Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

• the present invention relates to liquid detergent compositions containing synthetic surfactant, specific proteolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, and calcium ion.
• the compositions exhibit improved enzyme stability because boric acid stabilizes the proteases herein to a greater degree than it does other proteases.
• the compositions are preferably heavy-duty liquid laundry detergents, but can also be light-duty liquid detergents suitable for dishwashing or washing fine fabrics, detergent pretreatment compositions or all- purpose household liquid cleaners.
• Preferred laundry detergent compositions containing a relatively high level of anionic surfactant and detergency builder also provide improved cleaning performance, particularly through-the-wash, of enzyme-sensitive stains such as grass, blood, gravy and chocolate pudding.
• Laundry detergents containing high levels of anionic surfactant and builder, and capable of providing superior cleaning performance are currently available. Some of these compositions also contain enzymes to enhance removal of enzyme-sensitive stains. However, it is believed that such compositions are enzyme-limited in that they can denature and expose stains to enzymatic action faster than currently available enzymes can cleave and break up the stains.
• Enzyme performance can also be limited by a lack of adequate stability in liquid detergents.
• the stabilization of enzymes is particularly difficult in built, heavy-duty liquid detergents containing high levels of anionic surfactant and water.
• Anionic surfactants, especially alkyl sulfates, tend to denature enzymes and render them inactive.
• Detergent builders can sequester the calcium ion needed for enzyme activity and/or stability.
• the compositions can contain 10-60% surfactant, including anionics, and up to 40% builder.
• U.S. Patent 4,404,115, Tai, issued September 13, 1983 discloses liquid cleaning compositions, preferably built liquid detergents, containing enzyme, 1-15% alkali metal pentaborate, 0-15% alkali metal sulfite, and 0-15% of a polyol having 2-6 hydroxy groups.
• the compositions can contain 1-60% surfactant, preferably a mixture of anionic and nonionic in a weight ratio of 6:1 to 1:1, with or without soap.
• the compositions also preferably contain 5-50% builder.
• the compositions preferably contain from about 20% to 50% surfactant, which can be anionic. In a preferred embodiment, the compositions contain about 3% to 15% of a saturated fatty acid. They are otherwise substantially free of builders, but can contain minor amounts of sequestrants.
• the enzymes are said to be useful in laundry detergents, both liquid and granular. They can be combined with surfactants (including anionics), builders, bleach and/or fluorescent whitening agents, but there is no disclosure of specific detergent compositions.
• This invention relates to liquid detergent compositions comprising, by weight:
• the liquid detergents of the present invention contain, as essential components, synthetic detergent surfactant, specific proteolytic enzyme, boric acid or a boron compound capable of forming boric acid in the composition, calcium ion, and water.
• the compositions exhibit improved enzyme stability because boric acid stabilizes the proteases herein to a greater degree than it does other proteases. This is particularly surprising given that the proteases herein do not exhibit improved stability in the absence of boric acid.
• boric acid and calcium form intramolecular bonds which cross-link or staple the enzyme molecule together, thereby holding it in its active spatial conformation. This mechanism is apparently more effective for the proteases herein than for other proteases.
• anionic surfactant and builder in the preferred compositions herein provides an effective matrix for denaturing stains and exposing sites to enzymatic action.
• the anionic surfactant is believed to be the primary denaturing agent, whereas the builder controls water hardness that would otherwise complex the anionic surfactant and interfere with its denaturing action.
• the preferred surfactant and builder matrix herein can denature and expose more sites on stains than currently available enzymes can cleave during the washing process. This is particularly true at low washing temperatures (e.g., in the range of 15°C to 35°C) where enzymes are catalytically slow.
• the present proteolytic enzymes appear to be superior to other proteases in catalytic efficiency. They thus can take advantage of the stain denaturing power of the preferred compositions herein and provide significant stain removal benefits. In contrast, they provide little or no stain removal benefits in detergent compositions containing less anionic surfactant and builder.
