US3637339A - Stain removal - Google Patents

Stain removal Download PDF

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US3637339A
US3637339A US726571A US3637339DA US3637339A US 3637339 A US3637339 A US 3637339A US 726571 A US726571 A US 726571A US 3637339D A US3637339D A US 3637339DA US 3637339 A US3637339 A US 3637339A
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activator
perborate
sodium
percent
composition contains
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Frederick William Gray
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    • 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
    • C11D3/3942—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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • 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

Definitions

  • ABSTRACT Composition for removing stains from fabrics, including, an enzyme, a per-compound, and an activator for the perborate.
  • a novel and highly effective composition for use in the washing of clothes comprising a mixture of a proteolytic enzyme, sodium perborate, and an activator for the perborate.
  • an activator for the perborate for the perborate.
  • proteolytic enzymes which are employed in the instant invention are active upon protein matter and catalyze digestion or degradation of such matter when present as in linen or fabric stain in a hydrolysis reaction.
  • the enzymes are effective at a pH range of about 4-12, such as usually prevails in detergent cleaning procedures. Moreover, they may be effective even at moderately high temperatures so long as the temperature does not degrade them.
  • Some proteolytic enzymes are effective at up to about 80 C. and higher. They are also effective at ambient temperature and lower to about 10 C.
  • proteolytic enzymes which may be used in the instant invention include pepsin, trypsin, chymotrypsin, papain, bromelin, colleginase, keratinase, carboxylase, amino peptidase, elastase, subtilisia and aspergillopepidase A and B. They are available also under names such as Alcalase (Novo lndustri, Copenhagen, Denmark), Monzyme (Monsanto Chemical Co.), Maxatase (Royal Netherlands Fermentation, Delft, Netherlands), Protease AP (Sandoz-Ferment, Basle, Switzerland).
  • Protease 8-400 (Sandoz- Ferment), Protease ATP 40 (Sandoz-Ferment), Pancreatin NF (Pfizer), Pancreatin 6xNF (Armour), Fungal Protease (Miles), DSE Numbers 4-9 (Rohm and Haas), Exzyme 'DPX (Premier Malt), Protease 14-252 Digester (Premier Malt), Protease L-253 Digester (Premier Malt), Protease 1-423 (Premier Malt), Protease L-516 (Premier Malt), Protease L-517 (Premier Malt), Texzyme PX-l (Premier Malt), Protease P-G (Pfizer), Compound 37B (Miles), Serizyme (Wallerstein), Papain 100 (Wallerstein), Optimo Papain (Penick), Ficin (Miles), Bromelain (Miles), HT Proteolytic Concentrate (
  • Proteolytic enzymes such as Alcalase, Maxatase, Protease AP, Protease ATP 40, Protease ATP 120, Protease L-252 and Protease L-423 are derived from strains of spore-forming bacillus, such as Bacillus subtillis.
  • stain-removing enzymes have different degrees of effectiveness in aiding in the removal of stains from textiles and linen.
  • stain-removing enzymes are Alcalase, Maxatase, Protease AP, Protease ATP 40, and Rapidase.
  • Metalloproteases which contain divalent ions such as calcium, magnesium or zinc bound to their protein chains are of particular interest.
  • the perborate activators are a well-known class of materials, described for example in a series of articles by Gilbert in Detergent Age, June 1967 pp. 18-20, July 1967 pp. 30-33, and Aug. 1967 pp. 26, 27, and 67.
  • the perborate activators of greatest importance in the practice of this invention are compounds which are percarboxylic acid precursors. As explained by Gilbert, such compounds include esters and anhydrides and acyl amides. Examples of suitable activators are given by Gilbert who also described a test for suitability. Among the activators which may be used are the following:
  • N-acetyl phthalimide N-acetyl succinimide Triascetyl cyanurate N-benzoyl'succinimide Phenyl acetate Acetylsalicylic Acid N-p-anisoyl succinimide N-alpha-napthoyl succinimide N-beta-napthoyl succinimide N-benzoyl glutarimide N-p-chlorobenzoyl succinimide N-benzoyl succinimide N-p-chlorobenzoyl-S,S-dimethyl hydantoin N-o-chlorobenzoyl succinimide N-p-chlorobenzoyl phthalimide etc.
  • activator compounds of the imide type both cyclic and aliphatic, have the following structural formula:
  • X represents halogen, e.g., chloro and Z represents the atoms necessary to complete a heterocyclic nucleus selected from the group consisting of hydantoin and succinimide.
  • Another group of activator compounds comprises N-sulfonated cyclic imides including those of the following struclural formula:
  • R represents lower alkyl of from one to four carbon atoms and aryl and Z represents the atoms necessary to complete a heterocyclic ring selected from the group consisting of succinimide and phthalimide.
  • Specific examples of compounds of this type include, without necessary limitation, the following:
  • a further class of activator compounds comprises alkyl and aryl chloroformate derivatives, including for example:
  • methylchloroformate ethylchloroformate phenylchloroformate The proportions of per-compound, activator, and enzyme will be influenced by the physical and chemical properties of these ingredients, the time and temperature of the bleaching or laundering operation, and the degree of bleaching desired.
  • a preferred range of proportions of the perborate is one which provides a concentration of per-compound in the wash water equivalent to about 1 to 40 ppm. more preferably about 4 to 25 ppm. e.g., 8 to 20 ppm. of available oxygen; about 20 ppm. has thus far given best results.
