MXPA97005496A - Detergent compositions that buy from stabilized compounds in polyaminoac - Google Patents

Abstract

The present invention relates to a composition containing a surfactant, at least one polyamino acid compound and at least one protein, wherein said polyamino acid compound and said protein are in close physical proximity to each other.

Description

DETERGENT COMPOSITIONS THAT COMPRISE STABILIZED POLYAMINOACY COMPOUNDS FIELD OF LF > INVENTION The present invention relates to the use of polyacidic acid containing compounds and salts thereof in detergent compositions, Nuy in particular, refers to the use of a polyamino acid, including polyaspartic acid, wherein said non-acidic polyacid is in close physical proximity to a protein to protect it against degradation.

BACKGROUND OF THE INVENTION The polyarnino acid agents can be used in detergent compositions as builders or dispersing agents. Said description is given in EP 454126 which describes polyacids, including polyaspartic acid, co-builders or biodegradable co-builders in the formulation of detergents. Said polymers, especially those derived from aspartic acid, tartaric acid and mixtures thereof, are described as heat resistant, and pH stable, non-toxic, non-irritating and completely biodegradable. However, a problem encountered with such use is the degree of degradation of those polymers under storage and over a period. PCT / US93 / 12090 describes the use of polyaminoacetate protected against contact with a level of alkalinity that could cause degradation thereof. Said polyamino acid is provided with a coating, encapsulated or mixed in the form of an agglomerate or granulate with at least one other material which is preferably an alkaline or alkaline reaction compound. However, the research carried out by the applicant hereby revealed that this type of protection will also be degraded under storage. This is "partially" due to the enzymatic action and alkaline hydrolysis. It has now been found that a detergent composition containing a surfactant, at least one compound or polyamino acid and at least one protein wherein said polyarnino acid compound and said protein are in close physical proximity shows increased storage stability. An additional advantage to the close physical proximity of said amino acid compound and said protein is the increased stability and protection against bleaches. Another object of the present invention is to provide a detergent composition with effective removal performance of stains and dirt.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to a detergent composition comprising a detersive surfactant, at least one polyamide compound and at least one protein wherein said polyamino acid compound is in close physical proximity. For the purpose of the present invention, the term "close physical proximity" means one of the following: i) an agglomerate or extruded product in which said inoperated polyacid compound and said protein are in an intimate mixture; 11) a polyamino acid particulate material coated with one or more layers wherein at least one layer contains the protein; ni) a protein coated with one or more layers wherein at least one layer contains the polyamino acid compound. By close physical proximity it should be understood that the polyarnino acid compound and the protein are not two separate discrete particles in the detergent composition. The mixture of polyamino acid compound and protein may be present within the detergent composition in a selected form of an agglomerate, a granulated material, a tablet and mixtures thereof. A process for producing said mixture in the form of an agglomerate within a detergent composition is also provided herein.

TECHNICAL FIELD OF THE INVENTION The present invention contemplates detergent compositions containing a dispersant having excellent storage stability against enzymes as well as against bleaches. Very particularly, it relates to a detergent composition containing a detersive surfactant, at least one polyamino acid compound and at least one protein wherein said polyamino acid compound and said protein are in close physical proximity. An essential component for the purpose of the invention is a polyamino acid compound. The term "polyacid compound" includes here not only a polyamino acid as such but also a derivative thereof, such as an amide, an ester or a salt. The polyamino acid may be a copolymer or may be a copolymer of two or more amino acids. The amino acid may be a D-amino acid, an L-amino acid or a mixture, e.g., a racemic mixture thereof. The amino acids include, for example, alanine, glycine, tyrosine, cerin and licina although glutamic, carboxyglutatic and aspartic acids are preferred. Of these, aspartic acid is particularly preferred. Normally, for the purpose of formulating a detergent composition, in a laundry detergent composition, the. polyamino acid will be used in the form of a salt thereof, preferably an alkali metal salt and most preferably the sodium salt. It will be understood that the polyamino acid compound may be constituted by a mixture of two or more compounds of the appropriate description. The molecular weight of. The polyamino acid compound can vary within wide limits, preferably, the molecular weight is from 500 to 200,000, most preferably from 2,000 to 20,000. The polyamino acid described above will comprise from 10% to 90%, preferably from 10% to 40%, and preferably from 10% to 20% by weight of the polyamino acid-protein mixture. The other essential component useful for the purpose of the invention is a protein that is in intimate contact with the polyamino acid to protect it against attack by enzymes and by bleaches. By protein is meant any of a class of polymer compounds of high molecular weight compounds of a variety of alpha-amino acids joined by peptide bonds, excluding those from the group of catalytic proteins that are produced by living cells and which are mediators and promoters of the proteins. chemical processes of life without being altered or destroyed by themselves. The proteins suitable for the purpose of the invention are microorganisms (yeasts, bacteria, molds, etc.) and that proteins extracted therein, proteins of animal origin (collagen , gelatin, glue, keratin, casein, egg albumin, etc) and proteins of vegetable origin (soy proteins, wheat gluten, etc). A preferred protein is egg white albumin. The protein described herein will comprise from 10% to 90%, preferably from 1.0% to 40% and preferably from .10% to 20% by weight of the polyamino acid-protein mixture. In accordance with the present invention, a polyamino acid compound is stabilized against degradation enough to render it acceptably stable on storage. This is done, in particular, by protecting said compound against contact with enzymes, bleaches and high alkalinity. Said stabilization can be obtained by mixing said polyaspartate with a protein as described above wherein said polyarnino acid compound and said protein are in close physical proximity (e.g., the protein is mixed to the polyamino acid in an intimate contact such that the enzymes , source of damage to said polyamino acid, preferably and selectively will attack the protein in place of the polyamino acid compound). Another advantage to said mixture is the additional protection of the polyamino acid against bleaches and high alkalinity which has also been shown to be detrimental to the stability of said polyamino acid under storage. The stabilization or protection should be such that the amount of degradation of the polyamino acid compound in the detergent composition is less than 50% during a storage period of 4 weeks under adverse conditions (32.2 ° C and 80% relative humidity) and preferably less than 50%. of 30%. Additional components can be added to the mixture.

