WO2006045310A1 - Laundry bars with improved storage stability - Google Patents
Laundry bars with improved storage stability Download PDFInfo
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- WO2006045310A1 WO2006045310A1 PCT/DK2005/000674 DK2005000674W WO2006045310A1 WO 2006045310 A1 WO2006045310 A1 WO 2006045310A1 DK 2005000674 W DK2005000674 W DK 2005000674W WO 2006045310 A1 WO2006045310 A1 WO 2006045310A1
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- enzyme
- laundry
- enzymes
- boronic acid
- bars
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Classifications
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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
- 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
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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
- C11D3/16—Organic compounds
- C11D3/166—Organic compounds containing borium
-
- 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
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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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/04—Compositions of detergents based essentially on soap containing compounding ingredients other than soaps
- C11D9/22—Organic compounds, e.g. vitamins
Definitions
- TITLE LAUNDRY BARS WITH IMPROVED STORAGE STABILITY
- the present invention relates to laundry bars with improved enzyme stability and to a process for preparing said laundry bars and to uses of the laundry bars.
- GB 2186883 describes laundry bars with a water content of 10-33% and containing proteases in which the proteolytic enzyme is stabilized by a mixture of a boron compound, a polyol, an organic acid or its alkali metal salt, and an alkali metal salt of an inorganic acid which is not a boron compound.
- WO 98/54285 describes high-moisture protease containing laundry bars with improved prote ⁇ ase stability.
- the improved stability is obtained by adding a stabilizing agent made of a borate compound in conjunction with a polyol, a carboxylate salt, a carboxylic acid, or mixtures thereof.
- enzyme stability of a cellulase is improved by providing a laundry bar com ⁇ prising from about 0.5% to about 60% synthetic detergent surfactant, about 4% or less mois ⁇ ture in the finished bar composition, and from about 0.1% to about 10% non-liquid, thixotropic binding agents, as well as the cellulase enzyme.
- WO 98/18897 describes a process for incorporating enzymes into laundry detergent bar com- positions that minimizes the loss of enzyme stability during the manufacturing process of the bar. This is achieved by a process in which the enzyme prills are added after milling and cool ⁇ ing and then plodding the mixture.
- One object of the present invention is to provide enzyme containing laundry bars with im- proved storage stability.
- a further object of the present invention is to provide a process for manufacturing of a dry formulation such as laundry bars wherein the enzyme can be added in the initial phase of the laundry bar manufacturing process and still maintain a significant en ⁇ zyme activity after manufacturing.
- a first aspect of the present invention is a laundry bar comprising enzymes and phenyl boronic acid derivatives substituted in the para-position with a carbonyl group adjacent to the phenyl boronic acid.
- a second aspect of the present invention is a process for incorporating enzymes into laundry bars comprising the steps of: a) preparing a mixture of a detergent matrix and enzymes and a phenyl boronic acid derivative of the following formula:
- step (a) plodding the mixture from step (a);
- the present invention is further related to the use of the laundry bars of the invention.
- laundry bar includes soap bars, combo bars, syndet bars and detergent bars.
- a laun ⁇ dry bar is for hand washing laundry.
- the present invention relates to laundry bars which contain enzymes incorporated therein.
- the present invention is particularly concerned with the storage stability of laundry bars.
- a phenyl boronic acid derivative substituted in the para-position with a carbonyl group adjacent to the phenyl boronic acid e.g. 4-formylphenylboronic acid, 4-FPBA, is incorporated into the laundry bar to stabilize the enzyme.
- the present invention further relates to an improved process for incorporating enzymes into laundry bars by which process good enzyme stability and good mixing and thus a more homo ⁇ geneous incorporation is obtained at the same time.
- dry enzymes in the form of en- zyme granules as enzyme granules provide a protective layer around the enzymes which pre ⁇ vents hostile compounds of attacking the enzyme, whereas the liquid enzymes are completely exposed to hostile compounds in the detergent matrix when added, therefore the laundry bar industry has been reluctant to use liquid enzymes in the production of laundry bars due to the significant loss in enzyme stability.
- the granules can be added after said process steps, as in WO 98/18897 resulting in uneven distribution of enzymes in the laundry bars and still facing the plodding step where they still can get torn apart.