  • sodium perborate tetrahydrate (NaBO -4H O) the available oxygen content (or peroxy oxygen content) is about percent; i.e., one atom of available oxygen per molecule of the perborate.
  • the proportions of perborate for use in the detergent formulation can therefore readily be calculated if one knows how much of the total formulation is to be added to the wash water.
  • a preferred detergent formulation containing sodium perborate tetrahydrate designed for use at the 0.15 percent concentration in the wash water will therefore contain approximately 5 to percent of that compound, correspondingly roughly to the 8 to ppm. of available oxygen.
  • activators vary in structure and molecular weight as well as performance, it is convenient to relate the quantity of activator to be employed to the desired available oxygen present in the particular per-compound being used.
  • reactive aromatic monoacyl compounds such as metachlorobenzoyIdimethylhydantoin and metachlorobenzoylsuccinimide
  • strong bleaching is obtained when approximately equimolecular quantities of activator and peroxygen are present.
  • Bleaching is enhanced with increase in the concentration of activator and maintenance of about a 1:1 mol ratio of activator and the peroxygen present in the percompound.
  • By increase of the mol ratio of available oxygen to activator milder bleaching is obtained particularly when the ratio is greater than 2:1.
  • the mole ratio of available oxygen to activator is preferably 2:1, although higher (e.g., 6:1) or lower (e.g., about 1:1 or less) mol ratios may be employed.
  • the enzyme concentration can be varied widely, Typically the enzyme is present in amount in the range of about 0,001-4 percent by weight of the total detergent fonnulation, preferably in the range of about 0.05-1 percent and most preferably in the range of about 0.1 to 0.5 percent.
  • the uptimum proportion of enzyme to be used in a detergent composition containing per-compound and activator will of course depend upon the effective enzyme content of the enzyme preparation. As with per-compound content, the quantity of enzyme to be used for stains susceptible to enzyme action will be dependent upon a number of factors, particularly time, temperature, and proportions of per-compound and activator.
  • a preferred range of proportions is one which gives about 1 to 40 p'.p.m., more preferably about 2-8 ppm, of the Alcalase in the wash water.
  • This 2-8 p.p.m. concentration corresponds to about 0.003-0.0l2 Anson units per liter of wash water or, in a detergent formulation designed for use at a concentration of 1.5 gram per liter of wash water, about 0.0020.008 Anson units per gram of detergent formulation.
  • the enzyme, perborate and activator may be used together, as in the water used for a prerinse of the soiled clothes, without any surface-active detergent being present. It is preferable, however, to mix these ingredients into a surfaceactive detergent composition, such as a heavy-duty built granular detergent composition.
  • the surface-active agent which may be employed may be any commonly used compound having surface-active or detergent properties. Most preferred are those water-soluble surface-active compounds having anionic or nonionic properties.
  • Anionic surface-active agents include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group. Typical example of anionic solubilizing groups are sulfonate, sulfate, carboxylate, and phosphate.
  • Suitable anionic detergents which fall within the scope of the invention include the soaps, such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, e.g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about eight to 26, and preferably about 12 to 22, carbon atoms to the molecule.
  • the soaps such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, e.g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof
  • the sulfated and sulfonated synthetic detergents particularly those having about eight to 26, and preferably about 12 to 22, carbon atoms to the molecule.
  • suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the alkyl group in a straight or branched chain, e.g., the sodium salts of decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, or hexadecyl benzene sulfonate and the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamyl naphthalene sulfonate, and sodium dinonyl naphthalene sulfonate, sulfated aliphatic alcohols such as sodium lauryl and hexadecyl s
  • anionic surface-active agents which may be employed in the practice of this invention include olefin sulfonates, typically containing eight to 25 carbon atoms.
  • sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids e.g., coconut oil monoglycen'de monosulfate, tallow digylceride monosulfate; and the hydroxy sulfonated higher fatty acid esters such as the higher fatty acid esters of low-molecular weight alkylol sulfonic acids, e.g., oleic acid ester of isethionic acid.
  • Nonionic surface-active agents are those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido, or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.
  • nonionic surface-active agents there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of .isooctyl phenol with about six to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to 15 ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol mono-oleate and mannitan monopalmitate and the condensation products of polypropylene glycol with ethylene oxide.
  • ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol mono-oleate and mannitan monopalmitate and the condensation products of polypropylene glycol with ethylene oxide.
  • Cationic surface-active agents may also be employed. Such agents are those surface-active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.
  • suitable synthetic cationic detergents there may be noted the diamines such as those of the type RNHC H NH wherein R is an alkyl group of about 12 to 22 carbon atoms, such as N-aminoethyl ste'aryl amine and N- aminoethyl myristyl amine; amide-linked amines such as those of the type RCONllC H Nl-l wherein R' is an alkyl group of about 12 to 18 carbon atoms, such as N-amino ethyl-stearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 12 to 18 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain one to three carbon atoms, including such one to three carbon alkyl groups bearing inert substituents, such as phenyl groups, and there is present an
  • Typical quatemary ammonium detergents are ethyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl-stearyl ammonium chloride, trimethylcetyl ammonium bromide, methyl-ethyl-dilauryl ammonium chloride, dimethyl-propylmyristyl ammonium chloride, and the corresponding methosulfates and acetates.
  • the surface-active compounds which are used in the most preferred aspects of this invention are those having anionic or nonionic properties.
  • the most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, di-, and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of the higher alkyl benzene sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates.
  • the particular salt will be suitably selected depending upon the particular formulation and the proportions therein.
