Source: http://www.google.fr/patents/US5710115
Timestamp: 2013-05-20 00:51:09
Document Index: 534378962

Matched Legal Cases: ['Application No. 66', 'in fine', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08', 'application No. 08']

Brevet US5710115 - Automatic dishwashing composition containing particles of diacyl peroxides - Google�BrevetsRecherche Images Maps Play YouTube Actualit�s Gmail Drive Plus » Recherche avanc�e dans les brevets | Historique Web | Connexion Recherche avanc�e dans les brevets BrevetsAutomatic dishwashing detergent compositions comprising a diacyl peroxide particle are disclosed. The diacyl peroxide particles preferably comprise diacyl peroxide and a stabilizing additive in which the diacyl peroxide does not dissolve. The stabilizing additive is selected from the group consisting...http://www.google.fr/patents/US5710115?utm_source=gb-gplus-shareBrevet US5710115 - Automatic dishwashing composition containing particles of diacyl peroxides Num�ro de publicationUS5710115 AType de publicationOctroi Num�ro de demande08/713,043 Date de publication20 janv. 1998 Date de d�p�t11 sept. 1996 Date de priorit�9 d�c. 1994Autre r�f�rence de publicationEP0796317A1EP0796317B1WO1996017921A1 InventeursEdward Paul Fitch VAlan Scott GoldsteinJeffrey Donald PainterRashesh Naresh Patel Cessionnaire d'origineThe Procter & Gamble Company Classification aux �tats-Unis510/224510/226510/220510/230 Classification internationaleC11D3/395C11D3/39C11D17/00C11D17/06 Classification coop�rativeC11D3/3932C11D3/3942C11D3/0084C11D3/3951C11D3/3907C11D3/3945C11D17/0039 Classification europ�enneC11D 3/39B2FC11D 17/00DC11D 3/39B2DC11D 3/39DC11D 3/39FC11D 3/395BC11D 3/00B17R�f�rencesCitations de brevets (38)Citations hors brevets (13) R�f�renc� par (57)Liens externesUSPTO Cession USPTO EspacenetAutomatic dishwashing composition containing particles of diacyl peroxidesUS 5710115 A R�sum� Automatic dishwashing detergent compositions comprising a diacyl peroxide particle are disclosed. The diacyl peroxide particles preferably comprise diacyl peroxide and a stabilizing additive in which the diacyl peroxide does not dissolve. The stabilizing additive is selected from the group consisting of inorganic salts, transition metal chelants, antioxidants, binding agents, coating agents, and mixtures thereof. The compositions are effective in removing stains from plastics under various temperature and pH conditions.
What is claimed is: 1. An automatic dishwashing detergent composition in granular or powder form, which composition comprises: I) from about 1% to about 15% by weight of compositon of diacyl peroxide-containing particles which consist essentially of an admixture of: A) from about 1% to about 80% by weight of particle of a water-insoluble diacyl peroxide selected from the group consisting of dibenzoyl peroxide, benzoyl glutaryl peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl peroxide and mixtures thereof, and B) from about 0.1% to 95% by weight of particle of a watersoluble stabilizing additive in which the diacyl peroxide does not dissolve and which is selected from the group consisting of alkali metal sulfates and citrates, ethoxylated C.sub.16-20 alcohols, polyethylene glycols melting above 100 of molecular weight between 1000 and 80,000, ethylene diamine tetra-acetates, ethylene diamine disuccinates and mixtures of these stabilizing additives; II) from about 0.1% to 10% by weight of the composition of a low foaming nonionic surfactant; III) from about 5% to 70% by weight of the composition of a pH adjusting agent or builder component selected from the group consisting of alkali metal, ammonium and substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, bicarbonates, borates, hydroxides, polyacetates, carboxylates, polycarboxylates, silicates, aluminosilicates and mixtures of these pH adjusting agent or builder components; IV) from about 0.1% to 5.0% by weight of the composition of a chlorine bleach or additional peroxygen bleach; and V) from about 0.001% to 5% by weight of the composition of a detersive enzyme; said composition providing a wash solution pH of from about 9 to 12.
2. A composition according to claim 1 wherein the diacyl peroxide is dibenzoyl peroxide.
3. A composition according to claim 2 wherein the dibenzoyl peroxide-containing particles have a mean particle size of from about 600 to 800 microns and the dibenzoyl peroxide used to form such particles has a mean particle size less than about 150 microns.
4. A composition according to claim 3 which additionally contains a bleach activator selected from the group consisting of nonanoyloxybenzene sulfonate (NOBS), benzoylcaprolactam, benzoylvalerolactam, tetraacetyl ethylenediamine (TAED) and mixtures thereof.
5. A composition according to claim 3 which contains from about 3% to about 10% by weight of silicate.
6. A composition according to claim 3 which contains from about 0.005% to about 3% by weight of protease or amylase.
7. A composition according to claim 3 further comprising from about 0.001% to about 5.0% by weight of the composition of a silicone or alkyl phosphate ester suds suppressor.
8. A composition according to claim 1 wherein said diacyl peroxide is diphthaloyl peroxide.
The following examples illustrate the compositions of the present invention. These examples are not meant to limit or otherwise define the scope of the invention. All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified.
EXAMPLE I Granular automatic dishwashing detergent wherein plasticware stain removal benefits are achieved as follows:
TABLE 1______________________________________% by weightIngredients       A         B      C______________________________________Sodium Citrate (as anhydrous)             29.00     15.00  15.00Acusol 480N.sup.1 6.00 active)                       6.00   6.00Sodium carbonate  --        --     20.00Britesil H2O (as SiO.sub.2)             17.00     8.00   8.001-hydroxyethylidene-1,             0.50      0.50   0.501-diphosphonic acidNonionic surfactant.sup.2             --        2.00   --Nonionic surfactant.sup.3             1.50      --     1.50Savinase 12T      2.20      2.00   2.20Termamyl 60T      1.50      1.00   1.50Perborate monohydrate (as AvO)             0.30      1.50   0.30Perborate tetrahydrate (as AvO)             0.90      --     0.90Diacyl Peroxide Particulate.sup.3             6.70      2.70   2.70TAED              --        --     3.00Diethylene triamine penta             0.13      --     0.13methylene phosphonic acidParaffin          0.50      --     0.50Benzotriazole     0.30      --     0.30Sulfate, water, etc.             balance______________________________________ .sup.1 Dispersant from Rohm and Haas .sup.2 Poly Tergent SLF18 surfactant from Olin Corporation .sup.3 Purafac LF404 surfactant from BASF. .sup.4 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide, 40% sodium sulfate, 5% Acusol 480N polymer active, 2% maltodextrin, l2% ethoxylated stearyl alcohol, and balance water.
EXAMPLE II Granular automatic dishwashing detergent wherein increased levels of plasticware stain removal benefits are achieved as follows:
TABLE 2______________________________________% by weightIngredients       D         E      F______________________________________Sodium Citrate (as anhydrous)             15.00     15.00  15.00Acusol 480N.sup.1 6.00tive) 6.00   6.00Sodium carbonate  20.00     20.00  20.00Britesil H2O (as SiO.sub.2)             8.00      8.00   8.001-hydroxyethylidene-1,             0.50      0.50   0.501-diphosphonic acidNonionic surfactant.sup.2             2.00      2.00   2.00Savinase 12T      2.00      2.00   2.00Termamyl 60T      1.00      1.00   1.00Perborate monohydrate (as AvO)             1.50      1.50   1.50Diacyl Peroxide Particulate.sup.3             2.00      4.00   6.00TAED              --        --     --Sulfate, water, etc.             balance______________________________________ .sup.1 Dispersant from Rohm and Haas .sup.2 Polytergent SLF18 surfactant from Olin Corporation .sup.3 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide, 45% sodium sulfate, 5% Acusol 480N polymer active, 10% polyethylene glycol (4000 M.W.), and balance water.