Suitable components are those which have no deleterious effect on the properties of the mixture so that the amount of degradation of the polyamino acid remains as specified above. Suitable components that can be added to said mixture are carbonates (including bicarbonate), sulfates and aluosilicates. Another preferred embodiment suitable for the purpose of the invention comprises agglomerates formed from the mixture of polyamino acid and protein and contained in said detergent composition to increase the stabilization. Of course, other components may be included in said agglomerates. The agglomeration of the polyacid compound and the protein can be carried out using any suitable agglomeration technique and apparatus, if appropriate with compatible agglomeration aids. Said techniques, apparatuses and auxiliaries are well known in the detergent formulation art. Once the agglomerates are formed, they can be dried, if required, by conventional means. A suitable process for producing a detergent composition, containing said polyarninoacid-protein mixture in the form of an agglomerate, comprises the steps of: a) contacting said protein with the polyamino acid in the presence of water, b) stirring the resulting mixture to obtain a solid brittle agglomerate; c) grind said agglomerate to obtain a size of 250 μ to 800μ. d) incorporating the agglomerate in the detergent composition. A typical agglomerate formulation comprises: 10 to 90% polyamino acid compound rotates 10 to 40% The molten materials, i.e. the inoperated polyacid compound and the protein agglomerating agent, are fed to the agglomerator at a temperature between 35 ° C and 40 ° C. The resulting mass is then mixed for an additional 3 hours until a yellow / brown paste is formed. After stopping the mixing and the pasta is left in an oven at 35 ° C for 24 hours. The resulting solid is crushed to a fine powder in a mortar and pestle. The product is then sieved and the materials that are larger than 80 micras and less than 250 micras are removed. The stabilized polyarnino acid (e.g., the polyarninoacid-protein mixture) in accordance with the present invention is used as a dispersing agent (said term includes a clay dirt suspending agent and / or an anticaking agent). i redeposition) in solid detergent compositions (vr, granulated or particulate material) and will generally be employed thereon at a level of 0.1% to 50%, generally at least 0.4% preferably 1 to 15%, preferably from 1% to 10% and most preferably from 2.5% to 5.5% by weight of the detergent composition. The polyamino acid / protein mixture will generally have a ratio of said polyacid to said pro-eine from 9: 1 to 1: 9, preferably from 4: 1 to 1: 4 and most preferably from 2: 1 to 1: 2. Although the acid-protein polyacid mixture can be included in a wide variety of cleaning compositions, for example, hard surface and other household cleaning compositions and dishwashing compositions are particularly suitable for use in laundry detergent compositions, vr, Detergent compositions for general purposes or for heavy duty laundry. These will contain not only the stabilized mixture of polyarninoacid-protein compound and detersive surfactant but also optionally one or more components conventional in the art; these may be selected, for example, from a builder, a bleach (in particular a source of hydrogen peroxide, v.gr, sodium perborate or sodium percarbonate), a bleach activator, an enzyme, a releasing agent € polymeric dirt, a chelating agent, a conventional dispersing agent, a brightener, a suppressant * of foams, a regulatory agent < J- > pH, a dye, a dye transfer inhibiting agent or a pigment. It is understood that any of the aforementioned components, whether essential or optional, may be constituted, if desired, by a mixture of two or more compounds of the appropriate description.

Detersive surfactants The total amount of surfactants will generally be up to 70%, typically from 1 to 55%, preferably from 1 to 30%, most preferably from 5 to 25% and especially from 10 to 20% by weight of the surfactant. total composition. Non-limiting examples of surfactants useful herein include the conventional Cu Cie alkylbenzene sulphonates ("LAS") and the primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the secondary alkyl sulfates (2,3) Cio-Ciß of the formula CH3 (CH2) * (CH0S03-M +) CH3 and CH3 (CH2) and (CH0 03-M +) CH2CH3 where xy (y + 1) are integers of at least 7, preferably at least about 9, and M is a cation of solubilization in water, especially sodium, saturated materials such as oleum sulfate, the alkylalkysulfates of Cι-Ciß ("AExS" r especially ethoxysulfates EO 1-7), alkylalkoxycarboxylates of Cι-Ciß (especially ethoxycarboxylates EO 1-5), the glycolic ethers of Cio-Ciß. the alkyl polyglycosides of Cio-Cie and their corresponding sulfated polycosides, and C12-C18 alphasulfonated fatty acid esters. If desired, conventional non-ionic and amphoteric surfactants such as C12-C18 alkyletoxylates ("AE") including lo ?, termed alkylate. narrow-cough and the C6-C12 alkylphenol-alkoxylates (especially ethoxylates and ethoxy / mixed propoxy), C12-C18 betaines V sulphobetaines ("sultaines"), C14-C13 amine oxides, and the like can also be included in the global compositions. Cío-Ciß N-alkyl polyhydroxylic acid anudas can also be used. Typical examples include N-met? Iglucamins of C12-Cie. See UO 9,206,154. Other surfactants derived from sugar include the N-alkoxy polyhydric acid fatty acid amides, such as N- (3-methox? Propyl) glucanic acid of Cio-Ciß- The N-propyl to N-hexylglucamides of C12- C18 can be used for low foaming. Conventional C10-C20 soaps can also be used. If high spurnation is desired, branched chain Cio-Ciß soaps can be used. Other surfactants suitable for the purpose of the invention are alkali metal sarcosmates of the formula: wherein R is a linear or branched C9-C17 alkyl or alkenyl group, I is an alkyl group of C1; -C4 and H is a metal ion. Preferred examples are lauroyl, coco (C12-C14), ristinyl or oleyl-ineylsarcosinates in the form of their sodium salts. Mixtures of anionic and nonionic surfactants are especially useful. Other useful conventional surfactants such as cationics are listed in normal textbooks.

