be utilized, as well.
• the detergent composition of the invention optionally can contain various anionic, nonionic, zwitte ⁇ onic, etc. surfactants. If used, such surfactants are typically present at levels of from about 1 % to about 50%, more preferably from about 3% to about 35%, and most preferably from about 5% to about 25%, by weight of the composition.
• Nonlimiting examples of surfactants useful herein include the conventional Cn-Ci ⁇ alkyl benzene sulfonates ("LAS") and primary, branched-cham and random C10-C20 alk yl sulfates (“AS”), the C10-C18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH2) ⁇ (CHOS0 3 " M + ) CH3 and CH3 (CH 2 )y(CHOS ⁇ 3 " M + ) CH2CH3 where x and (y + 1 ) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10- 18 alkyl alkoxy sulfates (“AE X S”; especially EO 0.1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycar
• the conventional nonionic and amphote ⁇ c surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Ci2 _c 18 betames and sulfobetames (“sultaines”), C10-C18 am ⁇ ne oxides, and the like, can also be included in the overall compositions.
• the C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154.
• sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide.
• the N-propyl through N-hexyl Ci2 _c 18 glucamides can be used for low sudsing.
• o _c 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soa P s ma y De used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
• AE X S C10-C18 alkyl alkoxy sulfates
• AE C-12-C18 alkyl ethoxylates
• the detergent composition can also include suds boosters or suds, suppresses, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes (e.g. cellulases, proteases, lipases and amylases), and enzyme-stabilizing agents. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.
• a polymeric dispersant such as polyaspartic acid, may also be included in the detergent composition disclosed herein.
• Chelating agents are also described in U.S. Patent 4,663,071 , Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference.
• Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
• Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference.
• Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071 , Bush et al, issued May 5, 1987, both incorporated herein by reference.
• Fillers such as sulfates may be included at levels of from about 5% to about 50%, more preferably from about 10% to about 30%, by weight of the composition.
• This Example illustrates three perfume formulations in accordance with the invention. Specifically, Table I sets forth perfume formulations A, B and C which are suitable for use in the compositions of the invention.
• compositions set forth in Table II are made by conventional detergent processing techniques.
• the base granule ingredients are mixed together as a slurry and spray dried in a tower to produce granules.
• the dry ingredients are then admixed with the granules and the liquid ingredients are spray thereon to provide the finished composition.
• various liquid and dry ingredients can be agglomerated to provide high density agglomerates to which the remaining ingredients can be sprayed on or admixed as appropriate.
• Polyethylene glycol (M.W. 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8
• Protease enzyme 04 0.5 0.4 0.4 0.5 0.5
• Nonionic 3 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
• Neodol (23-9) commercially available from Shell Chemical Co.
• compositions set forth in Table III are made in accordance with the processes described with respect to Examples ll-IV hereinabove.

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• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Fats And Perfumes (AREA)

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Citations (3)

• 1996
  • 1996-03-25 EP EP96910538A patent/EP0821723A1/en not_active Withdrawn
  • 1996-03-25 CA CA002216778A patent/CA2216778A1/en not_active Abandoned
  • 1996-03-25 HU HU9801774A patent/HUP9801774A3/hu unknown
  • 1996-03-25 WO PCT/US1996/004023 patent/WO1996031590A1/en not_active Application Discontinuation
  • 1996-03-25 BR BR9604793A patent/BR9604793A/pt not_active Application Discontinuation
  • 1996-03-25 CZ CZ973087A patent/CZ308797A3/cs unknown
  • 1996-03-25 JP JP8530341A patent/JPH11503192A/ja active Pending
  • 1996-03-25 CN CN96194278A patent/CN1185804A/zh active Pending
  • 1996-03-25 MX MX9707588A patent/MX9707588A/es unknown
  • 1996-04-03 ZA ZA962667A patent/ZA962667B/xx unknown

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