EXAMPLE III Granular automatic dishwashing detergent wherein plasticware stain removal benefits are achieved with different diacyl peroxide particulates as follows:
TABLE 3______________________________________% by weightIngredients       G         H      I______________________________________Sodium Citrate (as anhydrous)             20.00     20.00  20.00Acusol 480N.sup.1 5.00      5.00   5.00Sodium carbonate  15.00     15.00  15.00Britesil H2O (as SiO.sub.2)             6.00      6.00   6.00Na.sub.3 HEDDS    0.20      0.20   0.20Nonionic surfactant.sup.2             1.50      1.50   1.50FN3               1.00      1.00   1.00LE17              1.00      1.00   1.00Perborate monohydrate (as AvO)             2.00      2.00   2.00Diacyl Peroxide Particulate             6.70.sup.3                       6.70.sup.4                              6.70.sup.5Sulfate, water, etc.             balance______________________________________ .sup.1 Dispersant from Rohm and Haas .sup.2 Polytergent SLF18 surfactant from Olin Corporation .sup.3 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle diameter 500 &#956;m, 40% sulfate, 2% HEDP, 5% Acusol 445N polymer active, 10% polyethylene glycol (4000 M.W.), 2% palmitic acid, and balanc water. .sup.4 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle diameter 100 &#956;m, 40% sulfate, 2% HEDP, 5% Acusol 445N polymer 10% polyethylene glycol (4000 M.W.), 2% palmitic acid, and balance water. .sup.5 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle diameter 50 &#956;m, 40% sulfate, 2% HEDP, 5% Acusol 445N polymer active, 10% polyethylene glycol (4000 M.W.), 2% palmitic acid, and balanc water.
EXAMPLE IV Granular automatic dishwashing detergent where plasticware stain removal benefits are achieved with different diacyl peroxide particulates as follows:
TABLE 4______________________________________% by weightIngredients       J         K      L______________________________________Sodium Citrate (as anhydrous)             15.00     15.00  15.00Acusol 480N.sup.1 6.00tive) 6.00   6.00Sodium carbonate  20.00     20.00  20.00Britesil H2O (as SiO.sub.2)             8.00      8.00   8.001-hydroxyethylidene-1,             0.50      0.50   0.501-diphosphonic acidNonionic surfactant.sup.2             2.00      2.00   2.00Savinase 12T      2.00      2.00   2.00Termamyl 60T      1.00      1.00   1.00Perborate monohydrate (as AvO)             1.50      1.50   1.50Diacyl Peroxide Particulate             5.00.sup.3                       5.00.sup.4                              5.00.sup.5TAED              --        --     --Sulfate, water, etc.             balance______________________________________ .sup.1 Dispersant from Rohm and Haas .sup.2 Polytergent SLF18 surfactant from Olin Corporation .sup.3 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle size 150 &#956;m, 40% sodium sulfate, 1% EDDS, 5% Acusol 980N (active), 10% PEG 4000, 2% palmitic acid, and balance water. .sup.4 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle size 150 &#956;m, 40% sodium citrate dihydrate, 1% EDDS, 8% maltodextrin, 10% PEG 4000, and balance water. .sup.5 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle size 150 &#956;m, 40% sodium sulfate, 1% EDDS, 0.1% BHT, 8% maltodextrin, 10% PEG 4000, and balance water.
EXAMPLE V Granular detergent compositions containing diacyl peroxide and chlorine bleach are as follows:
TABLE 5______________________________________% by weight                M______________________________________Sodium TripolyPhosphate                29.68(anhydrous basis)Nonionic Surfactant  2.50MSAP Suds Suppressor 0.08Sodium Carbonate     23.00Sodium Silicate (2.4r, as SiO2)                6.50NaDCC Bleach (as AvCl2)                1.10Sodium Sulfate       21.79Dibenzoyl Peroxide (% active)                0.80Perfume              0.14______________________________________
EXAMPLE VI Granular automatic dishwashing detergent where plasticware stain removal benefits are achieved with different diacyl peroxide particulates as follows:
TABLE 6______________________________________% by weightIngredients       N         O      P______________________________________Sodium Citrate (as anhydrous)             10.00     15.00  20.00Acusol 480N.sup.1 6.00tive) 6.00   6.00Sodium carbonate  15.00     10.00  5.00Sodium tripolyphosphate             10.00     10.00  10.00Britesil H2O (as SiO.sub.2)             8.00      8.00   8.001-hydroxyethylidene-1,             0.50      0.50   0.501-diphosphonic acidNonionic surfactant.sup.2             2.00      2.00   2.00Savinase 12T      2.00      2.00   2.00Termamyl 60T      1.00      1.00   1.00Perborate monohydrate (as AvO)             1.50      1.50   1.50Diacyl Peroxide Particulate             5.00.sup.3                       5.00.sup.4                              5.00.sup.5TAED              --        --     --Sulfate, water, etc.             balance______________________________________ .sup.1 Dispersant from Rohm and Haas .sup.2 Polytergent SLF18 surfactant from Olin Corporation .sup.3 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle size 150 &#956;m, 40% sodium sulfate, 1% EDDS, 5% Acusol 980N (active), 10% PEG 4000, 2% palmitic acid, and balance water. .sup.4 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle size 150 &#956;m, 40% sodium citrate dihydrate, 1% EDDS, 8% maltodextrin, 10% PEG 4000, and balance water. .sup.5 Diacyl Peroxide Particulate has 30% dibenzoyl peroxide with a mean particle size 150 &#956;m, 40% sodium sulfate, 1% EDDS, 0.1% BHT, 8% maltodextrin, 10% PEG 4000, and balance water.
TECHNICAL FIELD The present invention is in the field of automatic dishwashing detergents. More specifically, the invention relates to granular automatic dishwashing detergents which provide enhanced cleaning, e.g. improved stain removal on plastics. The automatic dishwashing compositions comprise adding a diacyl peroxide which has been stabilized by forming particles of the peroxide with a stabilizing additive.
BACKGROUND OF THE INVENTION Automatic dishwashing detergents (hereinafter ADDs) used for washing tableware (i.e. glassware, china, silverware, pots and pans, plastic, etc.) in the home or institutionally in machines especially designed for the purpose have long been known. Dishwashing in the seventies is reviewed by Mizuno in Vol. 5, Part III of the Surfactant Science Series, Ed. W. G. Cutler and R. C. Davis, Marcel Dekker, N.Y., 1973, incorporated by reference. The particular requirements of cleansing tableware and leaving it in a sanitary, essentially spotless, residue-free state has indeed resulted in so many particular ADD compositions that the body of art pertaining thereto is now recognized as quite distinct from other cleansing product art.
In light of legislation and current environmental trends, modem ADD products desirably contain low levels or are substantially free of inorganic phosphate builder salts and/or are concentrated formulations (i.e. 1/2 cup vs. full cup usage). Unfortunately, nonphosphated ADD products in technical terms may sacrifice efficacy, especially owing to the deletion of phosphate and, in some instances, chlorine mainstay cleansing ingredients. Concentrated or compact compositions similarly exhibit formulation problems.
Users of ADDs have come to expect tableware will be rendered essentially spotless and film-free in addition to cleaning. In practice, this means avoiding film-forming components. The formulator will generally employ ingredients which are sufficiently soluble that residues or build-up do not occur. Again, while some ingredients may be adequate on grounds of cleaning, spotting and filming, solubility considerations may dish their usefulness. Solubility considerations are even more acute with the newer "low usage", "concentrated", ADD compositions whose overall solubility can be less than that of conventional ("full cup") products.
It has generally been believed by the formulator of ADDs that inexpensive cleaning can be achieved via high alkalinity and/or high silicate levels (for example as provided by formulations comprising high percentages by weight of sodium hydroxide, silicate or metasilicate). Severe penalties can result in these compositions in terms of product corrosiveness to dishwashers and tableware, especially china and glassware and incompatibility with other detergent ingredients. It is therefore highly desirable, at least in some phosphate-free compact ADDs, to achieve good cleaning end-results without resorting to the use of high alkalinity/high silicate.
Chlorine and peroxygen bleaches are effective for stain and/or soil removal. Chlorine bleaches while effective cleaners are often not compatible with other detergent ingredients and/or require additional processing. Peroxygen bleaches on the other hand are less reactive, but such bleaches are temperature and/or pH dependent. As a consequence, there has been a substantial amount of research to develop bleaching systems which contain an activator that renders peroxygen bleaches effective in various wash liquor conditions. Also the conventional chlorine bleaches and peroxygen bleaches, i.e. perborate and percarbonate, have not been found to be effective in removing stains from plastics.
Another source of bleaching are the diacyl peroxides (DAPs). Although diacyl peroxides have been disclosed for use in the laundry and anti-acne area, they have not been employed in the ADD area. In the laundry field certain diacyl peroxides have been found to be effective in the removal of tea stains from fibrous material. In a dishwashing context however these diacyl peroxides have been found to be less effective than perborate and percarbonate on tea stain removal. Further, as discussed above, solubility of diacyl peroxides has been a concern in the laundry field as well.
It has been surprisingly discovered that DAPs can improve the stain removal performance (including dye transfer) of ADDs on plastics.