- the process of the invention allows the enzyme to be either on a granulate form or as a liquid formulation and to be added before or during the mixing step as opposed to the method de ⁇ scribed in WO 9854285.
- liquid enzyme formulations most likely reduces the mechanical stress on the enzyme product compared to when enzyme granulates is used like in. the con ⁇ ventional enzyme laundry bars. This might in turn reduce the amount of frictional heat devel ⁇ oped during mixing.
- the liquid enzyme formulation is also more quickly distributed in the soap mass resulting in a more homogeneous product and in a shorter time, thereby decreasing pro ⁇ duction time of the laundry bar.
- Laundry bars are mainly being sold in the third world and the cost of the laundry bars is there ⁇ fore a very important factor.
- the laundry bar of the present invention comprises a detergent matrix, enzymes and a phenyl boronic acid derivative substituted in the para-position with a carbonyl group adjacent to the phenyl boronic acid.
- Moisture content Moisture enhances the mixture of the bar ingredients.
- Moisture e.g. water can be added to the mixture by being included with an ingredient and/or as free water added to the bar mixture.
- the appearance of the laundry bars prepared with enzymes of the invention is significantly im ⁇ proved compared to known bars comprising enzyme stabilizers.
- bars stabi- lized with a phenyl boronic acid derivative substituted in the para-position with a carbonyl group adjacent to the phenyl boronic acid with bars stabilized with known stabilizer systems such as Borax together with MGP the bars stabilized with Borax and MGP feel slippery and gritty, whereas the bars stabilized with a phenyl boronic acid derivative substituted in the para-position with a carbonyl group adjacent to the phenyl boronic acid feel hard, smooth and non-slippery as bars without enzyme stabilizers added.
- the bars prepared with liquid enzyme have a more homogeneous look, compared to bars prepared with enzyme granules where granules can be visually spotted.
- the laundry bar of the invention comprises enzymes, a phenyl boronic acid derivative and a detergent matrix.
- the enzymes that can be stabilized by the process according to the invention are any enzyme which exerts their effects during the hand-washing process, e.g. having a cleaning, fabric care, anti-redeposition and stain removing effect in a hand-wash application and which enzymes are added for such a purpose.
- the enzyme in the context of the present invention may be any enzyme or combination of dif- ferent enzymes. Accordingly, when reference is made to "an enzyme” this will in general be understood to include one enzyme or a combination of enzymes.
- enzyme variants are included within the meaning of the term "enzyme”. Examples of such enzyme variants are disclosed, e.g. in EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and WO 94/02618 (Gist-Brocades NV).
- Enzymes can be classified on the basis of the handbook Enzyme Nomenclature from NC- IUBMB, 1992), see also the ENZYME site at the internet: http://www.expasy.ch/enzyme/.
- EN ⁇ ZYME is a repository of information relative to the nomenclature of enzymes. It is primarily based on the recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology (IUB-MB), Academic Press, Inc., 1992, and it describes each type of characterized enzyme for which an EC (Enzyme Commission) number has been provided (Bairoch A. The ENZYME database, 2000, Nucleic Acids Res 28:304-305). This IUB- MB Enzyme nomenclature is based on their substrate specificity and occasionally on their mo ⁇ lecular mechanism; such a classification does not reflect the structural features of these en- zymes.
- glycoside hydrolase enzymes such as endoglucanase, xy- lanase, galactanase, mannanase, dextranase and alpha-galactosidase
- endoglucanase xy- lanase
- galactanase galactanase
- mannanase mannanase
- dextranase alpha-galactosidase
- alpha-galactosidase alpha-galactosidase
- oxi- doreductases EC 1.-.-.-
- transferases EC 2.-.-.-
- hydrolases EC 3.-.-.-
- lyases EC 4.-.-.-
- isomerases EC 5.-.-.-
- ligases EC 6.-.-.-).
- Particularly suitable enzymes include lyases or hydrolases (EC 3.-.-.-), particularly proteases, amylases, lipases, pectate lyases, carbohydrases and/or cellulases.
- Preferred oxidoreductases in the context of the invention are peroxidases (EC 1.11.1), laccases (EC 1.10.3.2) and glucose oxidases (EC 1.1.3.4)].