  • the surface-active agent is typically present in amount of about 5-95 percent by weight of the detergent composition, preferably -25 percent by weight.
  • the enzyme may be present in powdered form admixed into the detergent formulation.
  • the detergent composition of the invention may include a builder for the detergent.
  • the builder may be any of the water-soluble inorganic builder salts commonly known in the art, or it may be a watersoluble organic sequestering agent such as sodium nitrilotriacetate, or mixtures thereof.
  • the water-soluble inorganic builder salts may be suitable alkali metal, alkaline earth metal, or heavy metal salt or combinations thereof. Ammonium or an ethanolammonium salt in a suitable amount may be added also, but generally the sodium and potassium salts are preferred. Examples are the watersoluble sodium and potassium phosphates, silicates, carbonates, bicarbonates, borates, sulfates and chlorides. Particularly preferred builder salts are the alkaline builder salts such as polyphosphates, silicates, borates, etc.
  • water-soluble inorganic builder salt mixtures used in the detergent compositions it is often preferred to have present a mixture of sodium tripolyphosphate and sodium or potassium bicarbonate, such as a combination or mixture of salts wherein the bicarbonate to tripolyphosophate ratio is selected from the range of about 1:1 to about 3: 1.
  • phase I and phase 11 sodium tripolyphosphate and mixtures thereof may be successfully used in the compositions.
  • the usual commercial tripolyphosphate consists mainly of the phase ll material.
  • the commercial tripolyphosphate material is usually essentially tripolyphosphate, e.g., 87-95 percent, with small amounts, e.g., 4-l3 percent of other phosphates,
  • pyrophosphate and orthophosphate e.g., pyrophosphate and orthophosphate.
  • Sodium tripolyphosphate in its hydrated form may be used also.
  • Trisodium orthophosphate may be used in the amounts indicated.
  • the sodium or potassium bicarbonate is an effective pH buffer.
  • the bicarbonate may be incorporated directly as anhydrous bicarbonate or in the form of sesquicarbonate, a hydrate containing both bicarbonate and carbonate.
  • Suitable builder salts which may be present include the water-soluble sodium and potassium silicates, carbonates, borates, chlorides, and sulfates.
  • the builder salt when present is employed in amount in the range of about 20-90 percent, preferably at least 25 percent, (e. g., 35 to 80 percent) of the detergent composition.
  • the composition may also contain polymeric additives such as sodium carboxymethylcellulose or polyvinyl alcohol (e.g., in amount of about 0.1-5 percent) or other polymeric additives to inhibit redeposition of soil.
  • Minor amounts of optical brighteners may be present, as in proportions in the range of about 0.01 to 0.15 percent; examples of such brighteners are the stilbene brighteners such as sodium-2-sulfo-4-( Z-naphtho- 1,2triazole) stilbene; disodium 4,4-bis(4-anilino-6- morpholino-s-triazin-Z-yl amino) stilbene disulfonate or disodium 4,4-bis(4,6-diani]ino-s-triazin-Zyl-amino) stilbenedisulfonate; and the oxazole brighteners, having for example a l-phenyl-2-benzoxazole ethylene structure. Per fumes, coloring agents, and preservatives may also be included
  • the activator, enzyme and perborate may be added in powdered form to the detergent composition and mixed therewith, as by dry blending.
  • one or more of these ingredients may be protected from the atmosphere or from contact .with the others.
  • the perborate or the activator or the enzyme or each of them may be encapulated or agglomerated by means of a coating of a protective material such as polyvinyl alcohol, a long chain fatty acid (e.g., lauric or stearic) or an amide thereof, a paraffin or a water-soluble or water-dispersible polyethylene glycol (e.g., a solid Carbowax").
  • a protective material such as polyvinyl alcohol, a long chain fatty acid (e.g., lauric or stearic) or an amide thereof, a paraffin or a water-soluble or water-dispersible polyethylene glycol (e.g., a solid Carbowax").
  • a protective material such as polyvin
  • compositions of this invention may be used for washing for short periods, e.g., 5 to 45 minutes, in cool water, e.g., at Q-100- E .9r in warm or hot water, e.g., at 110, 120 140,
  • - or 160 F. or even at or near the boil. They may alsoTif desired, be used for long period soaking at room temperature or in hot water, e.g., for soaking several hours or overnight.
  • a detergent composition contains the following ingredients: 10 percent nonionic detergent consisting of a primary alkanol of an average of 14 to 15 carbon atoms ethoxylated with an average of l 1 mols of ethylene oxide per mol of alkanol (Shell Neodol 45-11); 30 percent anhydrous pentasodium tripolyphosphate (designated TPP below); 5 percent trisodium 1 nitrilotriacetate monohydrate (designated NTA below); 0.5 percent sodium carboxymethyl cellulose (designated CMC below); 0.8 percent of the commercial proteolytic enzyme preparation known as Alcalase"; 16 percent of sodium perborate (NaBO -4H O); 24 percent of metachlorobenzoyldimethylhydantoin (an activator for the perborate); the balance sodium sulfate.
  • the mol ratio of perborate to activator is about 1:1 (specificallyitis 1.1:1).
  • the composition is used for the washing of standard cocoastained fabrics and standard coffee/tea-stained fabrics at F. for a period of 10 minutes, using 1 gram of the composition per liter of water in a Terg-O-Tometer.
  • the effectiveness of the composition is determined by reflectance readings (R,,,) on the fabrics before and after washing, using a Gardner Color Difference Meter for the measurement.