Auxiliary ingredients The compositions herein may optionally include one or more auxiliary detergent materials or other materials to assist or increase cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g. , dyes, dyes, etc.). The following are illustrative examples of said accompanying materials.

Detergency builders - Builders may optionally be included in the compositions herein to help control the hardness of minerals. Inorganic and organic builders can be used. Builders are typically used in fabric washing compositions to help remove particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% detergency builder. Liquid formulations typically comprise from about 10% to about 80%, very typically from about 15% to about 50% by weight of the surfactant enhancer. However, they do not exclude lower or higher detergency builder * levels. Inorganic builders or qu <; Do contain phosphate include, but are not limited to the alkali metal, ammonium and alkanolarnome salts of polyphosphate or *, (illustrated by the polynucleotides, pyrophosphates and metaphosphate). Non-phosphate builders can also be used. These include, but are not restricted to, phytic acid, silicates, alkali metal carbonates (including vicarbonates and sesquicarbonates), sulfates, alurninosilicates, rnonorneric polycarboxylates, acid *, polycarboxylic furnace or co-olyls or their salts in which the acid The polycarboxylic acid comprises at least two separated radicals, carboxylic acids, linked together by more than two carbon atoms, organic phosphonates and arninopolyalkylene phosphonates. The compositions herein work surprisingly well even in the presence of so-called "weak" detergency builders (as compared to phosphates) such as, or in the so-called "detergency sub-improvement" situation that may occur with the enhancement enhancers. detergency of zeolite or layered silicate.

Examples of silicate builders are the so-called 'amorphous' alkali metal silicates, particularly those having a ratio of 2: Na2? on the 1.6: 1 to 3.2: 1 scale and stratified silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SK -6"). Unlike zeolite builders, the NaSKS-6 silicate builder * does not contain aluminum. Fl NaSK -6 has the morphological form of delta-Na2? 0s of silLcato estra i icado. It can be prepared by methods such as those described in German Application DE-A-3, 417, 649 and DE-A-3,742,043. SKS-6 is a highly preferred stratified silicate for use herein, but other layered silicates, such as those having the general formula NaM i ?? 2x +? yH2? wherein 1 * 1 is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and is a number from 0 to 20, preferably 0 may be used herein. Some other stratified silicates from Hoechst include NaSKS ~ 5, NaSKS-7 and NaSKS-ll as the alpha, beta and gamma forms. As noted above, the delta-Na2 i0s (NaSKS-6) form is the preferred one for use herein. Other silicate can also be used, such as, for example, magnesium silicate, which can be used as a precipitating agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are the alkali metal and alkali metal carbonates as described in German Patent No. 2,321,001 published November 15, 1973. The detergent builders of aluminum are useful herein. invention. Aluminoside detergent builders are of great importance in the majority of commercially available heavy duty granular detergent compositions, and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosylic acid builders include those that have the empirical formula: NazC (ñi? 2) (S1O2) and 3- XH2O where z and y are integers of at least 6, the mol arde zay ratio is on the 1.0 scale to 0.5, and x is an integer from 15 to 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically derived alsosilicates. A method for producing alternosyl icate ion exchange materials is described in US Patent 3,985,669, Krumm 1 and others issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available Ba or the designations Zeolite fl, Zeolite P (), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the ion exchange material of crystalline alurnmosyl icate has the formula: Nai 2 T (P 102) 12 (YES 02) 12 H xF - O where x is from 20 to 30, especially around 27. The material is known as Zeolite fl. Dehydrated reolitas (x = 0 10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein "polycarboxylates" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate detergent builders can generally be added to the composition in acid form, but they can also be added in the form of a neutralized salt. When used in the salt form, alkali metals such as sodium, potassium and lithium, or alkanolaronium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders comprises polycarboxylates of ether, including oxydi succinate, as described in Berg, US Patent 3,128,287, issued April 7, 1964, and Lamberti et al., Patent. US Pat. No. 3,635,830, issued January 18, 1972. See also "TMS / TDS" detergency builders of US Pat. No. 4,663,071, issued to B? sh et al. on May 5, 1987. Suitable ether polycarboxylates they also include cyclic compounds, particularly alicyclic compounds, such as those described in the EUfl Patents. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of naleic anhydride with ethylene or methyl ether, or acrylic acid, 1, 3,5-tph? Drox? Benzene-2,4,6-tr sulfone? Acid and acid carboxy-rnetiioxy succinic, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediapunotetraacetic acid and nitropotriacetic acid, as well as polycarboxylates such as rnelitic acid, succinic acid, oxysuccinic acid, poly-alic acid, benzene-1 acid , 3, 5-t pcarboxylic acid and carboxymethyl cyclic lactic acid and soluble salts thereof. Citrate detergent builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations because of their availability from renewable resources and their biodegradability. The compositions can also be used * in granular compositions, specifically in combination with aeolith detergent builders and / or silicate is ratified. Oxydisuccinates are also especially useful in said compositions and combinations. Also suitable in the detergent compositions of the present invention are the -dicarboxy-4-oxa-l, 6-hexanedioates and the related compounds described in the U.S. Pat. 4,566,984. Useful succinic acid detergent builders include C5-C20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate detergency builders include lauryl succinate, iristi lsuccmat or, palrnitylyl succinate, 2-dodecemlsuccinate (preferred), 2-pentadecenylsuccina and the like. Lauplsuccinates are detergency builders of this group, and are described in EP Application 0,200,263. Other suitable polycarboxylates are the polyacetal carboxylates described in the U.S. Patent. 4,144,226 and in the Patent of E.U.A. 3,308,067. See also the Patent of E.U.fl. 3,723,322. Fatty acids, e.g., monocarboxylic acids of C12-C18 may also be incorporated into the compositions by themselves, or in combination with the aforementioned detergency builders, especially citrate and / or succinate builders, to provide additional detergency builder activity. Said use of fatty acids will generally result in the reduction of eupurnation, which would be considered by the formulator. In situations where phosphorus-based builders can be used, and especially in the bar formulations used for hand washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphates can be used, piro os ato of sodium and sodium. Phosphonate detergency builders such as ethan-1-hydroxyl, 1-d can also be used. osphonate and other known phosphonates (see, for example, U.S. Patent 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