• compositions of the present invention contain from about 1% to about 75%, preferably from about 5% to about 50%, and most preferably from about 15% to about 35%, by weight of a synthetic surfactant, which can be an anionic, nonionic,cationic, zwitterionic or ampholytic surfactant, or mixtures thereof.
• a synthetic surfactant which can be an anionic, nonionic,cationic, zwitterionic or ampholytic surfactant, or mixtures thereof.
• Suitable synthetic surfactants are disclosed in U.S. Patent 4,285,841, Barrat et al, issued August 25, 1981, and in U.S. Patent 3,929,678, Laughlin et al; issued December 30, 1975, both incorporated herein by reference.
• compositions herein contain from about 7% to about 50%, preferably from about 10% to about 40%, more preferably from about 15% to about 30%, by weight of an anionic synthetic surfactant.
• Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
• water-soluble salts particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
• alkyl is the alkyl portion of aryl groups.
• Exam- pies of this group of synthetic surfactants are the alkyl sulfates, especially those obtained by sulfating the higher alcohols (C e -C, s carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U. S. Patents 2,220,099 and 2,477,383.
• Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14.
• anionic surfactants herein are the water-soluble salts of: paraffin sulfonates containing from about 8 to about 24 (preferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C 8 . 18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates containing about 1 to about 4 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
• Other useful anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
• Preferred anionic surfactants are the C, o -C, a alkyl sulfates and alkyl ethoxy sulfates containing an average of up to about 4 ethylene oxide units per mole of alkyl sulfate, C,,-C,, linear alkylbenzene sulfonates, and mixtures thereof.
• compositions preferably contain from about 1% to about 5%, more preferably from about 2% to about 4%, by weight of unethoxylated alkyl sulfate.
• alkyl sulfates are desired for best detergency performance, in part because they are very denaturing to stains.
• a preferred cosurfactant used at a level of from about 1% to about 25%, preferably from about 3% to about 15%, by weight of the composition, is an ethoxylated nonionic surfactant of the formula R'(OC2H4) n OH, wherein R' is a C 10 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group, n is from about 3 to about 9, and said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from about 6 to about 14, preferably from about 10 to about 13.
• R' is a C 10 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group
• n is from about 3 to about 9
• said nonionic surfactant has an HLB (hydrophile-lipophile balance) of from about 6 to about 14, preferably from about 10 to about 13.
• Particularly preferred are condensation products of C, 2 -C,s alcohols with from about 3 to about 8 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
• Preferred cosurfactants for use with the above ethoxylated nonionic surfactants are amides of the formula wherein R' is an alkyl, hydroxyalkyl or alkenyl radical containing from about 8 to about 20 carbon atoms, and R 2 and R * are selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, 2-hydroxyethyf, 2-hydroxypropyl, 3-hydroxypropyl, and said radicals additionally containing up to about 5 ethylene oxide units, provided at least one of R 2 and R ; contains a hydroxyl group.
• Preferred amides are the C 8 -C 20 fatty acid alkylol amides in which each alkylol group contains from 1 to 3 carbon atoms, and additionally can contain up to about 2 ethylene oxide units. Particularly preferred are the C, z -C, 6 fatty acid monoethanol and diethanol amides.
• compositions herein preferably contain from about 5% to about 20%, preferably from about 6% to about 15%, more preferably from about 7% to about 12%, by weight of a mixture of the above ethoxylated nonionic surfactant and amide surfactant in a weight ratio of from about 4:1 to 1:4, preferably from about 3:1 to about 1:3, more preferably from about 2:1 to about 1:2.
• the weight ratio of anionic synthetic surfactant (on an acid basis) to the total nonionic surfactant (both the ethoxylated nonionic and the amide) should be from about 2:1 to about 4:1, preferably from about 2.5:1 to about 3.5:1, to ensure the formation and adsorption of sufficient hardness surfactants at the oil/water interface to provide good greasy/oily soil removal.