- An Example of a commercially available oxidoreductase (EC 1.-.-.-) is GluzymeTM (enzyme available from Novozymes A/S). Further oxidoreductases are available from other suppliers.
- Preferred transferases are transferases in any of the following sub-classes: a Transferases transferring one-carbon groups (EC 2.1); b transferases transferring aldehyde or ketone residues (EC 2.2); acyltransferases (EC 2.3); c glycosyltransferases (EC 2.4); d transferases transferring alkyl or aryl groups, other that methyl groups (EC 2.5); and e transferases transferring nitrogeneous groups (EC 2.6).
- a most preferred type of transferase in the context of the invention is a transglutaminase (protein-glutamine ⁇ -glutamyltransferase; EC 2.3.2.13).
- transglutaminases are described in WO 96/06931 (Novo Nordisk
- Preferred hydrolases in the context of the invention are: carboxylic ester hydrolases (EC
- phytases examples include Bio-FeedTM Phytase (Novozymes), RonozymeTM P (DSM Nutritional Products), NatuphosTM (BASF), FinaseTM (AB Enzymes), and the PhyzymeTM product series (Danisco).
- Other preferred phytases include those described in WO 98/28408, WO 00/43503, and WO 03/066847.
- carbohydrase is used to denote not only enzymes capable of breaking down carbohydrate chains (e.g. starches or cellulose) of especially five- and six- membered ring structures (i.e. glycosidases, EC 3.2), but also enzymes capable of isomerizing carbohydrates, e.g. six-membered ring structures such as D-glucose to five-membered ring structures such as D-fructose.
- Carbohydrases of relevance include the following (EC numbers in parentheses): ⁇ -amylases (EC 3.2.1.1), ⁇ -amylases (EC 3.2.1.2), glucan 1 ,4- ⁇ -glucosidases (EC 3.2.1.3), endo-1 ,4-beta-glucanase (cellulases, EC 3.2.1.4), endo-1 ,3(4)- ⁇ -glucanases (EC 3.2.1.6), endo-1 ,4- ⁇ -xylanases (EC 3.2.1.8), dextranases (EC 3.2.1.11), chitinases (EC 3.2.1.14), poly ⁇ galacturonases (EC 3.2.1.15), lysozymes (EC 3.2.1.17), ⁇ -glucosidases (EC 3.2.1.21), ⁇ - galactosidases (EC 3.2.1.22), ⁇ -galactosidases (EC 3.2.1.23), amylo-1
- the enzyme is a protease.
- the enzyme is a bacterial protease.
- examples of commercially available proteases include KannaseTM, EverlaseTM, EsperaseTM, AlcalaseTM, Alcalase UltraTM, NeutraseTM, DurazymTM, SavinaseTM, Savinase UltraTM, OvozymeTM, PyraseTM, Pancreatic Trypsin NOVO (PTN), Bio-FeedTM Pro and Clear- LensTM Pro (all available from Novozymes A/S, Bagsvaerd, Denmark).
- Other preferred proteases include those described in WO 01/58275 and WO 01/58276.
- proteases include RonozymeTM Pro, MaxataseTM, MaxacalTM, MaxapemTM, OpticleanTM, PropeaseTM, PurafectTM and Purafect OxTM (available from Genencor International Inc., Gist-Brocades, BASF, or DSM Nutritional Products).
- lipases include LipexTM, LipoprimeTM, LipopanTM, LipolaseTM, LipolaseTM Ultra, LipozymeTM, PalataseTM, ResinaseTM, NovozymTM 435 and LecitaseTM (all available from Novozymes A/S).
- lipases include LumafastTM (Pseudomonas mendocina lipase from Genencor International Inc.); LipomaxTM (Ps. pseudoalcaligenes lipase from Gist- Brocades/Genencor Int. Inc.; and Bacillus sp. lipase from Solvay enzymes. Further lipases are available from other suppliers.
