WO1998018897A1 - Procede pour incorporer des enzymes dans des produits lessiviels en barre - Google Patents

Procede pour incorporer des enzymes dans des produits lessiviels en barre Download PDF

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Publication number
WO1998018897A1
WO1998018897A1 PCT/US1996/017623 US9617623W WO9818897A1 WO 1998018897 A1 WO1998018897 A1 WO 1998018897A1 US 9617623 W US9617623 W US 9617623W WO 9818897 A1 WO9818897 A1 WO 9818897A1
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WO
WIPO (PCT)
Prior art keywords
mixture
enzymes
cooled
preferred
laundry
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Application number
PCT/US1996/017623
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English (en)
Inventor
Rohan Govind Murkunde
Ganapathy Venkata Ramanan
Rodolfo Uri Dimayacyac
Ulpiano Bonifacio Dulguime
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU77207/96A priority Critical patent/AU7720796A/en
Priority to PCT/US1996/017623 priority patent/WO1998018897A1/fr
Publication of WO1998018897A1 publication Critical patent/WO1998018897A1/fr

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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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0069—Laundry bars

Definitions

  • the present invention relates to the process for inco ⁇ orating enzymes into laundry detergent bars.
  • laundry detergent bars comprising synthetic organic surfactants and detergency builders are used in the laundering of clothes.
  • Synthetic laundry bars typically comprise a synthetic anionic surfactant such as the alkali metal salt of an alkyl benzene sulfonic acid or alkali metal salt of an alkyl sulfate and one or more alkaline builders such as alkali metal polyphosphates, carbonates or silicates.
  • Enzymes have been added to laundry bar compositions as a performance additive to improve cleaning performance. Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from surfaces such as textiles, for the prevention of dye transfer in laundering, and for fabric restoration. Typically, laundry bar compositions have contained enzymes such as proteases, cellulases, amylases and lipases, and mixtures thereof. See for example, PH 9809, Vasquez, issued March 26, 1976; and EP 425214 Lever, published May 2, 1991. Enzymes for detergent use are primarily provided in the form of prills.
  • a third problem with inco ⁇ orating enzymes into laundry bar compositions containing soap is that a milling step in the manufacturing process adversely affects the effectiveness of enzymes for use as a performance additive in the bar composition. Milling is essential to achieve good physical properties. Without being limited by theory, it is believed that the high shear action worked on the bar composition in a mill destroys the enzyme prill integrity and exposes the enzymes to attack by anionic surfactants.
  • the present invention is directed to a process for making a laundry detergent bar composition including enzymes, comprising the following steps:
  • step 2 milling the mixture of step 1 , whereby said mixture is cooled to a temperature of from about 35° to about 50°C; 3. adding enzymes and the cooled mixture of step 2 in a plodder; and
  • alkyl means a hydrocarbyl moiety which is straight or branched, saturated or unsaturated. Unless otherwise specified, alkyl are preferably saturated or unsaturated with double bonds, preferably with one or two double bonds.
  • tallow is used herein in connection with materials with fatty acid mixtures which typically are linear and have an approximate carbon chain length distribution of 2% C14, 29% C16, 23% Cjg, 2% palmitoleic, 41% oleic, and 3% linoleic (the first three fatty acids listed are saturated). Other mixtures with similar distribution, such as those from palm oil and those derived from various animal tallow and lard, are also included within the term tallow.
  • the tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.
  • coconut oil is used herein in connection with materials with fatty acid mixtures which typically are linear and have an approximate carbon chain length distribution of about 8% Cg, 7% C IQ, 48% C 2 , 17% C14, 9% Ci6, 2% Ci g, 7% oleic, and 2% linoleic (the first six fatty acids listed being saturated).
  • Other sources having similar carbon chain length distribution in their fatty acids, such as palm kernel oil and babassu oil, are included within the term coconut oil.
  • Synthetic anionic surfactants which are suitable for use herein include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium 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. (Included in the term "alkyl” is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg.
  • alkyl benzene sulfonates such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene 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.
  • linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11.13 LAS.
  • the alkali metal salts, particularly the sodium salts of these surfactants are preferred.
  • Alkyl benzene sulfonates and processes for making them are disclosed in U.S. Patent Nos. 2,220,099 and
  • Preferred synthetic anionic surfactants are CJO-18 unear alkyl benzene sulfonates, CiO-14 alkyl glyceryl ether sulfonates, and Cjo-ig alkyl sulfates.
  • the amount of synthetic anionic surfactant in the composition herein is from about 1% to about 15%, preferably from about 2% to about 10%.
  • salts of fatty acids means salts of fatty acids.