Bleaching Compounds-Bleaching Agents and Bleach Activators - The detergent compositions herein may contain bleaching agents or bleaching compositions containing bleaching agent and one or more bleach activators. When bleaching compounds are present, they will typically be at levels of 0.1% to 60%, typically from 1% to 30%, and most preferably from 5% to 20%, of the detergent composition, especially for fabric washing.

The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning or other cleaning purposes that are now known or will be known. The bleaching agent, a source of alkaline hydrogen peroxide in the washing solution, is a blanket of inorganic perhydrate normally in the form of the sodium or magnesium salt. The perhydrate may be any of the alkaline inorganic salts such as salts of perborate, rnonohydrate or tetrahydrate, percarbonate, perphosphate and persil icate, but is conventionally a perborate or alkaline metal pereabonater. Sodium percarbonate, which is the preferred perhydrate, is an addition compound having the formula corresponding to 2Na2C? 3.3H2O2, and is commercially available as a crystalline solid. The most commercially available material includes a low level of heavy metal sequestrant such as EDTA, 1-hydroxy ethanol, 1 -difosfomed acid (HEDP) or an ammonophonate, which is incorporated during the manufacturing process. . For the purposes of the detergent composition aspect of the invention, the percarbonate can be incorporated into the detergent compositions without additional protection, but the preferred embodiments of said compositions utilize a coated form of the material. A variety of coatings can be used including borosilicate, borate, boric acid and citrate or sodium silicate of a ratio of 2: 2? from 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to give a level of 2% to 10% (usually 3% to 5%) of silicate solids by weight of the percarbonate. However, the most preferred coating is a mixture of sodium carbonate and sulfate or sodium chloride. The particle size scale of crystalline carbonate is from 350 microns to 1500 microns with an average of approximately 500-1000 microns. Another category of bleaching agents, which may be used without restriction, surrounds the percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include (6-octylamino) -6-oxocaproic acid , (6 ~ non? lapuno) -6-oxo-caproic acid, (6-dec? lam? no) -fi-oxo-caproic acid, rnonoperoxy-magnesium phthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, acid 4-nomamino-4-oxoperoxybutyl p and diperoxide-decanedioic acid. Said bleaching agents are described in the North American patent 4, 483,781, North American patent 4,634,551, European patent 0,133,354, North American patent 4,412,934, North American patent 4,412,934 and European patent EP 0,170,386. Mixtures of bleaching agents can also be used. Peroxygen bleaching agents, per orates, perca bonatos, etc., are preferably combined with bleach activators, which lead to in situ production in the aqueous solution (ie, during the washing process) of the corresponding peroxyacid. to the bleach activator. Various non-limiting examples of activators are described in the U.S. Patent. 4,915,854 and in the U.S. Patent. 4,412,934. Typical activators of nonanoyloxy-benzenesulfonate (NOBS), i sononanoi loxi-benzenesulfonate (ISONOBS), and tetraacet i letilarní na (TflED) and mixtures thereof can also be used. Highly preferred ami-activated bleach activators are those of the formulas: R1N (R5) C) 0) R2C (0) LO R1C (0) N (RS) R2C (0) L wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms; carbon, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, alloys or contains it containing from about 1 to about 10 carbon atoms and L is any suitable residual group. A residual group is any group that is displaced from the bleach activator as a result of a nucleophilic attack on the bleach activator by the perhydroxylic anion. A preferred residual group is phenolsul onate. Preferred examples of bleach activators of the above formulas include (6-octanan-do-caproyl) oxybenzenesulfonate, (6-nonanamyldocaproyl) oxybenzenesulfonate and mixtures of 73 the same as described in the patent of E.U.fl. 4,634,551. Another class of bleach activators includes activators of the benzoxazine type described by Hodge et al. In the U.S. Patent. 4,966,723. A highly preferred bleach activator of the benzoxazm type is: Yet another class of preferred bleach activators includes acyl-lactam activators, especially acylcaprolactams and acylvalerolactams of the formulas: wherein R * is H or an alkyl, aryl, alkoxyalkyl or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactan activators include benzol lcaprolactam, oct anollcaprolactam, 3,5,5-tprnet-l-hexanoi-1-caprolactam, nonanoi-caprolactam, decanoylcaprolactan, undecanolacaprolactan, benzo-11-valerol et ama, octanoyl valerolactam, decanoylvalerolactam, undecenoylvalero-lactarine, nonane-1-valerolactam, 3,5 , 5- + prneti1hexanoiIvalero-lactam and mixtures thereof. See also the Patent of F.U.fl. 4,545,784 which describes acylcaprolactams, including benzoylcaprolac ma, adsorbed on sodium perborate. Yet another class of preferred bleach activators includes the cationic activators, valerolact plus and acylcaprolactane derivatives of the formulas: where x is 0 ol, the substituents R, R 'and R "are each linking Ci-Cio alkyl or hydroxyalkyl groups of C2-C4, or C (CyH2y) 0] n -R' '' where y = 2-4, n-1-20 and R '"is an alkyl group of C? ~ C" or hydrogen and X is an anion. Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One type of oxygen-free bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc phthalocyamines and /? of aluminum. See US Patent 4,033,718. If used, the detergent compositions will typically have 0.025% to 1.25%, by weight, of said bleaches, especially zinc sulfonate phthalocyte. If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in US Patent 5,246,621, US Patent 5,244,594; U.S. Patent 5,194,416; Paten e North American 5,114,606; and European Patent Application Publication Nos. 549.27101, 549.272fll, 544.44002, and 544.490fll. Preferred examples of these catalysts include MnIV2 (u-0) 3 (1, 4, 7-trimethyl-1,4,7-triazacyclononane) 2 (PFβ) 2, M 1 I t 2 (u-0) α (u-) 0Ac) 2 (1,4,7-trimeti 1-1,4, 7-triazacyclononane) 2 (CIO 4) 2; f1niv4 (? -O) e (1,4,7-tpazacyclononanoU (CIO4; ni? i and 4- (u-0)? (u-0Ac) 2 ~ (1, 4,7-trimethyl-l, 4, 7-triazacyclononane) 2 (CIO *) 3, -MnIV (1, 4,7-trimethyl-1, 4,7-triazacyclononane) (OCH 3) 3 (PFβ), and mixtures thereof. in metal include those described in U.S. Patent 4,430,243 and U.S. Patent 5,114,611.The use of manganese with various complex ligands to improve bleaching is also recorded in the following North American Patents: 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161 5,227,084 As a practical matter, and not as a? 6 In this regard, the compositions and processes of the present invention can be adjusted to provide the order of at least one part per ten million of the active bleach catalyst species in the aqueous wash solution, and preferably provide 0.1 ppm to 700 ppm, most preferably from 1 to 500 ppm, of the catalyst species in the laundry solution.