- carbohydrases examples include Alpha-GalTM, Bio-FeedTM Alpha, Bio-FeedTM Beta, Bio-FeedTM Plus, Bio-FeedTM Wheat, Bio-FeedTM Z, NovozymeTM 188, CarezymeTM, CelluclastTM, CellusoftTM, CelluzymeTM, CeremylTM, CitrozymTM, DenimaxTM, DezymeTM, DextrozymeTM, DuramylTM, EnergexTM, FinizymTM, FungamylTM, GamanaseTM, GlucanexTM, LactozymTM, LiquezymeTM, MaltogenaseTM, NatalaseTM, PentopanTM, PectinexTM, PromozymeTM, PulpzymeTM, NovamylTM, TermamylTM, AMGTM (Amyloglucosidase Novo), MaltogenaseTM, SweetzymeTM and AquazymTM (all available from Novozymes A/S).
- carbohydrases are available from other suppliers, such as the RoxazymeTM and RonozymeTM product series (DSM Nutritional Products), the AvizymeTM, PorzymeTM and GrindazymeTM product series (Danisco, Finnfeeds), and NatugrainTM (BASF) , PurastarTM and PurastarTM OxAm (Genencor).
- Other commercially available enzymes include MannawayTM, PectawayTM, StainzymeTM and RenozymeTM.
- the enzyme is a protease.
- protease Any protease suitable for use in a laundry bar can be used. Suitable proteases include those of animal, vegetable or microbial origin. Microbial origin is preferred. Chemically or genetically modified mutants are included. It may be a serine protease, preferably an alkaline microbial protease or a trypsin-like protease. Examples of alkaline proteases are subtilisins, especially those derived from Bacillus, e.g. subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168 (described in WO 89/06279).
- the enzymes added to the laundry bar are a mixture of proteases and one or more enzymes selected from the group consisting of cellulases, lipases, amylases, pectate lyases and carbohydrases.
- the enzyme can either be incorporated in a granule or in a liquid formulation.
- the enzyme is added to the process of the invention as a granule.
- the enzyme is added to the process as a liquid formulation.
- phenyl boronic acid derivatives substituted in the para-position with carbonyl group adjacent to the phenyl boronic acid.
- the phenyl boronic acid derivative enzyme stabilizer has the following formula:
- R is selected from the group consisting of hydrogen, hydroxy, C 1 -C 6 alkyl, substituted C 1 - C 6 alkyl, C 1 -C 6 alkenyl and substituted C 1 -C 6 alkenyl.
- the laundry bar comprise an enzyme and a phenyl boronic acid derivative enzyme stabilizer of the formula disclosed above, wherein R is a C 1 -C 6 alkyl, in particular wherein R is CH 3 , CH 3 CH 2 Or CH 3 CH 2 CH 2 , or wherein R is hydrogen.
- the laundry bar comprise a surfactant, an enzyme and a phenyl boronic acid derivative enzyme stabilizer of the formula disclosed above.
- 4-formyl-phenyl-boronic acid (4-FPBA) is significantly better than other boron stabilizing agents known in the art such as borax at stabilizing enzymes in laundry bars.
- the phenyl boronic acid de ⁇ rivative enzyme stabilizer is 4-FPBA.
- the laundry bar only comprises a phenyl boronic acid derivative as enzyme stabilizing agent.
- the laundry bar only comprises a 4-FPBA as enzyme stabilizing agent.
- the detergent composition may contain up to 500 mM of the stabilizer (the phenyl boronic acid derivative), preferably the detergent composition may contain 0.001-250 mM of the stabilizer, more preferably the composition may contain 0.005-100 mM of the stabilizer, most preferably the composition may contain 0.01-10 mM of the stabilizer.
- the phenyl boronic acid derivative may be an acid or the alkali metal salt of said acid.
- the laundry bar comprises at least 0.001 % w/w of the stabilizer.
- the detergent matrix may comprise but are not limited to ingredients such as soap, surfactants e.g. anionic synthetic surfactants, builders, polymeric soil release agents, detergent chelants, glycerine, stabilizing agents, fillers.dyes, colorants, dye transfer inhibitors, alkoxylated polycar ⁇ bonates, suds suppressers, structurants, binders, leaching agents, bleaching activators, clay soil removal agents, anti-redeposition agents, polymeric dispersing agents, brighteners, fabric softeners, perfumes and/or other compounds known in the art.