  • the fatty acids are linear or branched containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms.
  • the average carbon chain length for the fatty acid soaps is from about 12 to about 18 carbon atoms, preferably from about 14 to about 16 carbon atoms.
  • Preferred salts of the fatty acids are alkali metal salts, such as sodium and potassium, especially sodium. Also preferred salts are ammonium and alkylolammonium salts.
  • the fatty acids of soaps useful in the subject invention bars are preferably obtained from natural sources such as plant or animal esters; examples include coconut oil, palm oil, palm kernel oil, olive oil, peanut oil, corn oil, sesame oil, rice bran oil, cottonseed oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, grease, lard, and mixtures thereof.
  • Preferred fatty acids are obtained from coconut oil, tallow, palm oil (palm stearin oil), palm kernel oil, and mixtures thereof.
  • Fatty acids can be synthetically prepared, for example, by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
  • Alkali metal soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.
  • Preferred soap raw materials for the subject invention bars are soaps made from mixtures of fatty acids from tallow and coconut oil. Typical mixtures have tallowxoconut fatty acid ratios of 85:15, 80:20, 75:25, 70:30, and 50:50; preferred ratios are about 80:20 to 65:35.
  • Preferred soap raw materials for the subject invention are neat soaps made by kettle (batch) or continuous saponification.
  • Neat soaps typically comprise from about
  • soap raw material is soap noodles or flakes, which are typically neat soap which has been dried to a water content of from about 10% to about 20%.
  • the other components above are proportionally concentrated. Soaps are present in the compositions herein at levels of no more than about
  • a preferred level of soap is from about 20% to about 70%, more preferably 30% to about 50%.
  • Enzymes Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH- activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial and fungal enzymes are preferred, such as bacterial amylases and proteases. Enzymes are typically at levels up to about 5%, preferably about 0.5-3%, most preferably from about 0.01% to about 1% by weight of the composition. Builders
  • the laundry bars of the invention contains from about 2% to about 30%, preferably from about 3% to about 20% detergent builder.
  • These detergent builders can be, for example, water-soluble alkali-metal salts of phosphate, pyrophosphates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof.
  • Preferred builders are a water-soluble alkali-metal salt of tripolyphosphate, and a mixture of tripolyphosphate and pyrophosphate.
  • the builder can also be a non- phosphate detergent builder. Specific examples of non-phosphate, inorganic detergency builders include water-soluble inorganic carbonate and bicarbonate salts.
  • alkali metal e.g., sodium and potassium carbonates, bicarbonates, and silicates are particularly useful herein.
  • Specific preferred examples of builders include sodium tripolyphosphates (STPP) and tetra sodium pyrophosphates (TSPP), and mixtures thereof.
  • Other specifically preferred examples of builders include zeolites and polycarboxylates, and co-polymers of acrylic acid and maleic acid.
  • compositions of the subject invention comprise from about 10% to about 40% moisture, preferably from about 15% to about 30% moisture, more preferably from about 19% to about 27% moisture in the final bar composition.
  • Adjunct Ingredients The detergent bars of the present invention can contain other optional ingredients commonly used in detergent products.
  • optional surfactants e.g. nonionic, zwitterionic and amphoteric surfactants
  • optional alkaline builders such as sodium carbonate trisodium phosphate sodium silicate, etc. and other ingredients useful herein appears in U.S. Pat. No. 3,664,961, issued to Norris on May 23, 1972, and EP 550,652, published on April 16, 1992.
  • Such optional surfactants if present, can be included at levels up to a total of about 10%, preferably about 0.5-5%.
  • a preferred optional component in the laundry bar is a bleach component.
  • the bleaching component can be a source of "OOH group, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate.
  • Sodium percarbonate (2Na2C ⁇ 3*3H2 ⁇ 2) is preferred since it has a dual function of both a source of HOOH and a source of sodium carbonate.
  • Another optional bleaching component is a peracid per se, such as a formula: CH3(CH2)w-NH-C(O)-(CH2) z CO3H wherein z is from 2 to 4 and w is from 4 to 10.
  • the bleaching component can contain, as a bleaching component stabilizer, a chelating agent of polyaminocarboxylic acids, polyaminocarboxylates such as ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid, and ethylenediaminodisuccinic acid, and their salts with water-soluble alkali metals.
  • the bleach components if any, can be added to the bar, if any, at a level up to 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 6%.
  • a preferred adjunct ingredient is a fabric softening clay, preferably a smectite- type clay and a clay flocculating agent, having a high molecular weight greater than about 100,000.
  • Soil suspending agents can be optionally used. In the present invention, their use is balanced with the fabric softening clay/clay flocculating agent combination to provide optimum cleaning and fabric softening performance.