By the present invention, it has also been unexpectedly discovered that water-insoluble forms of DAP must be used to obtain the plastic stain removal performance.
Further, it has been surprisingly found that the water-insoluble diacyl peroxides do not adversely react with chlorine bleach. Thus, diacyl peroxides provide an additional dimension of stain removal not obtained with chlorine bleach alone.
The novel ADDs have the property of removing a wide variety of stains, including tea stain, fruit juice and carotenoid objected to by the consumer from plastic dishware. The compositions have other cleaning and spotlessness advantages such as enhanced glass care (i.e. reduction of cloudiness and iridescence negatives) and reduction of silicate/carbonate deposition filming negatives.
SUMMARY OF THE INVENTION The present invention encompasses automatic dishwashing detergent compositions, especially granular or powder-form automatic dishwashing detergent compositions which comprise by weight of the composition from about 0.1% to about 20% of a water in soluble diacyl peroxide, said diacyl peroxide having been added as a diacyl peroxide particle to the composition, said particle comprising, by weight of said particle, from about 1% to about 80%, preferably from about 5% to about 40% water-insoluble diacyl peroxide having the general formula:
RC(O)OO(O)CR1
wherein R and R1 can be the same or different, preferably no more than one is a hydrocarbyl chain of longer than ten carbon atoms, more preferably at least one has an aromatic nucleus and from about 0.01% to about 95%, preferably from about 40% to about 95% stabilizing additive in which said diacyl peroxide does not dissolve, said stabilizing additive is selected from the group consisting of inorganic salts, transition metal chelants, antioxidants, binding agents, coating agents and mixtures thereof.
While diacyl peroxide particulates comprising water-insoluble diacyl peroxide and stabilizing additive are the essential ingredients to the present invention, there are also provided embodiments wherein additional components, especially, bleaching agent, silicate, enzymes, detergency builder and/or detergency surfactant are desirably present. Highly preferred embodiments of the invention contain dibenzoyl peroxide.
The present invention also encompasses a method for cleaning soiled tableware comprising contacting said tableware with an aqueous medium having a pH in the range from about 8 to about 13, more preferably from about 9 to about 12, and comprising at least from about 0.01% to about 8% of a diacyl peroxide selected from the group consisting of dibenzoyl peroxide, benzoyl glutaryl peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl peroxide and mixtures thereof. The essential diacyl peroxide is added in a particulate form preferably with a stabilizing agent selected from the group consisting of inorganic salt, binding agent, coating agent and/or chelant.
DETAILED DESCRIPTION OF THE INVENTION An automatic dishwashing detergent composition comprising by weight: of the composition from about 0.01% to about 20% of a water-insoluble diacyl peroxide, said diacyl peroxide being added as a particulate comprising, by weight of said particulate, from about 1% to about 80% of a water-insoluble diacyl peroxide having the general formula:
RC(O)OO(O)CR.sup.1
wherein R and R.sup.1 can be the same or different, preferably no more than one is a hydrocarbyl chain of longer than ten carbon atoms, more preferably at least one has an aromatic nucleus and from about 0.01%% to about 95% stabilizing additive in which said diacyl peroxide does not dissolve, said stabilizing additive is selected from the group consisting of inorganic salts, antioxidants, binding agents, coating agents, chelants and mixtures thereof.
A particularly preferred embodiment contains dibenzoyl peroxide as the water-insoluble diacyl peroxide.
The term "diacyl peroxide does not dissolve" is defined herein to mean the diacyl peroxide does not dissolve in the stabilizing additive(s) under particle processing conditions and/or ADD product storage conditions.
The term "wash solution" is defined herein to mean an aqueous solution of the product dissolved at 1,000-6,000 ppm, preferably at 2,500-4,500 ppm, in an automatic dishwasher.
The term "water-insoluble" is defined herein to mean limited water solubility, i.e. less than 1%, preferably less than 0.5%, dissolves in water.
The term "stabilizing additive" is defined herein to mean a compound or compounds that prevents the diacyl peroxide from decomposing with other ingredients, especially components in which the diacyl peroxide is soluble in and with which the diacyl peroxide will react while stored in the product.
The ADD composition of the present invention contain from about 0.01% to about 20%, preferably from about 0.1% to about 10%, more preferably from about 0.2% to about 2% water-insoluble diacyl peroxide of the general formula:
wherein R and R.sup.1 can be the same or different, preferably no more than one is a hydrocarbyl chain of longer than ten carbon atoms, more preferably at least one has an aromatic nucleus.
Examples of suitable diacyl peroxides are selected from the group consisting of dibenzoyl peroxide, benzoyl glutaryl peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl peroxide and mixtures thereof, more preferably dibenzoyl peroxide, diphthaloyl peroxides and mixtures thereof. The preferred diacyl peroxide is dibenzoyl peroxide.
Without being bound by theory, it is believed that the free radical formed upon the decomposition of the diacyl peroxide is essential in plastic stain removal. Therefore the diacyl peroxide must thermally decompose in wash conditions (i.e. from about 100 to form free radicals.
Particle size can also play an important role in the performance of the diacyl peroxide in an ADD product. The mean particle size as measured by a laser particle size analyzer (e.g. Malvern) on an agitated mixture with water of the diacyl peroxide is preferably less than about 300 μm, more preferably less than about 150 μm. Although water insolubility is an essential characteristic of the diacyl peroxide of the present invention, the particle size is important for controlling residue formation in wash.
To provide the necessary storage stability it is essential to incorporate the diacyl peroxides in a particle compatible with an ADD formulation. The particle formed protects the diacyl peroxide from interacting with other ingredients and decomposing in the composition over time. This particle is formed by combining the diacyl peroxide with a "stabilizing additive" preferably selected from the group consisting of inorganic salts, antioxidants, chelants, binding agents, coating agents and mixtures thereof. The stabilizing additive should not dissolve the diacyl peroxide. The stabilizing additive in the particle is by weight of the particle from about 0.1% to about 95%, preferably from about 10% to about 95%, more preferably from about 40% to about 95% stabilizing additive.
Preferably, the stabilizing additive is not miscible with other components of the composition at temperatures at or below 100 120 agent would be soluble in the wash solution.
The inorganic salt, useful as a stabilizing additive include but are not limited to alkali metal sulfates, citric acid, and boric acid, and their salts, alkali metal carbonates, bicarbonates and silicates and mixtures thereof. Preferred inorganic salts are sodium sulfate and citric acid, which, because they are non-alkaline, prevent alkaline hydrolysis in product.
Binding agents and coating agents include but are not limited to certain water soluble polymers in which the diacyl peroxide does not dissolve, ethoxylated C16-C20 alcohols with sufficient ethoxylate groups to prevent dissolution of the diacyl peroxide, aliphatic fatty acids, aliphatic fatty alcohols, maltodextrins, dextrin, starch, gelatin, polyethylene glycols with melting points above 100 The polymers include polyacrylates with an average molecular weight of from about 1,000 to about 10,000, and acrylate/maleate or acrylate/fumarate copolymers with an average molecular weight of from about 2,000 to about 80,000 and a ratio of acrylate to maleate or fumarate segments of from about 30:1 to about 1:2. Examples of such copolymers based on a mixture of unsaturated mono- and dicarboxylate monomers are disclosed in European Patent Application No. 66,915, published Dec. 15, 1982, incorporated herein by reference. Other suitable copolymers are modified polyacrylate copolymers as disclosed in U.S. Pat. Nos. 4,530,766, and 5,084,535, both incorporated herein by reference.
Transition metal chelants which can be employed are selected from the group consisting of polyacetate and polycarboxylate builders such as the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, ethylenediamine disuccinic acid (especially the S,S- form), nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, mellitic acid, sodium benzene polycarboxylate salts; nitrilotris(methylenephosphonic acid) diethylenetrinitrilopentakis(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, other phosphonates chelants (e.g. Dequest line of products from Monsanto), ethylene-N,N'-bis(o-hydroxyphenylglycine), dipicolinic acid and mixtures thereof.
Antioxidants (radical trap, radical scavenger or free radical inhibitor) can also be suitable stabilizing additives. These compounds slow down or stop a reaction even though present in small amounts. In the present invention it is believed the antioxidant would trap or scavenge the radical formed due to thermal decomposition of the peroxide bond. This would prevent the radical from further reacting or propagating the formation of another radical (self-accelerated decomposition). Since this material would be used in small amounts in the particle, it most likely would not hurt overall performance of the ADD. Suitable antioxidants include but are not limited to citric acid, phosphoric acid, BHT, BHA, α-tocopherol, Irganox series C (Ciba Giegy), Tenox series (Kodax) and mixtures thereof.