  • the difference in reflectance before and after the washing is reported as AR Cocoa is a proteinaceous substance and cocoa-stained fabric is a commonly used material for testing the effectiveness of detergents for removing protein stains.
  • compositions (B) containing no enzyme, perborate or activator; (C) containing enzyme, but no perborate or activator; and (D) containing the enzyme plus a commercial bleach yielding hypochlorous ion (specifically a mixture of 4/5 potassium dichloroisocyamurate (KDCC) and 1/5 trichloroisocyanuric acid (TCCA).
  • KDCC potassium dichloroisocyamurate
  • TCCA trichloroisocyanuric acid
  • Composition A B C D Detergent 10% 10% 10% 10% 10% 10% TPP 30% 30% 30% 30% NTA 5% 5% 5% CMC 0.5% 0.5% 0.5% 0.5% 0.5% Alcalitsc" 0.8% 0 8% 0.8% Perboratc 16% Activator 24.8%
  • KDCC-TCCA 18.1% Na,SO, 0.5. 0.8. 0.5. 0.8.
  • EXAMPLE 2 In this example an enzyme, sodium perborate and activator are dry-blended with a spray-dried detergent fonnulation having the following composition: sodium linear tridecylbenzenesulfonate 12.6 percent (active ingredient); sodium tallow alcohol sulfate 11.6 percent (active ingredient); TPP 35.8 percent; sodium silicate (of 1:2.35 Na O:SiO ratio) 6.3 percent; CMC 0.5 percent; polyvinyl alcohol 0.2 percent; water (including water of hydration) 8.9 percent; Na SO balance.
  • Two blends are prepared, of the following compositions, in parts by weight:
  • composition A B Spray-dried detergent formulation 1.5 1.5
  • EXAMPLE 3 Examples 2A and B are repeated except that the spray-dried detergent has a different composition and is made in the following manner: In a crutcher there are mixed in the order given 139 parts of water, 213 parts of an aqueous slurry containing about 44 percent sodium linear tridecylbenzenesulfonate, 109.3 parts of anhydrous sodium sulfate, 4.4 parts of borax, 0.13 part of phenolic antioxidant (lphol 033), 71.4 parts of aqueous sodium silicate of 43.5 percent concentration (in which the Na O:SiO mol ratio is 1:2.35), and 157 parts of anhydrous pentasodium tripolyphosphate.
  • the aqueous mixture is spray dried to give a granular composition of the foregoing ingredients having a total moisture content of about 8% percent (including water of hydration).
  • EXAMPLE 4 1n this example there are used compositions as described in example 1A, except that the activator is (A) 1 1.9 percent of tetra acetyl ethylene diamine or (B) 10.4 percent tetra-acetyl hydrazine, or (C) 13.3 percent triacetylcyanurate. For comparison there are also used compositions (D) containing no activator and (E) containing no activator or perborate.
  • compositions are used for the soaking of standard cocoa-stained and standard coffee/tea-stained fabrics, using 1 gram of the composition per liter of water.
  • the water is initially at F. and cools to room temperature (about 76 F.) during the soaking period, which is continued for 18 hours.
  • the test fabrics are removed and dried and the AR,, values are obtained.
  • Pcrborate activators mol ratio 2:1 2:1 2:1 no activator M1 50 0.8. 0.5. OS. 0.8. 0.8.
  • a composition prepared as in example 4A is storage-tested by subjecting it for 3 days to a temperature of 120 F. in a sealed container. During this period there is little, if any, undesirable odor developed. Soaking tests with standard cocoastained and coffee/tea-stained fabrics give substantially identical results for the composition before the 3-day aging at 120 F. and after such aging.
  • EXAMPLE 5 Three separate compositions are prepared as in example 1A, using tetra-acetyl ethylenediamine (i.e., N,N,N'N-tetraacetyl ethylenediamine) as the activator in each case, with the following other changes:
  • tetra-acetyl ethylenediamine i.e., N,N,N'N-tetraacetyl ethylenediamine
  • the amount of activator is changed to 1 1.9 percent and the amount of TPP is changed to 54.5 percent.
  • the amount of activator is changed to 7.4 percent and the amount of perborate is changed to 10.0 percent.
  • EXAMPLE 6 81.8 parts of a spray-dried built detergent formulation are mixed with 0.8 part of Alcalase, 7.4 parts of tetra-acetyl ethylenediamine and 10 parts of sodium perborate.
  • the spraydried formulation contains 10.5 percent sodium linear tridecylbenzene-sulfonate, l percent pentasodium tripolyphosphate, 6 percent sodium silicate (Na O:SiO mol ratio 1235), 8.5 percent sodium chloride, 13 percent sodium sulfate, percent moisture (including water of hydration) and about 1 percent fluorescent brighteners.
  • the resulting composition is tested, using the washing tests described in example 1.
  • the results, in terms of AR,,,, for the cocoa-stained and cofiee/tea-stained fabrics are found to be substantially better than those for the same tests using the same composition except that no perborate or activator is present (these being replaced by an equal weight of sodium sulfate); the latter results are in turn substantially better (in terms of removal of cocoa stain) than when the same composition is used without any enzyme, perborate or activator (these being replaced by an equal weight of sodium sulfate).
  • the composition is also given a soaking test, as described in example 4.
  • the results, in terms of AR for the cocoa-stained and coffee/tea-stained fabrics are found to be substantially better than those for the same tests using the same composition except that no perborate or activator is present (these being replaced by an equal weight of sodium sulfate); the latter results are in turn substantially better than when the same composition is used without any enzyme, perborate or activator (these being replaced by an equal weight of sodium sulfate).