• cosurfactants used at a level of from about 0.5% to about 3%, preferably from about 0.7% to about 2%, by weight are the quaternary ammonium, amine or amine oxide surfactants described in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, incorporated herein by reference.
• compositions herein can contain di- long chain quaternary ammonium cationic surfactants (e.g., those having 2 chains, each containing an average of from about 16 to about 22 carbon atoms), such as disclosed in British Patent 2,041,968, Murphy, published September 19, 1979, incorporated herein by reference, the compositions preferably contain less than about 2%, more preferably less than about 1%, by weight of such surfactants. Most preferably, the compositions are substantially free of such surfactants because they appear to be detrimental to the stability of the proteolytic enzymes herein.
• di- long chain quaternary ammonium cationic surfactants e.g., those having 2 chains, each containing an average of from about 16 to about 22 carbon atoms
• the compositions preferably contain less than about 2%, more preferably less than about 1%, by weight of such surfactants.
• the compositions are substantially free of such surfactants because they appear to be detrimental to the stability of the proteolytic enzymes herein.
• compositions also preferably contain from about 5% to about 40%, more preferably from about 8% to about 30%, most preferably from about 10% to about 25%, by weight of a detergent builder material.
• the composition preferably contain at least about 20%, more preferably from about 25% to about 60%, most preferably from about 30% to about 50%, by weight of the anionic synthetic surfactant and builder. Since the proteolytic enzymes herein appear to provide optimum performance benefits versus other enzymes when the builder to water hardness ratio is dose to one, the compositions preferably contain sufficient builder to sequester from about 2 to about 10, preferably from about 3 to about 8, grains per gallon of hardness.
• Useful builders are fatty acids containing from about 10 to about 22 carbon atoms. Preferred are saturated fatty acids containing from about 10 to about 18, preferably from about 10 to about 14, carbon atoms. When present, the fatty acid preferably represents about 5% to about 20%, more preferably from about 8% to about 16%, by weight of the composition.
• Suitable saturated fatty acids can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil and coconut oil) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process).
• suitable saturated fatty acids for use in the compositions of this invention include capric, lauric, myristic, coconut and palm kernel fatty acid.
• Preferred are saturated coconut fatty acids; from about 5:1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid; mixtures of the above with minor amounts (e.g., 1 %-30% of total fatty acid) of oleic acid; and palm kernel fatty acid.
• Detergent builders useful herein also include the polycarboxylate, polyphosphonate and polyphosphate builders described in U.S. Patent 4,284,532, Leikhim et al, issued August 18, 1981, incorporated herein by reference. Water-soluble polycarboxylate builders, particularly citrates, are preferred of this group. Polycarboxylate builders preferably represent from about 1 % to about 20% by weight of the composition.
• Suitable polycarboxylate builders include the various aminopolycarboxylates, cycloalkane, polycarboxylates, ether polycarboxylates, alkyl polycarboxylates, epoxy polycarboxylates, tetrahydrofuran polycarboxylates, benzene polycarboxylates, and polyacetal polycarboxylates.
• polycarboxylate builders are sodium and potassium ethylenediaminetetraacetate; sodium and potassium nitrilotriacetate; and water-soluble salts of phytic acid, e.g., sodium and potassium phytates, disclosed in U.S. Patent 1,739,942, Eckey, issued March 27, 1956, incorporated herein by reference; the polycarboxylate materials described in U.S. Patent 3,364,103, incorporated herein by reference; and the water-soluble salts of polycarboxylate polymers and copolymers described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference.
• Useful detergent builders also include the water-soluble salts of polymeric aliphatic polycarboxylic acids having the following structural and physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (3) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms: (d) the site of attachment of the polymer chain of any carboxyl- containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl- containing radical.
• Specific examples of such builders are the polymers and copolymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid.
• Suitable polycarboxylate builders include the water-soluble salts, especially the sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohex- anehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid.