As stated, many of the above listed stabilizing additives can also provide other benefits in the ADD product (i.e. pH control, carbonate/silicate dispersion) as well as serve as the stabilizing additive. These ingredients therefore may also be added separately from the particulate. For example, agglomerated forms of the present invention may employ aqueous solutions of the polyacrylates discussed herein above as liquid binders for making the agglomerate.
The diacyl peroxide particles formed preferably have a mean particle size from about 400 μm to about 1000 μm, more preferably from about 600 μm to about 800 μm with less than 1% of the diacyl peroxide particle population being greater than 1180 μm (Tyler 14 mesh) and less than 1% less than or equal to 212 μm (Tyler 65 mesh). The compositions of the present invention comprise by weight of the composition from about 0.1% to about 30%, preferably from about 1% to about 15%, more preferably from about 1.5% to about 10% of diacyl peroxide particle.
The compositions herein have a pH of at least 7; therefore the compositions can comprise a pH-adjusting detergency builder component selected from water-soluble alkaline inorganic salts and water-soluble organic or inorganic builders. It has been discovered that to secure the benefits of the invention, the peroxide bleaching component must at least be combined with a pH-adjusting component which delivers a wash solution pH of from 7 to about 13, preferably from about 8 to about 12, more preferably from about 8 to about 11 The pH-adjusting component are selected so that when the ADD is dissolved in water at a concentration of 2000-6000 ppm, the pH remains in the ranges discussed above. The preferred non phosphate pH-adjusting component embodiments of the invention is selected from the group consisting of
Illustrative of highly preferred pH-adjusting component systems are binary mixtures of granular sodium titrate dihyrate with anhydrous sodium carbonate, and three-component mixtures of granular sodium titrate dihydrate, sodium carbonate and sodium disilicate.
The amount of the pH adjusting component in the instant ADD compositions is generally from about 0.9% to about 99%, preferably from about 5% to about 70%, more preferably from about 20% to about 60% by weight of the composition.
The essential pH-adjusting system can be complemented (i.e. for improved sequestration in hard water) by other optional detergency builder salts selected from phosphate or nonphosphate detergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium borates, hydroxysulfonates, polyacetates, and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of such materials. Alternate water-soluble, non-phosphorus organic builders can be used for their sequestering properties. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, ethylenediamine disuccinic acid (especially the S,S- form); nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydiacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, mellitic acid, and sodium benzene polycarboxylate salts.
The detergency builders used to form the base granules can be any of the detergency builders known in the art, which include the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, borates, polyhydroxysulfonates, polyacetates, carboxylates (e.g. citrates), aluminosilicates and polycarboxylates. Preferred are the alkali metal, especially sodium, salts of the above and mixtures thereof.
In general, pH values of the instant compositions can vary during the course of the wash as a result of the water and soil present. The best procedure for determining whether a given composition has the herein-indicated pH values is as follows: prepare an aqueous solution or dispersion of all the ingredients of the composition by mixing them in finely divided form with the required amount of water to have a 3000 ppm total concentration. Do not have any coatings on the particles capable of inhibiting dissolution. (In the case of the second pH adjusting component it should be omitted from the formula when determining the formula's initial pH value). Measure the pH using a conventional glass electrode at ambient temperature, within about 2 minutes of forming the solution or dispersion. To be clear, this procedure relates to pH measurement and is not intended to be construed as limiting of the ADD compositions in any way; for example, it is clearly envisaged that fully-formulated embodiments of the instant ADD compositions may comprise a variety of ingredients applied as coatings to other ingredients.
Other Optional Bleaches
The ADD compositions of the present invention can additionally and preferably do contain an additional amount other bleaching sources.
For example oxygen bleach can be employed in an amount sufficient to provide from 0.01% to about 8%, preferably from about 0.1% to about 5.0%, more preferably from about 0.3% to about 4.0%, most preferably from about 0.8% to about 3% of available oxygen (AvO) by weight of the ADD.
Available oxygen of an ADD or a bleach component is the equivalent bleaching oxygen content thereof expressed as % oxygen. For example, commercially available sodium perborate monohydrate typically has an available oxygen content for bleaching purposes of about 15% (theory predicts a maximum of about 16%). Methods for determining available oxygen of a formula after manufacture share similar chemical principles but depend on whether the oxygen bleach incorporated therein is a simple hydrogen peroxide source such as sodium perborate or percarbonate, is an activated type (e.g., perborate with tetra-acetyl ethylenediamine) or comprises a performed peracid such as monoperphthalic acid. Analysis of peroxygen compounds is well-known in the art: see, for example, the publications of Swern, such as "Organic Peroxides", Vol. I, D. H. Swern, Editor; Wiley, New York, 1970, LC #72-84965, incorporated by reference. See for example the calculation of "percent active oxygen" at page 499. This term is equivalent to the terms "available oxygen" or "percent available oxygen" as used herein.
Suitable oxygen-type bleaches are further described in U.S. Pat. No. 4,412,934 (Chung et al), issued Nov. 1, 1983, and peroxyacid bleaches described in European Patent Application 033,259. Sagel et al, published Sep. 13, 1989, both incorporated herein by reference, can be used.
Available chlorine of an ADD or a bleach component is the equivalent bleaching chlorine content thereof expressed as % equivalent Cl.sub.2 by weight.
For the excellent bleaching results of the present invention which may contain the optional peroxygen bleach component the composition is formulated with an activator (peracid precursor). The activator is present at levels of from about 0.01% to about 15%, preferably from about 1% to about 10%, more preferably from about 1% to about 8%, by weight of the composition. Preferred activators are selected from the group consisting of benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz), decanoyloxybenzenesulphonate (C.sub.10 -OBS), benzolyvalerolactam (BZVL), octanoyloxybenzenesulphonate (C.sub.8 -OBS), perhydrolyzable esters and mixtures thereof, most preferably benzoylcaprolactam and benzolyvalerolactam. Particularly preferred bleach activators in the pH range from about 8 to about 9.5 are those selected having an OBS or VL leaving group.
Quaternary substituted bleach activators may also be included. The present ADD compositions comprise a quaternary substituted bleach activator (QSBA) or a quaternary substituted peracid (QSP); more preferably, the former. Preferred QSBA structures are further described in copending U.S. Ser. No. 08/298,903, 08/298,650, 08/298,906 and 08/298,904 filed Aug. 31, 1994, incorporated herein by reference.
The bleach catalyst material which is an optional but preferable ingredient, can comprise the free acid form, the salts, and the like.
One type of bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium tungsten, molybenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. No. 4,430,243.
Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. No. 5,246,621 and U.S. Pat. No. 5,244,594. Preferred examples of theses catalysts include Mn.sup.IV.sub.2 (u-O).sub.3 (1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2 -(PF.sub.6).sub.2, Mn.sup.III.sub.2 (u-O).sub.1 (u-OAc).sub.2 (1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2 -(ClO.sub.4).sub.2, Mn.sup.IV.sub.4 (u-O).sub.6 (1,4,7-triazacyclononane).sub.4 -(ClO.sub.4).sub.2, Mn.sup.III Mn.sup.IV.sub.4 (u-O).sub.1 (u-OAc).sub.2 (1,4,7-trimethyl-1,4,7-triazacyclononane).sub.2 -(ClO.sub.4).sub.3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, and mixtures thereof.
The bleach catalysts useful in machine dishwashing compositions and concentrated powder detergent compositions may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. No. 4,246,612 and U.S. Pat. No. 5,227,084.
See also U.S. Pat. No. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane(OCH.sub.3).sub.3- (PF.sub.6).
U.S. Pat. No. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula: ##STR1## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 can each be selected from H, substituted alkyl and aryl groups such that each R.sup.1 --N═C--R.sup.2 and R.sup.3 --C═N--R.sup.4 form a five or six-membered ring. Said ring can further be substituted. B is a bridging group selected from O, S. CR.sup.5 R.sup.6 ; NR.sup.7 and C═O, wherein R.sup.5, R.sup.6, and R.sup.7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl.sub.2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine).sub.2 O.sub.2 ClO.sub.4, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.
Other examples include Mn gluconate, Mn(CF.sub.3 SO.sub.3).sub.2, Co(NH.sub.3).sub.5 Cl, and the binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N.sub.4 Mn.sup.III (u-O).sub.2 Mn.sup.IV N.sub.4).sup.+ and Bipy.sub.2 Mn.sup.III (u-O).sub.2 Mn.sup.IV bipy.sub.2 !-(ClO.sub.4).sub.3.