Chelating Agents The detergent compositions of the present invention may also optionally contain one or more iron and manganese chelating agents as an additive detergency builder material. Said chelating agents can be selected from the group consisting of ammocarboxylates, arnmc phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without limiting itself to theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from wash solutions by chelating soluble chelates. Ammocarboxylates useful as chelating agents include etiiendiaminotetraacetates, N-hydroxyetheiae, motroacetates, mtriloacetates, and ilendi -ammotet raproprionates, tpetile + retam nohexaacetates, ethylene-tparninopentaacetates and ethanold glycines, alkali metal salts, ammonium and substituted ammonium thereof and mixtures thereof. same. Preferred biodegradable non-phosphorus chelates for use herein are ethylenediarinodisuccinate ("EDDS"), especially the CS, S isomer described in the U.S.A. 4,704,233, et? Lend? Arn? No-N, N'-d? Glutarnate (EDDG) and 2-hydrox? Propylend? Am? No-N, N '-disuccinate (HPDDS). The inophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least two levels of total phosphorus are allowed in detergent compositions, and include nitrous oxide (rnetiienphosphonates) such as DEOUEST from Monsanto. Preferably, these ammonophosphates do not contain alkyl or alkenyl groups with more than six carbon atoms. Poly-functionally substituted aromatic chelating agents are also useful in the compositions herein. See patent of E.U.A. 3,812,044. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l, 2-dihydrox? -3,5-disulfobenzene. If used, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. Most preferably chelating agents will comprise from about 0.1% to about 3.0% in 78 weight of said compositions.