- surfactants e.g. anionic synthetic surfactants
- builders polymeric soil release agents
- detergent chelants e.glycerine
- stabilizing agents fillers.dyes, colorants, dye transfer inhibitors, alkoxylated polycar ⁇ bonates, suds suppressers, structurants, binders, leaching agents, bleaching activators, clay soil removal agents, anti-redeposition agents, polymeric dispersing agents, brighteners,
- the soap suitable for use according to the present invention includes water soluble salts of higher fatty acids. Soap can be made by direct saponification of fats and oils or by neutralisa ⁇ tion of free fatty acids. Suitable soaps are sodium, potassium, ammonium, and alkyloammo- nium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, such as from 12 to about 18 carbon atoms. In a particular embodiment the soap is selected from so ⁇ dium and potassium salts of mixtures of fatty acid derived from coconut oil and tallow, such as sodium or potassium tallow and coconut soaps.
- Synthetic anionic surfactants which are suitable for use herein include the water soluble salts, preferably the alkali metal, ammonium and alkyl ammonium salts of organic sulphuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulphuric acid ester group.
- Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8-I s carbon atoms) such as those produced by reducing the glyc- erides 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.
- Especially valuable are the linear straight chain alkyl benzene sulfonates (LAS) in which the average number of carbon atoms in the alkyl group is from about 11-13, abbreviated as C 11-13 LAS.
- the alkali metal salts, particularly the sodium salts of these surfactants are preferred.
- an anionic synthetic detergent suitable for use herein are the sodium alkyl glyceryl ether sulfonates (AES), especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and so ⁇ dium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
- AES sodium alkyl glyceryl ether sulfonates
- a suitable anionic synthetic detergent also includes the water soluble salts of ester of alpha- sulphonated fatty acids containing from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 carbon atoms in the ester group; water soluble salts of 2-acyloxyalkane-1 -sulfonic acids containing from about 2 to about 9 carbon atoms in the acyl group and from 9 to about 23 carbon atoms in the alkane moiety; water soluble salts of olefin and paraffin sulfonates containing from about 12 to about 20 carbon atoms; and beta- alkyloxy alkane sulfonates containing from about 1 to about 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
- Preferred anionic synthetic surfactant examples are C 1o- i 8 alkyl sulfates (AS), C 1O-18 linear alkyl benzene sulfonates (LAS), C 10-14 alkyl glyceryl ether sulfonates (AES), and mixtures thereof.
- ingredients comprised in a conventional laundry bar is: Linear alkyl benzene sulfonate, coco fatta alcohol sulphate, soda ash, sulphuric acid, sodium tripolyphophate, calcium carbonate, coco faaty alcohol, TiO 2 , cellulase, Diethylenetriamnie penta, coco monoethanolamide, fluorcent agents, substituted methylcellulose, perfume, mois ⁇ ture.
- detergent ingredients comprised in a conventional laundry bar is: LAS, soap, cellulase, protease, boric acid, borax, sodium formate, sodium citrate, sodium car ⁇ bonate, glycerol, propylene glycerol, ethylene glycol, MgSO 4 , soda ash, STPP, talc, moisture.
- the laundry bars of the present invention may be processed in conventional laundry bar mak ⁇ ing equipment such as but not limited to: mixer, plodder, mill, e.g a two stage vacuum plodder, extruder, cutter, logo-stamper, cooling tunnel and wrapper.
- the process is a way of incorporating enzymes into laundry bars comprising the steps of:
- R is selected from the group consisting of hydrogen, hydroxy, C 1 -C 6 alkyl substi ⁇ tuted C 1 -C 6 alkyl, C 1 -C 6 alkenyl and substituted C 1 -C 6 alkenyl, together in a mixer; b) plodding the mixture from step a).
- the process may further comprise the steps of; milling, extruding, cutting, stamping, cooling and/or wrapping.
- the phenyl boronic acid derivative can be added in several ways. It can be added to the en- zyme formulation before mixing, or it can be added to any of the ingredients comprised in the detergent matrix, e.g. it can be incorporated in the soap before mixing or it can be added to the mixing on its own.
- the phenyl boronic acid derivative is added to the enzyme formulation before the mixing step.
- the enzyme added is on liquid form.