  • a similar superiority for the enzyme-containing composition with perborate plus activator is observed.
  • Example 1A is repeated, except that the composition contains 100 parts of the detergent of example 1, 300 parts of the TPP, 50 parts of the NTA, 5 parts of the CMC, 240 parts of the sodium perborate and 371 parts of m-chlorobenzoylsuccinimide as the activator.
  • Example 1A is repeated using, in place of the activator and perborate, 25 percent of solid m-chloroperbenzoic acid.
  • Example 9 Example 4 is repeated, except that the amount of the perborate is 8 percent and the activator is m-chlorobenzoyldimethylhydantoin,present in amount of 13.9 percent (a 1:1 perborate: activator mol-ratio) AR, values of +l5.4 .(for cocoa-stainedfabric) and +6.9 (for coffee/tea-stained fabric) are obtained.
  • the Alcalase used in the foregoing examples is characterized as having its maximum proteolytic activity at a pH of 8-9. This activity as measured on the commercial enzyme available from Novo lndustri A/S, Copenhagen, Denmark is about 1.5 Anson Units per gram of the enzyme.
  • the commercial enzyme is a raw extract of bacillus subtillis culture and contains about 6 percent of pure crystallized proteolytic material.
  • the Monzyme used in examples 2 and 3 is a mixture of neutral and alkaline proteases (the neutral protease being present in largest amount) containing amylase also; its supplier, Monsanto Chemical Co., states that its proteolytic activity is about 1 million units per gram.
  • sodium perborate tetrahydrate is used; other forms of sodium perborate, such as the monohydrate, may be substituted in each case.
  • the pH of the wash liquor in the foregoing examples is usually within the range of about 8 to about 9.
  • percarboxylic i.e., peroxycarboxylic
  • percarboxylic acids particularly those having chloro or nitro substituents (e.g., m-chloroperoxybenzoic acid, as illustrated in example 6 above, or 2,4-dichloroperoxybenzoic acid). These acids may be protected against deterioration on storage by pelletizing them, preferably with a coating or agglomerating agent such as a low-melting paraffin wax.
  • compositions of the invention containing proteolytic enzymes have given outstanding results.
  • a proteolytic enzyme mixed with an amylase may also be employed. It is within the broader scope of the invention to use other enzymes in place of, or together with, the proteolytic enzymes.
  • stain-attacking enzymes as the amylases (such as the microbial amylases) or other carbohydrases (e.g., maltese saccharase, pectinase, lysozyme, or glycosidases) or the lipases such as microbial lipases, pancreatic lipase, plant lipases or gastric lipase may be used.
  • the Alcalase" may be replaced entirely (or partly) weight-for-weight by either (a) Novo bacterial amylase concentrate having a strength of 397,000 Novo amylase units per gram or (b) Pfizers Lipase P, a pancreatic lipase having a strength of 250 lipase units per gram.
  • a compound acting as a stabilizer against an undesirable type of decomposition of the perborate is particularly desirable.
  • such compounds are the sodium salts of diethylenetriamine pentaacetic acid, ethylene diamine tetra-acetic acid, hydroxyethylethylenediamine triacetic acid or nitrilotriacetic acid.
  • Magnesium silicate may also be present to aid in the stabilizing effect. Minor amounts of these agents, e.g., 5 percent, 1 percent, or less, are effective.
  • a process for removing stains from fabrics which comthe following composition has been added in amount sufficient to provide about i to 40 p.p.m. of available oxygen, said composition consisting essentially of effective amounts of an inorganic peroxygen compound, an activator for the peroxygen compound and about 0.001 to 4 percent of a proteolytic enzyme, said peroxygen compound being present in amount to provide about 1 to 40 p.p.m.
  • said activator having a carboxylic acyl group, said peroxygen compound being one which reacts with said activator to form the corresponding percarboxylic acid on addition of said composition to the wash water, said activator being present in amount effective to so convert said peroxygen compound and thereby increase the bleaching effect of said peroxygen compound 'on coffee/tea stains.
  • composition contains sodium perborate and a water-soluble surface-active nonionic detergent and said activator is a m-chlorobenzyol imid'e.
  • composition contains an organic water-soluble surface-active detergent.
  • composition contains an organic water-soluble surface-active nonionic deteracyl group is a 12.
  • gent 15 A process as in claim 6 in which the composition contains an organic water-soluble surface-active anionic detergent.
  • composition contains at least about one mol of sodium perborate per mol of activator.