  • One such soil suspending agent is an acrylic/maleic copolymer, commercially available as Sokolan®, from BASF Co ⁇ .
  • Other soil suspending agents include polyethylene glycols having a molecular weight of about 400 to 10,000, and ethoxylated mono- and polyamines, and quaternary salts thereof.
  • a particularly preferred optional component of the present invention is a detergent chelant.
  • Such chelants are able to sequester and chelate alkali cations (such as sodium, lithium and potassium), alkali metal earth cations (such as magnesium and calcium), and most importantly, heavy metal cations such as iron, manganese, zinc and aluminum.
  • Preferred cations include sodium, magnesium, zinc, and mixtures thereof.
  • the detergent chelant is particularly beneficial for maintaining good cleaning performance and improved surfactant mileage, despite the presence of the softening clay and the clay flocculating agent.
  • the detergent chelant is preferably a phosphonate chelant, particularly one selected from the group consisting of diethylenetriamine penta(methylene phosphonic acid), ethylene diamine tetra(methylene phosphonic acid), and mixtures and salts and complexes thereof, and an acetate chelant, particularly one selected from the group consisting of diethylenetriamine penta(acetic acid), ethylene diamine tetra(acetic acid), and mixtures and salts and complexes thereof.
  • Particularly preferred are sodium, zinc, magnesium, and aluminum salts and complexes of diethylenetriamine penta(methylene phosphonate) diethylenetriamine penta (acetate), and mixtures thereof.
  • such salts or complexes have a molar ratio of metal ion to chelant molecule of at least 1 :1, preferably at least 2:1.
  • the detergent chelant can be included in the laundry bar at a level up to about
  • Another preferred additional component of the laundry bar is fatty alcohol having an alkyl chain of 8 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms.
  • a preferred fatty alcohol has an alkyl chain predominantly containing from 16 to 18 carbon atoms, so-called "high-cut fatty alcohol,” which can exhibit less base odor of fatty alcohol relative to broad cut fatty alcohols.
  • fatty alcohol if any, is present in the laundry bar at up to a level of 10%, more preferably from about 0.75% to about 6%, most preferably from about 2% to about 5%.
  • the fatty alcohol is generally added to a laundry bar as free fatty alcohol. However, low levels of fatty alcohol can be introduced into the bars as impurities or as unreacted starting material.
  • laundry bars based on coconut fatty alkyl sulfate can contain, as unreacted starting material, from 0.1% to 3.5%, more typically from 2% to 3%, by weight of free coconut fatty alcohol on a coconut fatty alkyl sulfate basis.
  • Another preferred optional component in the laundry bar is a dye transfer inhibiting (DTI) ingredient to prevent diminishing of color fidelity and intensity in fabrics.
  • DTI ingredient can include polymeric DTI materials capable of binding fugitive dyes to prevent them from depositing on the fabrics, and decolorization DTI materials capable of decolorizing the fugitives dye by oxidation.
  • An example of a decolorization DTI is hydrogen peroxide or a source of hydrogen peroxide, such as percarbonate or perborate.
  • Non-limiting examples of polymeric DTI materials include polyvinylpyrridine N-oxide, polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymer, and mixtures thereof. Copolymers of N- vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPI") are also preferred for use herein.
  • the amount of DTI included in the subject compositions, if any, is about 0.05-5%, preferably about 0.2-2%.
  • Another preferred optional component in the laundry bar is a secondary fabric softener component in addition to the softening clay.
  • Such materials can be used, if any, at levels of about 0.1% to 5%, more preferably from 0.3%o to 3%, and can include: amines of the formula R4R5R6N, wherein R4 is C5 to C22 hydrocarbyl, R5 and R6 are independently Cl to C10 hydrocarbyl.
  • One preferred amine is ditallowmethyl amine; complexes of such amines with fatty acid of the formula R7COOH, wherein R7 is C9 to C22 hydrocarbyl, as disclosed in EP No. 0,133,804; complexes of such amines with phosphate esters of the formula R8 ⁇ -P(O)(OH)-OR ⁇ .
  • Rg and R9 are independently Cl to C20 alkyl of alkyl ethoxylate of the formula -alkyl-(OCH2CH2); cyclic amines such as imidazolines of the general formula 1 -(higher alkyl) amido (lower alkyl)-2-(higher alkyl)imidazoline, where higher alkyl is from 12 to 22 carbons and lower alkyl is from 1 to 4 carbons, such as described in UK Patent Application GB 2,173,827; and quaternary ammonium compounds of the formula RioRl lRl2Rl3N + X", wherein RlO is alkyl having 8 to 20 carbons, R ⁇ ⁇ is alkyl having 1 to 10 carbons, R12 and R13 are alkyl having 1 to 4 carbons, preferably methyl, and X is an anion, preferably Cl" or Br, such as C 12-13 alkyl trimethyl ammonium chloride
  • Sodium sulfate is a well-known filler that is compatible with the compositions of this invention. It can be a by-product of the surfactant sulfation and sulfonation processes, or it can be added separately. Other filler materials include bentonite and talc.
  • Calcium carbonate (also known as Calcarb) is also a well known and often used filler component of laundry bars.