- the enzyme is added at the same time as the phenyl boronic acid derivative, e.g. 4-FPBA.
- the mixing may take place in a mixer e.g. in a Double Sigma Amalgator type MSA-100 mixer.
- the mixing step takes preferably no more than 1 min., 5 min., 10 min., 15 min. 30 min., 45 min., no more than 1 hour.
- a plodder e.g. a Duplex plodder, in which the plod ⁇ ding step is performed.
- the plodder operates preferably at high vacuum, so that entrapped air/gas is removed.
- the product is extruded and the extruded bar subsequently moves to the cutter where the bar Js cut to the desired bar length.
- the pieces are stamped into their final shape in stamping presses. High-speed presses are normally used on high-volume production lines.
- the form of the stamp is established by designers, taking into account legal considerations such as the minimum net weight for a laundry bar.
- the bars are printed with the product brand name.
- the bar can be cooled, e.g. in a cooling tunnel, before it following normal procedure is wrapped, cased and sent to storage.
- the process of the invention further relates to a way of incorporating enzymes into laundry bars comprising the steps of:
- R is C 1 -C 6 alkyl, such as CH 3 , CH2CH 3 , CH2CH2CH 3 .
- the phenyl boronic acid derivative is in a particular embodiment 4-formylphenylboronic acid.
- the enzyme is added as a liquid formulation. In another particular embodiment the enzyme is added to the process as a powder or a granulate.
- the enzyme of the mixture is a protease.
- the mixture further comprises an enzyme selected from the group consisting of cellulases, lipases, amylases, pectate lyases and carbohydrases.
- the phenyl boronic acid derivative is added to the enzyme formulation before step a).
- the phenyl boronic acid derivative is added to any ingredients being part of the detergent matrix before step a).
- the phenyl boronic acid derivative is added to step a) on its own.
- the present invention further relates to a laundry bar obtainable by the process of the invention
- the laundry bar of the invention is for use in hand washing laundry.
- Example 1 The enzymes used in the study were:
- a protease comprising granule "Savinase 12 T, W"
- the Ultra system is a liquid stabilized by 4-FPBA, whereas the T enzyme is a granulate.
- Soap Matrix 80/20 Tallow/Coco. 78% TFM. 85% Na soap, produced by Italsilva.
- the enzyme formulation was added to the soap mass in a Double Sigma Amalgator type MSA-
- Soap mass and enzyme then flowed into a Duplex plodder comprising two steps, i.e. a milling compartment type B 100 followed by a plodder & extruder type MP 150 with a screw type nor- mally used for production of laundry bars.
- the temperature in MP 150 was regulated to 36-37 0 C.
- Table 1 The values of % residual activity were obtained through the eight weeks storage of the laundry bars at 30 0 C.
- the sample codes refer to the following dosage combinations:
- Savinase Ultra 16 XL has a very high stability performance in the laundry bar produced according to the process described above.
- Savinase 12 T 0.067 KNPU(S)/g. This means that there is an initial loss of activity during the entire manufacturing process de ⁇ scribed above (mixing - plodding - extrusion - cutting - stamping) as follows: Savinase Ultra 16 XL: 38.8%
- KNPU Kilo Novo Protease Units
- Savinase 16 L EX (not stabilized)
- Savinase Ultra 16 XL (stabilized with 4-FPBA) Stabilizing agents: Borax MPG (monopropylene glycol)
- A2 0.2% Savinase 16 L EX, 2 runs.
- B1 0.2% Savinase 16 L EX + 2% Borax + 4% MPG, 1 run.
- Washing performance test The storage period was eight weeks at 30 0 C. The washing efficiency was measured of week 0 samples, and of week 6 and 8 samples.
- Savinase Ultra 16 XL has the absolutely best storage stability (eight weeks, 30 0 C), and thus offers a significantly higher washing efficiency than Savinase 16 L EX with and without Borax +
- MPG as stabilizers, respectively.
- ⁇ R is 3.5 and addition of Bo- rax + MPG causes an increase of ⁇ R to 13.5 whereas Savinase Ultra 16 XL has a ⁇ R value of 18.0.
- the present example proves that a laundry bar produced with a liquid protease stabilized with 4-FPBA produced in industrial scale has a very satisfactory stability during the manufacturing process and during a storage period of eight weeks at 30°C.