  • composition contains pentasodium tripolyphosphate and sodium nitrilotriacetate.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
US726571A 1968-03-07 1968-05-03 Stain removal Expired - Lifetime US3637339A (en)

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US71120368A 1968-03-07 1968-03-07
US72657168A 1968-05-03 1968-05-03
US82910469A 1969-05-29 1969-05-29
US00164463A US3840466A (en) 1968-03-07 1971-07-20 Stain removal

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US00164463A Expired - Lifetime US3840466A (en) 1968-03-07 1971-07-20 Stain removal

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CH (1) CH506617A (enrdf_load_stackoverflow)
DE (1) DE1908905A1 (enrdf_load_stackoverflow)
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GB (1) GB1226493A (enrdf_load_stackoverflow)
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US3779931A (en) * 1970-12-10 1973-12-18 Henkel & Cie Gmbh Compositions useful in the aqueous cold-bleaching of textiles including optical brighteners
DE2338412A1 (de) * 1972-07-31 1974-02-14 Henkel & Cie Gmbh Zur verwendung in wasch- und bleichmitteln geeignetes bleichhilfsmittel und verfahren zu dessen herstellung
US3894960A (en) * 1972-05-22 1975-07-15 Colgate Palmolive Co Activated peroxygen detergent
US3928223A (en) * 1967-10-24 1975-12-23 Colgate Palmolive Co Bleaching and detergent compositions having imide activator and peroxygen bleach
US3974082A (en) * 1972-08-21 1976-08-10 Colgate-Palmolive Company Bleaching compositions
US3975280A (en) * 1974-03-21 1976-08-17 Henkel & Cie G.M.B.H. Storage-stable, readily-soluble detergent additives, coating compositions and process
US3982891A (en) * 1967-10-24 1976-09-28 Colgate-Palmolive Company Bleaching and detergent compositions having imide activator and peroxygen bleach
US3989634A (en) * 1972-09-14 1976-11-02 Tukovy Prumysl, Oborove Reditelstvi Detergent containing a tenside with activating power
US4003700A (en) * 1970-05-01 1977-01-18 Colgate-Palmolive Company Cleaning fabrics
US4009113A (en) * 1971-04-30 1977-02-22 Lever Brothers Company Protection of materials
US4169805A (en) * 1977-10-03 1979-10-02 Fmc Corporation Sulfonic anhydrides as peroxygen activators
US4300897A (en) * 1973-08-24 1981-11-17 Colgate-Palmolive Company Method for bleaching with peroxymonosulfate-based compositions
US4374747A (en) * 1979-04-20 1983-02-22 Lever Brothers Company Bleach products
FR2522676A1 (fr) * 1982-03-04 1983-09-09 Colgate Palmolive Co Composition de blanchiment sans silicate et procede utilisant une telle composition
US4443352A (en) * 1982-03-04 1984-04-17 Colgate-Palmolive Company Silicate-free bleaching and laundering composition
DE3338901A1 (de) * 1982-10-29 1984-05-03 PCUK-Produits Chimiques Ugine Kuhlmann, 92400 Courbevoie, Hauts-de-Seine Waschlauge zum waschen bei niedriger temperatur und zur reinigung von eiweissverschmutzungen
US4483778A (en) * 1983-12-22 1984-11-20 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
US4539130A (en) * 1983-12-22 1985-09-03 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions
US4568476A (en) * 1983-08-15 1986-02-04 Lever Brothers Company Enzymatic machine-dishwashing compositions
US4620936A (en) * 1983-08-15 1986-11-04 Lever Brothers Company Machine-dishwashing compositions
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
US4859800A (en) * 1986-11-06 1989-08-22 The Clorox Company Phenoxyacetate peracid precursors
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
US4956117A (en) * 1986-11-06 1990-09-11 The Clorox Company Phenoxyacetate peracid precursors and perhydrolysis systems therewith
US4957647A (en) * 1986-11-06 1990-09-18 The Clorox Company Acyloxynitrogen peracid precursors
US5049305A (en) * 1986-11-06 1991-09-17 Zielske Alfred G Phenoxyacetate peracid precursors and perhydrolysis systems therewith
US5089167A (en) * 1985-08-21 1992-02-18 The Clorox Company Stable peracid bleaching compositions: organic peracid, magnesium sulfate and controlled amounts of water
US5093021A (en) * 1985-08-21 1992-03-03 The Clorox Company Encapsulated enzyme in dry bleach composition
US5130045A (en) * 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
US5232620A (en) * 1991-02-28 1993-08-03 Fmc Corporation Sodium tripolyphosphate composition and method of producing it
US5234616A (en) * 1987-10-30 1993-08-10 The Clorox Company Method of laundering clothes using a delayed onset active oxygen bleach composition
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
US5296161A (en) * 1986-06-09 1994-03-22 The Clorox Company Enzymatic perhydrolysis system and method of use for bleaching
US5302375A (en) * 1992-11-19 1994-04-12 Colgate-Palmolive Company Oral composition having improved tooth whitening effect
US5328634A (en) * 1986-11-06 1994-07-12 The Clorox Company Acyloxynitrogen peracid precursors
US5629278A (en) * 1995-09-18 1997-05-13 The Proctor & Gamble Company Detergent compositions
US5635103A (en) 1995-01-20 1997-06-03 The Procter & Gamble Company Bleaching compositions and additives comprising bleach activators having alpha-modified lactam leaving-groups
US5635104A (en) 1993-06-24 1997-06-03 The Procter & Gamble Company Bleaching solutions and method utilizing selected bleach activators effective at low perhydroxyl concentrations