The bleach catalysts of the present invention may also be prepared by combining a water-soluble ligand with a water-soluble manganese salt in aqueous media and concentrating the resulting mixture by evaporation. Any convenient water-soluble salt of manganese can be used herein. Manganese (II), (III), (IV) and/or (V) is readily available on a commercial scale. In some instances, sufficient manganese may be present in the wash liquor, but, in general, it is preferred to add Mn cations in the compositions to ensure its presence in catalytically-effective mounts. Thus, the sodium salt of the ligand and a member selected from the group consisting of MnSO.sub.4, Mn(ClO.sub.4).sub.2 or MnCl.sub.2 (least preferred) are dissolved in water at molar ratios of ligand:Mn salt in the range of about 1:4 to 4:1 at neutral or slightly alkaline pH. The water may first be de-oxygenated by boiling and cooled by spraying with nitrogen. The resulting solution is evaporated (under N.sub.2, if desired) and the resulting solids are used in the bleaching and detergent compositions herein without further purification.
In an alternate mode, the water-soluble manganese source, such as MnSO.sub.4, is added to the bleach/cleaning composition or to the aqueous bleaching/cleaning bath which comprises the ligand. Some type of complex is apparently formed in situ, and improved bleach performance is secured. In such an in situ process, it is convenient to use a considerable molar excess of the ligand over the manganese, and mole ratios of ligand:Mn typically are 3:1 to 15:1. The additional ligand also serves to scavenge vagrant metal ions such as iron and copper, thereby protecting the bleach from decomposition. One possible such system is described in European patent application, publication no. 549,271.
The compositions of the type described herein optionally, but preferably comprise alkali metal silicates and/or metasilicates. The alkali metal silicates hereinafter described provide pH adjusting capability (as described above), protection against corrosion of metals and against attack on dishware, inhibition of corrosion to glasswares and chinawares. The SiO.sub.2 level is from about 0.5% to about 20%, preferably from about 1% to about 15%, more preferably from about 2% to about 12%, most preferably from about 3% to about 10%, based on the weight of the ADD.
The ratio of SiO.sub.2 to the alkali metal oxide (M.sub.2 O, where M=alkali metal) is typically from about 1 to about 3.2, preferably from about 1 to about 3, more preferably from about 1 to about 2.4. Preferably, the alkali metal silicate is hydrous, having from about 15% to about 25% water, more preferably, from about 17% to about 20%.
Anhydrous forms of the alkali metal silicates with a SiO.sub.2 :M.sub.2 O ratio of 2.0 or more are also less preferred because they tend to be significantly less soluble than the hydrous alkali metal silicates having the same ratio.
Sodium and potassium, and especially sodium, silicates are preferred. A particularly preferred alkali metal silicate is a granular hydrous sodium silicate having a SiO.sub.2 :Na.sub.2 O ratio of from 2.0 to 2.4 available from PQ Corporation, named Britesil H20 and Britesil H24. Most preferred is a granular hydrous sodium silicate having a SiO.sub.2 :Na.sub.2 O ratio of 2 While typical forms, i.e. powder and granular, of hydrous silicate particles are suitable, preferred silicate particles have a mean particle size between about 300 and about 900 microns with less than 40% smaller than 150 microns and less than 5% larger than 1700 microns. Particularly preferred is a silicate particle with a mean particle size between about 400 and about 700 microns with less than 20% smaller than 150 microns and less than 1% larger than 1700 microns.
NaMSi.sub.x O.sub.2x+1.y H.sub.2 O
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purpose of the present invention, x in the general formula above has a value of 2, 3 or 4 and is preferably s. The most preferred material is --Na.sub.2 Si.sub.2 O.sub.5, available from Hoechst AG as NaSKS-6.
When present, a dispersant polymer in the instant ADD compositions is typically in the range from 0 to about 25%, preferably from about 0.5% to about 20%, more preferably from about 1% to about 7% by weight of the ADD composition. Dispersant polymers are also useful for improved filming performance of the present ADD compositions, especially in higher pH embodiments, such as those in which wash pH exceeds about 9.5. Particularly preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on dishware.
Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. Such copolymers contain as monomer units: a) from about 90% to about 10%, preferably from about 80% to about 20% by weight acrylic acid or its salts and b) from about 10% to about 90%, preferably from about 20% to about 80% by weight of a substituted acrylic monomer or its salt and have the general formula: -- (C(R.sup.2)C(R.sup.1)(C(O)OR.sup.3)!-- wherein the incomplete valences inside the square braces are hydrogen and at least one of the substituents R.sup.1, R.sup.2 or R.sup.3, preferably R.sup.1 or R.sup.2, is a 1 to 4 carbon alkyl or hydroxyalkyl group, R.sup.1 or R.sup.2 can be a hydrogen and R.sup.3 can be a hydrogen or alkali metal salt. Most preferred is a substituted acrylic monomer wherein R.sup.1 is methyl, R.sup.2 is hydrogen and R.sup.3 is sodium.
Other dispersant polymers useful herein include the polyethylene glycols and polypropylene glycols having a molecular weight of from about 950 to about 30,000 which can be obtained from the Dow Chemical Company of Midland, Mich. Such compounds for example, having a melting point within the range of from about 30 at molecular weights of 1450, 3400, 4500, 6000, 7400, 9500, and 20,000. Such compounds are formed by the polymerization of ethylene glycol or propylene glycol with the requisite number of moles of ethylene or propylene oxide to provide the desired molecular weight and melting point of the respective polyethylene glycol and polypropylene glycol. The polyethylene, polypropylene and mixed glycols are referred to using the formula HO(CH.sub.2 CH.sub.2 O).sub.m (CH.sub.2 CH(CH.sub.3)O).sub.n (CH(CH.sub.3)CH.sub.2 O)OH wherein m, n, and o are integers satisfying the molecular weight and temperature requirements given above.
ADD compositions of the present invention can comprise low foaming nonionic surfactants (LFNIs). LFNI can be present in amounts from 0 to about 10% by weight, preferably from about 1% to about 8%, more preferably from about 0.25% to about 4%. LFNIs are most typically used in ADDs on account of the improved water-sheeting action (especially from glass) which they confer to the ADD product. They also encompass non-silicone, nonphosphate polymeric materials further illustrated hereinafter which are known to defoam food soils encountered in automatic dishwashing.
The invention encompasses preferred embodiments wherein LFNI is present, and wherein this component is solid at temperatures below about 100
Suitable block polyoxyethylene-polyoxypropylene polymeric compounds that meet the requirements described herein before include those based on ethylene glycol, propylene glycol, glycerol, trimethylolpropane and ethylenediamine as initiator reactive hydrogen compound. Polymeric compounds made from a sequential ethoxylation and propoxylation of initiator compounds with a single reactive hydrogen atom, such as C.sub.12-18 aliphatic alcohols, do not generally provide satisfactory suds control in the instant ADDs. Certain of the block polymer surfactant compounds designated PLURONIC Corp., Wyandotte, Mich., are suitable in ADD compositions of the invention.
LFNIs which may also be used include a C.sub.18 alcohol polyethoxylate, having a degree of ethoxylation of about 8, commercially available SLF18 from Olin Corp. and any biodegradable LFNI having the melting point properties discussed herein above.
Preferred alkyl(polyethoxy)sulfate surfactants comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C.sub.6 -C.sub.18 alcohol with an average of from about 0.5 to about 20, preferably from about 0.5 to about 5, ethylene oxide groups. The C.sub.6 -C.sub.18 alcohol itself is preferable commercially available. C.sub.12 -C.sub.15 alkyl sulfate which has been ethoxylated with from about 1 to about 5 moles of ethylene oxide per molecule is preferred. Where the compositions of the invention are formulated to have a pH of between 6.5 to 9.3, preferably between 8.0 to 9, wherein the pH is defined herein to be the pH of a 1% solution of the composition measured at 20 surprisingly robust soil removal, particularly proteolytic soil removal, is obtained when C.sub.10 -C.sub.18 alkyl ethoxysulfate surfactant, with an average degree of ethoxylation of from 0.5 to 5 is incorporated into the composition in combination with a proteolytic enzyme, such as neutral or alkaline proteases at a level of active enzyme of from 0.005% to 2%. Preferred alkyl(polyethoxy)sulfate surfactants for inclusion in the present invention are the C.sub.12 -C.sub.15 alkyl ethoxysulfate surfactants with an average degree of ethoxylation of from 1 to 5, preferably 2 to 4, most preferably 3.