  • Fillers include minerals, such as talc and hydrated magnesium silicate-containing minerals, where the silicate is mixed with other minerals, e.g., old mother rocks such as dolomite. Filler materials are typically used, if included, at levels up to 40%, preferably from about 5% to about 30%.
  • Binding agents for holding the bar together in a cohesive form can also be used, and include natural and synthetic starches, gums, thickeners, and mixtures thereof. Such materials, if included, are typically at levels up to about 20%, preferably about 0.5-10%. Glycerine is commonly inco ⁇ orated in laundry bar compositions. If included, it is typically at concentrations up to about 3%, preferably about 0.5-1.5%.
  • Optical brighteners are also preferred optional ingredients in laundry bars of the present invention. Preferred optical brighteners are diamino stilbene, distyrilbiphenyl-type optical brighteners.
  • Such brighteners are 4,4'-bis ⁇ [4-anilino-6-bis(2-hydoxyethyl) amino- 1 ,3 ,5 -trizin-2-y 1] amino ⁇ stilbene- 2,2'-disulfonic acid disodium salt, 4-4'-bis(2-sulfostyryl) biphenyl and 4,4'-bis[(4- anilino-6-mo ⁇ holino-l,3,5-triazin-2-yl) amino]stilbene-2,2'-disulfonic acid disodium salt.
  • Such optical brighteners, or mixtures thereof can be used at levels in the bar of from about 0.05% - 1.0%.
  • Dyes, pigments, germicides, and perfumes can also be added to the bar composition. If included, they are typically at levels up to about 0.5%.
  • Another optional component of the subject invention composition is a photobleach material, particularly phthalocyanine photobleaches which are described in U.S. Patent 4,033,718 issued July 5, 1977, inco ⁇ orated herein by reference.
  • Preferred photobleaches are metal phthalocyanine compounds, the metal preferably having a valance of +2 or +3; zinc and aluminum are preferred metals.
  • Such photobleaches are available, for example, under the tradename TINOLUS or as zinc phthalocyanine sulfonate.
  • the photobleach components, if included, are typically in the subject compositions at levels up to about 0.02%, preferably from about 0.001% to about 0.015%, more preferably from about 0.002% to about 0.01%.
  • the detergent laundry bars of the present invention can be processed in conventional soap or detergent bar making equipment with some or all of the following key equipment: blender/mixer, mill, refining plodder, two- stage vacuum plodder, logo printer/cutter, cooling tunnel and wrapper.
  • blender/mixer e.g. Sigma mixer
  • refining plodder e.g., a high shear mixer
  • logo printer/cutter e.g., logo printer/cutter
  • cooling tunnel and wrapper e.g., a typical process the raw materials are mixed in the blender.
  • Neat soap and water are added to a high shear mixer (e.g. Sigma mixer) and mixed for about 5 minutes.
  • Alkyl benzene sulfonic acid (when used) is added into the above mixture after adding sodium carbonate, and the resulting partly neutralized mixture is mechanically worked to effect homogeneity and to complete the neutralization of the mixture. Once the neutralization reaction is completed, builder and any additional adjunct ingredients are added and mixed well.
  • polyphosphate can be used as an alkaline salt in the neutralization.
  • the high shear mixing can take from one minute to one hour, with the usual mixing time being from about two to twenty minutes. It is critical that the temperature be from about 60°-75°C.
  • a preferred high shear mixer is the Sigma Mixer, manufactured by Mazzoni.
  • the blender mix is charged to a surge tank.
  • the product is conveyed from the surge tank to the mill.
  • the mixture is cooled to a temperature of from about 35°-50°C.
  • the mixture is cooled by the running of cool/chilled water through the mill, which in turn cools the mixture being milled.
  • the mixture is blended with enzymes in a low to medium shear mixer.
  • a preferred low to medium shear mixer is a L ⁇ edige KM mixer or a ribbon mixer. It is critical that the enzyme be blended at this point in the process and that the temperature of the mixture when the enzyme is blended in is from about
  • both the milled flakes formed from the milled mixture and the enzymes can be added into the hopper of the plodder directly, without mixing in a low to medium shear mixer.
  • the product is then conveyed to a duplex vacuum plodder, operating at high vacuum, e.g. 400 to 740 mm of mercury vacuum, so that entrapped air is removed.
  • the product is extruded and cut to the desired bar length, and printed with the product brand name.
  • the printed bar can be cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage.
  • the mixture is then milled, in which the mixture's temperature is lowered to about 35°-50°C in a 4-roll mill. Clearances of 4/8/12 ( 1/1000 in.) are maintained between 4th and 3rd, 3rd and 2nd, and 2nd and 1st rolls, respectively, during the milling.
  • the enzymes are added to the mixture in a KM mixer and mixed for about 1 minute. Preferably, the amount of enzymes is from about 0.01% to about 1% of the final bar composition.
  • One preferred enzyme is Savinase 4TTM, by Novo Nordisk.
  • the temperature of the mixture as the enzymes are being added is about 35°-50°C.
  • the mixture is then conveyed to a duplex vacuum plodder, and bars are formed by extrusion.
  • Another preferred process is adding the enzymes to the milled mixture, taking the milled mixture, which is in the form of flakes, and directly adding the milled flakes with the enzymes directly into the hopper of the plodder, plod the mixture and then extrude the bar.