- the stability performance meas ⁇ ured as washing efficiency of the laundry bar produced with liquid protease stabilized with 4- FPBA is significantly higher than that of the laundry bar produced with liquid protease stabi ⁇ lized with Borax + MPG (4%), which in turn is more stable than the laundry bar comprising a liquid protease as such (without stabilizer).
Abstract
Description
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Priority Applications (2)
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BRPI0517520A BRPI0517520B8 (en) | 2004-10-28 | 2005-10-19 | laundry bar, process for incorporating enzymes into laundry bars, and use of a laundry bar |
CN200580036959XA CN101048487B (en) | 2004-10-28 | 2005-10-19 | Laundry bars with improved storage stability |
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DKPA200401659 | 2004-10-28 | ||
DKPA200401659 | 2004-10-28 |
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CN (1) | CN101048487B (en) |
AR (1) | AR052320A1 (en) |
BR (1) | BRPI0517520B8 (en) |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102010043934A1 (en) | 2010-11-15 | 2012-05-16 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
Families Citing this family (2)
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EP2716644B1 (en) * | 2012-10-03 | 2017-04-05 | The Procter and Gamble Company | A stable enzyme stabilizer premix |
CN104140897A (en) * | 2014-07-16 | 2014-11-12 | 上海制皂(集团)如皋有限公司 | Washing and conditioning integrated laundry detergent enabling rinsing to be easy |
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WO1996021716A1 (en) * | 1995-01-09 | 1996-07-18 | Novo Nordisk A/S | Stabilization of liquid enzyme compositions |
WO1996041859A1 (en) * | 1995-06-13 | 1996-12-27 | Novo Nordisk A/S | 4-substituted-phenyl-boronic acids as enzyme stabilizers |
WO1998018897A1 (en) * | 1996-10-31 | 1998-05-07 | The Procter & Gamble Company | Process for incorporating enzymes into laundry bars |
WO1998054285A1 (en) * | 1997-05-30 | 1998-12-03 | The Procter & Gamble Company | Laundry bar with improved protease stability |
-
2005
- 2005-10-19 CN CN200580036959XA patent/CN101048487B/en active Active
- 2005-10-19 WO PCT/DK2005/000674 patent/WO2006045310A1/en active Application Filing
- 2005-10-19 BR BRPI0517520A patent/BRPI0517520B8/en active IP Right Grant
- 2005-10-19 JO JO2005157A patent/JO2476B1/en active
- 2005-10-27 AR ARP050104512A patent/AR052320A1/en active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996021716A1 (en) * | 1995-01-09 | 1996-07-18 | Novo Nordisk A/S | Stabilization of liquid enzyme compositions |
WO1996041859A1 (en) * | 1995-06-13 | 1996-12-27 | Novo Nordisk A/S | 4-substituted-phenyl-boronic acids as enzyme stabilizers |
WO1998018897A1 (en) * | 1996-10-31 | 1998-05-07 | The Procter & Gamble Company | Process for incorporating enzymes into laundry bars |
WO1998054285A1 (en) * | 1997-05-30 | 1998-12-03 | The Procter & Gamble Company | Laundry bar with improved protease stability |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102010043934A1 (en) | 2010-11-15 | 2012-05-16 | Henkel Ag & Co. Kgaa | Stabilized liquid enzyme-containing surfactant preparation |
WO2012065839A1 (en) | 2010-11-15 | 2012-05-24 | Henkel Ag & Co. Kgaa | Stabilized, liquid, enzyme-containing surfactant preparation |
EP2640818B1 (en) | 2010-11-15 | 2018-04-25 | Henkel AG & Co. KGaA | Stabilized liquid surfactant composition comprising enzym |
Also Published As
Publication number | Publication date |
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CN101048487A (en) | 2007-10-03 |
BRPI0517520A (en) | 2008-10-14 |
BRPI0517520B1 (en) | 2020-09-29 |
CN101048487B (en) | 2010-05-05 |
JO2476B1 (en) | 2009-01-20 |
AR052320A1 (en) | 2007-03-14 |
BRPI0517520B8 (en) | 2020-10-27 |
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