Alkyl(polyethoxy)carboxylates suitable for use herein include those with the formula RO(CH.sub.2 CH.sub.2 O)x CH.sub.2 COO--M wherein R is a C.sub.6 to C.sub.25 alkyl group, x ranges from 0 to 10, preferably chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-ethanol-ammonium, most preferably from sodium, potassium, ammonium and mixtures thereof with magnesium ions. The preferred alkyl(polyethoxy)carboxylates are those where R is a C.sub.12 to C.sub.18 alkyl group.
Highly preferred anionic cosurfactants herein are sodium or potassium salt-forms for which the corresponding calcium salt form has a low Kraft temperature, e.g., 30 or lower. Examples of such highly preferred anionic cosurfactants are the alkyl(polyethoxy)sulfates.
The compositions of this invention may optionally, but preferably, contain from 0 to about 8%, preferably from about 0.001% to about 5%, more preferably from about 0.003% to about 4%, most preferably from about 0.005% to about 3%, by weight, of active detersive enzyme. The knowledgeable formulator will appreciate that different enzymes should be selected depending on the pH range of the ADD composition. Thus, Savinase to deliver wash pH of 10, whereas Alcalase ADDs deliver wash pH of, say, 8 to 9. Moreover, the formulator will generally select enzyme variants with enhanced bleach compatibility when formulating oxygen bleaches containing compositions of the present invention.
The proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included by definition, as are close structural enzyme variants. Particularly preferred by way of proteolytic enzyme is bacterial serine proteolytic enzyme obtained from Bacillus, Bacillus subtilis and/or Bacillus licheniformis. Suitable commercial proteolytic enzymes include Alcalase Maxacal Purafect Preferred proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Ser. No. 87 303761.8, filed Apr. 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published Oct. 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A" herein. Most preferred is what is called herein "Protease C", which is a triple variant of an alkaline serine protease from Bacillus in which tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991, which is incorporated herein by reference. Genetically modified variants, particularly of Protease C, are also included herein. Some preferred proteolytic enzymes are selected from the group consisting of Savinase A and Protease B, and mixtures thereof. Bacterial serine protease enzymes obtained from Bacillus subtilis and/or Bacillus licheniformis are preferred. An especially preferred protease herein referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76 in combination with one or more amino acid residue position equivalent to those selected from the group consisting of +99, +101, +103, +107 and +123 in Bacillus amyloliquefaciens subtilisin as described in the concurrently filed patent application of A. Baeck, C. K. Ghosh, P. P. Greycar, R. R. Bott and L. J. Wilson, entitled "Protease-Containing Cleaning Compositions" and having U.S. Ser. No. 08/136,797 (P&G Case 5040). This application is incorporated herein by reference.
Suitable lipases for use herein include those of bacterial, animal, and fungal origin, including those from chemically or genetically modified mutants. Suitable bacterial lipases include those produced by Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034, incorporated herein by reference. Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase produced from the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application 53-20487, laid open on Feb. 24, 1978, which is incorporated herein by reference. This lipase is available under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Such lipases should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure according to Oucheterlon (Acta. Med. Scan., 133, pages 76-79 (1950)). These lipases, and a method for their immunological cross-reaction with Amano-P, are also described in U.S. Pat. No. 4,707,291, Thom et al., issued Nov. 17, 1987, incorporated herein by reference. Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum var. lipolyticum NRRlb 3673, and further Chromobacter viscosum lipases, and lipases ex Pseudomonas gladioli. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272. Other lipases of interest are Amano AKG and Bacillis Sp lipase (e.g. Solvay enzymes). Additional lipases which are of interest where they are compatible with the composition are those described in EP A 0 339 681, published Nov. 28, 1990, EP A 0 385 401, published Sep. 5, 1990, EO A 0 218 272, published Apr. 15, 1987, and PCT/DK 88/00177, published May 18, 1989, all incorporated herein by reference.
Any amylase suitable for use in a dishwashing detergent composition can be used in these compositions. Amylases include for example, 2-amylases obtained from a special strain of B. licheniforms, described in more detail in British Patent Specification No. 1,296,839. Amylolytic enzymes include, for example, Rapidase�, Maxamyl� , Termamyl� and BAN�. In a preferred embodiment, from about 0.001% to about 5%, preferably 0.005% to about 3%, by weight of active amylase can be used. Preferably from about 0.005% to about 3% by weight of active protease can be used. Preferably the amylase is Maxamyl� and/or Termamyl� and the protease is Savinase the formulator will use ordinary skill in selecting amylases or lipases which exhibit good activity within the pH range of the ADD composition.
Stability-Enhanced Amylase
Engineering of enzymes for improved stability, e.g., oxidative stability is known. See, for example J. Biological Chem., Vol. 260, No. 11, Jun. 1985, pp 6518-6521.
"Reference amylase" hereinafter refers to an amylase outside the scope of the amylase component of this invention and against which stability of an amylase within the invention can be measured.
The present invention also can makes use of amylases having improved stability in detergents, especially improved oxidative stability. A convenient absolute stability reference-point against which amylases used in the instant invention represent a measurable improvement is the stability of TERMAMYL (R) in commercial use in 1993 and available from Novo Nordisk A/S. This TERMAMYL (R) amylase is a "reference amylase". Amylases within the spirit and scope of the present invention share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60 a pH from about 8 to about 11, all measured versus the above-identified reference-amylase. Preferred amylases herein can demonstrate further improvement versus more challenging reference amylases, the latter reference amylases being illustrated by any of the precursor amylases of which the amylases within the invention are variants. Such precursor amylases may themselves be natural or be the product of genetic engineering. Stability can be measured using any of the art-disclosed technical tests. See references disclosed in WO 94/02597, itself and documents therein referred to being incorporated by reference.
(a) An amylase according to the hereinbefore incorporated WO/94/02597, Novo Nordisk A/S, published Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine (preferably threonine), of the methionine residue located in position 197 of the B.licheniformis alpha-amylase, known as TERMAMYL (R), or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus;
(b) Stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8,15,197,256,304,366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE(R) and SUNLIGHT(R);
Suitable chlorine scavenger unions are widely available, indeed ubiquitous, and are illustrated by salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired. In general, since the chlorine scavenger function can be performed by several of the ingredients separately listed under better recognized functions, (e.g., other components of the invention including oxygen bleaches), there is no requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment of the invention; even then, the scavenger is added only for optimum results. Moreover, the formulator will exercise a chemist's normal skill in avoiding the use of any scavenger which is extremely incompatible with other optional ingredients, if used. For example, formulation chemists generally recognize that combinations of reducing agents such as thiosulfate with strong oxidizers such as percarbonate are not wisely made unless the reducing agent is protected from the oxidizing agent in the solid-form ADD composition. In relation to the use of ammonium salts, such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in U.S. Pat. No. 4,652,392, Baginski et al.
Levels of the suds suppressor depend to some extent on the sudsing tendency of the composition, for example, an ADD for use at 2000 ppm comprising 2% octadecyldimethylamine oxide may not require the presence of a suds suppressor. Indeed, it is an advantage of the present invention to select cleaning-effective amine oxides which are inherently much lower in foam-forming tendencies than the typical coco amine oxides. In contrast, formulations in which amine oxide is combined with a high-foaming anionic cosurfactant, e.g., alkyl ethoxy sulfate, benefit greatly from the presence of suds suppressors.
Suitable corrosion inhibitors include paraffin oil typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50: preferred paraffin oil selected from predominantly branched C.sub.25-45 species with a ratio of cyclic to noncyclic hydrocarbons of about 32:68; a paraffin oil meeting these characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70.
Other suitable corrosion inhibitor compounds include benzotriazole and any derivatives thereof, mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms including lauryl mercaptan, thiophenol, thionapthol, thionalide and thioanthranol. Also suitable are the C.sub.12 -C.sub.20 fatty acids, or their salts, especially aluminum tristearate. The C.sub.12 -C.sub.20 hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-decane and other anti-oxidants such as betahydroxytoluene (BHT) are also suitable.
The present invention also encompasses methods for cleaning soiled tableware, especially plastic ware. A preferred method comprises contacting the tableware with a pH wash aqueous medium of at least 8. The aqueous medium comprising at least about 1% diacyl peroxide. The diacyl peroxide is added in a stabilized particle form.