Enzymes - Enzymes can be included in the formulations herein for a wide variety of laundry purposes of fabrics, including, for example, the removal of protein-based stains, based on carbohydrates or on the basis of glycemic tp, and to avoid the transfer of migratory dyes and the restoration of fabrics. Enzymes to be incorporated include proteases, arnilases, lipases, cellulases and peroxidases, as well as mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as vegetable, animal, bacterial, icotic and yeast origin. However, its choice is governed by several factors such as pH activity and / or optimum stability, terrnostability, stability against active detergents, builders, etc. In this respect, bacterial and fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, very typically about 0.01 mg to about 3 g of active enzyme per gram of the composition. Stated otherwise, the compositions herein typically comprise from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. 79 Suitable examples of proteases are sub-illicides that are obtained from particular strains of B.subt ili s and B.lichemforms. Another suitable protease is obtained from a strain of Bacillus which has maximum activity throughout the pH range of 8-12, developed by Novo Tndudtries fl / S under the trademark ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No.1,243, 784 by Novo. The commercially available proteolytic enzymes suitable for removing protein-based stains include those sold under the trademarks ALCALASE and 5AVINASE from Novo Industries A / S (Denmark) and MAXATASE from International B? O-Synthet? Cs, Ene. (Netherlands) . Other proteases include Protease fl (see 130,756) and Protease B (see 87303761.8). Arnilases include, for example, w-arnylase described in British Patent Specification No. 1,296, 839 (Novo), RflPtDASE, International Bioethics, Inc. and TERMAMYL, Novo Industries. FUNGAMYL (Novo) is especially useful. Cellulae useful in the present invention include both bacterial and fungal cellulase. Preferably, they should have an optimum pH of between 5 and 9.5. Suitable cellulases are described in the U.S. Patent. 4,435,307, which describes fungal cellulase produced by Hú cola nsolens and strain DMS 1800, from Hurm cola or a cellulase-producing fungus 212 for the genus fleromas, and cellulase extracted from the hepatopancreas of a marine mollusk (olabella auricula Solander). Suitable cellulases are also described in GB-A ~ 2,075,028; GB-fl-2.095.275 and DE-OS-2.247.832. ENDO O, CAREZYME both from Novo Industries fl / S are especially useful. Lipase enzymes suitable for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzep flTCC 19,154, as described in British Patent No. 1,372,034. See also lipases in Japanese Patent Application No. 53-20487, open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the brand name Lipase P " Amano ", hereinafter referred to as" Amano-P ". Other commercial lipases include Anano-CES, ex Chromobacter viscosum lipases, e.g. Chromobacter viscosum var. lipolyctun NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and in addition the Chromobacter viscosum lipases from U.S.

Boichemical Corp., E.U.A. and Disoynth Co., The Netherlands, and the lipases of ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Hurnico a lanuginosa and which is commercially available from Novo (see also EPO 341,947) is a preferred lipase for use in the present. The enzymes peroxidase are used in combination oxygen supplies, V.gr., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used to "bleaching solutions", that is, to avoid transfer of dyes or pigments removed from the substrates during the washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, perox dasa of radish, ligninase and halogenperoxidase such as chloroperoxidase and brornoperox asa. Detergent compositions containing peroxidase are described, for example, in International Application PCT UO 89/099813, assigned to Novo Indudtpes fl / S. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are described in U.S. Pat. 3,553,139. Finally, enzymes are described in the U.S. Patent. 4,101,457, and in the patent of E.U.fl. 4,507,219. Useful enzyme materials for liquid detergent formulations and their incorporation into such formulations are described in the U.S. Patent. 4,261,863. Enzymes for detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the U.S. Patent. 3,600,319 and European Patent Application No. G 199 405. Enzyme stabilization systems are also described, for example, in the U.S. Pat. 3,519,570.

Enzyme Stabilizers - The enzymes employed in the present are typically stabilized by the presence of water-soluble calcium ion and / or magnesium ions in the finished compositions that provide said ions to the enzymes. (Calcium ions are in some way generally more effective than magnesium ions and are preferred in the present if only one type of cation is being used). Additional stability can be provided by the presence of several other stabilizers described in the art, especially borate species: see Severson, E.U.A. 4,537,706. The level of calcium or magnesium ions should be selected in such a way that there is always a minimum level available for the enzyme after allowing it to complex with the detergency enhancers, fatty acids, etc., in the composition. Any water-soluble calcium or magnesium salt can be used as the calcium or magnesium ion supply, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, forrnia of calcium and calcium acetate and the corresponding magnesium salts. Frequently, a small amount of calcium ions, generally around * 0.05 to about 0.4 millimoles per liter, is also present in the composition due to the calcium present in the enzyme suspension and the water of the formula. In solid detergent compositions the formulation may include a sufficient amount of a supply of water-soluble calcium ions to provide such an amount in the wash solution. Alternatively, the hardness of the natural water may be sufficient. It should be understood that the aforementioned levels of calcium and / or magnesium ions are sufficient to provide enzyme stability. Additional calcium and / or magnesium ions can be added to the compositions to provide an additional measure of fat removal performance. Accordingly, as a general proposition, compositions herein typically should comprise from about 0.05% to about 2% by weight of a water soluble supply calcium or magnesium ions or both. The amount may vary, of course, depending on the amount and type of enzyme used in the composition. The compositions herein may also optionally contain, but preferably contain several additional stabilizers, especially borate type stabilizers. Typically, such stabilizers are used in the compositions at levels of from about 0.25% to about 10%, preferably from about 0.5% to about 5%, most preferably from about 0.75% to about 3% by weight of boric acid or other a borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid). Boric acid is preferredalthough other compounds such as boric oxide, borax and other alkali metal borates (eg sodium orthoborate, sodium metaborate and sodium pyroborate and sodium pentaborate) are suitable. Substituted boric acids (e.g., phenyl boronic acid, butane boronic acid and p-bromophenylboronic acid) can also be used instead of boric acid.