US5753138A (en) * 1993-06-24 1998-05-19 The Procter & Gamble Company Bleaching detergent compositions comprising bleach activators effective at low perhydroxyl concentrations
US5879409A (en) * 1996-02-23 1999-03-09 The Procter & Gamble Company Bleach additive and bleaching compositions having glycine anhydride activators
US6197737B1 (en) * 1993-05-20 2001-03-06 The Procter & Gamble Company Bleaching compounds comprising substituted benzoyl caprolactam bleach activators
US20070161535A1 (en) * 2004-06-25 2007-07-12 Bernhard Orlich Production of particle-shaped peroxycarboxylic acid compounds
EP0736085B2 (en) † 1993-12-21 2009-12-16 The Procter & Gamble Company Detergent compositions containing percarbonate, amylase and protease
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DE2422691A1 (de) * 1973-05-14 1974-12-05 Procter & Gamble Stabile bleichmittel
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US4489574A (en) * 1981-11-10 1984-12-25 The Procter & Gamble Company Apparatus for highly efficient laundering of textiles
DE3264685D1 (en) * 1981-11-13 1985-08-14 Unilever Nv Enzymatic liquid cleaning composition
DE3218889A1 (de) * 1982-05-19 1983-11-24 Hoechst Ag, 6230 Frankfurt Verfahren zum gleichzeitigen entschlichten und bleichen von textilmaterial aus cellulosefasern
GR79703B (enrdf_load_stackoverflow) * 1982-10-04 1984-10-31 Colgate Palmolive Co
US4525292A (en) * 1983-03-07 1985-06-25 Cushman Mark E Bleaching detergent compositions comprising sulfosuccinate bleach promoters
USRE32672E (en) * 1985-09-09 1988-05-24 Allergan, Inc. Method for simultaneously cleaning and disinfecting contact lenses using a mixture of peroxide and proteolytic enzyme
US5364554A (en) * 1986-06-09 1994-11-15 The Clorox Company Proteolytic perhydrolysis system and method of use for bleaching
AU603101B2 (en) * 1986-06-09 1990-11-08 Clorox Company, The Enzymatic perhydrolysis system and method of use for bleaching
GB8803113D0 (en) * 1988-02-11 1988-03-09 Bp Chem Int Ltd Anhydrides in detergent compositions
GB8803114D0 (en) * 1988-02-11 1988-03-09 Bp Chem Int Ltd Bleach activators in detergent compositions
US4906399A (en) * 1988-08-19 1990-03-06 Dow Corning Corporation Organosilicon oxygen bleach activator compositions
GB8900525D0 (en) * 1989-01-10 1989-03-08 Procter & Gamble Liquid detergent composition containing enzyme and enzyme stabilization system
EP0596185A1 (en) * 1992-11-06 1994-05-11 The Procter & Gamble Company Stable liquid detergent compositions inhibiting dye transfer
US5783548A (en) * 1992-11-06 1998-07-21 The Procter & Gamble Company Stable liquid detergent compositions inhibiting dye transfer
ATE187765T1 (de) * 1994-04-22 2000-01-15 Procter & Gamble Bleichmittelzusammensetzungen mit protease
DE4430071A1 (de) * 1994-08-25 1996-02-29 Degussa Aktivatoren für anorganische Peroxoverbindungen und sie enthaltende Mittel
US5804543A (en) * 1994-10-11 1998-09-08 The Procter & Gamble Company Detergent compositions with optimized surfactant systems to provide dye transfer inhibition benefits
WO1998024965A1 (en) * 1996-12-04 1998-06-11 Novo Nordisk Biochem North America, Inc. Alkaline enzyme scouring of cotton textiles
CA2285075A1 (en) * 1997-04-04 1998-10-15 Jyoti Varadarajan Low sudsing granular detergent composition containing optimally selected levels of a foam control agent and enzymes
GB9727470D0 (en) * 1997-12-30 1998-02-25 Genencor Int Bv Proteases from gram positive organisms
US6448062B1 (en) 1998-10-30 2002-09-10 Metrex Research Corporation Simultaneous cleaning and decontaminating compositions and methods
US6331515B1 (en) * 2001-08-06 2001-12-18 Colgate-Palmolive Co. Color changing liquid cleaning composition comprising red dyes
FR2880623B1 (fr) * 2005-01-11 2007-03-09 Ceetal Sa Sa Lab Composition solide, divisee, stable, comprenant du phmbg et un liberateur d'oxygene pour le traitement de l'eau
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Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3982891A (en) * 1967-10-24 1976-09-28 Colgate-Palmolive Company Bleaching and detergent compositions having imide activator and peroxygen bleach
US3928223A (en) * 1967-10-24 1975-12-23 Colgate Palmolive Co Bleaching and detergent compositions having imide activator and peroxygen bleach
US4003700A (en) * 1970-05-01 1977-01-18 Colgate-Palmolive Company Cleaning fabrics
US3779931A (en) * 1970-12-10 1973-12-18 Henkel & Cie Gmbh Compositions useful in the aqueous cold-bleaching of textiles including optical brighteners
US4009113A (en) * 1971-04-30 1977-02-22 Lever Brothers Company Protection of materials
US3894960A (en) * 1972-05-22 1975-07-15 Colgate Palmolive Co Activated peroxygen detergent
DE2338412A1 (de) * 1972-07-31 1974-02-14 Henkel & Cie Gmbh Zur verwendung in wasch- und bleichmitteln geeignetes bleichhilfsmittel und verfahren zu dessen herstellung
US3974082A (en) * 1972-08-21 1976-08-10 Colgate-Palmolive Company Bleaching compositions
US3989634A (en) * 1972-09-14 1976-11-02 Tukovy Prumysl, Oborove Reditelstvi Detergent containing a tenside with activating power
US4300897A (en) * 1973-08-24 1981-11-17 Colgate-Palmolive Company Method for bleaching with peroxymonosulfate-based compositions