A preferred method for cleaning soiled tableware comprises using the diacyl peroxide particle, enzyme, low foaming surfactant and detergency builder. The aqueous medium is formed by dissolving a solid-form automatic dishwashing detergent in an automatic dishwashing machine. A particularly preferred method also includes low levels of silicate, preferably from about 3% to about 10% SiO.sub.2.
Process for Preparing Diacyl Peroxide Particles
A variety of methods may be employed to prepare the diacyl peroxide particles. Conventional methods of agitating, mixing, agglomerating and coating particulate components are well-known to those skilled in the art.
For examples, in one embodiment the water-insoluble diacyl peroxide is provided in a solid form and intimately mixed with a redox stable inorganic salt, such as sodium sulfate. To this mixture are added other stabilizing additives by liquid spray-on in any of a variety of conventional liquid-to-solids contacting equipment to provide an agglomerated particle with a size suitable for mixing into a granular ADD and preventing segregation of the particle within the composition. If the stabilizing additives are used as aqueous solutions or dispersions, then excess water is dried off using conventional drying equipment. Liquid-to-solids contacting, and drying can be done in the same equipment or in two separate steps depending on the specific application.
Chelants and/or antioxidants can be added as solids to the dry mix of the diacyl peroxide and the redox stable inorganic salt formed above, or as liquids along with the liquid binder used to agglomerate the particles of the dry mix.
In a preferred embodiment, the agglomerated particle described above is further coated with a material in which the diacyl peroxide does not dissolve under particle processing and/or product storage conditions. Preferred materials are water soluble. Particularly preferred materials are also non-aqueous, have a melting point below that of the diacyl peroxide, preferably between about 100 F., most preferably between about 120 and are not miscible at temperatures up to 100 120
In another embodiment the water-insoluble solid-form diacyl peroxide is provided with a very fine particle size (preferably less than 300 μm, more preferably less than 150 μm). If this is not the size achieved in the basic production process, then this size can be achieved through grinding, either in the wet or dry state. This can be done before addition of a redox stable inorganic salt, or preferably as a dry mix with an inorganic salt. Reduction of the particle size, while making the stabilization challenge even greater helps keep the diacyl peroxide from remaining as residue after the dishwashing process.
In an alternate method, a mixture of the diacyl peroxide and a redox-stable inorganic salt and other optional stabilizing additives are co extruded with a stabilizing binder in which the diacyl peroxide does not dissolve to provide an extrudate. The extrudate shape reduces the surface area for interaction with incompatible materials in the ADD composition as compared to a roughly spherical agglomerate. The stabilizing binder would most preferably have the same properties as described above.
In yet another alternate method, the water insoluble diacyl peroxide (e.g. dibenzoyl peroxide) is provided as an aqueous suspension, or mixed into an aqueous solution of a binding agent (e.g.. Acusol 445N). This mixture is then combined with an inorganic salt, to form a granulated particle. Excess water is dried off using conventional drying equipment. This particulate is then coated as described above.
In still another method, the water insoluble diacyl peroxide is mixed in with a non-aqueous coating agent in which the diacyl peroxide is not soluble to form a paste. It is particularly preferred when the non-aqueous coating agent has a melting point above 120 above the melting point of the coating agent) is then combined with an inorganic salt and cooled to form a particle. A variety of granulation techniques can be used to intimately mix the paste and the inorganic salt, including, but not limited to agglomeration, coating, extrusion, and flaking. By embedding the diacyl peroxide within the coating agent, deleterious interactions with incompatible components in the final product can be avoided.
This is a continuation of application Ser. No. 08/352,468, filed on Dec. 9, 1994 now abandoned.
Citations de brevets Brevet cit� Date de d�p�t Date de publication D�posant TitreUS295590525 juil. 195611 oct. 1960Lever Brothers CompanyPeroxide-ester bleaching process and compositionsUS360699012 f�vr. 197021 sept. 1971Colgate-Palmolive Co.Process for washing laundry and detergent composition for working of this processUS363426623 juil. 196911 janv. 1972Procter & Gamble Co.:TheLiquid detergent compositions containing amylolytic enzymesUS402136015 oct. 19753 mai 1977Desoto, Inc.Powder detergent compositionsUS40254539 f�vr. 197624 mai 1977Shell Oil CompanyActivated bleaching process and compositions thereforUS40338945 juin 19755 juil. 1977Desoto, Inc.Powder detergent compositionsUS408617522 nov. 197625 avr. 1978Shell Oil CompanyActivated bleaching process and compositions thereforUS40861779 f�vr. 197625 avr. 1978Shell Oil CompanyActivated bleaching process and compositions thereforUS409225821 ao�t 197530 mai 1978Desoto, Inc.Powder detergent compositionsUS410009527 ao�t 197611 juil. 1978The Procter & Gamble CompanyPeroxyacid bleach composition having improved exotherm controlUS43870445 oct. 19817 juin 1983Pennwalt CorporationSafe, dry, free-flowing solid peroxide/unsubstituted or alkyl substituted benzoic acid compositionsUS444467417 mars 198324 avr. 1984The Procter & Gamble CompanyGranular bleach activator compositions and detergent compositions containing themUS453076624 sept. 198423 juil. 1985Rohm And Haas CompanyMethod of inhibiting scaling in aqueous systems with low molecular weight copolymersUS454730514 juil. 198315 oct. 1985Lever Brothers CompanyLow temperature bleaching detergent compositions comprising peracids and persalt activatorUS45684766 ao�t 19844 f�vr. 1986Lever Brothers CompanyEnzymatic machine-dishwashing compositionsUS46559535 d�c. 19847 avr. 1987Lever Brothers CompanyDetergent bleach compositionsUS472035314 avr. 198719 janv. 1988Richardson-Vicks Inc.Stable pharmaceutical w/o emulsion compositionUS498836315 juin 198929 janv. 1991Lever Brothers Company, Division Of Conopco, Inc.Detergent bleach composition and method of cleaning fabricsUS50891628 mai 198918 f�vr. 1992Lever Brothers Company, Division Of Conopco, Inc.Cleaning compositions with bleach-stable colorantUS513004431 janv. 198914 juil. 1992The Clorox CompanyDelayed onset active oxygen bleach compositionUS51300455 juin 199014 juil. 1992The Clorox CompanyDelayed onset active oxygen bleach compositionUS517320731 mai 199122 d�c. 1992Colgate-Palmolive CompanyPowered automatic dishwashing composition containing enzymesUS52137068 nov. 199125 mai 1993Lever Brothers Company, Division Of Conopco, Inc.Homogeneous detergent gel compositions for use in automatic dishwashersUS524661221 ao�t 199221 sept. 1993Lever Brothers Company, Division Of Conopco, Inc.Machine dishwashing composition containing peroxygen bleach, manganese complex and enzymesUS525813231 mars 19922 nov. 1993Lever Brothers Company, Division Of Conopco, Inc.Wax-encapsulated particlesUS531463928 janv. 199124 mai 1994Akzo N.V.Agglomeration of solid peroxidesUS533847425 f�vr. 199216 ao�t 1994Lever Brothers Company, Division Of Conopco, Inc.System for releasing bleach from a bleach precursor in the wash using an enzyme activatorEP0239379A225 mars 198730 sept. 1987Amway CorporationWater spot control and dish-washing compositionsEP0295093A19 juin 198814 d�c. 1988Unilever N.V.Liquid machine dishwashing compositionEP0337535A224 mars 198918 oct. 1989Unilever N.V.Bleaching compositionEP0504091A112 mars 199216 sept. 1992Cleantabs A/SA phosphate-free automatic dishwashing compositionEP0516553A229 mai 19922 d�c. 1992Colgate-Palmolive CompanyPowdered automatic dishwashing composition containing enzymesEP0619366A15 avr. 199312 oct. 1994THE PROCTER &amp; GAMBLE COMPANYLavatory blocks