Other ingredients A wide variety of other functional ingredients commonly used in detergent compositions can be included in the present invention. These include additional soil retardation / anti-redeposition clay agents, polyrnomeric soil release agents, dye transfer inhibiting agents, brighteners, foam suppressors and fabric softeners. The soil retention / soil anti-redeposition agents may include copolymers based on acrylic and maleic, polyethylene glycol (PEG), water-soluble ethoxylated amines and carboxymethyl cellulose (CMC). Other useful ingredients in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, sunscreens for bar compositions, etc. If high sputtering is desired, foaming enhancers such as Cι-C alca alkanolamines can be incorporated into the compositions, typically at levels of 1% -10%. The nonoethanol and diethanolarnins of C? O-C? < i illustrate a typical class of such foam improvers. The use of said foam enhancers with auxiliary surfactants with high foaming such as amine oxides, betaines and sultaines mentioned above is also advantageous. If desired, the soluble magnesium salts such as MgCl 2, MgSO 4 and the like, can be added at typically 0.1% -2% levels, to provide additional foaming and to increase the fat removal performance. Various detersive ingredients employed in the present compositions can be further stabilized by absorbing said ingredients on a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant prior to being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash liquor, where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT DIO, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic surfactant of ethoxylated alcohol of C13-1S (EO 7). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with agitation in silicone oil (Various viscosities of silicone oil can be used on the scale of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions. The liquid detergent compositions may contain water and other solvents as carriers. The low molecular weight primary and secondary alcohols illustrated by methanol, ethanol, propanol and isopropanol are suitable. Unhydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol) can also be used. , glycerin and 1, -propanod? oL). The compositions may contain from 5% to 90%, typically from 10% to 50% of said vehicles. The detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. Liquid product formulations for dishwashing preferrably + have a pH between 6.8 and 9.0. Laundry products typically have a pH of 9 to 11. Techniques for controlling pH at recommended levels of use include the use of pH regulators., alkalis, acids, etc., and are well known to those skilled in the art. The bulk density of the granulated bleaching compositions (so-called granular detergent compositions) is typically at least 450 g / liter, preferably at least 600 g / liter and preferably preferably at least 650 g / liter at 1000 g / liter . The invention is illustrated in the following non-limiting examples in which all percentages are on a weight basis unless otherwise indicated. In the detergent compositions, the abbreviated identifications of the components have the following meanings: LAS: C12 linear sodium alkoxybenzene sulfonate TAS Seboalqui Sodium sodium phosphate XYflS: Sodium alkylsulfate of C? - C? V C24EY: A predominantly linear primary alcohol of C12-14 condensed with an average of Y moles of ethylene oxide. C25EY: A predominantly linear primary alcohol of C12-15 condensed with an average of Y moles of ethylene oxide. C45EY: A predominantly linear primary alcohol, of C14-1S condensed with an average of Y moles of ethylene oxide. CXYEZS: Sodium alkylsulfate of C ?? -C? condensed with an average of Z moles of ethylene oxide per mole. N-Lauroyl-N-methyglucamide amide. polyhydroxylic acid NaSK? -6: Crystalline layered silicate of formula 6Na2SÍ2? s. Carbonate: Anhydrous sodium carbonate. Silicato amorphous sodium silicate (the ratio of S.io2. "Na2 proceeds normally) MO / flfl: Maleic acid / acrylic copoly1: 4, average molecular weight of about 70,000.

Zeolite fl: Hydrated sodium oluninosilicate of formula Nai2 C (fll? 2) (SÍO2)] 12 - 27H20 having a primary particle size on the scale of 1 to 10 microns. Photo- Phthalocyanine zinc tetrasul fonada bleach Citrate: Citrate of trisodium dihi dratado. Acid citric anhydrous citric acid PB1 Sodium perborate bleach monohydrate of nominal formula NaB0- 2H2 Ü2 PB4 Sodium perborate bleach tetrahydrate of nominal formula NaBO-2H2? 2. 3H20 Percarbonate Anhydrous sodium percarbonate bleach of empirical formula 2NaBO2. H2O2. 3H2O coated with a mixed salt of formula Na2 SO *. n .N 2 C03 where n is 0.29 and where the weight ratio of percarbonate to mixed salt is 19: 1. TflED Tetraacetiiet ílendiamma Sa masa Proteolytic enzyme activity 4 KNPU / g Alcalase Proteolytic enzyme activity 3.3 flU / g Lipolase Enzyme activity Ii policy 100 KLU / g Cellulase Cellulose enzyme activity of 1000 SCEVU / g Endo fl Cellulosic enzyme activity of 5000 SCEVU / g all sold by NOVO Industries fl / S. PVNO PolyN-oxide poly1 pin dina molecular weight l, 000 PVPVI Polypoly(pyrrolidone-co-m? Dazole) molecular weight in the scale of 100 to 1000000 gS04 Sulphate of anhydrous magnesium SRP Dirt release poly modified ammonium polyester CMC Carboxymethyl sodium cellulose. EDDS Acid et? Uend? Arn? No-N, N'd? Succ? Co, isoCS, S3 in the form of the sodium salt Abrillan4,4'-b? S (2-eulfoest? R? L) b Disodium phenotype DETPMP Diethylenetriammopent amet ienphosphonic acid, marketed by Monsanto under the trade name Dequest 2060 Suppressor 25% paraffin wax pf 50 ° C, 17% silica hydrophobic foams, 58% fine oil . mixed EXAMPLE 1 Preparation of the polyamino acid-protein agglote contained in a detergent composition 100 g of a solution of polyaspartic acid (25% active) was mixed with 20 g of albumin (100% active) in a round bottom flask. The resulting mixture was then stirred for an additional 3 hours at a temperature between 35 ° C and 40 ° C at a blade speed of 150 r.p.rn, until a yellow / brown paste formed. The mixture was then stopped and the pulp was left in an oven at 35 ° C for an additional 24 hours. The resulting solid was ground into a fine powder (yellow / brown) using a mortar and pestle. The product after sieving and materials that were greater than 80 micras and less than 250 micras were removed. The remaining material was used in the test. 4.8% by weight of said agglote of polyaspartic acid / albumin was collected and incorporated into a detergent matrix of zero dispersant (100 g). The zero dispersant detergent matrix had the following composition in percent by weight: shape of an agglote Storage stability results of the polyaspartic acid-albumin agglote contained in a detergent composition against a pure polyaspartate granule contained in a detergent composition after a period of 4 weeks of storage under adverse conditions (32.2"C) and moisture 80% relative) A comparative composition containing 4% by weight of the polyaspartic acid null was prepared and incorporated into 100 g of the null dispersant detergent matrix described above. the stored product, after a period of 4 weeks of storage under adverse conditions (32.2 ° C and relative units d 80%), using HPLC. The results are the following: It can be seen that the polyaspartic acid / albumin agglomerate contained in the detergent composition shows increased storage stability on the polyaspartic acid granule contained in the same detergent composition.