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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)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un nouveau procédé permettant d'incorporer des enzymes dans des compositions de détergent lessiviel en barre, en réduisant au minimum la perte de stabilité enzymatique pendant le processus de fabrication de la barre. L'invention concerne aussi un procédé de fabrication d'une composition de détergent en barre comprenant des enzymes. Le procédé consiste à 1) mélanger du savon, un tensio-actif synthétique et d'autres ingrédients facultatifs dans un mélangeur à cisaillement élevé, à une température comprise entre environ 60° et environ 75 °C; 2) concasser le mélange obtenu à l'étape 1 et refroidir ledit mélange à une température comprise entre environ 35° et environ 50 °C; 3) placer dans une boudineuse des enzymes et le mélange refroidi obtenu à l'étape 2; et 4) procéder au boudinage du mélange obtenu à l'étape 3 pour former des barres.
PCT/US1996/017623 1996-10-31 1996-10-31 Procede pour incorporer des enzymes dans des produits lessiviels en barre WO1998018897A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU77207/96A AU7720796A (en) 1996-10-31 1996-10-31 Process for incorporating enzymes into laundry bars
PCT/US1996/017623 WO1998018897A1 (fr) 1996-10-31 1996-10-31 Procede pour incorporer des enzymes dans des produits lessiviels en barre