• water-soluble salts especially the sodium and potassium salts, of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyloxymalonic acid, cis-cyclohex- anehexacarboxylic acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid.
• 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 4,146,495, issued March 27, 1979 to Crutchfield et al, both incorporated herein by reference.
• detergent builders useful herein include the aluminosilicate ion exchange material described in U.S. Patent 4,405,483, Kuzel et al, issued September 20, 1983, incorporated herein by reference.
• the compositions herein preferably contain from about 0.1% to about 1%, more preferably from about 0.2% to about 0.6%, by weight of water-soluble salts of ethylenediamine tetramethylenephosphonic acid, diethylenetriamine pentamethylenephosphonic acid, ethylenediamine tetraacetic acid, or diethylenetriamine pentaacetic acid to enhance cleaning performance when pretreating fabrics.
• compositions of the present invention contain from about 0.01% to about 5%, preferably from about 0.1 % to about 2%, by weight of the composition of Protease A as previously defined, or variants thereof in which the Gly at position 166 is replaced with Ser or Asn, the Gly at position 169 is replaced with Ser, or the Met at position 222 is replaced with Phe.
• the above enzyme is preferably included in an amount sufficient to provide an activity of from about 0.001 to about 0.1, more preferably from about 0.005 to about 0.07, most preferably from about 0.01 to about 0.04, Anson units per gram of composition.
• proteases herein are preferably purified, prior to incorporation in the finished composition, so that they have no detectable odor at a concentration of less than about 0.002 Anson units per gram in distilled water. They preferably have no detectable odor at a concentration of less than about 0.0025, more preferably less than about 0.003, Anson units per gram of distilled water.
• Proteases herein can be odor purified by any method known in the art. Examples include the solvent precipitation methods described in Precipitation of the Enzymes and Their Stability in High Alcohol Concentrations by Bauer et al in the Israel J. Chem. 5(3), pages 117-20 (1967) and Enzyme Preparations by Sugiura et al and Yakusaigaku 1967, Volume 27(2), pages 135-9.
• Solvent initiated precipitation of a crude commercial enzyme solution results in most of the enzymatic activity being precipitated from solution and most of the odor and color impurities remaining in the supernatant liquid. Decantation or centrifugation of the supernatant liquid from the precipitated enzyme results in an enzyme fraction with enriched enzymatic activity/gram and improved odor and color.
• solvents or solvent pair combinations can be used to effect the desired precipitation.
• methanol, ethanol, acetone, other organic solvents, and combinations of organic solvents with and without water can be used.
• a highly preferred solvent is a combination of water and 30-70% by weight ethanol. This appears to be optimal to prevent enzyme deactivation and maximum recovery of activity.
• Purification of protease enzymes also provide benefits in the area of product color stability.
• compositions of the present invention also contain from about 0.1% to about 10%, more preferably from about 0.25% to about 5%, most preferably from about 0.5% to about 3%, by weight of boric acid or a compound capable of forming boric acid in the composition (calculated on the basis of the boric acid).
• Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta-and pyroborate, and sodium pentaborate) are suitable.
• Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
• the composition also contains from about 0.01 to about 50, preferably from about 0.1 to about 30, more preferably from about 1 to about 20, millimoles of calcium ion per liter.
• the level of calcium ion should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, etc., in the composition.
• Any water-soluble calcium salt can be used as the source of calcium ion, including calcium chloride, calcium formate, and calcium acetate.
• a small amount of calcium ion generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water.
• compositions herein contain from about 10% to about 95%, preferably from about 20% to about 70%, more preferably from about 30% to about 50%, by weight of water.
• polyols containing only carbon, hydrogen and oxygen atoms are polyols containing only carbon, hydrogen and oxygen atoms. They preferably contain from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups. Examples include propylene glycol (especially 1,2 propane diol, which is preferred), ethylene glycol, glycerol, sorbitol, mannitol, and glucose.