US3975280A (en) * 1974-03-21 1976-08-17 Henkel & Cie G.M.B.H. Storage-stable, readily-soluble detergent additives, coating compositions and process
US4169805A (en) * 1977-10-03 1979-10-02 Fmc Corporation Sulfonic anhydrides as peroxygen activators
US4374747A (en) * 1979-04-20 1983-02-22 Lever Brothers Company Bleach products
US4430244A (en) 1982-03-04 1984-02-07 Colgate-Palmolive Company Silicate-free bleaching and laundering composition
FR2522676A1 (fr) * 1982-03-04 1983-09-09 Colgate Palmolive Co Composition de blanchiment sans silicate et procede utilisant une telle composition
US4443352A (en) * 1982-03-04 1984-04-17 Colgate-Palmolive Company Silicate-free bleaching and laundering composition
DE3338901A1 (de) * 1982-10-29 1984-05-03 PCUK-Produits Chimiques Ugine Kuhlmann, 92400 Courbevoie, Hauts-de-Seine Waschlauge zum waschen bei niedriger temperatur und zur reinigung von eiweissverschmutzungen
US4568476A (en) * 1983-08-15 1986-02-04 Lever Brothers Company Enzymatic machine-dishwashing compositions
US4620936A (en) * 1983-08-15 1986-11-04 Lever Brothers Company Machine-dishwashing compositions
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
US4539130A (en) * 1983-12-22 1985-09-03 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions
US4483778A (en) * 1983-12-22 1984-11-20 The Procter & Gamble Company Peroxygen bleach activators and bleaching compositions
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
US5093021A (en) * 1985-08-21 1992-03-03 The Clorox Company Encapsulated enzyme in dry bleach composition
US4863626A (en) * 1985-08-21 1989-09-05 The Clorox Company Encapsulated enzyme in dry bleach composition
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
US5089167A (en) * 1985-08-21 1992-02-18 The Clorox Company Stable peracid bleaching compositions: organic peracid, magnesium sulfate and controlled amounts of water
US5296161A (en) * 1986-06-09 1994-03-22 The Clorox Company Enzymatic perhydrolysis system and method of use for bleaching
US4859800A (en) * 1986-11-06 1989-08-22 The Clorox Company Phenoxyacetate peracid precursors
US5049305A (en) * 1986-11-06 1991-09-17 Zielske Alfred G Phenoxyacetate peracid precursors and perhydrolysis systems therewith
US4957647A (en) * 1986-11-06 1990-09-18 The Clorox Company Acyloxynitrogen peracid precursors
US4956117A (en) * 1986-11-06 1990-09-11 The Clorox Company Phenoxyacetate peracid precursors and perhydrolysis systems therewith
US5328634A (en) * 1986-11-06 1994-07-12 The Clorox Company Acyloxynitrogen peracid precursors
US5380457A (en) * 1986-11-06 1995-01-10 The Clorox Company Acyloxynitrogen peracid precursors
US5130045A (en) * 1987-10-30 1992-07-14 The Clorox Company Delayed onset active oxygen bleach composition
US5234616A (en) * 1987-10-30 1993-08-10 The Clorox Company Method of laundering clothes using a delayed onset active oxygen bleach composition
US5232620A (en) * 1991-02-28 1993-08-03 Fmc Corporation Sodium tripolyphosphate composition and method of producing it
US5302375A (en) * 1992-11-19 1994-04-12 Colgate-Palmolive Company Oral composition having improved tooth whitening effect
US6197737B1 (en) * 1993-05-20 2001-03-06 The Procter & Gamble Company Bleaching compounds comprising substituted benzoyl caprolactam bleach activators
US6352562B1 (en) 1993-05-20 2002-03-05 The Procter & Gamble Co. Method of cleaning fabrics using bleaching compounds comprising substituted benzoyl caprolactam bleach activators
US5635104A (en) 1993-06-24 1997-06-03 The Procter & Gamble Company Bleaching solutions and method utilizing selected bleach activators effective at low perhydroxyl concentrations
US5753138A (en) * 1993-06-24 1998-05-19 The Procter & Gamble Company Bleaching detergent compositions comprising bleach activators effective at low perhydroxyl concentrations
EP0736085B2 (en) † 1993-12-21 2009-12-16 The Procter & Gamble Company Detergent compositions containing percarbonate, amylase and protease
US5635103A (en) 1995-01-20 1997-06-03 The Procter & Gamble Company Bleaching compositions and additives comprising bleach activators having alpha-modified lactam leaving-groups
US5803986A (en) * 1995-09-18 1998-09-08 The Procter & Gamble Company Detergent compositions
US5629278A (en) * 1995-09-18 1997-05-13 The Proctor & Gamble Company Detergent compositions
US5879409A (en) * 1996-02-23 1999-03-09 The Procter & Gamble Company Bleach additive and bleaching compositions having glycine anhydride activators
US20070161535A1 (en) * 2004-06-25 2007-07-12 Bernhard Orlich Production of particle-shaped peroxycarboxylic acid compounds
WO2012104861A1 (en) 2011-02-01 2012-08-09 Maharshi Dayanand University Polyvinyl chloride surface co-immobilized with enzymes and uses thereof

Also Published As

Publication number Publication date
BE729544A (enrdf_load_stackoverflow) 1969-08-18
DE1908905A1 (enrdf_load_stackoverflow) 1969-11-27
NL7309965A (enrdf_load_stackoverflow) 1973-09-25
GB1226493A (enrdf_load_stackoverflow) 1971-03-31
NL6903616A (enrdf_load_stackoverflow) 1969-09-09
US3714050A (en) 1973-01-30
NL7309966A (enrdf_load_stackoverflow) 1973-09-25
CH506617A (de) 1971-04-30
US3840466A (en) 1974-10-08
CA943891A (en) 1974-03-19
FR2003378A1 (enrdf_load_stackoverflow) 1969-11-07

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