EXAMPLE 2 The following detergent compositions (parts by weight) were prepared. The compositions A, B, C, D, E are according to the present invention, wherein the agglomerate of polyaspartic acid / albumin is co or defined in example 1 and composition F is a comparative composition wherein the agglomerate of polyaspartic acid / albumin is replaced by a maleic acid / acrylic acid copolymer supplied by BASF.

It was found that compositions A through E have good storage stability of polyaspartic acid.

Test protocol-stain removal Four white cotton sheets were previously washed in a null polymer detergent matrix with a density of approximately 700 rng / liter. After 10 spots were applied to one sheet, 10 spots to the second sheet, 10 spots to the third and 10 to the fourth. From each sheet, 8 square test samples of 10cm x 10cm were cut. The series of fabric samples were subjected to a washing cycle in an automatic washing machine (Miele short wash cycle). Samples after evaluated for the removal of particulate, greasy enzymatic and bleach stains using a clarity measurement method in established. In more detail, a Miele 756 WM automatic washing machine was used, and the short cycle program at 90 ° C was selected. Water of a German hardness of 35 ° (= 3.75 moles of Ca 2+ / liter) was used. 100 g of detergent, assorted from a granule dispensing device, were used. A sample of each type of fabric was washed together with a 2.6 kg balasta load of lightly soiled sheets. Stain removal was evaluated by making LAB measurements (clarity) using an X-rite eye color spectrometer (trade name). A non-stained cotton sheet was used as a reference. A stain removal index, R, was calculated as follows: R = C (L lavida'L not washed '/ (L na lavada'L di reference)] X 100 where the differences of R less than 4% They are not significant.

Test compares i to-removal of spots The above test protocol was followed in comparison with the efficiency of compositions A and F in the removal of a different type of dispersant-sensitive stains. The results obtained were the following: All results are non-significant differences The removal of spots obtained for each of compositions A and F is shown to be comparable. In this way, the presence of albumin as a co-agglomerating agent of polyaspartic acid, in composition A does not significantly compromise the stain removal capacity of the composition against that of composition F.

Claims (12)

NOVELTY OF THE INVENTION CLAIMS

1. - A composition containing a surfactant, at least one polyamino acid compound and at least one protein, wherein said polyarnino acid compound and said protein are in close physical proximity.

2. A detergent composition according to claim 1, further characterized in that said polyarnino acid compound is selected from the group consisting of homopolymers, copolymers of two or more amino acids and mixtures thereof.

3. A detergent composition according to one of claims 1 or 2, further characterized in that said protein is selected from the group consisting of microorganisms and proteins obtained from them, proteins of animal origin and proteins of plant origin.

4. A detergent composition according to claim 3, further characterized in that the ratio of said polyamino acid compound and said protein is from about 9: 1 to about 1: 9 by weight.

5. A detergent composition according to claim 4, further characterized in that the ratio of said polyamino acid compound and said protein is from about 4: 1 to about 1: 4 by weight.

6. A detergent composition according to claim 5, further characterized in that said polyarninoaid compound is selected from. group consisting of polyaspartic acid and polyglutaric acid.

7. A detergent composition according to claim 6, further characterized in that said mixture of poly-amino acid compound and protein is in a form of the group consisting of an agglomerate, a granulated material and a tablet.

8. A detergent composition according to claim 7, further characterized in that it comprises enzymes, bleaches, detergency builders and optional ingredients.

9. A process for producing a detergent composition containing a detersive surfactant, at least one polyamino acid compound selected from the group consisting of homopolymers, two or more amino acid copolymers and mixtures thereof and at least one protein selected from the group consisting of microorganisms and proteins obtained therefrom, proteins of animal origin and proteins of vegetable origin; and comprising the steps of: a) contacting said protein with the polyamino acid compound in the presence of water, b) stirring the resulting mixture to obtain a solid brittle agglomerate, c) grinding-said agglomerate to obtain a particle size. about 250 or about 800μ, d) incorporating the agglomerate in the detergent composition.

10. A method according to claim 9, further characterized in that the ratio of said polyamino acid compound to said protein is from about 9: 1 to about 1: 9 by weight.

11. - A method according to claim 10, further characterized in that the ratio of said polyamino acid compound to said protein is from about 4: 1 to about 1: 4 by weight.

12. A process according to claim 10, further characterized in that said polyamino acid compound is selected from the group consisting of polyaspartic acid and poly-luthanic acid.