containing active oxygenFR2311089A1 Titre non disponibleGB1022893A Titre non disponibleGB1293063A Titre non disponibleGB2285629A Titre non disponibleWO1995033817A118 mai 199514 d�c. 1995Unilever N.V.Encapsulates containing surfactant for improved release and dissolution ratesCitations hors brevetsR�f�rence1"Peroxides and Peroxy Compounds, Organic".2"The Stability of a Benzoyl Peroxide Acne Cream Product" published in the Canadian Journal of Pharmaceutical Sciences, Dec. 1967.3Peroxides and Peroxy Compounds, Organic .4The Stability of a Benzoyl Peroxide Acne Cream Product published in the Canadian Journal of Pharmaceutical Sciences, Dec. 1967.5U.S. application No. 08/052,850, Raleigh et al., filed Arp. 26, 1993.6U.S. application No. 08/106,022, Burckett St. Laurent, Aug. 13, 1993.7U.S. application No. 08/106,022, Burckett-St. Laurent, Aug. 13, 1993.8U.S. application No. 08/147,219, Sadlowski, filed Nov. 3, 1993.9U.S. application No. 08/147,224, Sadlowski, filed Nov. 3, 1993.10U.S. application No. 08/172,627, Sadlowski, filed Dec. 23, 1993.11U.S. application No. 08/172,630, Sadlowski, filed Dec. 23, 1993.12U.S. application No. 08/226,929, Taylor et al., filed Apr. 13, 1994.13U.S. application No. 08/263,165, Painter, filed Dec. 16, 1991. R�f�renc� par Brevet citant Date de d�p�t Date de publication D�posant TitreUS57633782 avr. 19969 juin 1998The Procter & Gamble CompanyPreparation of composite particulates containing diacyl peroxide for use in dishwashing detergent compositionsUS583766323 d�c. 199617 nov. 1998Lever Brothers Company, Division Of Conopco, Inc.Machine dishwashing tablets containing a peracidUS606374712 juil. 199616 mai 2000The Procter & Gamble CompanyDetergent compositions in compacted solid formUS614704518 juil. 199614 nov. 2000The Procter & Gamble Co.Detergent compositions comprising specific amylase and a specific surfactant systemUS630621918 juil. 199723 oct. 2001The Procter & Gamble CompanyMethod for stain removal on hard surfaces with detergent compositions containing bleachUS644092018 juil. 199727 ao�t 2002The Procter & Gamble CompanySprayable, liquid or gel detergent compositions containing bleachUS653995424 nov. 19991 avr. 2003Clariant GmbhMachine dishwashing detergentUS664556930 janv. 200211 nov. 2003The Procter & Gamble CompanyMethod of applying nanoparticlesUS686393330 janv. 20028 mars 2005The Procter And Gamble CompanyMethod of hydrophilizing materialsUS687244430 janv. 200229 mars 2005The Procter & Gamble CompanyEnhancement of color on surfacesUS726508112 mai 20034 sept. 2007Reckitt Benckisder N.V.Detergent composition comprising a bleach and an edible oilUS731911215 sept. 200315 janv. 2008The Procter & Gamble Co.Non-halogenated antibacterial agents and processes for making sameUS761880130 oct. 200717 nov. 2009Danison US Inc.Streptomyces proteaseUS76489538 mai 200819 janv. 2010The Dial CorporationEco-friendly laundry detergent compositions comprising natural essenceUS767875220 mars 200716 mars 2010The Procter & Gamble CompanyFabric care composition comprising organosilicone microemulsion and anionic/nitrogen-containing surfactant systemUS770943624 juil. 20084 mai 2010The Dial CorporationLow carbon footprint compositions for use in laundry applicationsUS787978829 sept. 20091 f�vr. 2011Danisco Us Inc.Methods of cleaning using a streptomyces 1AG3 serine proteaseUS79280528 d�c. 200519 avr. 2011Dow Global Technologies LlcEnzyme stabilizationUS798556931 mai 200726 juil. 2011Danisco Us Inc.Cellulomonas 69B4 serine protease variantsUS79941103 mai 20069 ao�t 2011Evonik Degussa GmbhSolid redispersible emulsionUS800824516 sept. 200930 ao�t 2011The Procter & Gamble CompanyFabric care compositions and systems comprising organosilicone microemulsions and methods employing sameUS818302410 nov. 200922 mai 2012Danisco Us Inc.Compositions and methods comprising a subtilisin variantUS83947529 d�c. 200912 mars 2013The Procter & Gamble CompanyPearlescent agent slurry for liquid treatment compositionEP1241112A211 juil. 200118 sept. 2002THE PROCTER &amp; GAMBLE COMPANYFlexible multiple compartment pouchEP1975225A125 f�vr. 20081 oct. 2008The Procter and Gamble CompanyDetergent compositionEP1978081A223 oct. 20018 oct. 2008The Procter and Gamble CompanyStabilized liquid compositionsEP2053119A114 oct. 200829 avr. 2009The Procter and Gamble CompanyFabric softening compositions having improved stability upon storageEP2169040A130 sept. 200831 mars 2010The Procter and Gamble CompanyLiquid detergent compositions exhibiting two or multicolor effectEP2169041A130 sept. 200831 mars 2010The Procter and Gamble CompanyLiquid detergent compositions exhibiting two or multicolor effectEP2169042A130 sept. 200831 mars 2010The Procter and Gamble CompanyComposition comprising microcapsulesEP2319857A24 mars 200411 mai 2011Yeda Research And Development Co., Ltd.Pon polypeptides, polynucleotides encoding same and compositions and methods utilizing sameEP2322593A112 nov. 200918 mai 2011The Procter and Gamble CompanyLiquid laundry detergent compositionEP2322595A112 nov. 200918 mai 2011The Procter and Gamble CompanySolid laundry detergent compositionEP2426192A120 mars 20077 mars 2012The Procter and Gamble CompanyLiquid treatment compositionWO1999020726A123 oct. 199829 avr. 1999Baeck, Andre, CesarBleaching compositions comprising multiply-substituted protease variantsWO2002018531A113 ao�t 20017 mars 2002Hindustan Lever LtdCleaning aidWO2002087793A11 mai 20027 nov. 2002The Procter & Gamble CompanyStable liquid or gel bleaching composition containing diacyl peroxide particlesWO2005014768A17 juil. 200417 f�vr. 2005Degussa AgBleaching-action dishwasher detergent with improved yellowing resistance and process for its productionWO2007031387A121 ao�t 200622 mars 2007Degussa AgPellets made of diacyl peroxide in a polysaccharide matrixWO2009058679A124 oct. 20087 mai 2009Danisco Us Inc., Genencor DivisionStreptomyces proteaseWO2010108000A118 mars 201023 sept. 2010The Procter & Gamble CompanyStructured fluid detergent compositions comprising dibenzylidene polyol acetal derivatives and detersive enzymesWO2010108002A118 mars 201023 sept. 2010The Procter & Gamble CompanyStructured fluid detergent compositions comprising dibenzylidene sorbitol acetal derivativesWO2011059714A128 oct. 201019 mai 2011The Procter & Gamble CompanySolid laundry detergent compositionWO2011060028A110 nov. 201019 mai 2011The Procter & Gamble CompanyLiquid laundry detergent compositionWO2011130222A212 avr. 201120 oct. 2011Danisco Us Inc.Compositions and methods comprising variant proteasesWO2011150157A226 mai 20111 d�c. 2011Danisco Us Inc.Detergent compositions containing streptomyces griseus lipase and methods of use thereofWO2012001078A129 juin 20115 janv. 2012Hindustan Unilever LimitedPackaged fabric cleaning compositionsWO2012001079A129 juin 20115 janv. 2012Hindustan Unilever LimitedPackaged fabric cleaning compositionsWO2012075086A230 nov. 20117 juin 2012The Procter & Gamble CompanyFabric care compositionWO2012075212A11 d�c. 20117 juin 2012The Procter & Gamble CompanyFabric care compositionsWO2012075213A11 d�c. 20117 juin 2012The Procter & Gamble CompanyFabric care composition and a method of making itWO2012135411A129 mars 20124 oct. 2012The Procter & Gamble CompanyFabric care compositions comprising front-end stability agentsWO2012149317A127 avr. 20121 nov. 2012Danisco Us Inc.Detergent compositions containing bacillus agaradhaerens mannanase and methods of use thereofWO2012149325A127 avr. 20121 nov. 2012Danisco Us Inc.Detergent compositions containing geobacillus tepidamans mannanase and methods of use thereofWO2012149333A127 avr. 20121 nov. 2012Danisco Us Inc.Detergent compositions containing bacillus sp. mannanase and methods of use thereofWO2012151480A24 mai 20128 nov. 2012The Procter & Gamble CompanyCompositions and methods comprising serine protease variantsWO2012151534A14 mai 20128 nov. 2012Danisco Us Inc.Compositions and methods comprising serine protease variantsFaire pivoterImage d'origineAccueil Google - Plan du site - T�l�chargements par lot sur l'USPTO - R�gles de confidentialit� - Conditions d'utilisation - � propos de Google�Brevets - Envoyer des commentairesDonn�es fournies par IFI CLAIMS Patent Services©2012 Google