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Application Number Priority Date Filing Date Title
PCT/US1996/017623 WO1998018897A1 (fr) 1996-10-31 1996-10-31 Procede pour incorporer des enzymes dans des produits lessiviels en barre

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000005332A1 (fr) * 1998-07-22 2000-02-03 The Procter & Gamble Company Procede de fabrication d'un pain de detergent pour laver le linge
WO2006045310A1 (fr) * 2004-10-28 2006-05-04 Novozymes A/S Barres de lessive a stabilite au stockage amelioree

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798181A (en) * 1970-11-03 1974-03-19 Colgate Palmolive Co Enzymatic detergent bar
EP0425214A2 (fr) * 1989-10-23 1991-05-02 Unilever Plc Compositions détergentes contenant un enzyme et leur utilisation
GB2271120A (en) * 1992-09-30 1994-04-06 Unilever Plc Shaped detergent composition comprising mutant subtilisin
GB2274849A (en) * 1993-02-05 1994-08-10 Unilever Plc Detergent bars containing enzymes.
WO1995027036A1 (fr) * 1994-03-30 1995-10-12 The Procter & Gamble Company Detergent en pains de lessive contenant de l'argile adoucissant le tissu et de la cellulase

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798181A (en) * 1970-11-03 1974-03-19 Colgate Palmolive Co Enzymatic detergent bar
PH9809A (en) * 1970-11-03 1976-03-26 S Vasquez Enzymatic detergent bar
EP0425214A2 (fr) * 1989-10-23 1991-05-02 Unilever Plc Compositions détergentes contenant un enzyme et leur utilisation
GB2271120A (en) * 1992-09-30 1994-04-06 Unilever Plc Shaped detergent composition comprising mutant subtilisin
GB2274849A (en) * 1993-02-05 1994-08-10 Unilever Plc Detergent bars containing enzymes.
WO1995027036A1 (fr) * 1994-03-30 1995-10-12 The Procter & Gamble Company Detergent en pains de lessive contenant de l'argile adoucissant le tissu et de la cellulase

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000005332A1 (fr) * 1998-07-22 2000-02-03 The Procter & Gamble Company Procede de fabrication d'un pain de detergent pour laver le linge
WO2006045310A1 (fr) * 2004-10-28 2006-05-04 Novozymes A/S Barres de lessive a stabilite au stockage amelioree

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