• the polyol generally represents from about 1% to about 15%, preferably from about 1.5% to about 10%, by weight of the composition.
• the weight ratio of polyol to boric acid is at least 1, more preferably at least about 1.3.
• compositions can also contain the water-soluble, short chain carboxylates described in U.S. Patent 4,318,818, Letton et al, issued March 9, 1982, incorporated herein by reference.
• the for- mates are preferred and can be used at levels of from about 0.05% to about 5%, preferably from about 02% to about 2%, most preferably from about 0.4% to about 1.5%, by weight of the composition.
• compositions herein preferably have an initial pH of from about 6.5 to about 10.0, preferably from about 7 to about 8.5, most preferably from about 7.2 to about 8.0, at a concentration of 0.2% by weight in distilled water at 20°C.
• Preferred pH buffers include monoethanolamine and triethanolamine.
• Monoethanolamine and triethanolamine also further enhance enzyme stability, and preferably are included at levels of from about 0.5% to about 10%, preferably from about 1 % to about 4%, by weight of the composition.
• optional components for use in the liquid detergents herein include soil removal agents, antire-deposition agents, suds regulants, hydrotropes, opacifiers, antioxidants, bactericides, dyes, perfumes, and brighteners known in the art.
• Such optional components generally represent less than about 15%, preferably from about 1% to about 10%, by weight of the composition.
• the following detergent compositions were prepared. in which about 20% by weight of the material has a value of u higher than 5 is dissolved at about 15% level in anhydrous ethanol; cooled to about 10°C; the insoluble portion ( ⁇ 20%) is filtered; and enough ethanol is distilled to reduce the ethanol level to within the level in the formula.
• proteases were added to the above Compositions B, C and D at a level to provide an initial activity of 0.015 Anson units per gram. Protease stability, in terms of percent retained activity, was then determined after storage of the compositions for the indicated number of weeks. The results were as follows.
• Protease A and Maxatase had comparable stability in Composition B without boric acid.
• the addition of boric acid improved the stability of both proteases, but to a much greater degree for Protease A, particularly at longer storage times and higher temperatures.
• Composition D Alcalase and Maxatase were significantly more stable than Protease A.
• boric acid directionally improved the stability of Protease A but decreased the stability of Alcalase and Maxatase, as demonstrated by the following results.
• Protease A has a substantially diferent stability profile in combination with boric acid than does Alcalase or Maxatase.
• composition B with boric acid protease A and variants of Protease A in which the Gly at position 166 is replaced with Ser or Asn, the Gly at position 169 is replaced with Ser, or the Met at position 222 is replaced with Phe, also exhibited improved stability versus Alcalase and the variant of Protease A in which the Met at position 222 is replaced with Gln, as demonstrated by the following results.
• compositions A and E of the present invention contain 0.75% of a slurry of Protease A, providing an activity of 0.015 Anson units per gram of composition, and 1.25% boric acid in place of water.
• the invention herein can also be utilized in light-duty liquid detergent compositions, such as those described in U.S. Patent 3,634,266, Thiele et al, U.S. Patent 3,799,879, Francke et al, U.S. Patent 3,707,505, Maeda et al, U.S. Patent 4,316,824, Pancheri, and U.S. Patent 4,457,856, Mitchell et al, and in hard surface cleaning compositions, such as described in U.S. Patent 3,981,826, Munro, and U.S. Patent 3,985,668, Hartman.

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• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Enzymes And Modification Thereof (AREA)
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• 1986
  • 1986-04-07 AT AT86200586T patent/ATE77649T1/de not_active IP Right Cessation
  • 1986-04-07 EP EP86200586A patent/EP0199405B1/fr not_active Expired
  • 1986-04-07 DE DE8686200586T patent/DE3685769T2/de not_active Expired - Fee Related
  • 1986-04-14 CA CA000506568A patent/CA1302925C/fr not_active Expired - Fee Related
  • 1986-04-15 JP JP61086963A patent/JPS62596A/ja active Pending

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